TW201800554A - Surface treatment agent - Google Patents
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- TW201800554A TW201800554A TW106105915A TW106105915A TW201800554A TW 201800554 A TW201800554 A TW 201800554A TW 106105915 A TW106105915 A TW 106105915A TW 106105915 A TW106105915 A TW 106105915A TW 201800554 A TW201800554 A TW 201800554A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/22—Esters containing halogen
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09K3/00—Materials not provided for elsewhere
- C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
- D06M15/277—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof containing fluorine
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Abstract
Description
本發明係關於一種包含撥水撥油性聚合物及高分子界面活性劑之表面處理劑。具體而言,本發明可對於纖維製品(例如地毯)、紙、不織布、石材、靜電膜、防塵罩、燃料電池的零件賦予優異的撥水性、撥油性、防污性。 The invention relates to a surface treatment agent containing a water- and oil-repellent polymer and a polymer surfactant. Specifically, the present invention can impart excellent water repellency, oil repellency, and antifouling properties to components of fiber products (such as carpets), paper, nonwoven fabrics, stone materials, electrostatic membranes, dust covers, and fuel cells.
以往已提案多種含氟化合物。含氟化合物係有耐熱性、抗氧化性、耐候性等特性優異之優點。利用含氟化合物之自由能低(亦即不易附著)之特性,其係例如被使用作為撥水撥油劑及防污劑。 Various fluorine-containing compounds have been proposed in the past. The fluorine-containing compound has the advantages of excellent characteristics such as heat resistance, oxidation resistance, and weather resistance. Taking advantage of the low free energy of the fluorine-containing compound (that is, it is not easy to adhere), it is used as a water and oil repellent and antifouling agent, for example.
就可使用作為撥水撥油劑之含氟化合物而言,可列舉將具有氟烷基之(甲基)丙烯酸酯作為構成單體之含氟聚合物。在表面處理劑對纖維之實用處理中,由至今之多種研究結果來看,係顯示就其表面特性而言,重要的不是靜態接觸角而是動態接觸角,特別重要的是後退接觸角。亦即,雖然水的前進接觸角不會依存於氟烷基的側鏈碳數,但是就水的後退接觸角而言,相較於側鏈的碳數8以上者,側鏈的碳數7以下者係顯著變小。對應於此,X 射線分析顯示側鏈的碳數為7以上者會發生側鏈的結晶化。已知實用上的撥水性係與側鏈的結晶性有所關聯,並且表面處理劑分子的運動性係呈現實用性能的重要要素(例如前川隆茂,精緻化學品(fine chemical),Vol23,No.6,P12(1994))。由於上述理由,具有其側鏈碳數短達7以下(尤其是6以下)之氟烷基的(甲基)丙烯酸酯系聚合物係有因側鏈的結晶性低,故無法滿足實用性能之問題。 Examples of the fluorine-containing compound that can be used as a water- and oil-repellent agent include fluorine-containing polymers having a (meth) acrylate having a fluoroalkyl group as a constituent monomer. In the practical treatment of fibers by surface treatment agents, from the results of various studies to date, it is shown that in terms of their surface characteristics, what is important is not the static contact angle but the dynamic contact angle, and particularly important is the receding contact angle. That is, although the advancing contact angle of water does not depend on the carbon number of the side chain of the fluoroalkyl group, in terms of the receding contact angle of water, the number of carbons of the side chain is 7 compared to those of the side chain having 8 or more The following are significantly smaller. Corresponding to this, X Ray analysis showed that the number of carbons in the side chain is 7 or more, and side chain crystallization occurs. It is known that the practical water repellent system is related to the crystallinity of the side chain, and the mobility of the surface treatment agent molecule exhibits an important element of practical performance (for example, Maekawa Takao, Fine Chemicals, Vol23, No. 6, P12 (1994)). For the above reasons, (meth) acrylate-based polymers having a fluoroalkyl group with a side chain carbon number as short as 7 or less (especially 6 or less) have low side chain crystallinity and therefore cannot satisfy practical performance. problem.
已提案有製品安定性優異之含氟表面處理劑。 Fluorine-containing surface treatment agents with excellent product stability have been proposed.
日本特開平9-118877號公報揭示一種雜質安定性優異之水分散型撥水撥油劑組成物,其含有下述(a)及(b):分散於水系媒質中之包含含有聚氟烷基的丙烯酸酯或甲基丙烯酸酯的聚合單元的聚合物(a)、以及界面活性劑(b);其中,界面活性劑(b)至少包含界面活性劑(c)、界面活性劑(d)及界面活性劑(e)這3種界面活性劑。 Japanese Patent Laid-Open No. 9-118877 discloses a water-dispersed water- and oil-repellent composition with excellent impurity stability, which contains the following (a) and (b): the polyfluoroalkyl group containing Acrylate or methacrylate polymer units of polymer (a) and surfactant (b); wherein, surfactant (b) contains at least surfactant (c), surfactant (d) and Surfactant (e) These three surfactants.
日本特開平9-125051號公報揭示一種安定性優異之水分散型撥水撥油劑組成物,其包含:水系媒質、分散於水系媒質中之包含含有聚氟烷基的丙烯酸酯或甲基丙烯酸酯的聚合單元之聚合物(a)、以及界面活性劑(b)。 Japanese Patent Laid-Open No. 9-125051 discloses a water-dispersible water- and oil-repellent composition with excellent stability, which comprises: an aqueous medium and an acrylate or methacrylic acid containing a polyfluoroalkyl group dispersed in the aqueous medium The polymer (a) of the polymerized unit of the ester and the surfactant (b).
日本特開2015-120984號公報揭示一種纖維製品,其係經賦予由氧化金屬、吡啶系化合物及陽離子系聚合物中選出之1種以上之抗菌劑,與由吸水劑、非離子系柔軟劑及陽離子系柔軟劑中選出之1種以上之化合物者。 Japanese Patent Laid-Open No. 2015-120984 discloses a fibrous product, which is provided with one or more antibacterial agents selected from metal oxides, pyridine-based compounds and cationic polymers, and water-absorbing agents, nonionic softeners and One or more compounds selected from cationic softeners.
傳統的含氟撥水撥油劑,係撥水撥油加工 之加工安定性不充分。 The traditional fluorine-containing water and oil repellent agent is used for water and oil repellent processing. The processing stability is insufficient.
[專利文獻1]日本特開平9-118877號公報 [Patent Document 1] Japanese Patent Laid-Open No. 9-118877
[專利文獻2]日本特開平9-125051號公報 [Patent Document 2] Japanese Patent Laid-Open No. 9-125051
[專利文獻3]日本特開2015-120984號公報 [Patent Document 3] Japanese Patent Laid-Open No. 2015-120984
本發明之一目的係提供一種表面處理劑,其係使纖維等的撥水撥油加工之加工安定性、尤其是膠黏附(gum-up)性經改良者。 An object of the present invention is to provide a surface treatment agent which improves the processing stability, especially the gum-up property, of water and oil repellent processing of fibers and the like.
本發明另一目的係提供一種表面處理劑,其係化學安定性(雜質安定性)及機械安定性優異者。 Another object of the present invention is to provide a surface treatment agent which is excellent in chemical stability (impurity stability) and mechanical stability.
本發明提供一種表面處理劑,其係包含下述(A)、(B)、(C)而成之表面處理劑:(A)撥水撥油性聚合物,其具有由具有氟烷基之含氟單體(A1)及長鏈(甲基)丙烯酸酯單體(A2)中之一者或兩者衍生出之重複單元;(B)高分子型界面活性劑;以及(C)液狀媒質。 The present invention provides a surface treatment agent comprising the following (A), (B), and (C): (A) a water- and oil-repellent polymer having a fluoroalkyl group Repeating units derived from one or both of fluoromonomer (A1) and long-chain (meth) acrylate monomer (A2); (B) polymer surfactant; and (C) liquid medium .
本發明又提供一種表面處理劑之製造方法,其係具有下述步驟: (i)於液狀媒質存在下,將包含具有氟烷基之含氟單體(A1)或長鏈(甲基)丙烯酸酯單體(A2)而成之單體進行聚合,而得到具有由具有氟烷基之含氟單體(A1)或長鏈(甲基)丙烯酸酯單體(A2)衍生出之重複單元的撥水撥油性聚合物之水性分散液之步驟;以及(ii)於撥水撥油性聚合物之水性分散液添加高分子型界面活性劑之步驟。 The invention also provides a method for manufacturing a surface treatment agent, which has the following steps: (i) In the presence of a liquid medium, a monomer comprising a fluoroalkyl group-containing fluorinated monomer (A1) or a long-chain (meth) acrylate monomer (A2) is polymerized to obtain Steps of an aqueous dispersion of a water- and oil-repellent polymer of a repeating unit derived from a fluorine-containing monomer (A1) having a fluoroalkyl group or a long-chain (meth) acrylate monomer (A2); and (ii) Step of adding polymer surfactant to the aqueous dispersion of water and oil repellent polymer.
本發明之表面處理劑係不會引起粒子的沉澱,也不會使輥體附著有聚合物而污染物料。 The surface treatment agent of the present invention does not cause the precipitation of particles, nor does it cause the roller body to be attached with polymer and contaminant material.
依據本發明,能夠得到優異的撥水性、撥油性、防污性及去污性,例如,能夠得到撥水撥油性優異的耐久性。 According to the present invention, excellent water repellency, oil repellency, antifouling properties and decontamination properties can be obtained, for example, durability with excellent water repellency and oil repellency can be obtained.
本發明之表面處理劑可使用作為撥水撥油劑、防污劑及/或去污劑。 The surface treatment agent of the present invention can be used as a water and oil repellent, antifouling agent and / or detergent.
一般而言,表面處理劑係撥水撥油性聚合物之水性乳劑。 In general, the surface treatment agent is an aqueous emulsion of water- and oil-repellent polymers.
表面處理劑係包含下述(A)、(B)、(C)所成者:(A)撥水撥油性聚合物,其具有由具有氟烷基之含氟單體(A1)或長鏈(甲基)丙烯酸酯單體(A2)中之一者或兩者衍生出之重複單元;(B)高分子型界面活性劑;以及 (C)液狀媒質。 The surface treatment agent includes the following (A), (B), and (C): (A) a water-repellent oil-repellent polymer, which has a fluorine-containing monomer (A1) having a fluoroalkyl group or a long chain Repeating units derived from one or both of (meth) acrylate monomers (A2); (B) polymeric surfactants; and (C) Liquid medium.
撥水撥油性聚合物係具有由具有氟烷基之含氟單體或長鏈(甲基)丙烯酸酯單體衍生出之重複單元的均聚物、具有由具有氟烷基之含氟單體及長鏈(甲基)丙烯酸酯單體中選出之2種以上之單體衍生出之重複單元的共聚物、或具有由具有氟烷基之含氟單體或長鏈(甲基)丙烯酸酯單體衍生出之重複單元與由可共聚合之其他聚合性化合物衍生出之重複單元的共聚物。 The water- and oil-repellent polymer is a homopolymer having a repeating unit derived from a fluorine-containing monomer having a fluoroalkyl group or a long-chain (meth) acrylate monomer, and having a fluorine-containing monomer having a fluoroalkyl group And a copolymer of repeating units derived from two or more monomers selected from long-chain (meth) acrylate monomers, or having a fluorine-containing monomer or long-chain (meth) acrylate having a fluoroalkyl group A copolymer of repeating units derived from monomers and repeating units derived from copolymerizable other polymerizable compounds.
撥水撥油性聚合物為含氟聚合物或非氟聚合物。含氟聚合物為具有由具有氟烷基之含氟單體衍生出之重複單元的聚合物,非氟聚合物係具有由長鏈(甲基)丙烯酸酯單體衍生出之重複單元的聚合物。 The water- and oil-repellent polymer is a fluoropolymer or a non-fluoropolymer. Fluoropolymers are polymers with repeating units derived from fluoromonomers with fluoroalkyl groups, and non-fluoropolymers are polymers with repeating units derived from long-chain (meth) acrylate monomers .
本發明中,撥水撥油性聚合物(A)可為僅以由(A1)具有氟烷基之含氟單體衍生出之重複單元及/或由(A2)長鏈(甲基)丙烯酸酯單體衍生出之重複單元所構成者,但較佳為:除了具有重複單元(A1)及/或(A2)以外,還具有由(A3)非氟非交聯性單體衍生出之重複單元及由(A4)非氟交聯性單體衍生出之重複單元中之一者或兩者。 In the present invention, the water- and oil-repellent polymer (A) may be a repeating unit derived only from (A1) a fluorine-containing monomer having a fluoroalkyl group and / or from (A2) a long-chain (meth) acrylate It is composed of repeating units derived from monomers, but preferably has repeating units derived from (A3) non-fluorine non-crosslinkable monomers in addition to repeating units (A1) and / or (A2) And one or both of the repeating units derived from the (A4) non-fluorine crosslinkable monomer.
撥水撥油性聚合物(A)係具有由(A1)具有氟烷基之含氟單體及(A2)長鏈(甲基)丙烯酸酯單體中之一者或兩者衍生出之重複單元。亦即,撥水撥油性聚合物(A)具有由(A1)具有氟烷基之含氟單體衍生出之重複單元及由(A2)長鏈(甲基)丙烯酸酯單體衍生出之重複單元中之一者 或兩者。 The water- and oil-repellent polymer (A) is a repeating unit derived from one or both of (A1) a fluorine-containing monomer having a fluoroalkyl group and (A2) a long-chain (meth) acrylate monomer . That is, the water- and oil-repellent polymer (A) has a repeating unit derived from (A1) a fluorine-containing monomer having a fluoroalkyl group and a repeating unit derived from (A2) a long chain (meth) acrylate monomer One of the units Or both.
(A1)含氟單體 (A1) Fluorine-containing monomer
一般而言,含氟單體係具有全氟烷基或全氟烯基及丙烯酸基或甲基丙烯酸基或α-取代丙烯酸基之聚合性化合物。 Generally speaking, the fluorine-containing monosystem has a polymer compound of a perfluoroalkyl group or a perfluoroalkenyl group and an acrylic group or a methacrylic group or an α-substituted acrylic group.
含氟單體較佳為下述式所示之化合物:CH2=C(-X)-C(=O)-Y-Z-Rf[式中,X為氫原子、一價有機基或鹵原子,Y為-O-或-NH-,Z為直接鍵結或二價有機基,Rf為碳數1至20之氟烷基]。 The fluorine-containing monomer is preferably a compound represented by the following formula: CH 2 = C (-X) -C (= O) -YZ-Rf [where X is a hydrogen atom, a monovalent organic group or a halogen atom, Y is -O- or -NH-, Z is a direct bond or a divalent organic group, and Rf is a fluoroalkyl group having 1 to 20 carbons].
Z例如可為:碳數1至20之直鏈狀或分枝狀脂肪族基(尤其是伸烷基),例如式-(CH2)x-(式中,x為1至10)所示之基;或是式-R2(R1)N-SO2-或式-R2(R1)N-CO-所示之基(式中,R1為碳數1至10之烷基,R2為碳數1至10之直鏈伸烷基或分枝狀伸烷基);或是式-CH2CH(OR3)CH2-(Ar-O)p-所示之基(式中,R3為氫原子或碳數1至10之醯基(例如甲醯基或乙醯基等),Ar為視所需而具有取代基之伸芳基,p表示0或1);或是式-CH2-Ar-(O)q-所示之基(式中,Ar為視所需而具有取代基之伸芳基,q為0或1)、-(CH2)m-SO2-(CH2)n-基或-(CH2)m-S-(CH2)n-基(惟m為1至10,n為0至10)。 Z can be, for example, a linear or branched aliphatic group with a carbon number of 1 to 20 (especially an alkylene group), for example, represented by the formula-(CH 2 ) x- (where x is 1 to 10) Group; or a group represented by the formula -R 2 (R 1 ) N-SO 2 -or the formula -R 2 (R 1 ) N-CO- (wherein R 1 is an alkyl group having 1 to 10 carbon atoms) , R 2 is a straight-chain alkylene or branched alkylene having 1 to 10 carbon atoms); or a group represented by the formula -CH 2 CH (OR 3 ) CH 2- (Ar-O) p- ( In the formula, R 3 is a hydrogen atom or an acyl group with a carbon number of 1 to 10 (for example, a methylene group or an acetyl group, etc.), Ar is an aryl group having a substituent as necessary, and p represents 0 or 1); Or a group represented by the formula -CH 2 -Ar- (O) q- (where Ar is an aryl group having a substituent as required, and q is 0 or 1),-(CH 2 ) m- SO 2- (CH 2 ) n -group or-(CH 2 ) m -S- (CH 2 ) n -group (but m is 1 to 10, n is 0 to 10).
X之具體例為H、CH3、Cl、Br、I、F、CN、CF3。較佳為X係甲基或氯原子,特佳為氯原子。 Specific examples of X are H, CH 3 , Cl, Br, I, F, CN, and CF 3 . Preferably, X is a methyl group or a chlorine atom, and particularly preferably a chlorine atom.
