TW201803964A - Water repellent aid, non-fluorine water repellent composition, and method for producing water-repellent fiber product - Google Patents

Water repellent aid, non-fluorine water repellent composition, and method for producing water-repellent fiber product Download PDF

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TW201803964A
TW201803964A TW106105712A TW106105712A TW201803964A TW 201803964 A TW201803964 A TW 201803964A TW 106105712 A TW106105712 A TW 106105712A TW 106105712 A TW106105712 A TW 106105712A TW 201803964 A TW201803964 A TW 201803964A
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fluorine
water
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carbon atoms
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TWI738723B (en
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前田高輔
後藤昌央
拓植好揮
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日華化學股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
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    • 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
    • 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
    • D06M15/227—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated
    • D06M15/233—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated aromatic, e.g. styrene
    • 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
    • D06M15/244—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons
    • D06M15/248—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons containing chlorine
    • 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
    • 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
    • D06M15/347—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated ethers, acetals, hemiacetals, ketones or aldehydes
    • 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
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
    • 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
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10—Repellency against liquids
    • D06M2200/12—Hydrophobic properties

Abstract

A water repellent aid for a non-fluorine water repellent includes an organo-modified silicone represented by general formula (1). [In formula (1), R20, R21, R22 each independently represent a hydrogen atom, methyl group, ethyl group, or C1-4 alkoxy group, R23 represents either a C8-40 hydrocarbon group having an aromatic ring or a C3-22 alkyl group, R30, R31, R32, R33, R34, and R35 each independently represent a hydrogen atom, methyl group, ethyl group, C1-4 alkoxy group, C8-40 hydrocarbon group having an aromatic ring, or C3-22 alkyl group, a represents an integer of 0 or higher, b represents an integer of 1 or higher, and (a + b) is 10-200].

Description

撥水助劑、非氟系撥水劑組合物、及撥水性纖維製品之製造方法Water-repellent auxiliary agent, non-fluorine-based water-repellent agent composition, and manufacturing method of water-repellent fiber product

本發明係關於一種撥水助劑、非氟系撥水劑組合物、及撥水性纖維製品之製造方法。The invention relates to a manufacturing method of a water-repellent auxiliary agent, a non-fluorine-based water-repellent agent composition, and a water-repellent fiber product.

先前，已知有具有含氟之基之氟系撥水劑，且已知有藉由將該氟系撥水劑處理於纖維製品等而對其表面賦予撥水性之纖維製品。此種氟系撥水劑通常係藉由使具有氟烷基之單體聚合或者共聚合而製造。 經氟系撥水劑處理之纖維製品雖會揮發出優異之撥水性，但為了表現出撥水性而必須整合氟烷基之配向性，故而必須於使氟系撥水劑附著於纖維製品後以超過130℃之溫度實施熱處理。然而，高溫下之熱處理需要較高之能量，於國際性省能量化之趨勢中存在問題。 又，具有氟烷基之單體由於價格較高，故而於經濟方面並不滿足，進而，具有氟烷基之單體難以分解，故而於環境方面亦存在問題。 另一方面，於纖維製品之撥水加工之領域，為了實現品質之穩定化及成本削減，期待即便以較低之濃度或較低之熱處理溫度亦可對纖維製品賦予優異之撥水性之撥水劑。 因此，近年來，正在對不含氟之非氟系撥水劑進行研究。例如，於非專利文獻1中揭示有乳化分散有石蠟或蠟般之烴化合物、脂肪酸金屬鹽或烷基尿素之撥水劑。 又，於專利文獻1中提出有為了賦予與先前之氟系撥水劑相比並不遜色之撥水性而乳化分散有特定之非氟系聚合物之撥水劑。 [先前技術文獻] [專利文獻] [專利文獻1]日本專利特開2006-328624號公報 [非專利文獻] [非專利文獻1]「超撥水加工、加工劑之全容與透濕防水素材之新動向」，Osaka Chemical Marketing Center, Inc.發行，1996年，p.7～9Conventionally, a fluorine-based water-repellent agent having a fluorine-containing group is known, and a fiber product that imparts water-repellency to its surface by treating the fluorine-based water-repellent agent on a fiber product or the like is known. Such a fluorine-based water-repellent agent is usually produced by polymerizing or copolymerizing a monomer having a fluoroalkyl group. Although the fibrous products treated with a fluorine-based water-repellent agent will volatilize excellent water-repellent properties, in order to show the water-repellent properties, the orientation of the fluoroalkyl group must be integrated. Heat treatment is performed at a temperature exceeding 130 ° C. However, heat treatment at high temperatures requires higher energy, and there are problems in the international energy saving trend. In addition, since monomers having a fluoroalkyl group are relatively expensive, they are not economically satisfactory. Furthermore, the monomers having a fluoroalkyl group are difficult to decompose, so there are problems in terms of the environment. On the other hand, in the field of water-repellent processing of fiber products, in order to stabilize the quality and reduce costs, it is expected that even at a lower concentration or a lower heat treatment temperature, the fiber products can be provided with excellent water-repellent water-repellent water-repellent properties. Agent. Therefore, in recent years, research is being conducted on non-fluorine-based water-repellent agents containing no fluorine. For example, Non-Patent Document 1 discloses a water-repellent agent in which a paraffin or wax-like hydrocarbon compound, a fatty acid metal salt, or an alkyl urea is emulsified and dispersed. In addition, Patent Document 1 proposes a water-repellent agent in which a specific non-fluorine-based polymer is emulsified and dispersed in order to impart water repellency that is not inferior to that of the conventional fluorine-based water-repellent agent. [Prior Art Documents] [Patent Documents] [Patent Documents 1] Japanese Patent Laid-Open No. 2006-328624 [Non-Patent Documents] [Non-Patent Documents 1] "Full Capacity of Water Repellent Processing and Processing Agents and Moisture-permeable Waterproof Materials "New Trends", issued by Osaka Chemical Marketing Center, Inc., 1996, p. 7-9

[發明所欲解決之問題] 然而，先前之撥水劑存在無法充分地獲得耐久撥水性之情形。 本發明係鑒於上述情況而完成者，目的在於提供一種可提高非氟系撥水劑之耐久撥水性之撥水助劑以及使用其之非氟系撥水劑組合物、及撥水性纖維製品之製造方法。 [解決問題之技術手段] 本發明提供一種撥水助劑，其係非氟系撥水劑用之撥水助劑，並且包含下述通式(1)所表示之有機改性聚矽氧。 [化1]

Figure TW201803964AD00001
[式(1)中，R20 、R21 及R22 分別獨立地表示氫原子、甲基、乙基或碳數1～4之烷氧基，R23 表示具有芳香族環之碳數8～40之烴基或碳數3～22之烷基，R30 、R31 、R32 、R33 、R34 及R35 分別獨立地表示氫原子、甲基、乙基、碳數1～4之烷氧基、具有芳香族環之碳數8～40之烴基或碳數3～22之烷基，a表示0以上之整數，b表示1以上之整數，(a＋b)為10～200，於a為2以上之情形時，存在有複數個之R20 及R21 可分別相同，亦可不同，於b為2以上之情形時，存在有複數個之R22 及R23 可分別相同，亦可不同] 根據本發明之撥水助劑，藉由與非氟系撥水劑併用，可提高非氟系撥水劑之耐久撥水性。 又，本發明提供一種包含上述本發明之撥水助劑與非氟系撥水劑之非氟系撥水劑組合物。 上述非氟系撥水劑亦可包含含有源自下述通式(A-1)所表示之(甲基)丙烯酸酯單體(A)之結構單元之非氟系聚合物。 [化2]
Figure TW201803964AD00002
[式(A-1)中，R1 表示氫或甲基，R2 表示亦可具有取代基之碳數12以上之1價烴基]。 上述非氟系聚合物亦可進而含有源自選自(B1)HLB為7～18之下述通式(I-1)所表示之化合物、(B2)HLB為7～18之下述通式(II-1)所表示之化合物、及(B3)HLB為7～18之於具有羥基及聚合性不飽和基之油脂加成碳數2～4之環氧烷而成之化合物中之至少1種反應性乳化劑(B)之結構單元。 [化3]
Figure TW201803964AD00003
[式(I-1)中，R3 表示氫或甲基，X表示碳數1～6之直鏈或者支鏈之伸烷基，Y1 表示包含碳數2～4之伸烷基氧基之2價基] [化4]
Figure TW201803964AD00004
[式(II-1)中，R4 表示具有聚合性不飽和基之碳數13～17之1價不飽和烴基，Y2 表示包含碳數2～4之伸烷基氧基之2價基]。 上述非氟系聚合物亦可進而含有源自氯乙烯及偏二氯乙烯中之至少任1種單體(E)之結構單元。 上述非氟系撥水劑亦可包含使包含上述通式(A-1)所表示之(甲基)丙烯酸酯單體(A)之乳化物或分散物乳化聚合或分散聚合而成之非氟系聚合物。 上述乳化物或上述分散物亦可進而包含選自(B1)HLB為7～18之上述通式(I-1)所表示之化合物、(B2)HLB為7～18之上述通式(II-1)所表示之化合物、及(B3)HLB為7～18之對具有羥基及聚合性不飽和基之油脂加成碳數2～4之環氧烷而成之化合物中之至少1種反應性乳化劑(B)。 上述乳化物或上述分散物亦可進而含有氯乙烯及偏二氯乙烯中之至少任1種單體(E)。 於上述本發明之非氟系撥水劑組合物中，上述有機改性聚矽氧之含量亦可相對於上述非氟系聚合物100質量份而為1～50質量份。 又，本發明提供一種撥水性纖維製品之製造方法，其具備利用包含上述本發明之非氟系撥水劑組合物之處理液對纖維製品進行處理之步驟。 根據本發明之撥水性纖維製品之製造方法，藉由使用包含本發明之撥水助劑之非氟系撥水劑組合物，可穩定地製造耐久撥水性優異之撥水性纖維製品。又，本發明之撥水性纖維製品之製造方法無需高溫下之熱處理，因此可實現省能量化，並且由於係使用非氟系撥水劑，因此可降低對環境之負荷。 [發明之效果] 根據本發明，可提供一種可提高非氟系撥水劑之耐久撥水性之撥水助劑及包含其之非氟系撥水劑組合物。 又，本發明之非氟系撥水劑組合物雖為不包含具有氟烷基或氟之化合物之撥水劑組合物，但亦表現出優異之撥水性，可用來代替氟系撥水劑，從而可消除氟供給源或對環境等之影響之擔憂。再者，較佳為於使撥水劑組合物附著於纖維製品等後通常進行熱處理，但由於本發明之非氟系撥水劑組合物未使用具有氟烷基之單體，故而即便於在130℃以下之溫和之條件下進行熱處理之情形時，亦可發揮較高之撥水性，又，於在超過130℃之高溫下進行熱處理之情形時，可較氟系撥水劑之情形時縮短熱處理時間。因此，可抑制被處理物之因熱所導致之變質，故而質地變得柔軟，並且於可削減熱處理所耗之熱量等成本方面亦優異。 進而，根據本發明，藉由使用特定之反應性乳化劑代替一般之界面活性劑作為用於非氟系聚合物之乳化或分散聚合之乳化分散劑，可減少撥水劑組合物所包含之界面活性劑之量。其結果為可抑制所獲得之纖維製品等之撥水性之降低，從而可實現較先前之非氟系撥水劑更高之撥水性。[Problems to be Solved by the Invention] However, the conventional water-repellent agents may not be able to sufficiently obtain durable water-repellent properties. The present invention has been made in view of the foregoing circumstances, and an object thereof is to provide a water-repellent auxiliary agent capable of improving the durable water repellency of a non-fluorine-based water-repellent agent, a non-fluorine-based water-repellent composition using the same, and a water-repellent fiber product. Production method. [Technical means to solve the problem] The present invention provides a water-repellent auxiliary agent, which is a water-repellent auxiliary agent for a non-fluorine-based water-repellent agent, and includes an organic modified polysiloxane represented by the following general formula (1). [Chemical 1]
Figure TW201803964AD00001
[In formula (1), R 20 , R 21, and R 22 each independently represent a hydrogen atom, a methyl group, an ethyl group, or an alkoxy group having 1 to 4 carbon atoms, and R 23 represents an 8 to 6 carbon atom having an aromatic ring. A hydrocarbon group of 40 or an alkyl group having 3 to 22 carbon atoms, and R 30 , R 31 , R 32 , R 33 , R 34, and R 35 each independently represent a hydrogen atom, a methyl group, an ethyl group, and an alkyl group having 1 to 4 carbon atoms An oxygen group, a hydrocarbon group having 8 to 40 carbon atoms or an alkyl group having 3 to 22 carbon atoms having an aromatic ring, a represents an integer of 0 or more, b represents an integer of 1 or more, (a + b) is 10 to 200, and a is In the case of 2 or more, a plurality of R 20 and R 21 may be the same or different, and when b is 2 or more, the R 22 and R 23 may be the same or different. ] According to the water-repellent additive of the present invention, the durable water repellency of the non-fluorine-based water-repellent agent can be improved by being used in combination with the non-fluorine-based water-repellent agent. The present invention also provides a non-fluorine-based water-repellent composition comprising the water-repellent auxiliary agent of the present invention and a non-fluorine-based water-repellent agent. The non-fluorine-based water-repellent agent may include a non-fluorine-based polymer containing a structural unit derived from a (meth) acrylate monomer (A) represented by the following general formula (A-1). [Chemical 2]
Figure TW201803964AD00002