含氟單體係以下述通式所示之丙烯酸酯或丙烯醯胺為較佳:CH2=C(-X)-C(=O)-Y-Z-Rf (I)[式中,X為氫原子、碳數1至21之直鏈狀或分枝狀之烷基、氟原子、氯原子、溴原子、碘原子、CFX1X2基(惟X1及X2為氫原子、氟原子、氯原子、溴原子或碘原子)、氰基、碳數1至21之直鏈狀或分枝狀之氟烷基、取代或非取代之苯甲基、取代或非取代之苯基;Y為-O-或-NH-;Z為直接鍵結、碳數1至10之脂肪族基、碳數6至18之芳香族基或環狀脂肪族基、-CH2CH2N(R1)SO2-基(惟R1為碳數1至4之烷基)、-CH2CH(OZ1)CH2-(Ph-O)p-基(惟Z1為氫原子或乙醯基,Ph為伸苯基,p為0或1)、-(CH2)n-Ph-O-基(惟Ph為伸苯基,n為0至10)、-(CH2)m-SO2-(CH2)n-基或-(CH2)m-S-(CH2)n-基(惟m為1至10,n為0至10);Rf為碳數1至20之直鏈狀或分枝狀之氟烷基]。 The fluorine-containing single system is preferably acrylate or acrylamide represented by the following general formula: CH 2 = C (-X) -C (= O) -YZ-Rf (I) [wherein, X is hydrogen Atom, linear or branched alkyl group with 1 to 21 carbon atoms, fluorine atom, chlorine atom, bromine atom, iodine atom, CFX 1 X 2 group (but X 1 and X 2 are hydrogen atom, fluorine atom, Chlorine atom, bromine atom or iodine atom), cyano group, linear or branched fluoroalkyl group having 1 to 21 carbon atoms, substituted or unsubstituted benzyl group, substituted or unsubstituted phenyl group; Y is -O- or -NH-; Z is a direct bond, an aliphatic group having 1 to 10 carbon atoms, an aromatic group or cyclic aliphatic group having 6 to 18 carbon atoms, -CH 2 CH 2 N (R 1 ) SO 2 -group (but R 1 is an alkyl group having 1 to 4 carbon atoms), -CH 2 CH (OZ 1 ) CH 2- (Ph-O) p -group (but Z 1 is a hydrogen atom or an acetyl group, Ph is phenylene, p is 0 or 1),-(CH 2 ) n -Ph-O- group (but Ph is phenylene, n is 0 to 10),-(CH 2 ) m -SO 2- (CH 2 ) n -group or-(CH 2 ) m -S- (CH 2 ) n -group (but m is 1 to 10, n is 0 to 10); Rf is a straight chain of carbon number 1 to 20 Or branched fluoroalkyl].
含氟單體中,Rf基較佳為全氟烷基。Rf基的碳數係1至12,例如較佳為1至6,特別較佳為4至6,特別更佳為6。Rf基的例為:-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、-C8F17等。 In the fluorine-containing monomer, the Rf group is preferably a perfluoroalkyl group. The carbon number of the Rf group is 1 to 12, for example, preferably 1 to 6, particularly preferably 4 to 6, and even more preferably 6. Examples of Rf groups are: -CF 3 , -CF 2 CF 3 , -CF 2 CF 2 CF 3 , -CF (CF 3 ) 2 , -CF 2 CF 2 CF 2 CF 3 , -CF 2 CF (CF 3 ) 2 , -C (CF 3 ) 3 ,-(CF 2 ) 4 CF 3 ,-(CF 2 ) 2 CF (CF 3 ) 2 , -CF 2 C (CF 3 ) 3 , -CF (CF 3 ) CF 2 CF 2 CF 3 ,-(CF 2 ) 5 CF 3 ,-(CF 2 ) 3 CF (CF 3 ) 2 ,-(CF 2 ) 4 CF (CF 3 ) 2 , -C 8 F 17 etc.
Z較佳為碳數1至10之脂肪族基、碳數6至18之芳香族基或環狀脂肪族基、-CH2CH2N(R1)SO2-基(惟 R1為碳數1至4之烷基)、-CH2CH(OZ1)CH2-(Ph-O)p-基(惟Z1為氫原子或乙醯基,Ph為伸苯基,p為0或1)、-(CH2)n-Ph-O-基(惟Ph為伸苯基,n為0至10)、-(CH2)m-SO2-(CH2)n-基或-(CH2)m-S-(CH2)n-基(惟m為1至10,n為0至10)。脂肪族基較佳為伸烷基(特別較佳為碳數係1至4,例如1或2)。芳香族基或環狀脂肪族基可為經取代者或未經取代者。S基或SO2基可直接鍵結於Rf基。 Z is preferably an aliphatic group having 1 to 10 carbon atoms, an aromatic group having 6 to 18 carbon atoms or a cyclic aliphatic group, a -CH 2 CH 2 N (R 1 ) SO 2 -group (but R 1 is carbon Number 1 to 4 alkyl), -CH 2 CH (OZ 1 ) CH 2- (Ph-O) p -group (but Z 1 is a hydrogen atom or acetyl group, Ph is a phenylene group, p is 0 or 1),-(CH 2 ) n -Ph-O- group (but Ph is phenylene, n is 0 to 10),-(CH 2 ) m -SO 2- (CH 2 ) n -group or-( CH 2 ) m -S- (CH 2 ) n -group (but m is 1 to 10, n is 0 to 10). The aliphatic group is preferably an alkylene group (particularly preferably a carbon number system of 1 to 4, such as 1 or 2). The aromatic group or cyclic aliphatic group may be substituted or unsubstituted. The S group or the SO 2 group may be directly bonded to the Rf group.
含氟單體之具體例可例示例如以下者,惟並不限定於該等者。 Specific examples of the fluorine-containing monomer are as follows, but not limited to these.
CH2=C(-H)-C(=O)-O-(CH2)2-Rf CH2=C(-H)-C(=O)-O-C6H4-Rf CH2=C(-Cl)-C(=O)-O-(CH2)2-Rf CH2=C(-H)-C(=O)-O-(CH2)2N(-CH3)SO2-Rf CH2=C(-H)-C(=O)-O-(CH2)2N(-C2H5)SO2-Rf CH2=C(-H)-C(=O)-O-CH2CH(-OH)CH2-Rf CH2=C(-H)-C(=O)-O-CH2CH(-OCOCH3)CH2-Rf CH2=C(-H)-C(=O)-O-(CH2)2-S-Rf CH2=C(-H)-C(=O)-O-(CH2)2-S-(CH2)2-Rf CH2=C(-H)-C(=O)-O-(CH2)3-SO2-Rf CH2=C(-H)-C(=O)-O-(CH2)2-SO2-(CH2)2-Rf CH2=C(-H)-C(=O)-NH-(CH2)2-Rf CH2=C(-CH3)-C(=O)-O-(CH2)2-S-Rf CH2=C(-CH3)-C(=O)-O-(CH2)2-S-(CH2)2-Rf CH2=C(-CH3)-C(=O)-O-(CH2)3-SO2-Rf CH2=C(-CH3)-C(=O)-O-(CH2)2-SO2-(CH2)2-Rf CH2=C(-CH3)-C(=O)-NH-(CH2)2-Rf CH2=C(-F)-C(=O)-O-(CH2)2-S-Rf CH2=C(-F)-C(=O)-O-(CH2)2-S-(CH2)2-Rf CH2=C(-F)-C(=O)-O-(CH2)2-SO2-Rf CH2=C(-F)-C(=O)-O-(CH2)2-SO2-(CH2)2-Rf CH2=C(-F)-C(=O)-NH-(CH2)2-Rf CH2=C(-Cl)-C(=O)-O-(CH2)2-S-Rf CH2=C(-Cl)-C(=O)-O-(CH2)2-S-(CH2)2-Rf CH2=C(-Cl)-C(=O)-O-(CH2)2-SO2-Rf CH2=C(-Cl)-C(=O)-O-(CH2)2-SO2-(CH2)2-Rf CH2=C(-Cl)-C(=O)-NH-(CH2)2-Rf CH2=C(-CF3)-C(=O)-O-(CH2)2-S-Rf CH2=C(-CF3)-C(=O)-O-(CH2)2-S-(CH2)2-Rf CH2=C(-CF3)-C(=O)-O-(CH2)2-SO2-Rf CH2=C(-CF3)-C(=O)-O-(CH2)2-SO2-(CH2)2-Rf CH2=C(-CF3)-C(=O)-NH-(CH2)2-Rf CH2=C(-CF2H)-C(=O)-O-(CH2)2-S-Rf CH2=C(-CF2H)-C(=O)-O-(CH2)2-S-(CH2)2-Rf CH2=C(-CF2H)-C(=O)-O-(CH2)2-SO2-Rf CH2=C(-CF2H)-C(=O)-O-(CH2)2-SO2-(CH2)2-Rf CH2=C(-CF2H)-C(=O)-NH-(CH2)2-Rf CH2=C(-CN)-C(=O)-O-(CH2)2-S-Rf CH2=C(-CN)-C(=O)-O-(CH2)2-S-(CH2)2-Rf CH2=C(-CN)-C(=O)-O-(CH2)2-SO2-Rf CH2=C(-CN)-C(=O)-O-(CH2)2-SO2-(CH2)2-Rf CH2=C(-CN)-C(=O)-NH-(CH2)2-Rf CH2=C(-CF2CF3)-C(=O)-O-(CH2)2-S-Rf CH2=C(-CF2CF3)-C(=O)-O-(CH2)2-S-(CH2)2-Rf CH2=C(-CF2CF3)-C(=O)-O-(CH2)2-SO2-Rf CH2=C(-CF2CF3)-C(=O)-O-(CH2)2-SO2-(CH2)2-Rf CH2=C(-CF2CF3)-C(=O)-NH-(CH2)2-Rf CH2=C(-F)-C(=O)-O-(CH2)3-S-Rf CH2=C(-F)-C(=O)-O-(CH2)3-S-(CH2)2-Rf CH2=C(-F)-C(=O)-O-(CH2)3-SO2-Rf CH2=C(-F)-C(=O)-O-(CH2)3-SO2-(CH2)2-Rf CH2=C(-F)-C(=O)-NH-(CH2)3-Rf CH2=C(-Cl)-C(=O)-O-(CH2)3-S-Rf CH2=C(-Cl)-C(=O)-O-(CH2)3-S-(CH2)2-Rf CH2=C(-Cl)-C(=O)-O-(CH2)3-SO2-Rf CH2=C(-Cl)-C(=O)-O-(CH2)3-SO2-(CH2)2-Rf CH2=C(-CF3)-C(=O)-O-(CH2)3-S-Rf CH2=C(-CF3)-C(=O)-O-(CH2)3-S-(CH2)2-Rf CH2=C(-CF3)-C(=O)-O-(CH2)3-SO2-Rf CH2=C(-CF3)-C(=O)-O-(CH2)3-SO2-(CH2)2-Rf CH2=C(-CF2H)-C(=O)-O-(CH2)3-S-Rf CH2=C(-CF2H)-C(=O)-O-(CH2)3-S-(CH2)2-Rf CH2=C(-CF2H)-C(=O)-O-(CH2)3-SO2-Rf CH2=C(-CF2H)-C(=O)-O-(CH2)3-SO2-(CH2)2-Rf CH2=C(-CN)-C(=O)-O-(CH2)3-S-Rf CH2=C(-CN)-C(=O)-O-(CH2)3-S-(CH2)2-Rf CH2=C(-CN)-C(=O)-O-(CH2)3-SO2-Rf CH2=C(-CN)-C(=O)-O-(CH2)3-SO2-(CH2)2-Rf CH2=C(-CF2CF3)-C(=O)-O-(CH2)3-S-Rf CH2=C(-CF2CF3)-C(=O)-O-(CH2)3-S-(CH2)2-Rf CH2=C(-CF2CF3)-C(=O)-O-(CH2)3-SO2-Rf CH2=C(-CF2CF3)-C(=O)-O-(CH2)2-SO2-(CH2)2-Rf[上述式中,Rf為碳數1至20之氟烷基]。 CH 2 = C (-H) -C (= O) -O- (CH 2 ) 2 -Rf CH 2 = C (-H) -C (= O) -OC 6 H 4 -Rf CH 2 = C ( -Cl) -C (= O) -O- (CH 2 ) 2 -Rf CH 2 = C (-H) -C (= O) -O- (CH 2 ) 2 N (-CH 3 ) SO 2- Rf CH 2 = C (-H) -C (= O) -O- (CH 2 ) 2 N (-C 2 H 5 ) SO 2 -Rf CH 2 = C (-H) -C (= O)- O-CH 2 CH (-OH) CH 2 -Rf CH 2 = C (-H) -C (= O) -O-CH 2 CH (-OCOCH 3 ) CH 2 -Rf CH 2 = C (-H) -C (= O) -O- (CH 2 ) 2 -S-Rf CH 2 = C (-H) -C (= O) -O- (CH 2 ) 2 -S- (CH 2 ) 2 -Rf CH 2 = C (-H) -C (= O) -O- (CH 2 ) 3 -SO 2 -Rf CH 2 = C (-H) -C (= O) -O- (CH 2 ) 2- SO 2- (CH 2 ) 2 -Rf CH 2 = C (-H) -C (= O) -NH- (CH 2 ) 2 -Rf CH 2 = C (-CH 3 ) -C (= O)- O- (CH 2 ) 2 -S-Rf CH 2 = C (-CH 3 ) -C (= O) -O- (CH 2 ) 2 -S- (CH 2 ) 2 -Rf CH 2 = C (- CH 3 ) -C (= O) -O- (CH 2 ) 3 -SO 2 -Rf CH 2 = C (-CH 3 ) -C (= O) -O- (CH 2 ) 2 -SO 2- ( CH 2 ) 2 -Rf CH 2 = C (-CH 3 ) -C (= O) -NH- (CH 2 ) 2 -Rf CH 2 = C (-F) -C (= O) -O- (CH 2 ) 2 -S-Rf CH 2 = C (-F) -C (= O) -O- (CH 2 ) 2 -S- (CH 2 ) 2 -Rf CH 2 = C (-F) -C ( = O) -O- (CH 2 ) 2 -SO 2 -Rf CH 2 = C (-F) -C (= O) -O- (CH 2 ) 2 -SO 2- (CH 2 ) 2 -Rf CH 2 = C (-F) -C (= O) -NH- (CH 2 ) 2 -Rf CH 2 = C (-Cl) -C (= O) -O- (CH 2 ) 2 -S-Rf CH 2 = C (-Cl) -C (= O) -O- (CH 2 ) 2 -S- (CH 2 ) 2 -Rf CH 2 = C (-Cl) -C (= O) -O- (CH 2 ) 2 -SO 2 -Rf CH 2 = C (-Cl) -C (= O) -O- (CH 2 ) 2 -SO 2- (CH 2 ) 2 -Rf CH 2 = C (-Cl) -C (= O) -NH- (CH 2 ) 2 -Rf CH 2 = C ( -CF 3 ) -C (= O) -O- (CH 2 ) 2 -S-Rf CH 2 = C (-CF 3 ) -C (= O) -O- (CH 2 ) 2 -S- (CH 2 ) 2 -Rf CH 2 = C (-CF 3 ) -C (= O) -O- (CH 2 ) 2 -SO 2 -Rf CH 2 = C (-CF 3 ) -C (= O) -O -(CH 2 ) 2 -SO 2- (CH 2 ) 2 -Rf CH 2 = C (-CF 3 ) -C (= O) -NH- (CH 2 ) 2 -Rf CH 2 = C (-CF 2 H) -C (= O) -O- (CH 2 ) 2 -S-Rf CH 2 = C (-CF 2 H) -C (= O) -O- (CH 2 ) 2 -S- (CH 2 ) 2 -Rf CH 2 = C (-CF 2 H) -C (= O) -O- (CH 2 ) 2 -SO 2 -Rf CH 2 = C (-CF 2 H) -C (= O)- O- (CH 2 ) 2 -SO 2- (CH 2 ) 2 -Rf CH 2 = C (-CF 2 H) -C (= O) -NH- (CH 2 ) 2 -Rf CH 2 = C (- CN) -C (= O) -O- (CH 2 ) 2 -S-Rf CH 2 = C (-CN) -C (= O) -O- (CH 2 ) 2 -S- (CH 2 ) 2 -Rf CH 2 = C (-CN) -C (= O) -O- (CH 2 ) 2 -SO 2 -Rf CH 2 = C (-CN) -C (= O) -O- (CH 2 ) 2 -SO 2- (CH 2 ) 2 -Rf CH 2 = C (-CN) -C (= O) -NH- (CH 2 ) 2 -Rf CH 2 = C (-CF 2 CF 3 ) -C ( = O) -O- (CH 2 ) 2 -S-Rf CH 2 = C (-CF 2 CF 3 ) -C (= O) -O- (CH 2 ) 2 -S- (CH 2 ) 2 -Rf CH 2 = C (-CF 2 CF 3 ) -C (= O) -O- (CH 2 ) 2 -SO 2 -Rf CH 2 = C (-CF 2 CF 3 ) -C (= O ) -O- (CH 2 ) 2 -SO 2- (CH 2 ) 2 -Rf CH 2 = C (-CF 2 CF 3 ) -C (= O) -NH- (CH 2 ) 2 -Rf CH 2 = C (-F) -C (= O) -O- (CH 2 ) 3 -S-Rf CH 2 = C (-F) -C (= O) -O- (CH 2 ) 3 -S- (CH 2 ) 2 -Rf CH 2 = C (-F) -C (= O) -O- (CH 2 ) 3 -SO 2 -Rf CH 2 = C (-F) -C (= O) -O- ( CH 2 ) 3 -SO 2- (CH 2 ) 2 -Rf CH 2 = C (-F) -C (= O) -NH- (CH 2 ) 3 -Rf CH 2 = C (-Cl) -C ( = O) -O- (CH 2 ) 3 -S-Rf CH 2 = C (-Cl) -C (= O) -O- (CH 2 ) 3 -S- (CH 2 ) 2 -Rf CH 2 = C (-Cl) -C (= O) -O- (CH 2 ) 3 -SO 2 -Rf CH 2 = C (-Cl) -C (= O) -O- (CH 2 ) 3 -SO 2- (CH 2 ) 2 -Rf CH 2 = C (-CF 3 ) -C (= O) -O- (CH 2 ) 3 -S-Rf CH 2 = C (-CF 3 ) -C (= O)- O- (CH 2 ) 3 -S- (CH 2 ) 2 -Rf CH 2 = C (-CF 3 ) -C (= O) -O- (CH 2 ) 3 -SO 2 -Rf CH 2 = C ( -CF 3 ) -C (= O) -O- (CH 2 ) 3 -SO 2- (CH 2 ) 2 -Rf CH 2 = C (-CF 2 H) -C (= O) -O- (CH 2 ) 3 -S-Rf CH 2 = C (-CF 2 H) -C (= O) -O- (CH 2 ) 3 -S- (CH 2 ) 2 -Rf CH 2 = C (-CF 2 H ) -C (= O) -O- (CH 2 ) 3 -SO 2 -Rf CH 2 = C (-CF 2 H) -C (= O) -O- (CH 2 ) 3 -SO 2- (CH 2 ) 2 -Rf CH 2 = C (-CN) -C (= O) -O- (CH 2 ) 3 -S-Rf CH 2 = C (-CN) -C (= O) -O- (CH 2 ) 3 -S- (CH 2 ) 2 -Rf CH 2 = C (-CN) -C (= O) -O- (CH 2 ) 3 -SO 2 -Rf CH 2 = C (-CN) -C (= O) -O- (CH 2 ) 3 -SO 2- (CH 2 ) 2 -Rf CH 2 = C (-CF 2 CF 3 ) -C (= O) -O- (CH 2 ) 3 -S-Rf CH 2 = C (-CF 2 CF 3 ) -C (= O) -O- (CH 2 ) 3 -S- (CH 2 ) 2 -Rf CH 2 = C (-CF 2 CF 3 ) -C (= O) -O- (CH 2 ) 3 -SO 2 -Rf CH 2 = C (-CF 2 CF 3 ) -C (= O) -O- (CH 2 ) 2 -SO 2- (CH 2 ) 2 -Rf [In the above formula, Rf Is a fluoroalkyl group having 1 to 20 carbons].