[In the formula (A-1), R 1 represents hydrogen or a methyl group, and R 2 represents a monovalent hydrocarbon group having 12 or more carbon atoms which may have a substituent]. The non-fluorine-based polymer may further contain a compound selected from (B1) a compound represented by the following general formula (I-1) having an HLB of 7 to 18, and (B2) an HLB having a general formula of the following 7 to 18 At least one of the compounds represented by (II-1) and (B3) HLB of 7 to 18 is a compound obtained by adding an alkylene oxide having 2 to 4 carbon atoms to an oil having a hydroxyl group and a polymerizable unsaturated group. The structural unit of a reactive emulsifier (B). [Chemical 3]
Figure TW201803964AD00003
[In the formula (I-1), R 3 represents hydrogen or a methyl group, X represents a linear or branched alkylene group having 1 to 6 carbon atoms, and Y 1 represents an alkylene oxide group having 2 to 4 carbon atoms. 2-valent base] [Chemical 4]
Figure TW201803964AD00004
[In formula (II-1), R 4 represents a monovalent unsaturated hydrocarbon group having 13 to 17 carbon atoms having a polymerizable unsaturated group, and Y 2 represents a divalent group containing an alkyleneoxy group having 2 to 4 carbon atoms. ]. The non-fluorine-based polymer may further contain a structural unit derived from at least one of the monomers (E) in vinyl chloride and vinylidene chloride. The non-fluorine-based water-repellent agent may include non-fluorine-based emulsion polymerization or dispersion polymerization of an emulsion or dispersion containing the (meth) acrylate monomer (A) represented by the general formula (A-1). Department of polymers. The emulsion or the dispersion may further include a compound selected from the group consisting of (B1) the compound represented by the general formula (I-1) having an HLB of 7 to 18, and (B2) the general formula (II-) having an HLB of 7 to 18 1) Reactivity of at least one of the compounds represented by (B3) and (B3) a compound obtained by adding an alkylene oxide having a carbon number of 2 to 4 to a fat or oil having a hydroxyl group and a polymerizable unsaturated group with an HLB of 7 to 18 Emulsifier (B). The emulsion or the dispersion may further contain at least any one of monomers (E) in vinyl chloride and vinylidene chloride. In the non-fluorine-based water-repellent composition of the present invention, the content of the organically modified polysiloxane may be 1 to 50 parts by mass relative to 100 parts by mass of the non-fluorine-based polymer. The present invention also provides a method for producing a water-repellent fiber product, which includes a step of treating the fiber product with a treatment liquid containing the non-fluorine-based water-repellent composition of the present invention. According to the method for producing a water-repellent fiber product of the present invention, by using the non-fluorine-based water-repellent composition containing the water-repellent auxiliary agent of the present invention, a water-repellent fiber product having excellent durability and water repellency can be stably produced. In addition, the manufacturing method of the water-repellent fiber product of the present invention does not require heat treatment at high temperature, so that energy saving can be achieved, and because a non-fluorine-based water-repellent agent is used, the load on the environment can be reduced. [Effects of the Invention] According to the present invention, it is possible to provide a water-repellent auxiliary agent capable of improving the durable water repellency of a non-fluorine-based water-repellent agent and a non-fluorine-based water-repellent agent composition containing the same. In addition, although the non-fluorine-based water-repellent composition of the present invention is a water-repellent composition that does not include a compound having a fluoroalkyl group or fluorine, it also exhibits excellent water-repellency and can be used instead of a fluorine-based water-repellent. This eliminates concerns about fluorine supply sources or environmental impact. Furthermore, it is preferred that the water-repellent composition is usually subjected to a heat treatment after being attached to a fiber product or the like. However, the non-fluorine-based water-repellent composition of the present invention does not use a monomer having a fluoroalkyl group. When heat treatment is performed under mild conditions below 130 ° C, higher water repellency can also be exerted, and when heat treatment is performed at temperatures higher than 130 ° C, it can be shortened compared to the case of fluorine water repellent. Heat treatment time. Therefore, deterioration of the object to be treated due to heat can be suppressed, so that the texture becomes soft, and it is also excellent in terms of reducing costs such as heat consumed by heat treatment. Furthermore, according to the present invention, by using a specific reactive emulsifier instead of a general surfactant as an emulsifying and dispersing agent for emulsification or dispersion polymerization of a non-fluorine-based polymer, the interface included in the water repellent composition can be reduced. Amount of active agent. As a result, a reduction in water repellency of the obtained fiber products and the like can be suppressed, and a higher water repellency than that of the conventional non-fluorine-based water repellent agent can be achieved.

本實施形態之非氟系撥水劑用之撥水助劑包含下述通式(1)所表示之有機改性聚矽氧。再者，於下述通式(1)中，各結構單元不論為嵌段抑或是無規，均可交替地排列。 [化5]

Figure TW201803964AD00005
[式(1)中，R20 、R21 及R22 分別獨立地表示氫原子、甲基、乙基或碳數1～4之烷氧基，R23 表示具有芳香族環之碳數8～40之烴基或碳數3～22之烷基，R30 、R31 、R32 、R33 、R34 及R35 分別獨立地表示氫原子、甲基、乙基、碳數1～4之烷氧基、具有芳香族環之碳數8～40之烴基或碳數3～22之烷基，a表示0以上之整數，b表示1以上之整數，(a＋b)為10～200，於a為2以上之情形時，存在有複數個之R20 及R21 可分別相同，亦可不同，於b為2以上之情形時，存在有複數個之R22 及R23 可分別相同，亦可不同] 於本實施形態之有機改性聚矽氧中，上述碳數1～4之烷氧基可為直鏈狀，亦可為支鏈狀。作為碳數1～4之烷氧基，例如可列舉甲氧基、乙氧基、丙氧基、丁氧基等。就工業上容易製造且容易獲取之方面而言，R20 、R21 及R22 較佳為分別獨立地為氫原子或甲基，更佳為甲基。 作為上述具有芳香族環之碳數8～40之烴基，例如可列舉碳數8～40之芳烷基、下述通式(2)或(3)所表示之基等。 [化6]
Figure TW201803964AD00006
[式(2)中，R40 表示碳數2～6之伸烷基，R41 表示單鍵或碳數1～4之伸烷基，c表示0～3之整數；於c為2或3之情形時，存在有複數個之R41 可相同，亦可不同] 上述伸烷基可為直鏈狀，亦可為支鏈狀。 [化7]
Figure TW201803964AD00007
[式(3)中，R42 表示碳數2～6之伸烷基，R43 表示單鍵或碳數1～4之伸烷基，d表示0～3之整數；於d為2或3之情形時，存在有複數個之R43 可相同，亦可不同] 上述伸烷基可為直鏈狀，亦可為支鏈狀。 作為上述碳數8～40之芳烷基，例如可列舉苯基乙基、苯基丙基、苯基丁基、苯基戊基、苯基己基、萘基乙基等。其中，就工業上容易製造且容易獲取之方面而言，較佳為苯基乙基及苯基丙基。 於上述通式(2)所表示之基中，就工業上容易製造且容易獲取之方面而言，R40 較佳為碳數2～4之伸烷基，c較佳為0或1，更佳為0。 於上述通式(3)所表示之基中，就工業上容易製造且容易獲取之方面而言，R42 較佳為碳數2～4之伸烷基，d較佳為0或1，更佳為0。 作為上述具有芳香族環之碳數8～40之烴基，就工業上容易製造且容易獲取之方面而言，較佳為上述碳數8～40之芳烷基及上述通式(2)所表示之基，就可提高所獲得之纖維製品之撥水性之方面而言，更佳為上述碳數8～40之芳烷基。 上述碳數3～22之烷基可為直鏈狀，亦可為支鏈狀。作為碳數3～22之烷基，例如可列舉己基、庚基、辛基、壬基、癸基、十一烷基、十二烷基、肉豆蔻基、鯨蠟基、硬脂基等。作為碳數3～22之烷基，就可提高所獲得之纖維製品之撥水性之方面而言，較佳為碳數8～20之烷基，更佳為碳數12～18之烷基。 於本實施形態之有機改性聚矽氧中，R30 、R31 、R32 、R33 、R34 及R35 分別獨立地為氫原子、甲基、乙基、碳數1～4之烷氧基、具有芳香族環之碳數8～40之烴基或碳數3～22之烷基。就工業上容易製造且容易獲取之方面而言，R30 、R31 、R32 、R33 、R34 及R35 較佳為分別獨立地為氫原子、甲基、乙基或碳數1～4之烷氧基，其中更佳為甲基。 於本實施形態之有機改性聚矽氧中，a為0以上之整數。就工業上容易製造、容易獲取且所獲得之纖維製品對樹脂塗層之剝離強度更優異之方面而言，a較佳為40以下，更佳為30以下。 於本實施形態之有機改性聚矽氧中，(a＋b)為10～200。就工業上容易製造且容易獲取之方面而言，(a＋b)較佳為20～100，更佳為40～60。若(a＋b)為上述範圍內，則有聚矽氧本身之製造或處理變得容易之傾向。 本實施形態之有機改性聚矽氧可藉由先前公知之方法合成。本實施形態之有機改性聚矽氧例如可藉由使具有乙烯基之芳香族化合物及/或α-烯烴與具有SiH基之聚矽氧進行矽氫化反應而獲得。 作為上述具有SiH基之聚矽氧，例如可列舉聚合度為10～200之甲基氫聚矽氧或二甲基矽氧烷與甲基氫矽氧烷之共聚物等。該等之中，就工業上容易製造且容易獲取之方面而言，較佳為甲基氫聚矽氧。 上述具有乙烯基之芳香族化合物係成為上述通式(1)中之R23 中具有芳香族環之碳數8～40之烴基之來源的化合物。