(A2)長鏈(甲基)丙烯酸酯單體 (A2) Long chain (meth) acrylate monomer
長鏈(甲基)丙烯酸酯單體可為下述式所示之化合物:CH2=CA11-C(=O)-O-A12[式中,A11為氫原子或甲基,A12為碳數18至30之直鏈或分枝的烴基]。 The long-chain (meth) acrylate monomer may be a compound represented by the following formula: CH 2 = CA 11 -C (= O) -OA 12 [In the formula, A 11 is a hydrogen atom or a methyl group, and A 12 is Straight chain or branched hydrocarbon group having 18 to 30 carbons].
長鏈(甲基)丙烯酸酯單體不具有氟烷基。長鏈(甲基)丙烯酸酯單體雖亦可含有氟原子,但以不含有氟原子為較 佳。 The long-chain (meth) acrylate monomer does not have a fluoroalkyl group. Although long-chain (meth) acrylate monomers can also contain fluorine atoms, it is better not to contain fluorine atoms. good.
A11係以甲基為特佳。 The A 11 series is particularly preferably methyl.
A12為直鏈狀或分枝狀的烴基。直鏈狀或分枝狀的烴基,特別可為直鏈狀的烴基。直鏈狀或分枝狀的烴基係碳數為18至30。直鏈狀或分枝狀的烴基係以碳數18至28為佳,尤其是以18或22為佳,一般而言是以飽和之脂肪族烴基為佳,尤其是以烷基為較佳。 A 12 is a linear or branched hydrocarbon group. The straight-chain or branched hydrocarbon group may particularly be a straight-chain hydrocarbon group. The linear or branched hydrocarbon group has 18 to 30 carbon atoms. Straight-chain or branched hydrocarbon groups are preferably 18 to 28 carbon atoms, especially 18 or 22, generally saturated aliphatic hydrocarbon groups, especially alkyl groups.
長鏈(甲基)丙烯酸酯單體的較佳具體例為(甲基)丙烯酸硬脂酯、(甲基)丙烯酸山萮酯(behenyl (meth)acrylate)。以(甲基)丙烯酸硬脂酯為特佳。 Preferred specific examples of long-chain (meth) acrylate monomers are stearyl (meth) acrylate and behenyl (meth) acrylate. Stearyl (meth) acrylate is particularly preferred.
藉由長鏈(甲基)丙烯酸酯單體的存在,使撥水撥油性聚合物所賦予的撥水性、撥油性及質感會提升。 With the presence of long-chain (meth) acrylate monomers, the water repellency, oil repellency and texture imparted by the water repellent oil repellent polymer will be improved.
(A3)非氟非交聯性單體 (A3) Non-fluorine non-crosslinkable monomer
非氟非交聯性單體(A3)係長鏈(甲基)丙烯酸酯單體(A2)以外的單體。非氟非交聯性單體(A3)為不含有氟原子的單體。非氟非交聯性單體(A3)不具有交聯性官能基。非氟非交聯性單體(A3)係與交聯性單體(A4)相異,為非交聯性。非氟非交聯性單體(A3)較佳為具有碳-碳雙鍵之非氟單體。非氟非交聯性單體(A3)較佳為不含氟之乙烯系單體。一般而言,非氟非交聯性單體(A3)係具有1個碳-碳雙鍵之化合物。 The non-fluorine non-crosslinkable monomer (A3) is a monomer other than the long-chain (meth) acrylate monomer (A2). The non-fluorine non-crosslinkable monomer (A3) is a monomer that does not contain a fluorine atom. The non-fluorine non-crosslinkable monomer (A3) does not have a crosslinkable functional group. The non-fluorine non-crosslinkable monomer (A3) is different from the crosslinkable monomer (A4) and is non-crosslinkable. The non-fluorine non-crosslinkable monomer (A3) is preferably a non-fluorine monomer having a carbon-carbon double bond. The non-fluorine non-crosslinkable monomer (A3) is preferably a fluorine-free vinyl monomer. Generally speaking, the non-fluorine non-crosslinkable monomer (A3) is a compound having one carbon-carbon double bond.
較佳之非氟非交聯性單體(A3)係下述式所示之化合物: CH2=CA-T[式中,A為氫原子、甲基、或氟原子以外之鹵原子(例如氯原子、溴原子及碘原子);T為氫原子、碳數1至30的鏈狀或環狀的烴基、或具有酯鍵之鏈狀或環狀的碳數1至31之有機基]。 The preferred non-fluorine non-crosslinkable monomer (A3) is a compound represented by the following formula: CH 2 = CA-T [where A is a hydrogen atom, a methyl group, or a halogen atom other than a fluorine atom (such as chlorine Atom, bromine atom and iodine atom); T is a hydrogen atom, a chain or cyclic hydrocarbon group having 1 to 30 carbon atoms, or a chain or cyclic organic group having 1 to 31 carbon atoms having an ester bond].
碳數1至30的鏈狀或環狀的烴基的例為:碳數1至30之直鏈或分枝的脂肪族烴基、碳數4至30之環狀脂肪族基、碳數6至30之芳香族烴基、碳數7至30之芳香脂肪族烴基。 Examples of the linear or cyclic hydrocarbon group having 1 to 30 carbon atoms are: straight-chain or branched aliphatic hydrocarbon group having 1 to 30 carbon atoms, cyclic aliphatic group having 4 to 30 carbon atoms, and 6 to 30 carbon atoms. Aromatic hydrocarbon groups, aromatic aliphatic hydrocarbon groups having 7 to 30 carbon atoms.
具有酯鍵之鏈狀或環狀的碳數1至31之有機基的例為-C(=O)-O-Q及-O-C(=O)-Q(其中,Q為碳數1至30之直鏈或分枝的脂肪族烴基、碳數4至30之環狀脂肪族基、碳數6至30之芳香族烴基、碳數7至30之芳香脂肪族烴基)。 Examples of chain or cyclic organic groups having 1 to 31 carbon atoms having an ester bond are -C (= O) -OQ and -OC (= O) -Q (wherein, Q is straight from 1 to 30 carbon atoms) (Chain or branched aliphatic hydrocarbon group, cyclic aliphatic group having 4 to 30 carbon atoms, aromatic hydrocarbon group having 6 to 30 carbon atoms, aromatic aliphatic hydrocarbon group having 7 to 30 carbon atoms).
非氟非交聯性單體(A3)之較佳例包括例如:乙烯(ethylene)、乙酸乙烯酯(vinyl acetate)、丙烯腈、苯乙烯、聚乙二醇(甲基)丙烯酸酯、聚丙二醇(甲基)丙烯酸酯、甲氧基聚乙二醇(甲基)丙烯酸酯、甲氧基聚丙二醇(甲基)丙烯酸酯及乙烯基烷基醚。非氟非交聯性單體(A3)並不限定於該等例。 Preferred examples of non-fluorinated non-crosslinkable monomers (A3) include, for example: ethylene, vinyl acetate, acrylonitrile, styrene, polyethylene glycol (meth) acrylate, polypropylene glycol (Meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate and vinyl alkyl ether. The non-fluorine non-crosslinkable monomer (A3) is not limited to these examples.
非氟非交聯性單體(A3)可為具有烷基之(甲基)丙烯酸酯。烷基的碳原子之數可為1至17。例如,非氟非交聯性單體(A3)可為下述通式所示之丙烯酸酯:CH2=CA1COOA2 [式中,A1為氫原子、甲基、或氟原子以外之鹵原子(例如,氯原子、溴原子及碘原子);A2為CnH2n+1(n=1至17)所表示的烷基]。 The non-fluorine non-crosslinkable monomer (A3) may be a (meth) acrylate having an alkyl group. The number of carbon atoms of the alkyl group may be from 1 to 17. For example, the non-fluorine non-crosslinkable monomer (A3) may be an acrylate represented by the following general formula: CH 2 = CA 1 COOA 2 [wherein, A 1 is other than a hydrogen atom, a methyl group, or a fluorine atom Halogen atom (for example, chlorine atom, bromine atom, and iodine atom); A 2 is an alkyl group represented by C n H 2n + 1 (n = 1 to 17)].
含氟單體可不具有由具有碳原子數1至17之烷基之(甲基)丙烯酸酯衍生出之重複單元。 The fluorine-containing monomer may not have a repeating unit derived from a (meth) acrylate having an alkyl group having 1 to 17 carbon atoms.
非氟非交聯性單體(A3)可為具有環狀烴基之(甲基)丙烯酸酯單體。具有環狀烴基之(甲基)丙烯酸酯單體係具有(較佳為一價的)環狀烴基及一價(甲基)丙烯酸酯基之化合物。一價環狀烴基與一價(甲基)丙烯酸酯基係直接鍵結。環狀烴基係飽和或不飽和,可列舉單環基、多環基、交聯環基等。環狀烴基係以飽和者為較佳。環狀烴基的碳數係以4至20為較佳。環狀烴基可列舉:碳數4至20(尤其是5至12)之環狀脂肪族基、碳數6至20之芳香族基、碳數7至20之芳香脂肪族基。環狀烴基的碳數係15以下,例如以10以下為特佳。環狀烴基的環中之碳原子係以直接鍵結於(甲基)丙烯酸酯基之酯基為較佳。環狀烴基係以飽和之環狀脂肪族基為較佳。 The non-fluorine non-crosslinkable monomer (A3) may be a (meth) acrylate monomer having a cyclic hydrocarbon group. (Meth) acrylate monomer system having a cyclic hydrocarbon group A compound having a (preferably monovalent) cyclic hydrocarbon group and a monovalent (meth) acrylate group. The monovalent cyclic hydrocarbon group is directly bonded to the monovalent (meth) acrylate group. The cyclic hydrocarbon group is saturated or unsaturated, and examples thereof include monocyclic groups, polycyclic groups, and cross-linked ring groups. The cyclic hydrocarbon group is preferably saturated. The carbon number of the cyclic hydrocarbon group is preferably 4 to 20. Examples of the cyclic hydrocarbon group include a cyclic aliphatic group having 4 to 20 carbon atoms (especially 5 to 12), an aromatic group having 6 to 20 carbon atoms, and an aromatic aliphatic group having 7 to 20 carbon atoms. The carbon number of the cyclic hydrocarbon group is 15 or less, for example, 10 or less is particularly preferable. The carbon atom in the ring of the cyclic hydrocarbon group is preferably an ester group directly bonded to the (meth) acrylate group. The cyclic hydrocarbon group is preferably a saturated cyclic aliphatic group.
環狀烴基的具體例為環己基、第三丁基環己基、異莰基、二環戊基、二環戊烯基、金剛烷基。丙烯酸酯基係以丙烯酸酯基或甲基丙烯酸酯基為較佳,以甲基丙烯酸酯基為特佳。具有環狀烴基之單體之具體例,可列舉:(甲基)丙烯酸環己酯、(甲基)丙烯酸第三丁基環己酯、(甲基)丙烯酸苯甲酯、(甲基)丙烯酸異莰酯、(甲基)丙烯酸二環戊酯、(甲基)丙烯酸二環戊烯酯、(甲基)丙烯酸二環戊 氧基乙酯、(甲基)丙烯酸三環戊酯、(甲基)丙烯酸金剛烷酯、(甲基)丙烯酸2-甲基-2-金剛烷酯、(甲基)丙烯酸2-乙基-2-金剛烷酯等。 Specific examples of the cyclic hydrocarbon group are cyclohexyl group, third butylcyclohexyl group, isobornyl group, dicyclopentyl group, dicyclopentenyl group, and adamantyl group. The acrylate group is preferably an acrylate group or a methacrylate group, and particularly preferably a methacrylate group. Specific examples of the monomer having a cyclic hydrocarbon group include cyclohexyl (meth) acrylate, tert-butylcyclohexyl (meth) acrylate, benzyl (meth) acrylate, (meth) acrylic acid Isocamprene, dicyclopentyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentyl (meth) acrylate Oxyethyl ester, tricyclopentyl (meth) acrylate, adamantyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, 2-ethyl (meth) acrylate- 2-adamantanyl ester, etc.
非氟非交聯性單體(A3)可為鹵化烯烴。鹵化烯烴可為經1至10個氯原子、溴原子或碘原子取代之碳數2至20之鹵化烯烴。鹵化烯烴(b)係碳數2至20之氯化烯烴,尤其是以具有1至5個氯原子的碳數2至5之烯烴為較佳。鹵化烯烴(b)之較佳具體例為:鹵化乙烯,例如氯化乙烯、溴化乙烯、碘化乙烯;鹵化亞乙烯(vinylidene halide),例如氯化亞乙烯、溴化亞乙烯、碘化亞乙烯。 The non-fluorine non-crosslinkable monomer (A3) may be a halogenated olefin. The halogenated olefin may be a halogenated olefin having 2 to 20 carbon atoms substituted with 1 to 10 chlorine atoms, bromine atoms or iodine atoms. The halogenated olefin (b) is a chlorinated olefin having 2 to 20 carbon atoms, and particularly preferably an olefin having 2 to 5 carbon atoms having 1 to 5 chlorine atoms. Preferred specific examples of halogenated olefins (b) are: halogenated ethylene, such as vinyl chloride, ethylene bromide, and ethylene iodide; vinylidene halide, such as vinyl chloride, vinylidene bromide, and vinyl iodide Ethylene.
(A4)非氟交聯性單體 (A4) Non-fluorinated crosslinkable monomer
撥水撥油性聚合物可具有由非氟交聯性單體(A4)衍生出之重複單元。非氟交聯性單體(A4)為不含有氟原子的單體。非氟交聯性單體(A4)可為具有至少2個反應性基及/或碳-碳雙鍵且不含氟之化合物。非氟交聯性單體(A4)可為具有至少2個碳-碳雙鍵之化合物、或是具有至少1個碳-碳雙鍵及至少1個反應性基之化合物。反應性基的例為羥基、環氧基、氯甲基、嵌段異氰酸酯基、胺基、羧基等。 The water and oil repellent polymer may have a repeating unit derived from a non-fluorinated crosslinkable monomer (A4). The non-fluorinated crosslinkable monomer (A4) is a monomer that does not contain a fluorine atom. The non-fluorinated crosslinkable monomer (A4) may be a compound having at least 2 reactive groups and / or carbon-carbon double bonds and containing no fluorine. The non-fluorinated crosslinkable monomer (A4) may be a compound having at least two carbon-carbon double bonds, or a compound having at least one carbon-carbon double bond and at least one reactive group. Examples of reactive groups are hydroxyl groups, epoxy groups, chloromethyl groups, blocked isocyanate groups, amine groups, carboxyl groups, and the like.