作為具有乙烯基之芳香族化合物，例如可列舉苯乙烯、α-甲基苯乙烯、乙烯基萘、烯丙基苯基醚、烯丙基萘基醚、烯丙基-對異丙苯基苯基醚、烯丙基-鄰苯基苯基醚、烯丙基-三(苯基乙基)-苯基醚、烯丙基-三(2-苯基丙基)苯基醚等。 上述α-烯烴係上述通式(1)中之R23 成為碳數3～22之烷基之來由之化合物。作為α-烯烴，例如可列舉丙烯、1-丁烯、1-戊烯、1-己烯、1-庚烯、1-辛烯、1-壬烯、1-癸烯、1-十一烯、1-十二烯、1-十四烯、1-十六烯、1-十八烯等碳數3～22之α-烯烴。 上述矽氫化反應亦藉由視需要於觸媒之存在下，使上述具有乙烯基之芳香族化合物及上述α-烯烴階段性地或者一次性與具有上述SiH基之聚矽氧反應而進行。 用於矽氫化反應之具有SiH基之聚矽氧、具有乙烯基之芳香族化合物及α-烯烴之使用量可分別根據具有SiH基之聚矽氧之SiH基當量或數量平均分子量等適當選擇。 作為用於矽氫化反應之觸媒，例如可列舉鉑、鈀等之化合物，其中較佳為鉑化合物。作為鉑化合物，例如可列舉氯化鉑(IV)等。 矽氫化反應之反應條件並無特別限制，可適當地進行調整。反應溫度例如為10～200℃，較佳為50～150℃。反應時間例如於反應溫度為50～150℃時，可設為3～12小時。 又，矽氫化反應較佳為於惰性氣體環境下進行。作為惰性氣體，例如可列舉氮氣、氬氣等。雖於無溶劑之情況下亦會進行反應，但亦可使用溶劑。作為溶劑，例如可列舉二㗁烷、甲基異丁基酮、甲苯、二甲苯、乙酸丁酯等。 對本實施形態之非氟系撥水劑組合物進行說明。 本實施形態之非氟系撥水劑組合物包含上述本實施形態之撥水助劑與非氟系撥水劑。 就儲存穩定性優異，並且即便於未進行熱處理之情形時亦可對纖維製品等賦予充分之撥水性，從而可獲得質地及撥水性優異之撥水性纖維製品之方面而言，上述非氟系撥水劑較佳為包含含有源自下述通式(A-1)所表示之(甲基)丙烯酸酯單體(A)(以下，亦稱為「(A)成分」)之結構單元之非氟系聚合物。 [化8]
Figure TW201803964AD00008
[式(A-1)中，R1 表示氫或甲基，R2 表示亦可具有取代基之碳數12以上之1價烴基] 此處，所謂「(甲基)丙烯酸酯」，意指「丙烯酸酯」或與其對應之「甲基丙烯酸酯」，於「(甲基)丙烯酸」、「(甲基)丙烯醯胺」等中亦為相同意義。 本實施形態中所使用之上述通式(A-1)所表示之(甲基)丙烯酸酯單體(A)具有亦可具有取代基之碳數為12以上之1價烴基。該烴基可為直鏈狀，亦可為支鏈狀，可為飽和烴基，亦可為不飽和烴基，進而亦可具有脂環式或芳香族之環狀。該等之中，較佳為直鏈狀者，更佳為直鏈狀之烷基。於該情形時，撥水性變得更加優異。於碳數12以上之1價烴基具有取代基之情形時，作為其取代基，可列舉羥基、胺基、羧基、環氧基、異氰酸基、封端異氰酸基及(甲基)丙烯醯氧基等中之1種以上。於本實施形態中，於上述通式(A-1)中，R2 較佳為未經取代之烴基。 上述烴基之碳數較佳為12～24。若碳數未達12，則於使非氟系聚合物附著於纖維製品等之情形時，無法發揮充分之撥水性。另一方面，若碳數超過24，則與碳數處於上述範圍之情形時相比，於使非氟系聚合物附著於纖維製品等之情形時，有纖維製品之質地變得粗硬之傾向。 上述烴基之碳數更佳為12～21。於碳數為該範圍之情形時，撥水性與質地變得尤其優異。作為烴基，尤佳為碳數為12～18之直鏈狀之烷基。 作為上述(A)成分，例如可列舉(甲基)丙烯酸硬脂酯、(甲基)丙烯酸鯨蠟酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸十二烷基酯、(甲基)丙烯酸肉豆蔻酯、(甲基)丙烯酸十五烷基酯、(甲基)丙烯酸十七烷基酯、(甲基)丙烯酸十九烷基酯、(甲基)丙烯酸二十烷基酯、(甲基)丙烯酸二十一烷基酯、(甲基)丙烯酸山崳酯、(甲基)丙烯酸二十六烷基酯、(甲基)丙烯酸三十烷基酯。 上述(A)成分可具有選自由可與交聯劑反應之羥基、胺基、羧基、環氧基及異氰酸基所組成之群中之至少1種官能基。於該情形時，可進而提高所獲得之纖維製品之耐久撥水性。異氰酸基亦可形成經封端化劑保護之封端異氰酸基。又，於上述(A)成分具有胺基之情形時，可進而提高所獲得之纖維製品之質地。 上述(A)成分較佳為1分子內具有1個聚合性不飽和基之單官能之(甲基)丙烯酸酯單體。 上述(A)成分可單獨使用1種，亦可將2種以上組合使用。 就所獲得之纖維製品之耐久撥水性之方面而言，上述(A)成分較佳為將丙烯酸酯單體(a1)與甲基丙烯酸酯單體(a2)併用。所調配之(a1)成分之質量與(a2)成分之質量之比(a1)/(a2)較佳為30/70～90/10，更佳為40/60～85/15，進而較佳為50/50～80/20。