非氟交聯性單體(A4)可例示例如:二丙酮丙烯醯胺、(甲基)丙烯醯胺、N-羥甲基丙烯醯胺、(甲基)丙烯酸羥基甲酯、(甲基)丙烯酸羥基乙酯、(甲基)丙烯酸3-氯-2-羥基丙酯、(甲基)丙烯酸2-乙醯基乙醯氧基乙酯、(甲基)丙烯酸N,N-二甲基胺基乙酯、(甲基)丙烯酸N,N-二乙基胺 基乙酯、丁二烯、異戊二烯、氯丁二烯、(甲基)丙烯酸缩水甘油酯等,惟並不限定於該等。 Examples of non-fluorinated crosslinkable monomers (A4) are: diacetone acrylamide, (meth) acrylamide, N-methylol acrylamide, hydroxymethyl (meth) acrylate, (meth) Hydroxyethyl acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, 2-ethoxyacetoxyethyl (meth) acrylate, N, N-dimethylamine (meth) acrylate Ethyl ethyl ester, (meth) acrylic acid N, N-diethylamine Ethyl ethyl ester, butadiene, isoprene, chloroprene, glycidyl (meth) acrylate, etc., but not limited to these.
藉由使非氟非交聯性單體(A3)及/或非氟交聯性單體(A4)共聚合,可視所需而改善撥水撥油性和防污性及該等性能之耐清潔性、耐洗滌性、對溶劑的溶解性、硬度、觸感等多種性質。 By copolymerizing the non-fluorinated non-crosslinkable monomer (A3) and / or the non-fluorinated crosslinkable monomer (A4), the water and oil repellency and antifouling properties and the cleaning resistance of these properties can be improved as required Various properties such as resistance, washing resistance, solubility in solvents, hardness, touch.
可在由嵌段異氰酸酯化合物及有機聚矽氧烷(organopolysiloxane)化合物所成群組中選出之至少1種化合物之存在下將單體進行聚合。相對於單體100重量份,嵌段異氰酸酯化合物(或有機聚矽氧烷化合物)的量可為0至100重量份,例如為1至50重量份。 The monomer can be polymerized in the presence of at least one compound selected from the group consisting of block isocyanate compounds and organopolysiloxane compounds. The amount of the block isocyanate compound (or organic polysiloxane compound) may be 0 to 100 parts by weight relative to 100 parts by weight of the monomer, for example, 1 to 50 parts by weight.
藉由在嵌段異氰酸酯化合物之存在下將單體進行聚合,能夠得到具有嵌段異氰酸酯基之聚合物。嵌段異氰酸酯化合物係藉由至少一種嵌段劑而嵌段之異氰酸酯。嵌段劑之例可列舉:肟類、酚類、醇類、硫醇類、醯胺類、醯亞胺類、咪唑類、尿素類、胺類、亞胺類、吡唑類及活性亞甲基化合物類。嵌段劑之其他例可列舉:羥基吡啶(pyridinol)類、硫酚(thiophenol)類、二酮類及酯類。嵌段異氰酸酯化合物可經具有親水性基之化合物變性。 By polymerizing the monomer in the presence of a block isocyanate compound, a polymer having a block isocyanate group can be obtained. The block isocyanate compound is an isocyanate blocked by at least one blocking agent. Examples of blocking agents include oximes, phenols, alcohols, thiols, amides, amides, imidazoles, ureas, amines, imines, pyrazoles and active methylene Base compounds. Other examples of block agents include pyridinols, thiophenols, diketones, and esters. The block isocyanate compound can be denatured by a compound having a hydrophilic group.
藉由在有機聚矽氧烷化合物(例如巰基官能性有機聚矽氧烷、乙烯基官能性有機聚矽氧烷)的存在下將單體進行聚合,能夠得到具有矽氧烷基之聚合物。一實施形態中,巰基官能性有機聚矽氧烷係包含具有下述平均式之矽氧基單元: (R2SiO)a(RRNSiO)b(RRSSiO)c[式中,a為0至4000,或0至1000,或0至400;b為1至1000,或1至100,或1至50;c為1至1000,或1至100,或1至50;R獨立地為一價有機基,或是,R為碳數1至30的烴基,或是,R為碳數1至12的一價烷基,或是,R為甲基;RN為如上述定義之一價胺基官能性之有機基,RS為如上述定義之一價巰基官能性之有機基。] By polymerizing the monomer in the presence of an organic polysiloxane compound (for example, mercapto-functional organic polysiloxane, vinyl-functional organic polysiloxane), a polymer having a siloxane group can be obtained. In one embodiment, the mercapto-functional organopolysiloxane contains siloxy units having the following average formula: (R 2 SiO) a (RR N SiO) b (RR S SiO) c [where a is 0 to 4000, or 0 to 1000, or 0 to 400; b is 1 to 1000, or 1 to 100, or 1 to 50; c is 1 to 1000, or 1 to 100, or 1 to 50; R is independently A monovalent organic group, or, R is a hydrocarbon group having 1 to 30 carbon atoms, or R is a monovalent alkyl group having 1 to 12 carbon atoms, or R is a methyl group; R N is one of the above definitions Valence amine functional organic group, R S is a monovalent mercapto functional organic group as defined above. ]
相對於撥水撥油性聚合物,含氟單體(A1)及長鏈(甲基)丙烯酸酯單體(A2)之各自的量(或是單體(A1)及單體(A2)的總計)(惟單體(A1)及單體(A2)的總計係100重量%以下)係可為30至100重量%,較佳為32至98重量%,例如為35至95重量%,尤其是40至90重量%。 Relative to the water- and oil-repellent polymer, the respective amounts of the fluorinated monomer (A1) and the long-chain (meth) acrylate monomer (A2) (or the total of the monomer (A1) and the monomer (A2) ) (However, the total of monomer (A1) and monomer (A2) is 100% by weight or less) can be 30 to 100% by weight, preferably 32 to 98% by weight, for example 35 to 95% by weight, especially 40 to 90% by weight.
撥水撥油性聚合物中,相對於含氟單體(A1)及長鏈(甲基)丙烯酸酯單體(A2)的總計100重量份,非氟非交聯性單體(A3)的量係可為1000重量份以下,例如0.1至300重量份,尤其是1至200重量份;非氟交聯性單體(A4)的量係可為50重量份以下,例如為30重量份以下,尤其是0.1至20重量份。 In the water- and oil-repellent polymer, the amount of the non-fluorinated non-crosslinkable monomer (A3) relative to the total of 100 parts by weight of the fluoromonomer (A1) and the long-chain (meth) acrylate monomer (A2) The system may be 1000 parts by weight or less, for example 0.1 to 300 parts by weight, especially 1 to 200 parts by weight; the amount of the non-fluorinated crosslinkable monomer (A4) may be 50 parts by weight or less, for example 30 parts by weight or less, Especially 0.1 to 20 parts by weight.
相對於撥水撥油性聚合物(或單體(A1)與單體(A2)與單體(A3)的總計),非氟非交聯性單體(A3)的量可為2至68重量%,例如為5至65重量%,尤其是10至60重量%。 The amount of the non-fluorinated non-crosslinkable monomer (A3) may be 2 to 68 weight relative to the water- and oil-repellent polymer (or the total of the monomer (A1) and the monomer (A2) and the monomer (A3)) % Is, for example, 5 to 65% by weight, especially 10 to 60% by weight.
撥水撥油性聚合物之數平均分子量(Mn),一般而言係1000至1000000,例如可為2000至500000,尤其是3000至200000。撥水撥油性聚合物之數平均分子量(Mn),一般而言係藉由GPC(膠體滲透層析)測定。 The number-average molecular weight (Mn) of the water- and oil-repellent polymer is generally 1,000 to 1,000,000, for example, 2,000 to 500,000, especially 3,000 to 200,000. The number average molecular weight (Mn) of the water-repellent oil-repellent polymer is generally determined by GPC (colloid permeation chromatography).
(B)高分子型界面活性劑 (B) Macromolecular surfactant
高分子型界面活性劑,可為於聚合前添加之聚合用界面活性劑及/或於聚合結束後添加之後添加用界面活性劑。高分子型界面活性劑係以後添加用界面活性劑為較佳。 The polymer type surfactant may be a surfactant for polymerization added before polymerization and / or a surfactant for addition after addition after completion of polymerization. It is preferable that the polymer type surfactant is a surfactant for later addition.
高分子型界面活性劑係以陽離子性高分子型界面活性劑、尤其是四級銨鹽系聚合物為較佳。高分子型界面活性劑中,係以氮原子形成亞胺基為較佳。高分子型界面活性劑中,係以氮原子形成主鏈的一部分為較佳。 The polymer surfactant system is preferably a cationic polymer surfactant, especially a quaternary ammonium salt-based polymer. Among the polymer surfactants, it is preferable that the nitrogen atom forms an imine group. Among the polymer surfactants, it is preferable that the nitrogen atom forms part of the main chain.
高分子型界面活性劑可具有下述式所示之重複單元:-[(N+Y4)]r(X-)r-[式中,X為鹵原子或C1至C4之脂肪酸鹽基;各個Y係相同或相異,為直接鍵結、或1價或2價的可具有氧原子之碳數1至10之烴基;至少2個Y可與鄰接之氮原子一起形成環;r為1或2]。 A polymeric surfactant may have a repeating unit represented by the following formula: - [(N + Y 4 )] r (X -) r - [ wherein, X is a halogen atom or a C 1 to C 4 fatty acid salts of Each Y is the same or different, and is a direct bond, or a monovalent or divalent hydrocarbon group having 1 to 10 carbon atoms which may have an oxygen atom; at least 2 Y may form a ring together with the adjacent nitrogen atom; r Is 1 or 2].
X中,鹵原子之具體例為氯原子、溴原子、碘原子。脂肪酸鹽基為由脂肪酸去除氫原子之基。脂肪酸係以碳數2至20之脂肪酸為較佳。脂肪酸之具體例為乙 酸、丁酸。 In X, specific examples of the halogen atom are a chlorine atom, a bromine atom, and an iodine atom. The fatty acid salt group is a group in which hydrogen atoms are removed from fatty acids. The fatty acid is preferably a fatty acid having 2 to 20 carbon atoms. The specific example of fatty acid is B Acid, butyric acid.
Y較佳為1價或2價的可具有氧原子之碳數1至10之直鏈狀及/或分枝狀之脂肪族基(例如烷基或伸烷基)。可具有氧原子之脂肪族基的例為羥基烷基或羥基伸烷基(例如-CH2CH(OH)CH2-)、或是氧烷基或氧伸烷基(例如-OCH2CH2-)。 Y is preferably a monovalent or divalent linear and / or branched aliphatic group having 1 to 10 carbon atoms which may have an oxygen atom (for example, an alkyl group or an alkylene group). Examples of aliphatic groups which may have oxygen atoms are hydroxyalkyl or hydroxyalkylene (eg -CH 2 CH (OH) CH 2- ), or oxyalkyl or oxyalkylene (eg -OCH 2 CH 2 -).
r為2時,8個Y基可分別為相同或相異。 When r is 2, the 8 Y groups may be the same or different.
較佳之高分子型界面活性劑為下述式所示之化合物:-[(-Y1-(-Y2-N+(Z1)(Z2)-Y3-)r-Y4-)(X-)r]n-[式中,X為鹵原子或C1至C4之脂肪酸鹽基;Y1、Y2、Y3及Y4為直接鍵結、或可具有氧原子之碳數1至10之2價脂肪族基;Y2與Y3可與鄰接之氮原子一起形成環;Z1及Z2為碳數1至10之直鏈狀及/或分枝狀之脂肪族基;r為1或2;n為2以上之數]。 A preferred polymer surfactant is a compound represented by the following formula:-[(-Y 1 -(-Y 2 -N + (Z 1 ) (Z 2 ) -Y 3- ) r -Y 4- ) (X -) r] n - [ wherein, X is a halogen atom or a C 1 to C 4 fatty acid salt of; Y 1, Y 2, Y 3 and Y 4 is a direct bond, oxygen or carbon atoms can have A divalent aliphatic group of 1 to 10; Y 2 and Y 3 can form a ring together with the adjacent nitrogen atom; Z 1 and Z 2 are straight-chain and / or branched aliphatic groups with carbon numbers of 1 to 10 Base; r is 1 or 2; n is a number of 2 or more].
X中,鹵原子之具體例為氯原子、溴原子、碘原子。脂肪酸鹽基為由脂肪酸去除氫原子之基。脂肪酸係以碳數2至20之脂肪酸為較佳。脂肪酸之具體例為乙酸、丁酸。 In X, specific examples of the halogen atom are a chlorine atom, a bromine atom, and an iodine atom. The fatty acid salt group is a group in which hydrogen atoms are removed from fatty acids. The fatty acid is preferably a fatty acid having 2 to 20 carbon atoms. Specific examples of fatty acids are acetic acid and butyric acid.
Y1、Y2、Y3及Y4係以直接鍵結或碳數1至10之伸烷基為較佳。Y2與Y3與鄰接之氮原子一起形成環時,所形成的環係以5員環或6員環為較佳。所形成的環之具體例較 佳為:氮丙啶環、吡咯啶環、哌啶環、哌環、嗎啉環。以吡咯啶環為佳。 Y 1 , Y 2 , Y 3 and Y 4 are preferably directly bonded or alkylene having 1 to 10 carbon atoms. When Y 2 and Y 3 form a ring together with the adjacent nitrogen atom, the ring system formed is preferably a 5-membered ring or a 6-membered ring. Specific examples of the formed ring are preferably: aziridine ring, pyrrolidine ring, piperidine ring, piper Ring, morpholine ring. Pyrrolidine ring is preferred.
Z1及Z2之具體例為甲基及乙基。 Specific examples of Z 1 and Z 2 are methyl and ethyl.
n為5至10000之數,例如可為10至1000。 n is a number from 5 to 10000, for example, 10 to 1000.
高分子界面活性劑係以不具有氧伸烷基或OH基的一者為較佳,以氧伸烷基及OH基的兩者(皆)不具有為又更佳。 The polymer surfactant is preferably one that does not have an oxyalkylene group or an OH group, and it is more preferable to use both (or both) of an oxyalkylene group and an OH group.
高分子型界面活性劑之較佳具體例,係如下所述:聚氯化二烯丙基二甲基銨、
高分子型界面活性劑之重量平均分子量為3,000至100,000,特別係以5,000至50,000為較佳。重量平均分子量可將聚乙二醇作為標準物質而藉由膠體滲透層析(GPC)測定。 The weight average molecular weight of the polymer surfactant is 3,000 to 100,000, particularly preferably 5,000 to 50,000. The weight average molecular weight can be determined by colloidal permeation chromatography (GPC) using polyethylene glycol as a standard substance.
相對於撥水撥油性聚合物100重量份,高分子型界面活性劑之量可為0.01至10重量份,例如為0.02至5重量份,尤其是0.03至2重量份。 The amount of the polymer-based surfactant may be 0.01 to 10 parts by weight, for example, 0.02 to 5 parts by weight, especially 0.03 to 2 parts by weight, relative to 100 parts by weight of the water- and oil-repellent polymer.
(C)液狀媒質 (C) Liquid medium
液狀媒質為水性媒質,亦即,可單獨為水、或是水與(水混和性)有機溶媒之混合物。相對於液狀媒質,有機溶媒的量可為30重量%以下,例如為10重量%以下(較佳為0.1%以上)。液狀媒質係以單獨為水為較佳。液狀媒質可僅為有機溶媒。 The liquid medium is an aqueous medium, that is, it may be water alone or a mixture of water and (water-miscible) organic solvent. The amount of the organic solvent may be 30% by weight or less relative to the liquid medium, for example, 10% by weight or less (preferably 0.1% or more). The liquid medium is preferably water alone. The liquid medium may only be an organic solvent.
相對於表面處理劑,液狀媒質的量可為30至99.1重量%,尤其是50至99重量%。 The amount of the liquid medium may be 30 to 99.1% by weight relative to the surface treatment agent, especially 50 to 99% by weight.
(D)聚合用界面活性劑 (D) Surfactant for polymerization
本發明中,一般而言,較佳係在聚合用界面活性劑之存在下將單體進行聚合。 In the present invention, in general, it is preferable to polymerize the monomer in the presence of a surfactant for polymerization.
本發明中,聚合用界面活性劑可為由非離子性界面活性劑、陽離子性界面活性劑、陰離子界面活性劑及兩性界面活性劑中選出之至少1種。 In the present invention, the surfactant for polymerization may be at least one selected from nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants.
(D-1)非離子性界面活性劑 (D-1) Nonionic surfactant
非離子性界面活性劑之例可列舉:醚、酯、酯醚、烷醇醯胺、多元醇及氧化胺。 Examples of nonionic surfactants include ethers, esters, ester ethers, alkanolamides, polyols, and amine oxides.
醚之例為具有氧伸烷基(較佳為聚氧伸乙基)之化合物。 Examples of ethers are compounds with oxyalkylene groups (preferably polyoxyethylidene groups).