於(a1)/(a2)為上述範圍內之情形時，所獲得之纖維製品之耐久撥水性變得更加良好。於(a1)/(a2)超過90/10之情形時或者未達30/70之情形時，有所獲得之纖維製品之耐久撥水性降低之傾向。 就所獲得之纖維製品之撥水性及耐久撥水性之方面而言，非氟系聚合物中之上述(A)成分之單體之合計構成比率相對於構成非氟系聚合物之單體成分之總量，較佳為50～100質量%，更佳為55～97質量%，進而較佳為60～95質量%。 非氟系聚合物之重量平均分子量較佳為10萬以上。若重量平均分子量未達10萬，則有所獲得之纖維製品之撥水性變得不充分之傾向。進而，非氟系聚合物之重量平均分子量更佳為50萬以上。於該情形時，所獲得之纖維製品可更充分地發揮撥水性。非氟系聚合物之重量平均分子量之上限較佳為500萬左右。 於本實施形態中，非氟系聚合物之105℃下之熔融黏度較佳為1000 Pa・s以下。若105℃下之熔融黏度超過1000 Pa・s，則有所獲得之纖維製品之質地變得粗硬之傾向。又，若非氟系聚合物之熔融黏度過高，則於使非氟系聚合物乳化或分散後製成撥水劑組合物之情形時，存在非氟系聚合物析出或沈澱之情況，從而有撥水劑組合物之儲存穩定性降低之傾向。再者，105℃下之熔融黏度更佳為500 Pa・s以下。於該情形時，所獲得之纖維製品等充分地發揮撥水性，並且質地亦變得更加優異。 所謂「105℃下之熔融黏度」，係指使用高架式流變儀(例如，島津製作所製造 CFT-500)，向安裝有模具(長度10 mm、直徑1 mm)之汽缸內加入非氟系聚合物1 g，於105℃下保持6分鐘，並藉由柱塞施加100 kg・f/cm2 之負載後進行測定時之黏度。 於非氟系聚合物之重量平均分子量相等之情形時，有非氟系(甲基)丙烯酸酯單體之調配比率越高而經附著之纖維製品之撥水性變得更高之傾向。又，藉由使可共聚合之非氟系單體共聚合，可提高經附著之纖維製品之耐久撥水性或質地等性能。 就可提高所獲得之纖維製品之撥水性、及非氟系聚合物之乳化聚合或分散聚合時及聚合後之組合物中之乳化穩定性之方面而言，非氟系聚合物較佳為除(A)成分以外，亦含有選自(B1)HLB為7～18之下述通式(I-1)所表示之化合物、(B2)HLB為7～18之下述通式(II-1)所表示之化合物、及(B3)HLB為7～18之對具有羥基及聚合性不飽和基之油脂加成碳數2～4之環氧烷而成之化合物中之至少1種反應性乳化劑(B)(以下，亦稱為「(B)成分」)作為單體成分。 [化9]
Figure TW201803964AD00009
[式(I-1)中，R3 表示氫或甲基，X表示碳數1～6之直鏈或者支鏈之伸烷基，Y1 表示包含碳數2～4之伸烷基氧基之2價基] [化10]
Figure TW201803964AD00010
[式(II-1)中，R4 表示具有聚合性不飽和基之碳數13～17之1價不飽和烴基，Y2 表示包含碳數2～4之伸烷基氧基之2價基] 所謂「反應性乳化劑」，係指具有自由基反應性之乳化分散劑即分子內具有1個以上之聚合性不飽和基之界面活性劑，可與(甲基)丙烯酸酯般之單體共聚合。 又，所謂「HLB」，係指將伸乙基氧基視作親水基、將除此以外之基全部視作親油基並利用Griffin法算出之HLB值。 本實施形態中所使用之上述(B1)～(B3)之化合物之HLB為7～18，就非氟系聚合物之乳化聚合或分散聚合時及聚合後之組合物中之乳化穩定性(以下，簡稱為乳化穩定性)之方面而言，較佳為9～15。進而，就非氟系撥水劑之儲存穩定性之方面而言，更佳為將具有上述範圍內之不同之HLB之2種以上之反應性乳化劑(B)併用。 於本實施形態中所使用之上述通式(I-1)所表示之反應性乳化劑(B1)中，R3 為氫或甲基，就與(A)成分之共聚性之方面而言，更佳為甲基。X為碳數1～6之直鏈或者支鏈之伸烷基，於本實施形態之非氟系聚合物之乳化穩定性之方面而言，更佳為碳數2～3之直鏈伸烷基。Y1 為包含碳數2～4之伸烷基氧基之2價基。關於Y1 中之伸烷基氧基之種類、組合及加成數，可以成為上述HLB之範圍內之方式適當選擇。又，於伸烷基氧基為2種以上之情形時，該等可具有嵌段加成結構或無規加成結構。 作為上述通式(I-1)所表示之化合物，較佳為下述通式(I-2)所表示之化合物。 [化11]
Figure TW201803964AD00011