酯之例為醇與脂肪酸之酯。醇之例為1至6價(尤其是2至5價)的碳數1至50(尤其是碳數3至30)之醇(例如脂肪族醇)。脂肪酸之例為碳數2至50(尤其是碳數5至30)的飽和或不飽和之脂肪酸。 Examples of esters are esters of alcohols and fatty acids. Examples of alcohols are 1 to 6 valent (especially 2 to 5 valent) alcohols having 1 to 50 carbon atoms (especially 3 to 30 carbon atoms) (for example, aliphatic alcohols). Examples of fatty acids are saturated or unsaturated fatty acids having 2 to 50 carbon atoms (especially 5 to 30 carbon atoms).
酯醚之例為對於醇與脂肪酸之酯加成環氧烷(alkylene oxide)(尤其是環氧乙烷(ethylene oxide)))而成之化合物。醇之例為1至6價(尤其是2至5價)的碳數1至50(尤其是碳數3至30)之醇(例如脂肪族醇)。脂肪酸之例為碳數2至50(尤其是碳數5至30)的飽和或不飽和之脂肪酸。 Examples of ester ethers are compounds obtained by adding alkylene oxide (especially ethylene oxide) to an ester of alcohol and fatty acid. Examples of alcohols are 1 to 6 valent (especially 2 to 5 valent) alcohols having 1 to 50 carbon atoms (especially 3 to 30 carbon atoms) (for example, aliphatic alcohols). Examples of fatty acids are saturated or unsaturated fatty acids having 2 to 50 carbon atoms (especially 5 to 30 carbon atoms).
烷醇醯胺之例為由脂肪酸與烷醇胺所形成之化合物。烷醇醯胺可為單烷醇醯胺或二烷醇醯胺。脂肪酸之例為碳數2至50(尤其是碳數5至30)的飽和或不飽和之脂肪酸。烷醇胺可為具有1至3個胺基及1至5個羥基之碳數2至50(尤其是碳數5至30)的烷醇。 Examples of alkanolamides are compounds formed from fatty acids and alkanolamines. The alkanolamide may be a monoalkanolamide or a dialkanolamide. Examples of fatty acids are saturated or unsaturated fatty acids having 2 to 50 carbon atoms (especially 5 to 30 carbon atoms). The alkanolamine may be an alkanol having 2 to 50 carbon atoms (especially 5 to 30 carbon atoms) having 1 to 3 amine groups and 1 to 5 hydroxyl groups.
多元醇可為2至5價之碳數15至30的醇。 The polyol may be a 2 to 5 valent alcohol having 15 to 30 carbon atoms.
氧化胺可為胺(二級胺或較佳為三級胺)之氧化物(例如碳數5至50)。 The amine oxide may be an oxide of amine (secondary amine or preferably tertiary amine) (for example, carbon number 5 to 50).
非離子性界面活性劑係以具有氧伸烷基(較 佳為聚氧伸乙基)之非離子性界面活性劑為較佳。氧伸烷基中之伸烷基的碳數係以2至10為較佳。非離子性界面活性劑之分子中之氧伸烷基的數目,一般而言係以2至100為較佳。 Non-ionic surfactants are based on oxyalkylene Non-ionic surfactants (polyoxyethylidene) are preferred. The carbon number of the alkylene group in the oxyalkylene group is preferably 2 to 10. The number of oxyalkylene groups in the molecule of the nonionic surfactant is generally 2 to 100.
非離子性界面活性劑係由醚、酯、酯醚、烷醇醯胺、多元醇及氧化胺所成群組中選出,並且是以具有氧伸烷基之非離子性界面活性劑為較佳。 The nonionic surfactant is selected from the group consisting of ethers, esters, ester ethers, alkanolamides, polyols and amine oxides, and is preferably a nonionic surfactant with an oxyalkylene group .
非離子性界面活性劑可為直鏈狀及/或分枝狀之脂肪族(飽和及/或不飽和)基的環氧烷加成物、直鏈狀及/或分枝狀脂肪酸(飽和及/或不飽和)之聚伸烷二醇酯、聚氧伸乙基(POE)/聚氧伸丙基(POP)共聚物(無規共聚物或嵌段共聚物)、乙炔二醇之環氧烷加成物等。該等之中,係以環氧烷加成部分及聚伸烷二醇部分的結構為聚氧伸乙基(POE)或聚氧伸丙基(POP)或POE/POP共聚物(可為無規共聚物亦可為嵌段共聚物)者為較佳。 Nonionic surfactants can be linear and / or branched aliphatic (saturated and / or unsaturated) alkylene oxide adducts, linear and / or branched fatty acids (saturated and (Or unsaturated) polyalkylene glycol ester, polyoxyethylene (POE) / polyoxypropylene (POP) copolymer (random copolymer or block copolymer), epoxy of acetylene glycol Alkane adducts, etc. Among these, the structure of the alkylene oxide addition part and the polyalkylene glycol part is polyoxyethylene (POE) or polyoxypropylene (POP) or POE / POP copolymer (may be Regular copolymers may also be block copolymers).
而且,就環境上的問題(生物分解性、環境激素等)而言,非離子性界面活性劑係以不含芳香族基之結構為較佳。 Furthermore, in terms of environmental problems (biodegradability, environmental hormones, etc.), it is preferable that the nonionic surfactant has a structure that does not contain an aromatic group.
非離子性界面活性劑可為下述式所示之化合物:R1O-(CH2CH2O)p-(R2O)q-R3[式中,R1為碳數1至22之烷基或碳數2至22之烯基或醯基;R2分別獨立地相同或相異,為碳數3以上(例如3至10)的伸烷基; R3為氫原子、碳數1至22之烷基或碳數2至22之烯基;p為2以上之數;q為0或1以上之數]。 The nonionic surfactant may be a compound represented by the following formula: R 1 O- (CH 2 CH 2 O) p- (R 2 O) q -R 3 [In the formula, R 1 is carbon number 1 to 22 Alkyl group or alkenyl group or acyl group having 2 to 22 carbon atoms; R 2 is independently the same or different, and is an alkylene group having 3 or more carbon atoms (for example, 3 to 10); R 3 is a hydrogen atom, a carbon number Alkyl of 1 to 22 or alkenyl of 2 to 22 carbons; p is a number of 2 or more; q is a number of 0 or more].
R1為碳數8至20,特別係以碳數10至18為較佳。R1之較佳具體例可列舉月桂基、十三基(tridecyl)、油基。 R 1 is a carbon number of 8 to 20, particularly preferably a carbon number of 10 to 18. Preferred specific examples of R 1 include lauryl, tridecyl and oleyl.
R2之例為丙烯基、丁烯基。 Examples of R 2 are propenyl and butenyl.
非離子性界面活性劑中,p可為3以上之數(例如5至200)。q可為2以上之數(例如5至200)。亦即,-(R2O)q-可形成聚氧伸烷基鏈。 In the nonionic surfactant, p may be a number of 3 or more (for example, 5 to 200). q can be a number greater than 2 (eg, 5 to 200). That is,-(R 2 O) q -can form a polyoxyalkylene chain.
非離子性界面活性劑可為於中央含有親水性之聚氧伸乙基鏈與疏水性之氧伸烷基鏈(尤其是聚氧伸烷基鏈)的聚氧伸乙基伸烷基烷基醚。疏水性之氧伸烷基鏈可列舉:氧伸丙基鏈、氧伸丁基鏈、苯乙烯鏈等,其中尤以氧伸丙基鏈為較佳。 The nonionic surfactant may be a polyoxyethylene alkylene ether containing a hydrophilic polyoxyalkylene chain and a hydrophobic oxyalkylene chain (especially polyoxyalkylene chain) in the center. . Examples of hydrophobic oxyalkylene chains include oxypropylene chains, oxyalkylene chains, and styrene chains, among which oxypropylene chains are particularly preferred.
較佳之非離子性界面活性劑為下述式所示之界面活性劑:R1O-(CH2CH2O)p-H[式中,R1及p為與上述相同意義]。 A preferable nonionic surfactant is an surfactant represented by the following formula: R 1 O- (CH 2 CH 2 O) p -H [wherein, R 1 and p have the same meaning as above].
非離子性界面活性劑之具體例為:C10H21O-(CH2CH2O)p-(C3H6O)q-H C12H25O-(CH2CH2O)p-(C3H6O)q-H C16H31O-(CH2CH2O)p-(C3H6O)q-H C16H33O-(CH2CH2O)p-(C3H6O)q-H C18H35O-(CH2CH2O)p-(C3H6O)q-H C18H37O-(CH2CH2O)p-(C3H6O)q-H C12H25O-(CH2CH2O)p-(C3H6O)q-C12H25 C16H31O-(CH2CH2O)p-(C3H6O)q-C16H31 C16H33O-(CH2CH2O)p-(C3H6O)q-C12H25 iso-C13H27O-(CH2CH2O)p-(C3H6O)q-H C10H21COO-(CH2CH2O)p-(C3H6O)q-H C16H33COO-(CH2CH2O)p-(C3H6O)q-C12H25[式中,p及q為與上述相同意義]等。 Specific examples of nonionic surfactants are: C 10 H 21 O- (CH 2 CH 2 O) p- (C 3 H 6 O) q -HC 12 H 25 O- (CH 2 CH 2 O) p- (C 3 H 6 O) q -HC 16 H 31 O- (CH 2 CH 2 O) p- (C 3 H 6 O) q -HC 16 H 33 O- (CH 2 CH 2 O) p- (C 3 H 6 O) q -HC 18 H 35 O- (CH 2 CH 2 O) p- (C 3 H 6 O) q -HC 18 H 37 O- (CH 2 CH 2 O) p- (C 3 H 6 O) q -HC 12 H 25 O- (CH 2 CH 2 O) p- (C 3 H 6 O) q -C 12 H 25 C 16 H 31 O- (CH 2 CH 2 O) p- (C 3 H 6 O) q -C 16 H 31 C 16 H 33 O- (CH 2 CH 2 O) p- (C 3 H 6 O) q -C 12 H 25 iso-C 13 H 27 O- (CH 2 CH 2 O) p- (C 3 H 6 O) q -HC 10 H 21 COO- (CH 2 CH 2 O) p- (C 3 H 6 O) q -HC 16 H 33 COO- (CH 2 CH 2 O) p- (C 3 H 6 O) q -C 12 H 25 [wherein, p and q have the same meaning as above] and the like.
非離子性界面活性劑之具體例包含:環氧乙烷與己基酚、異辛基酚、十六醇、油酸、烷烴(C12-C16)硫醇、山梨醇酐單脂肪酸(C7-C19)或烷基(C12-C18)胺等之縮合生成物。 Specific examples of nonionic surfactants include: ethylene oxide and hexylphenol, isooctylphenol, cetyl alcohol, oleic acid, alkane (C 12 -C 16 ) mercaptan, sorbitan mono fatty acid (C 7 -C 19 ) or alkyl (C 12 -C 18 ) amines and other condensation products.
聚氧伸乙基嵌段的比率相對於非離子性界面活性劑(共聚物)之分子量可為5至80重量%,例如為30至75重量%、尤其是40至70重量%。 The ratio of the polyoxyethylidene block to the molecular weight of the nonionic surfactant (copolymer) may be 5 to 80% by weight, for example 30 to 75% by weight, especially 40 to 70% by weight.
非離子性界面活性劑之平均分子量,一般而言係300至5,000,例如500至3,000。 The average molecular weight of the nonionic surfactant is generally 300 to 5,000, for example 500 to 3,000.
非離子性界面活性劑可為單獨1種,亦可將2種以上併用。 The nonionic surfactant may be one kind alone, or two or more kinds may be used in combination.
非離子性界面活性劑係以2種以上之組合為較佳。2種以上之組合中,至少1種非離子性界面活性劑,可為R1O-(CH2CH2O)p-(R2O)q-R3[尤其是 R1O-(CH2CH2O)p-H]所示之化合物,其中之R1基(及/或R3基)為分枝烷基(例如異十三基)。相對於非離子性界面活性劑之總計100重量份,R1基為分枝烷基的非離子性界面活性劑之量係可為5至100重量份,例如為8至50重量份,尤其是10至40重量份。2種以上之組合中,剩餘的非離子性界面活性劑可為R1O-(CH2CH2O)p-(R2O)q-R3[尤其是R1O-(CH2CH2O)p-H]所示之化合物,其中之R1基(及/或R3基)為(飽和及/或不飽和的)直鏈烷基(例如月桂基(正月桂基))。 The combination of two or more nonionic surfactants is preferred. At least one nonionic surfactant can be R 1 O- (CH 2 CH 2 O) p- (R 2 O) q -R 3 [especially R 1 O- (CH 2 CH 2 O) p -H], wherein the R 1 group (and / or R 3 group) is a branched alkyl group (such as isotridecyl). The amount of the nonionic surfactant in which the R 1 group is a branched alkyl group may be 5 to 100 parts by weight, for example, 8 to 50 parts by weight relative to the total of 100 parts by weight of the nonionic surfactant, especially 10 to 40 parts by weight. In the combination of 2 or more, the remaining nonionic surfactant can be R 1 O- (CH 2 CH 2 O) p- (R 2 O) q -R 3 [especially R 1 O- (CH 2 CH 2 O) The compound represented by p -H], wherein the R 1 group (and / or R 3 group) is a (saturated and / or unsaturated) linear alkyl group (for example, lauryl (n-lauryl)).
非離子性界面活性劑可列舉例如:聚氧伸乙基烷基醚、聚氧伸乙基烷基苯基醚、聚氧伸乙基脂肪酸酯、山梨醇酐脂肪酸酯、聚氧伸乙基山梨醇酐脂肪酸酯、聚氧伸乙基山梨醇脂肪酸酯、甘油脂肪酸酯、聚氧伸乙基甘油脂肪酸酯、聚甘油脂肪酸酯、蔗糖脂肪酸酯、聚氧伸乙基烷基胺、聚氧伸乙基脂肪醯胺、脂肪酸烷醇醯胺、烷基烷醇醯胺、乙炔二醇、乙炔二醇之氧伸乙基加成物、聚乙二醇聚丙二醇嵌段共聚物等。 Examples of nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, and polyoxyethylene Sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, glycerin fatty acid ester, polyoxyethyl glycerin fatty acid ester, polyglycerin fatty acid ester, sucrose fatty acid ester, polyoxyethylen Alkylamines, polyoxyethylidene fatty amides, fatty acid alkanolamides, alkylalkanolamides, acetylene glycol, oxyethylene adducts of acetylene glycol, polyethylene glycol polypropylene glycol block Copolymers, etc.
(D-2)陽離子性界面活性劑 (D-2) Cationic surfactant
陽離子性界面活性劑係以不具有醯胺基之化合物為較佳。 The cationic surfactant is preferably a compound having no amide group.
陽離子性界面活性劑之例可列舉:胺、胺鹽、四級銨鹽、咪唑啉及咪唑啉鎓鹽(imidazolium salt)。 Examples of cationic surfactants include amines, amine salts, quaternary ammonium salts, imidazolines and imidazolium salts.
陽離子性界面活性劑係以胺鹽、四級銨鹽、氧伸乙基加成型銨鹽為較佳。陽離子性界面活性劑之具體例並無特 別限定,可列舉:烷基胺鹽、胺基醇脂肪酸衍生物、聚胺脂肪酸衍生物、咪唑啉等胺鹽型界面活性劑;烷基三甲基銨鹽、二烷基二甲基銨鹽、烷基二甲基苯甲基銨鹽、吡啶鎓鹽、烷基異喹啉鎓鹽、苄索氯銨(benzethonium chloride)等四級銨鹽型界面活性劑等。 The cationic surfactant is preferably an amine salt, a quaternary ammonium salt, and an oxyethylated ammonium salt. There are no specific examples of cationic surfactants Unless otherwise limited, amine salt type surfactants such as alkyl amine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, imidazoline, etc .; alkyl trimethyl ammonium salts, dialkyl dimethyl ammonium salts , Alkyl dimethyl benzyl ammonium salt, pyridinium salt, alkyl isoquinolinium salt, benzethonium chloride (benzethonium chloride) and other quaternary ammonium salt type surfactants.
陽離子性界面活性劑之例為下述式之化合物:R21-N+(-R22)(-R23)(-R24)X-[式中,R21、R22、R23及R24係分別獨立地相同或相異,為氫原子或碳數1至50的烴基;X為陰離子性基]。烴基可具有氧原子,例如可為聚氧伸烷基等氧伸烷基(伸烷基的碳數係例如2至5)。R21、R22、R23及R24係以碳數1至30的烴基(例如脂肪族烴基、芳香族烴基或芳香脂肪族烴基)為較佳。 The compound of the following formula examples of the cationic surfactant of is: R 21 -N + (-R 22 ) (- R 23) (- R 24) X - [ wherein, R 21, R 22, R 23 and R The 24 series are independently the same or different, and are a hydrogen atom or a hydrocarbon group having 1 to 50 carbon atoms; X is an anionic group]. The hydrocarbon group may have an oxygen atom, and for example, it may be an oxyalkylene group such as a polyoxyalkylene group (the carbon number of the alkylene group is, for example, 2 to 5). R 21 , R 22 , R 23 and R 24 are preferably a hydrocarbon group having 1 to 30 carbon atoms (for example, an aliphatic hydrocarbon group, an aromatic hydrocarbon group or an aromatic aliphatic hydrocarbon group).
R21、R22、R23及R24之具體例為烷基(例如甲基、丁基、硬脂基、軟脂基)、芳基(例如苯基)、芳烷基(例如苯甲基(苯基甲基)、苯乙基(苯基乙基))。 Specific examples of R 21 , R 22 , R 23 and R 24 are alkyl (e.g. methyl, butyl, stearyl, palmitate), aryl (e.g. phenyl), aralkyl (e.g. benzyl (Phenylmethyl), phenethyl (phenylethyl)).
X之具體例為鹵(例如氯)、酸(例如鹽酸等無機酸、乙酸等有機酸(尤其是脂肪酸))。 Specific examples of X are halogen (for example, chlorine) and acids (for example, inorganic acids such as hydrochloric acid and organic acids (especially fatty acids) such as acetic acid).
陽離子性界面活性劑係以單烷基三甲基銨鹽(烷基的碳數為4至30)為特佳。 The cationic surfactant is particularly preferably a monoalkyl trimethyl ammonium salt (the carbon number of the alkyl group is 4 to 30).
陽離子性界面活性劑係以銨鹽,尤其是四級銨鹽為較佳。陽離子性界面活性劑可為下述式所示之銨鹽: R31 p-N+R32 qX-[式中,R31係分別獨立地相同或相異,為C12以上(例如C12至C50)之直鏈狀及/或分枝狀之脂肪族(飽和及/或不飽和)基;R32係分別獨立地相同或相異,為H或C1至4之烷基、苯甲基、聚氧伸乙基(氧伸乙基(oxyethylene)的數為例如1(尤其是2,更尤其是3)至50)(以CH3、C2H5為特佳);X為鹵原子(例如氯及溴)、C1至C4之脂肪酸鹽基;p為1或2,q為2或3,且p+q=4]。 R31的碳數為12至50,例如可為12至30。 The cationic surfactant is preferably an ammonium salt, especially a quaternary ammonium salt. The cationic surfactant may be an ammonium salt as shown in the following formula: R 31 p -N + R 32 q X - [ wherein, R 31 each independently the same system or different, a C12 or higher (e.g. C 12 to C 50 ) linear and / or branched aliphatic (saturated and / or unsaturated) groups; R 32 is independently the same or different, and is H or C 1-4 alkyl, benzyl , Polyoxyethylidene (oxyethylene) (oxyethylene) number is for example 1 (especially 2, more particularly 3) to 50) (CH 3 , C 2 H 5 is particularly preferred); X is a halogen atom (Such as chlorine and bromine), C 1 to C 4 fatty acid base; p is 1 or 2, q is 2 or 3, and p + q = 4]. The carbon number of R 31 is 12 to 50, for example, 12 to 30.
陽離子性界面活性劑之具體例中,包括:乙酸十二基三甲基銨、氯化三甲基十四基銨、溴化十六基三甲基銨、氯化三甲基十八基銨、氯化(十二基甲基苯甲基)三甲基銨、氯化苯甲基十二基二甲基銨、氯化甲基十二基二(氫聚氧伸乙基)銨、氯化苯甲基十二基二(氫聚氧伸乙基)銨。 Specific examples of cationic surfactants include: dodecyl trimethyl ammonium acetate, trimethyl tetradecyl ammonium chloride, cetyl trimethyl ammonium bromide, trimethyl octadecyl ammonium chloride , (Dodecyl methyl benzyl) trimethyl ammonium chloride, benzyl dodecyl dimethyl ammonium chloride, methyl dodecyl di (hydrogen polyoxyethylene) ammonium chloride, chlorine Benzyl dodecyl bis (hydropolyoxyethylidene) ammonium.
(D-3)陰離子性界面活性劑 (D-3) Anionic surfactant
陰離子性界面活性劑係以有機酸的鹽(例如有機酸與無機鹼或胺的鹽)為較佳。 The anionic surfactant is preferably a salt of an organic acid (for example, a salt of an organic acid and an inorganic base or amine).
陰離子性界面活性劑之具體例可列舉:月桂基硫酸鈉、月桂基硫酸三乙醇胺、聚氧伸乙基月桂基醚硫酸鈉、聚氧伸乙基壬基苯基醚硫酸鈉、聚氧伸乙基月桂基醚硫酸三乙醇胺、椰油醯基肌胺酸鈉(sodium cocoyl sarcosinate)、N-椰油醯基甲基牛磺酸鈉、聚氧伸乙基椰脂烷基醚硫酸 鈉、二醚己基磺酸基琥珀酸鈉、α-烯烴磺酸鈉、月桂基磷酸鈉、聚氧伸乙基月桂基醚磷酸鈉、全氟烷基羧酸鹽(商品名Unidyne DS-101、102(大金工業股份有限公司製))等。 Specific examples of anionic surfactants include sodium lauryl sulfate, triethanolamine lauryl sulfate, sodium polyoxyethyl lauryl ether sulfate, sodium polyoxyethyl ethyl nonyl phenyl ether sulfate, polyoxyethylene Lauryl ether triethanolamine sulfate, sodium cocoyl sarcosinate, sodium N-cocoyl methyl taurine, polyoxyethylene ethyl cocoyl alkyl ether sulfate Sodium, sodium diether hexylsulfonate succinate, sodium α-olefin sulfonate, sodium lauryl phosphate, sodium polyoxyethyl lauryl ether phosphate, perfluoroalkyl carboxylate (trade name Unidyne DS-101, 102 (made by Daikin Industries Co., Ltd.)), etc.
(D-4)兩性界面活性劑 (D-4) Amphoteric surfactant
兩性界面活性劑之具體例可列舉:丙胺酸類、咪唑啉鎓甜菜鹼類、醯胺甜菜鹼類、乙酸甜菜鹼等,具體而言,可列舉:月桂基甜菜鹼、硬脂基甜菜鹼、月桂基羧基甲基羥基乙基咪唑啉甜菜鹼、月桂基二甲基胺基乙酸甜菜鹼、脂肪酸醯胺丙基二甲基胺基乙酸甜菜鹼等。 Specific examples of amphoteric surfactants include alanine, imidazolinium betaines, amide betaines, and betaine acetate. Specifically, they include lauryl betaine, stearyl betaine, and lauryl. Carboxymethyl hydroxyethyl imidazoline betaine, lauryl dimethyl amino acetate betaine, fatty acid amide propyl dimethyl amino acetate betaine, etc.
非離子性界面活性劑、陽離子性界面活性劑、陰離子性界面活性劑及兩性界面活性劑之各者係可為1種或2種以上之組合。 Each of the nonionic surfactant, cationic surfactant, anionic surfactant and amphoteric surfactant may be one kind or a combination of two or more kinds.
相對於撥水撥油性聚合物100重量份,聚合用界面活性劑之量係可為0.05至20重量份,例如為0.1至10重量份。 The amount of the surfactant for polymerization may be 0.05 to 20 parts by weight relative to 100 parts by weight of the water- and oil-repellent polymer, for example, 0.1 to 10 parts by weight.
(E)其他成分 (E) Other ingredients
表面處理劑可含有非氟撥水性化合物及添加劑中之至少1種作為撥水撥油性聚合物、液狀媒質及界面活性劑以外之其他成分。 The surface treatment agent may contain at least one of a non-fluorine water-repellent compound and an additive as a component other than the water-repellent oil-repellent polymer, liquid medium, and surfactant.
(E-1)非氟撥水性化合物 (E-1) Non-fluorine water repellent compound
表面處理劑有含有不含氟原子的撥水性化合物(非氟撥水性化合物)之情形。 The surface treatment agent may contain a water-repellent compound containing no fluorine atoms (non-fluorine water-repellent compound).
非氟撥水性化合物可為非氟丙烯酸酯聚合物、飽和或不飽和之烴化合物、或聚矽氧(silicone)系化合物。 The non-fluorinated water repellent compound may be a non-fluorinated acrylate polymer, a saturated or unsaturated hydrocarbon compound, or a silicone-based compound.
非氟丙烯酸酯聚合物,係由1種非氟丙烯酸酯單體所構成之均聚物、或由至少2種非氟丙烯酸酯單體所構成之共聚物、或是由至少1種非氟丙烯酸酯單體及至少1種其他非氟單體(乙烯性不飽和化合物,例如乙烯、乙烯系單體)所構成之共聚物。 Non-fluoroacrylate polymer is a homopolymer composed of one non-fluoroacrylate monomer, or a copolymer composed of at least two non-fluoroacrylate monomers, or a copolymer composed of at least one non-fluoroacrylate A copolymer composed of an ester monomer and at least one other non-fluorinated monomer (ethylenically unsaturated compound, such as ethylene, vinyl monomer).
構成非氟丙烯酸酯聚合物之非氟丙烯酸酯單體為下述式所示之化合物:CH2=CA-T[式中,A為氫原子、甲基、或氟原子以外之鹵原子(例如氯原子、溴原子及碘原子);T為氫原子、碳數1至30的鏈狀或環狀的烴基、或具有酯鍵之鏈狀或環狀的碳數1至31之有機基]。 The non-fluoroacrylate monomer constituting the non-fluoroacrylate polymer is a compound represented by the following formula: CH 2 = CA-T [where A is a hydrogen atom, a methyl group, or a halogen atom other than a fluorine atom (for example Chlorine atom, bromine atom and iodine atom); T is a hydrogen atom, a chain or cyclic hydrocarbon group having 1 to 30 carbon atoms, or a chain or cyclic organic group having 1 to 31 carbon atoms having an ester bond].
碳數1至30的鏈狀或環狀的烴基的例為:碳數1至30之直鏈或分枝的脂肪族烴基、碳數4至30之環狀脂肪族基、碳數6至30之芳香族烴基、碳數7至30之芳香脂肪族烴基。 Examples of the linear or cyclic hydrocarbon group having 1 to 30 carbon atoms are: straight-chain or branched aliphatic hydrocarbon group having 1 to 30 carbon atoms, cyclic aliphatic group having 4 to 30 carbon atoms, and 6 to 30 carbon atoms. Aromatic hydrocarbon groups, aromatic aliphatic hydrocarbon groups having 7 to 30 carbon atoms.
具有酯鍵之鏈狀或環狀的碳數1至31之有機基的例為:-C(=O)-O-Q及-O-C(=O)-Q(其中,Q為碳數1至30之直鏈或分枝的脂肪族烴基、碳數4至30之環狀脂肪族基、碳數6至30之芳香族烴基、碳數7至30之芳香脂肪族烴基)。 Examples of chain or cyclic organic groups having 1 to 31 carbon atoms having an ester bond are: -C (= O) -OQ and -OC (= O) -Q (wherein Q is a carbon number of 1 to 30) Straight chain or branched aliphatic hydrocarbon group, cyclic aliphatic group having 4 to 30 carbon atoms, aromatic hydrocarbon group having 6 to 30 carbon atoms, aromatic aliphatic hydrocarbon group having 7 to 30 carbon atoms).
非氟丙烯酸酯單體的例中,包括例如:(甲 基)丙烯酸烷酯、聚乙二醇(甲基)丙烯酸酯、聚丙二醇(甲基)丙烯酸酯、甲氧基聚乙二醇(甲基)丙烯酸酯、甲氧基聚丙二醇(甲基)丙烯酸酯。 Examples of non-fluoroacrylate monomers include, for example: (A Base) alkyl acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, methoxy polypropylene glycol (meth) acrylic ester.
非氟丙烯酸酯單體係以(甲基)丙烯酸烷酯為較佳。其烷基的碳原子數可為1至30,例如可為6至30(例如10至30)。非氟丙烯酸酯單體之具體例為月桂基(甲基)丙烯酸酯、(甲基)丙烯酸硬脂酯及(甲基)丙烯酸山萮酯。 As the non-fluoroacrylate monosystem, alkyl (meth) acrylate is preferred. The alkyl group may have 1 to 30 carbon atoms, for example, 6 to 30 (for example, 10 to 30). Specific examples of non-fluoroacrylate monomers are lauryl (meth) acrylate, stearyl (meth) acrylate, and behenate (meth) acrylate.
非氟丙烯酸酯聚合物可依據與撥水撥油性聚合物相同的聚合方法製造。 The non-fluoroacrylate polymer can be produced according to the same polymerization method as the water- and oil-repellent polymer.
飽和或不飽和的烴系化合物係以飽和的烴為較佳。飽和或不飽和的烴系化合物中,碳數為15以上,較佳為20至300,例如可為25至100。飽和或不飽和的烴系化合物之具體例為石蠟等。 The saturated or unsaturated hydrocarbon-based compound is preferably a saturated hydrocarbon. In the saturated or unsaturated hydrocarbon-based compound, the carbon number is 15 or more, preferably 20 to 300, and for example, 25 to 100. Specific examples of saturated or unsaturated hydrocarbon-based compounds are paraffin wax and the like.
聚矽氧系化合物,一般而言係被使用作為撥水劑。聚矽氧系化合物只要是會表現撥水性之化合物,即無限定。 Polysilicone compounds are generally used as water repellents. The polysiloxane compound is not limited as long as it can express water repellency.
相對於撥水撥油性聚合物之100重量份,非氟撥水性化合物之量係可為500重量份以下,例如為5至200重量份、尤其是5至100重量份。 The amount of the non-fluorinated water-repellent compound may be 500 parts by weight or less relative to 100 parts by weight of the water-repellent oil-repellent polymer, for example, 5 to 200 parts by weight, especially 5 to 100 parts by weight.
(E-2)添加劑 (E-2) Additive
表面處理劑可含有添加劑。 The surface treatment agent may contain additives.
添加劑之例為含矽化合物、蠟、丙烯酸系乳劑等。添加劑之其他例為:其他的含氟聚合物、乾燥速度調整劑、交聯劑、造膜助劑、相容化劑、界面活性劑、抗凍劑、黏 度調整劑、紫外線吸收劑、抗氧化劑、pH調整劑、消泡劑、質感調整劑、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、難燃劑等。 Examples of additives are silicon-containing compounds, waxes, and acrylic emulsions. Other examples of additives are: other fluoropolymers, drying speed modifiers, cross-linking agents, film-forming aids, compatibilizers, surfactants, antifreeze agents, adhesives Degree adjuster, ultraviolet absorber, antioxidant, pH adjuster, defoamer, texture adjuster, smoothness adjuster, antistatic agent, hydrophilizing agent, antibacterial agent, preservative, insecticide, fragrance, hard Fuel, etc.
本發明之撥水撥油性聚合物及非氟聚合物可依據通常之任意的聚合方法製造,而且可任意地選擇聚合反應的條件。如此之聚合方法可列舉:溶液聚合、懸浮聚合、乳化聚合。 The water- and oil-repellent polymer and non-fluoropolymer of the present invention can be produced according to any conventional polymerization method, and the conditions of the polymerization reaction can be arbitrarily selected. Examples of such polymerization methods include solution polymerization, suspension polymerization, and emulsion polymerization.
溶液聚合,可採用下述方法:於聚合起始劑之存在下,使單體溶解於有機溶媒,經進行氮取代後,於30至120℃的範圍進行加熱攪拌1至10小時之方法。聚合起始劑可列舉例如:偶氮雙異丁腈、過氧化苯甲醯基、過氧化二第三丁基、過氧化月桂基、氫過氧化異丙苯、過氧三甲基乙酸第三丁基酯、過氧二碳酸二異丙酯等。相對於單體100重量份,聚合起始劑可為0.01至20重量份,例如於0.01至10重量份的範圍使用。 For solution polymerization, the following method may be used: in the presence of a polymerization initiator, the monomer is dissolved in an organic solvent, and after nitrogen substitution, heating and stirring are performed in the range of 30 to 120 ° C for 1 to 10 hours. Examples of the polymerization initiator include azobisisobutyronitrile, benzoyl peroxide, di-tert-butyl peroxide, lauryl peroxide, cumene hydroperoxide, and trimethyl peroxyacetic acid. Butyl ester, diisopropyl peroxydicarbonate, etc. The polymerization initiator may be used in the range of 0.01 to 20 parts by weight relative to 100 parts by weight of the monomer, for example, in the range of 0.01 to 10 parts by weight.
有機溶媒係對單體為惰性且將該等單體溶解者,例如可為:酯(例如碳數2至30的酯,具體而言為乙酸乙酯、乙酸丁酯)、酮(例如碳數2至30的酮,具體而言為甲基乙基酮、二異丁基酮)、醇(例如碳數1至30的醇,具體而言為異丙基醇)。有機溶媒之具體例可列舉:丙酮、氯仿、HCHC225、異丙醇、戊烷、己烷、庚烷、辛烷、環己烷、苯、甲苯、二甲苯、石油醚、四氫呋喃、1,4-二烷、甲基乙基酮、甲基異丁基酮、二異丁基酮、乙酸乙酯、乙酸丁酯、1,1,2,2-四氯乙烷、1,1,1-三氯乙烷、三氯乙烯、 過氯乙烯、四氯二氟乙烷、三氯三氟乙烷等。相對於單體的總計100重量份,有機溶媒係可為10至2000重量份,例如於50至1000重量份的範圍使用。 Organic solvents are inert to monomers and dissolve such monomers, for example: esters (such as esters with carbon numbers 2 to 30, specifically ethyl acetate, butyl acetate), ketones (such as carbon numbers Ketones of 2 to 30, specifically methyl ethyl ketone, diisobutyl ketone), alcohols (for example, alcohols having 1 to 30 carbon atoms, specifically isopropyl alcohol). Specific examples of organic solvents include acetone, chloroform, HCHC225, isopropanol, pentane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, petroleum ether, tetrahydrofuran, 1,4- two Alkanes, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, ethyl acetate, butyl acetate, 1,1,2,2-tetrachloroethane, 1,1,1-trichloro Ethane, trichloroethylene, perchloroethylene, tetrachlorodifluoroethane, trichlorotrifluoroethane, etc. The organic solvent system may be used in the range of 10 to 2000 parts by weight relative to 100 parts by weight of the monomer in total, for example, in the range of 50 to 1000 parts by weight.