[式(I-2)中，R3 表示氫或甲基，X表示碳數1～6之直鏈或者支鏈之伸烷基，A1 O表示碳數2～4之伸烷基氧基，m可以成為上述HLB之範圍內之方式適當選擇，具體而言，較佳為1～80之整數，當m為2以上時，m個A1 O可相同，亦可不同] 於上述通式(I-2)所表示之化合物中，R3 為氫或甲基，就與(A)成分之共聚合性之方面而言，更佳為甲基。X為碳數1～6之直鏈或者支鏈之伸烷基，就非氟系聚合物之乳化穩定性之方面而言，更佳為碳數2～3之直鏈伸烷基。A1 O為碳數2～4之伸烷基氧基。A1 O之種類及組合以及m之數可以成為上述HLB之範圍內之方式適當選擇。就非氟系聚合物之乳化穩定性之方面而言，m較佳為1～80之整數，更佳為1～60之整數。當m為2以上時，m個A1 O可相同，亦可不同。又，於A1 O為2種以上之情形時，該等可具有嵌段加成結構或無規加成結構。 上述通式(I-2)所表示之反應性乳化劑(B1)可利用先前公知之方法獲得，並無特別限定。又，可自市售品容易地獲取，例如可列舉花王股份有限公司製造之「Latemul PD-420」、「Latemul PD-430」、「Latemul PD-450」等。 於本實施形態中所使用之上述通式(II-1)所表示之反應性乳化劑(B2)中，R4 為具有聚合性不飽和基之碳數13～17之1價不飽和烴基，可列舉十三碳烯基、十三碳二烯基、十四碳烯基、十四碳二烯基、十五碳烯基、十五碳二烯基、十五碳三烯基、十七碳烯基、十七碳二烯基、十七碳三烯基等。就非氟系聚合物之乳化穩定性之方面而言，R4 更佳為碳數14～16之1價不飽和烴基。 Y2 為包含碳數2～4之伸烷基氧基之2價基。Y2 中之伸烷基氧基之種類、組合及加成數可以成為上述HLB之範圍內之方式適當選擇。又，於伸烷基氧基為2種以上之情形時，該等可具有嵌段加成結構或無規加成結構。就非氟系聚合物之乳化穩定性之方面而言，伸烷基氧基更佳為伸乙基氧基。 作為上述通式(II-1)所表示之化合物，較佳為下述通式(II-2)所表示之化合物。 [化12]
Figure TW201803964AD00012
[式(II-2)中，R4 表示具有聚合性不飽和基之碳數13～17之1價不飽和烴基，A2 O表示碳數2～4之伸烷基氧基，n可以成為上述HLB之範圍內之方式適當選擇，具體而言，較佳為1～50之整數，當n為2以上時，n個A2 O可相同，亦可不同] 上述通式(II-2)所表示之化合物中之R4 可列舉與上述通式(II-1)中之R4 相同者。 A2 O為碳數2～4之伸烷基氧基。就非氟系聚合物之乳化穩定性之方面而言，A2 O之種類及組合以及n之數可以成為上述HLB之範圍內之方式適當選擇。就非氟系聚合物之乳化穩定性之方面而言，A2 O更佳為伸乙基氧基，n較佳為1～50之整數，更佳為5～20之整數，進而較佳為8～14之整數。當n為2以上時，n個A2 O可相同，亦可不同。又，於A2 O為2種以上之情形時，該等可具有嵌段加成結構或無規加成結構。 本實施形態中所使用之上述通式(II-2)所表示之反應性乳化劑(B2)可藉由利用先前公知之方法對對應之具有不飽和烴基之酚加成環氧烷而合成，並無特別限定。例如，可藉由使用苛性鈉、苛性鉀等鹼觸媒於加壓下以120～170℃加成特定量之環氧烷而合成。 上述對應之具有不飽和烴基之酚除工業上製造之純品或混合物以外，亦包含自植物等提取、精製而成之以純品或混合物之形式存在者。例如，可列舉自腰果之殼等提取、被統稱為腰果酚之3-[8(Z),11(Z),14-十五碳三烯基]酚、3-[8(Z),11(Z)-十五碳二烯基]酚、3-[8(Z)-十五碳烯基]酚、3-[11(Z)-十五碳烯基]酚等。 本實施形態中所使用之反應性乳化劑(B3)係HLB為7～18之對具有羥基及聚合性不飽和基之油脂加成碳數2～4之環氧烷而成之化合物。作為具有羥基及聚合性不飽和基之油脂，可列舉亦可包含羥基不飽和脂肪酸(棕櫚油酸、油酸、亞麻油酸、α-次亞麻油酸、花生四烯酸、二十碳五烯酸、二十二碳五烯酸等)之脂肪酸之單或二縮水甘油酯、包含至少1種羥基不飽和脂肪酸(蓖麻油酸、蓖麻反油酸、2-羥基二十四烯酸等)之脂肪酸之甘油三酸。就非氟系聚合物之乳化穩定性之方面而言，較佳為包含至少1種羥基不飽和脂肪酸之脂肪酸之甘油三酸之環氧烷加成物，更佳為蓖麻油(包含蓖麻油酸之脂肪酸之甘油三酸)之碳數2～4之環氧烷加成物，進而較佳為蓖麻油之環氧乙烷加成物。進而，環氧烷之加成莫耳數可以成為上述HLB之範圍內之方式適當選擇，就非氟系聚合物之乳化穩定性之方面而言，更佳為20～50莫耳，進而較佳為25～45莫耳。又，於環氧烷為2種以上之情形時，該等可具有嵌段加成結構或無規加成結構。 本實施形態中所使用之反應性乳化劑(B3)可藉由利用先前公知之方法對具有羥基及聚合性不飽和基之油脂加成環氧烷而合成，並無特別限定。例如，可藉由使用苛性鈉、苛性鉀等鹼觸媒於加壓下以120～170℃對包含蓖麻油酸之脂肪酸之甘油三酸即蓖麻油加成特定量之環氧烷而合成。 就可提高所獲得之纖維製品之撥水性、及非氟系聚合物之乳化聚合或分散聚合時及聚合後之組合物中之乳化穩定性之觀點而言，非氟系聚合物中之上述(B)成分之單體之構成比率相對於構成非氟系聚合物之單體成分之總量，較佳為0.5～20質量%，更佳為1～15質量%，進而較佳為3～10質量%。 就可提高所獲得之纖維製品之耐久撥水性之方面而言，非氟系撥水劑所包含之非氟系聚合物較佳為除(A)成分以外，亦含有選自由下述(C1)、(C2)、(C3)、(C4)及(C5)所組成之群中之至少1種第2(甲基)丙烯酸酯單體(C)(以下，亦稱為「C成分」)作為單體成分。 (C1)(C5)以外之下述通式(C-1)所表示之(甲基)丙烯酸酯單體 [化13]