乳化聚合,係可採用下述方法:於聚合起始劑及乳化劑之存在下,使單體在水中乳化,經進行氮取代後,於50至80℃的範圍攪拌1至10小時而使進行聚合之方法。聚合起始劑可使用:過氧化苯甲醯基、過氧化月桂醯基、過氧苯甲酸第三丁酯、氫過氧化1-羥基環己基、過氧化3-羧基丙醯基、過氧化乙醯基、偶氮雙異丁基脒-二鹽酸鹽、偶氮雙異丁腈、過氧化鈉、過硫酸鉀、過硫酸銨等水溶性者;和偶氮雙異丁腈、過氧化苯甲醯基、過氧化二第三丁基、過氧化月桂基、氫過氧化異丙苯、過氧三甲基乙酸第三丁基酯、過氧二碳酸二異丙酯等油溶性者。相對於單體100重量份,聚合起始劑可於0.01至10重量份的範圍使用。 For emulsification polymerization, the following method can be used: in the presence of a polymerization initiator and an emulsifier, the monomer is emulsified in water, after nitrogen substitution, stirring is carried out at 50 to 80 ° C for 1 to 10 hours to carry out Method of aggregation. The polymerization initiator can be used: benzoyl peroxide, lauryl peroxide, tert-butyl peroxybenzoate, 1-hydroxycyclohexyl hydroperoxide, 3-carboxypropionyl peroxide, ethyl peroxide Acyl, azobisisobutylamidine-dihydrochloride, azobisisobutyronitrile, sodium peroxide, potassium persulfate, ammonium persulfate and other water-soluble ones; and azobisisobutyronitrile, benzene peroxide Oil-soluble persons such as formyl, di-tert-butyl peroxide, lauryl peroxide, cumene hydroperoxide, tert-butyl peroxytrimethylacetate, diisopropyl peroxydicarbonate, etc. The polymerization initiator can be used in the range of 0.01 to 10 parts by weight relative to 100 parts by weight of the monomer.
為了得到放置安定性優異的聚合物水分散液,係以使用如高壓均質機或超音波均質機等可賦予強力的破碎能量之乳化裝置,將單體在水中進行微粒子化並進行聚合為理想。而且,乳化劑係可使用陰離子性、陽離子性或是非離子性之各種乳化劑,相對於單體100重量份,可使用0.5至20重量份的範圍。以使用陰離子性及/或非離子性及/或陽離子性之乳化劑為較佳。單體未完全相容時,較佳為添加使該等單體成為充分相容之相容化劑(例如水溶性有機溶媒和低分子量的單體)。藉由相容化劑之添 加,可提高乳化性及共聚性。 In order to obtain a polymer aqueous dispersion excellent in placement stability, it is desirable to emulsify the monomer in water and polymerize it by using an emulsifying device such as a high-pressure homogenizer or an ultrasonic homogenizer that can give strong crushing energy. In addition, as the emulsifier, various anionic, cationic or nonionic emulsifiers can be used, and the range of 0.5 to 20 parts by weight can be used with respect to 100 parts by weight of the monomer. It is preferable to use anionic and / or nonionic and / or cationic emulsifiers. When the monomers are not completely compatible, it is preferable to add a compatibilizer (such as a water-soluble organic solvent and a low-molecular-weight monomer) that makes the monomers sufficiently compatible. With the addition of compatibilizers Add, can improve emulsification and copolymerization.
水溶性有機溶媒可列舉:丙酮、甲基乙基酮、乙酸乙酯、丙二醇、二丙二醇單甲基醚、二丙二醇、三丙二醇、乙醇等,相對於水100重量份,其可於1至50重量份之範圍使用,例如於10至40重量份之範圍使用。而且,低分子量的單體可列舉:甲基丙烯酸甲酯、甲基丙烯酸縮水甘油酯、甲基丙烯酸2,2,2-三氟乙酯等,相對於單體的總量100重量份,其可於1至50重量份之範圍使用,例如於10至40重量份之範圍使用。 Examples of the water-soluble organic solvent include acetone, methyl ethyl ketone, ethyl acetate, propylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol, tripropylene glycol, ethanol, etc., which can be in the range of 1 to 50 with respect to 100 parts by weight of water. It is used in the range of parts by weight, for example, in the range of 10 to 40 parts by weight. In addition, the low-molecular-weight monomers include methyl methacrylate, glycidyl methacrylate, 2,2,2-trifluoroethyl methacrylate, and the like. It can be used in the range of 1 to 50 parts by weight, for example, in the range of 10 to 40 parts by weight.
聚合中可使用鏈轉移劑。因應鏈轉移劑之使用量,可改變聚合物之分子量。鏈轉移劑之例為:月桂基硫醇、硫乙二醇(thioglycol)、硫丙三醇(thioglycerol)等含有硫醇基之化合物(尤其是(例如碳數1至30的)烷基硫醇),次磷酸鈉(sodium hypophosphite)、亞硫酸氫鈉(sodium hydrogen sulfite)等無機鹽等。相對於單體的總量100重量份,鏈轉移劑之使用量可為0.01至10重量份,例如於0.1至5重量份之範圍使用。 A chain transfer agent can be used in the polymerization. Depending on the amount of chain transfer agent used, the molecular weight of the polymer can be changed. Examples of chain transfer agents are: compounds containing thiol groups such as lauryl mercaptan, thioglycol, thioglycerol (especially (e.g., carbon number 1 to 30) alkyl mercaptans ), Inorganic salts such as sodium hypophosphite, sodium hydrogen sulfite, etc. The chain transfer agent may be used in an amount of 0.01 to 10 parts by weight relative to 100 parts by weight of the total amount of monomers, for example, in a range of 0.1 to 5 parts by weight.
本發明之處理劑可為溶液、乳劑(尤其是水性分散液)或氣溶膠之形態,惟以水性分散液為較佳。處理劑係包含撥水撥油性聚合物(表面處理劑之活性成分)及媒質(尤其是液狀媒質,例如有機溶媒及/或水)而成者。媒質的量係例如相對於處理劑而可為5至99.9重量%,尤其是10至80重量%。 The treatment agent of the present invention may be in the form of solution, emulsion (especially aqueous dispersion) or aerosol, but aqueous dispersion is preferred. The treatment agent includes a water-repellent oil-repellent polymer (the active ingredient of the surface treatment agent) and a medium (especially a liquid medium, such as an organic solvent and / or water). The amount of the medium may be, for example, 5 to 99.9% by weight relative to the treatment agent, especially 10 to 80% by weight.
處理劑中,撥水撥油性聚合物之濃度可為0.01至95 重量%,例如5至50重量%。 The concentration of water- and oil-repellent polymer in the treatment agent can be 0.01 to 95 % By weight, for example 5 to 50% by weight.
本發明之處理劑可藉由過去習知的方法而應用於被處理物。通常可採用下述方法:將該處理劑分散於有機溶媒或水而稀釋,藉由如浸漬塗佈、噴霧塗佈、泡塗佈等習知的方法附著於被處理物之表面,並進行乾燥之方法。而且,若有需要,亦可與合適的交聯劑(例如經嵌段之異氰酸酯)一起適用而進行熟化(curing)。再者,亦可於本發明之處理劑中添加併用防蟲劑、柔軟劑、抗菌劑、難燃劑、抗靜電劑、塗料固定劑、抗皺劑等。與基材接觸之處理液中之撥水撥油性聚合物之濃度可為0.01至10重量%(尤其是浸漬塗佈時),例如0.05至10重量%。 The treatment agent of the present invention can be applied to an object to be treated by a method known in the past. Generally, the following method can be adopted: the treatment agent is dispersed in an organic solvent or water for dilution, and then adhered to the surface of the object to be processed by conventional methods such as dip coating, spray coating, bubble coating, etc., and dried Method. Moreover, if necessary, it can also be applied together with a suitable cross-linking agent (for example, blocked isocyanate) for curing. In addition, an insecticide, softener, antibacterial agent, flame retardant, antistatic agent, paint fixing agent, anti-wrinkle agent, etc. may be added to the treatment agent of the present invention. The concentration of the water- and oil-repellent polymer in the treatment liquid in contact with the substrate may be 0.01 to 10% by weight (especially during dip coating), for example, 0.05 to 10% by weight.
本發明之處理劑(例如撥水撥油劑)所能處理的被處理物,可列舉:纖維製品、石材、過濾器(例如靜電過濾器)、防塵罩、燃料電池的零件(例如氣體擴散電極及氣體擴散支撐物)、玻璃、紙、木、皮革、毛皮、石綿、紅磚、水泥、金屬及氧化物、窯業製品、塑膠、塗面及石膏(plaster)等。纖維製品可列舉多種例子。可列舉例如:綿、麻、羊毛、蠶絲等動植物性天然纖維;聚醯胺、聚酯、聚乙烯醇、聚丙烯腈、聚氯化乙烯、聚丙烯等合成纖維;嫘縈、乙酸酯等半合成纖維;玻璃纖維、碳纖維、石棉纖維等無機纖維;或是該等的混合纖維。 The objects to be treated by the treatment agent (for example, water- and oil-repellent agent) of the present invention include fiber products, stone materials, filters (such as electrostatic filters), dust covers, and fuel cell components (such as gas diffusion electrodes) And gas diffusion supports), glass, paper, wood, leather, fur, asbestos, red brick, cement, metal and oxides, kiln products, plastics, coating and plaster (plaster), etc. There are various examples of fiber products. Examples include natural fibers such as cotton, hemp, wool, and silk; synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, and polypropylene; rayon, acetate, etc. Semi-synthetic fibers; inorganic fibers such as glass fibers, carbon fibers, asbestos fibers; or mixed fibers of these.
纖維製品可為纖維、布等形態之任一者。 The fiber product may be in any form such as fiber and cloth.
本發明之處理劑可使用作為內部脫模劑或是外部脫模劑。 The treatment agent of the present invention can be used as an internal mold release agent or an external mold release agent.
撥水撥油性聚合物可藉由以液體處理纖維製品用之已知方法中之任一方法而應用於纖維狀基材(例如纖維製品等)。當纖維製品為布時,可將布浸於溶液,或可將溶液附著或噴霧於布。為了使經處理的纖維製品呈現撥油性,係進行乾燥,較佳為例如經100℃至200℃加熱。 The water- and oil-repellent polymer can be applied to a fibrous substrate (for example, fiber products, etc.) by any of the known methods for treating fiber products with a liquid. When the fiber product is cloth, the cloth may be dipped in the solution, or the solution may be attached or sprayed on the cloth. In order to make the treated fiber product exhibit oil repellency, it is dried, preferably, for example, heated at 100 ° C to 200 ° C.
或者,撥水撥油性聚合物可藉由清潔方法應用於纖維製品,例如,可在洗滌應用或乾洗法等中應用於纖維製品。 Alternatively, the water- and oil-repellent polymer can be applied to fiber products by a cleaning method, for example, it can be applied to fiber products in washing applications or dry cleaning methods.
所能處理的纖維製品,典型者為布,此係包含織物、編物及不織布、衣料品形態的布及地毯,但亦可為纖維或紗線或中間纖維製品(例如棉條(sliver)或粗紗等)。纖維製品材料可為天然纖維(例如綿或羊毛等)、化學纖維(例如黏液嫘縈(viscose rayon)或萊賽爾纖維(lyocell)等)、或合成纖維(例如聚酯、聚醯胺或丙烯酸系纖維等)、或纖維的混合物(例如天然纖維及合成纖維的混合物等)。本發明之撥水撥油性聚合物係在使纖維素系纖維(例如綿或嫘縈等)成為疏油性及撥油性的方面係特別有效果。而且,一般而言,本發明之方法係使纖維製品成為疏水性及撥水性。 The fibrous products that can be processed are typically cloth, which includes fabrics, knitted fabrics and non-woven fabrics, cloths and carpets in the form of clothing, but can also be fibers or yarns or intermediate fiber products (such as sliver or roving) Wait). The fiber product material can be natural fiber (such as cotton or wool, etc.), chemical fiber (such as viscose rayon or lyocell, etc.), or synthetic fiber (such as polyester, polyamide or acrylic Fiber, etc.), or a mixture of fibers (eg, a mixture of natural fibers and synthetic fibers). The water-repellent and oil-repellent polymer of the present invention is particularly effective in making cellulose-based fibers (such as cotton or rayon, etc.) oleophobic and oil-repellent. Moreover, in general, the method of the present invention makes the fiber product hydrophobic and water repellent.
或者,纖維狀基材亦可為皮革。為了使皮革成為疏水性及疏油性,可於皮革加工之各種階段中,例如於皮革之濕潤加工的期間中、或於皮革之完工的期間中,將撥水撥油性聚合物以水溶液或水性乳化物應用於皮革。 Alternatively, the fibrous base material may be leather. In order to make the leather hydrophobic and oleophobic, the water- and oil-repellent polymer can be emulsified with an aqueous solution or water in various stages of leather processing, such as during the wet processing of leather or during the completion of leather Applied to leather.
或者,纖維狀基材亦可為紙。可將撥水撥油性聚合物應用於預先形成的紙、或應用於製紙的各種階段中,例如應用於紙的乾燥期間中。 Alternatively, the fibrous base material may be paper. The water- and oil-repellent polymer can be applied to preformed paper or to various stages of paper making, for example, during the drying period of paper.
「處理」係意指將處理劑藉由浸漬、噴霧、塗佈等而應用於被處理物。藉由處理,使屬於處理劑之有效成分的聚合物滲透至被處理物之內部及/或附著於被處理物之表面。 "Treatment" means that the treatment agent is applied to the object by dipping, spraying, coating, etc. Through the treatment, the polymer which is the active ingredient of the treatment agent penetrates into the interior of the treatment object and / or adheres to the surface of the treatment object.
以下列舉實施例而詳細說明本發明,惟本發明並不限定於該等實施例。 The following examples are given to explain the present invention in detail, but the present invention is not limited to these examples.
以下,若無特別標註,「份」、「%」或「比」即表示重量份、重量%或重量比。 In the following, unless otherwise noted, "parts", "%" or "ratio" means parts by weight,% by weight or weight ratio.
試驗的順序如後所述。 The test sequence will be described later.
撥水性試驗 Water repellency test
依照JIS-L-1092(AATCC-22)的噴霧法評估處理布的撥水性。如下述記載的表1所示,藉由撥水性No.來表示。分數越高,表示撥水性越良好,視狀態而以中間值(95、85、75)、+ -來標示優劣。 The water repellency of the treated cloth was evaluated in accordance with the spray method of JIS-L-1092 (AATCC-22). As shown in Table 1 described below, it is represented by the water-repellent No. The higher the score, the better the water repellency. Depending on the state, the median value (95, 85, 75), +-is used to indicate the pros and cons.
膠黏附(gum-up)性 Gum-up
將聚合物之水性分散液以使固形分成為濃度1.8重量%之方式使用自來水稀釋,並於可調整溫度為40℃之浴槽饋入處理浴,以於壓軋機之輥(mangle roll)使綿布成為輪而可連續處理之方式,以壓力5.5kgf/cm2進行連續處理。目視觀察1小時後之聚合物對壓軋機的附著狀態,藉由下述記載之表2的基準判定膠黏附性。 The aqueous dispersion of the polymer is diluted with tap water in such a way that the solid content becomes 1.8% by weight, and fed into the treatment bath in a bath with an adjustable temperature of 40 ° C, so that the cotton roll becomes a mangle roll In turn, continuous treatment can be carried out at a pressure of 5.5 kgf / cm 2 . The adhesion state of the polymer to the rolling mill after 1 hour was visually observed, and the adhesiveness was judged by the criteria of Table 2 described below.
製造例1 Manufacturing Example 1
於500mL高壓釜饋入C6F13CH2CH2OCOC(CH3)=CH2(C6SFMA)=80g、丙烯酸硬脂酯=20g、純水=200g、三丙二醇=30g、聚氧伸乙基(POE)油基醚=3g、聚氧伸乙基(POE)異十三基醚=7g,於攪拌下以60℃、15分鐘用超音波使其乳化分散。於乳化後將高壓釜內進行氮取代,之後添加2,2-偶氮雙(2-甲脒基丙烷)2鹽酸鹽=1g,以60℃使反應3小時,得到聚合物之水性分散液。再以純水將固形分濃度調整至30%。 Feed C 6 F 13 CH 2 CH 2 OCOC (CH 3 ) = CH 2 (C6SFMA) = 80g, stearyl acrylate = 20g, pure water = 200g, tripropylene glycol = 30g, polyoxyethylidene in a 500mL autoclave (POE) oleyl ether = 3 g, polyoxyethylene (POE) isotridecyl ether = 7 g, which was emulsified and dispersed with ultrasound at 60 ° C and 15 minutes under stirring. After emulsification, nitrogen was replaced in the autoclave, and then 2,2-azobis (2-carboxamidopropane) 2 hydrochloride = 1 g was added, and the reaction was carried out at 60 ° C for 3 hours to obtain an aqueous dispersion of the polymer . Then adjust the solid concentration to 30% with pure water.
製造例2 Manufacturing Example 2
於500mL高壓釜饋入C6F13CH2CH2OCOC(CH3)=CH2(C6SFMA)=80g、丙烯酸硬脂酯=20g、純水=200g、三丙二醇=30g、聚氧伸乙基(POE)油基醚=3g、聚氧伸乙基(POE)異十三基醚=4g、氯化二(十八基)二甲基銨(DOdDMAC)= 3g,於攪拌下以60℃、15分鐘用超音波使其乳化分散。於乳化後將高壓釜內進行氮取代,之後添加2,2-偶氮雙(2-甲脒基丙烷)2鹽酸鹽=1g,以60℃使反應3小時,得到聚合物之水性分散液。再以純水將固形分濃度調整至30%。 Feed C 6 F 13 CH 2 CH 2 OCOC (CH 3 ) = CH 2 (C6SFMA) = 80g, stearyl acrylate = 20g, pure water = 200g, tripropylene glycol = 30g, polyoxyethylidene in a 500mL autoclave (POE) oleyl ether = 3g, polyoxyethylene (POE) isotridecyl ether = 4g, bis (octadecyl) dimethyl ammonium chloride (DOdDMAC) = 3g, under stirring at 60 ℃, Emulsify and disperse with ultrasound in 15 minutes. After emulsification, nitrogen was replaced in the autoclave, and then 2,2-azobis (2-carboxamidopropane) 2 hydrochloride = 1 g was added, and the reaction was carried out at 60 ° C for 3 hours to obtain an aqueous dispersion of the polymer . Then adjust the solid concentration to 30% with pure water.
製造例3 Manufacturing Example 3
於500mL高壓釜饋入C6F13CH2CH2OCOC(CH3)=CH2(C6SFMA)=60g、丙烯酸硬脂酯=10g、甲基丙烯酸異莰酯=10g、純水=200g、三丙二醇=30g、聚氧伸乙基(POE)油基醚=3g、聚氧伸乙基(POE)異十三基醚=7g,於攪拌下以60℃、15分鐘用超音波使其乳化分散。於乳化後將高壓釜內進行氮取代,之後將氯化乙烯(VCM)=20g壓入填充,添加2,2-偶氮雙(2-甲脒基丙烷)2鹽酸鹽=1g,以60℃使反應3小時,得到聚合物之水性分散液。再以純水將固形分濃度調整至30%。 Feed C 6 F 13 CH 2 CH 2 OCOC (CH 3 ) = CH 2 (C6SFMA) = 60g, stearyl acrylate = 10g, isocampreyl methacrylate = 10g, pure water = 200g, three in 500mL autoclave Propylene glycol = 30g, polyoxyethylene (POE) oleyl ether = 3g, polyoxyethylene (POE) isotridecyl ether = 7g, which is emulsified and dispersed with ultrasound at 60 ℃ and 15 minutes under stirring . After emulsification, nitrogen is replaced in the autoclave, and then vinyl chloride (VCM) = 20g is press-filled, and 2,2-azobis (2-carboxamidopropane) 2 hydrochloride = 1g, 60 The reaction was allowed to proceed at 3 ° C for 3 hours to obtain an aqueous dispersion of polymer. Then adjust the solid concentration to 30% with pure water.
製造例4 Manufacturing Example 4
於500mL高壓釜饋入C6F13CH2CH2OCOC(Cl)=CH2(C6SFCLA)=80g、丙烯酸硬脂酯=20g、純水=200g、三丙二醇=30g、聚氧伸乙基(POE)油基醚=3g、聚氧伸乙基(POE)異十三基醚=7g,於攪拌下以60℃、15分鐘用超音波使其乳化分散。於乳化後將高壓釜內進行氮取代,之後添加2,2-偶氮雙(2-甲脒基丙烷)2鹽酸鹽=1g,以60℃使反應3小時,得到聚合物之水性分散液。再以純水將固形分濃度調整至 30%。 In a 500mL autoclave, feed C 6 F 13 CH 2 CH 2 OCOC (Cl) = CH 2 (C6SFCLA) = 80g, stearyl acrylate = 20g, pure water = 200g, tripropylene glycol = 30g, polyoxyethylene ( POE) oleyl ether = 3g, polyoxyethylene (POE) isotridecyl ether = 7g, which was emulsified and dispersed with ultrasound at 60 ° C and 15 minutes under stirring. After emulsification, nitrogen was replaced in the autoclave, and then 2,2-azobis (2-carboxamidopropane) 2 hydrochloride = 1 g was added, and the reaction was carried out at 60 ° C for 3 hours to obtain an aqueous dispersion of the polymer . Then adjust the solid concentration to 30% with pure water.
製造例5 Manufacturing Example 5
於500mL高壓釜饋入C6F13CH2CH2OCOC(Cl)=CH2(C6SFCLA)=60g、丙烯酸月桂酯=20g、甲基丙烯酸異莰酯=20g、純水=200g、三丙二醇=30g、聚氧伸乙基(POE)油基醚=3g、聚氧伸乙基(POE)異十三基醚=7g,於攪拌下以60℃、15分鐘用超音波使其乳化分散。於乳化後將高壓釜內進行氮取代,之後添加2,2-偶氮雙(2-甲脒基丙烷)2鹽酸鹽=1g,以60℃使反應3小時,得到聚合物之水性分散液。再以純水將固形分濃度調整至30%。 In a 500mL autoclave, C 6 F 13 CH 2 CH 2 OCOC (Cl) = CH 2 (C6SFCLA) = 60g, lauryl acrylate = 20g, isobornyl methacrylate = 20g, pure water = 200g, tripropylene glycol = 30g, polyoxyethylene (POE) oleyl ether = 3g, polyoxyethylene (POE) isotridecyl ether = 7g, which was emulsified and dispersed by ultrasound at 60 ° C for 15 minutes with stirring. After emulsification, nitrogen was replaced in the autoclave, and then 2,2-azobis (2-carboxamidopropane) 2 hydrochloride = 1 g was added, and the reaction was carried out at 60 ° C for 3 hours to obtain an aqueous dispersion of the polymer . Then adjust the solid concentration to 30% with pure water.
製造例6 Manufacturing Example 6
於500mL高壓釜饋入C6F13CH2CH2OCOC(Cl)=CH2(C6SFCLA)=40g、丙烯酸月桂酯=20g、甲基丙烯酸異莰酯=20g、純水=200g、三丙二醇=30g、聚氧伸乙基(POE)油基醚=3g、聚氧伸乙基(POE)異十三基醚=7g,於攪拌下以60℃、15分鐘用超音波使其乳化分散。於乳化後將高壓釜內進行氮取代,之後擠入填充氯化乙烯(VCM)=20g,添加2,2-偶氮雙(2-甲脒基丙烷)2鹽酸鹽=1g,以60℃使反應3小時,得到聚合物之水性分散液。再以純水將固形分濃度調整至30%。 In a 500mL autoclave, feed C 6 F 13 CH 2 CH 2 OCOC (Cl) = CH 2 (C6SFCLA) = 40g, lauryl acrylate = 20g, isobornyl methacrylate = 20g, pure water = 200g, tripropylene glycol = 30g, polyoxyethylene (POE) oleyl ether = 3g, polyoxyethylene (POE) isotridecyl ether = 7g, which was emulsified and dispersed by ultrasound at 60 ° C for 15 minutes with stirring. After emulsification, nitrogen is replaced in the autoclave, then squeezed and filled with vinyl chloride (VCM) = 20g, 2,2-azobis (2-carboxamidine propane) 2 hydrochloride = 1g, at 60 ℃ The reaction was allowed to proceed for 3 hours to obtain an aqueous dispersion of polymer. Then adjust the solid concentration to 30% with pure water.
製造例7 Manufacturing Example 7
於500mL高壓釜饋入丙烯酸硬脂酯=90g、甲基丙烯酸2,3-二羥基丙酯=10g、純水=200g、三丙二醇=30g、聚氧伸乙基(POE)油基醚=3g、聚氧伸乙基(POE)異十三基醚=7g,於攪拌下以60℃、15分鐘用超音波使其乳化分散。於乳化後將高壓釜內進行氮取代,之後添加2,2-偶氮雙(2-甲脒基丙烷)2鹽酸鹽=1g,以60℃使反應3小時,得到聚合物之水性分散液。再以純水將固形分濃度調整至30%。 A 500mL autoclave was fed with stearyl acrylate = 90g, 2,3-dihydroxypropyl methacrylate = 10g, pure water = 200g, tripropylene glycol = 30g, polyoxyethylene (POE) oleyl ether = 3g 1. Polyoxyethylene (POE) isotridecyl ether = 7g, which is emulsified and dispersed with ultrasound at 60 ° C and 15 minutes under stirring. After emulsification, nitrogen was replaced in the autoclave, and then 2,2-azobis (2-carboxamidopropane) 2 hydrochloride = 1 g was added, and the reaction was carried out at 60 ° C for 3 hours to obtain an aqueous dispersion of the polymer . Then adjust the solid concentration to 30% with pure water.
製造例8 Manufacturing Example 8
於500mL高壓釜饋入丙烯酸硬脂酯=70g、甲基丙烯酸2,3-二羥基丙酯=10g、純水=200g、三丙二醇=30g、聚氧伸乙基(POE)油基醚=3g、聚氧伸乙基(POE)異十三基醚=7g,於攪拌下以60℃、15分鐘用超音波使其乳化分散。於乳化後將高壓釜內進行氮取代,之後添加2,2-偶氮雙(2-甲脒基丙烷)2鹽酸鹽=1g,以60℃使反應1小時,之後將氯化乙烯=20g壓入填充,更進一步使反應2小時而得到聚合物之水性分散液。再以純水將固形分濃度調整至30%。 A 500mL autoclave was fed with stearyl acrylate = 70g, 2,3-dihydroxypropyl methacrylate = 10g, pure water = 200g, tripropylene glycol = 30g, polyoxyethylene (POE) oleyl ether = 3g 1. Polyoxyethylene (POE) isotridecyl ether = 7g, which is emulsified and dispersed with ultrasound at 60 ° C and 15 minutes under stirring. After emulsification, nitrogen was replaced in the autoclave, and then 2,2-azobis (2-carboxamidopropane) 2 hydrochloride = 1g was added, and the reaction was carried out at 60 ° C for 1 hour, after which ethylene chloride = 20g Pressing and filling, and further reacting for 2 hours to obtain an aqueous dispersion of the polymer. Then adjust the solid concentration to 30% with pure water.
關於各製造例之組成係彙整於表3。 Table 3 summarizes the composition of each manufacturing example.
實施例1 Example 1
對於製造例1所製造之聚合分散液(30%)100份,混合聚氯化二烯丙基二甲基銨(分子量9000)(PDADMAC-9000)之30%水溶液0.1份,而調製水性分散液。將該分散液以使固形分濃度成為0.15重量%、0.30重量%、0.60重量%之方式使用自來水稀釋而調製試驗溶液,將聚酯布浸於該試驗溶液之後,通過壓軋機,評估經160℃熱處理2分鐘之試驗布的撥水性(低濃度撥水性)。而且,對於以使分散液的固形分濃度成為0.60重量%且分散染料成為0.006重量%之方式使用自來水稀釋而成之試驗溶液,亦進行相同的撥水性評估。再進一步就膠黏附性進行評估。 For 100 parts of the polymer dispersion (30%) produced in Production Example 1, 0.1 part of a 30% aqueous solution of polydiallyldimethylammonium chloride (molecular weight 9000) (PDADMAC-9000) was mixed to prepare an aqueous dispersion . This dispersion liquid was diluted with tap water to prepare a test solution so that the solid content concentration became 0.15 wt%, 0.30 wt%, and 0.60 wt%, and after immersing the polyester cloth in the test solution, it was evaluated by a rolling mill at 160 ° C. The water repellency (low concentration water repellency) of the test cloth after heat treatment for 2 minutes. In addition, the same water repellency evaluation was also performed on the test solution diluted with tap water so that the solid content concentration of the dispersion liquid became 0.60% by weight and the dispersion dye became 0.006% by weight. Further evaluate the adhesiveness.
實施例2 Example 2
對於製造例1所製造之聚合分散液(30%)100份,混合聚氯化二烯丙基二甲基銨(分子量30000)(PDADMAC-30000)之30%水溶液0.1份,而調製水性分散液,並進行與實施例1相同的評估。 To 100 parts of the polymer dispersion (30%) produced in Production Example 1, 0.1 part of a 30% aqueous solution of polydiallyldimethylammonium chloride (molecular weight 30,000) (PDADMAC-30000) was mixed to prepare an aqueous dispersion And performed the same evaluation as in Example 1.
實施例3 Example 3
對於製造例1所製造之聚合分散液(30%)100份,混合聚氯化二烯丙基二甲基銨(分子量30000)(PDADMAC-30000)之30%水溶液0.5份,而調製水性分散液,並進行與實施例1相同的評估。 For 100 parts of the polymer dispersion (30%) produced in Production Example 1, 0.5 part of a 30% aqueous solution of polydiallyldimethylammonium chloride (molecular weight 30,000) (PDADMAC-30000) was mixed to prepare an aqueous dispersion And performed the same evaluation as in Example 1.
實施例4 Example 4
對於製造例1所製造之聚合分散液(30%)100份,混合二甲基胺環氧氯丙烷縮合體鹽(分子量9000)(PDMAECH-9000)之30%水溶液0.1份,而調製水性分散液,並進行與實施例1相同的評估。 To 100 parts of the polymer dispersion (30%) produced in Production Example 1, 0.1 part of a 30% aqueous solution of dimethylamine epichlorohydrin condensate salt (molecular weight 9000) (PDMAECH-9000) was mixed to prepare an aqueous dispersion And performed the same evaluation as in Example 1.
實施例5至11 Examples 5 to 11
對於製造例2至8所製造之聚合分散液(30%)100份,混合聚氯化二烯丙基二甲基銨(分子量30000)(PDADMAC-30000)之30%水溶液0.1份,而調製水性分散液,並進行與實施例1相同的評估。 For 100 parts of the polymer dispersion (30%) produced in Production Examples 2 to 8, 0.1 part of a 30% aqueous solution of polydiallyldimethylammonium chloride (molecular weight 30,000) (PDADMAC-30000) was mixed to prepare an aqueous solution The dispersion was subjected to the same evaluation as in Example 1.
比較例1 Comparative example 1
於製造例1所製造之聚合分散液(30%)中不進行任何添加,而進行與實施例1相同的評估。 The polymerization dispersion liquid (30%) produced in Production Example 1 was subjected to the same evaluation as in Example 1 without any addition.
比較例2 Comparative example 2
對於製造例1所製造之聚合分散液(30%)100份,混合氯化聚氧伸乙基牛脂烷基苯甲基銨(TBzPOEC)之30%水溶液0.1份,而調製水性分散液,並進行與實施例1相同的評估。 To 100 parts of the polymerization dispersion (30%) produced in Production Example 1, 0.1 part of a 30% aqueous solution of polyoxyethylene tallow alkyl benzyl ammonium chloride (TBzPOEC) was mixed to prepare an aqueous dispersion and proceed The same evaluation as in Example 1.
比較例3 Comparative Example 3
對於製造例1所製造之聚合分散液(30%)100份,混合氧化月桂基二甲基胺(LDMAO)之30%水溶液0.1份,而調製水性分散液,並進行與實施例1相同的評估。 For 100 parts of the polymer dispersion (30%) produced in Production Example 1, 0.1 part of a 30% aqueous solution of lauryl dimethylamine oxide (LDMAO) was mixed to prepare an aqueous dispersion, and the same evaluation as in Example 1 was performed. .
比較例4 Comparative Example 4
對於製造例1所製造之聚合分散液(30%)100份,混合硬脂酸二甲基胺基丙基醯胺(StDMAPAD)之30%水溶液0.1份,而調製水性分散液,並進行與實施例1相同的評估。 For 100 parts of the polymer dispersion (30%) produced in Production Example 1, 0.1 part of a 30% aqueous solution of dimethylaminopropyl stearate (StDMAPAD) was mixed to prepare an aqueous dispersion and proceed with the implementation. Example 1 same evaluation.
比較例5至8 Comparative Examples 5 to 8
以製造例8取代製造例1,進行與比較例1至4相同的調製及評估。 Production Example 1 was replaced with Production Example 8, and the same modulation and evaluation as Comparative Examples 1 to 4 were performed.
各例之性能係示於表4及表5。 The performance of each case is shown in Table 4 and Table 5.
本發明之表面處理劑,例如可使用作為撥水撥油劑、防污劑及去污劑。 The surface treatment agent of the present invention can be used as a water and oil repellent, an antifouling agent, and a detergent, for example.
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