Figure TW201803964AD00013
[式(C-1)中，R5 表示氫或甲基，R6 表示具有選自由羥基、胺基、羧基、環氧基、異氰酸基及(甲基)丙烯醯氧基所組成之群中之至少1種官能基之碳數1～11之1價鏈狀烴基；其中，分子內之(甲基)丙烯醯氧基之數量為2以下] (C2)下述通式(C-2)所表示之(甲基)丙烯酸酯單體 [化14]
Figure TW201803964AD00014
[式(C-2)中，R7 表示氫或甲基，R8 表示亦可具有取代基之碳數1～11之1價環狀烴基] (C3)下述通式(C-3)所表示之甲基丙烯酸酯單體 [化15]
Figure TW201803964AD00015
[式(C-3)中，R9 表示未經取代之碳數1～4之1價鏈狀烴基] (C4)下述通式(C-4)所表示之(甲基)丙烯酸酯單體 [化16]
Figure TW201803964AD00016
[式(C-4)中，R10 表示氫或甲基，p表示2以上之整數，S表示(p＋1)價有機基，T表示具有聚合性不飽和基之1價有機基] (C5)下述通式(C-5)所表示之(甲基)丙烯酸酯單體 [化17]
Figure TW201803964AD00017
[式(C-5)中，R11 表示氫或甲基，R12 表示具有選自由氯基及溴基所組成之群中之至少1種官能基與羥基之碳數3～6之1價鏈狀飽和烴基] 上述(C1)之單體係酯部分具有具備選自由羥基、胺基、羧基、環氧基、異氰酸基及(甲基)丙烯醯氧基所組成之群中之至少1種官能基之碳數1～11之1價鏈狀烴基且上述(C5)以外之(甲基)丙烯酸酯單體。就可與交聯劑反應之方面而言，上述碳數1～11之1價鏈狀烴基較佳為具有選自由羥基、胺基、羧基、環氧基及異氰酸基所組成之群中之至少1種官能基。於將含有具有可與該等交聯劑反應之基之(C1)之單體之非氟系聚合物與交聯劑一併處理於纖維製品之情形時，可於維持所獲得之纖維製品之質地之情況下提高耐久撥水性。異氰酸基亦可為經封端化劑保護之封端異氰酸基。 上述鏈狀烴基可為直鏈狀，亦可為支鏈狀，可為飽和烴基，亦可為不飽和烴基。又，鏈狀烴基除上述官能基以外，亦可進而具有取代基。其中，就可提高所獲得之纖維製品之耐久撥水性之方面而言，較佳為直鏈狀及/或飽和烴基。 作為具體之(C1)之單體，可列舉(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸二甲胺基乙酯、(甲基)丙烯酸縮水甘油酯、異氰酸1,1-雙(丙烯醯氧基甲基)乙酯等。該等單體可單獨使用1種，亦可將2種以上組合使用。其中，就可提高所獲得之纖維製品之耐久撥水性之方面而言，較佳為(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸縮水甘油酯、異氰酸1,1-雙(丙烯醯氧基甲基)乙酯。進而，就可提高所獲得之纖維製品之質地之方面而言，較佳為(甲基)丙烯酸二甲胺基乙酯。 就所獲得之纖維製品之撥水性及質地之觀點而言，非氟系聚合物中之上述(C1)之單體之構成比率相對於構成非氟系聚合物之單體成分之總量，較佳為1～30質量%，更佳為3～25質量%，進而較佳為5～20質量%。 上述(C2)之單體係酯部分具有碳數1～11之1價環狀烴基之(甲基)丙烯酸酯單體，作為環狀烴基，可列舉異𦯉基、環己基、二環戊基等。該等環狀烴基亦可具有烷基等取代基。其中，於取代基為烴基之情形時，選擇取代基及環狀烴基之碳數之合計成為11以下之烴基。又，就提高耐久撥水性之觀點而言，該等環狀烴基較佳為直接鍵結於酯鍵。環狀烴基可為脂環式，亦可為芳香族，於脂環式之情形時，可為飽和烴基，亦可為不飽和烴基。作為具體之單體，可列舉(甲基)丙烯酸異𦯉酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸二環戊酯等。該等單體可單獨使用1種，亦可將2種以上組合使用。其中，就可提高所獲得之纖維製品之耐久撥水性之方面而言，較佳為(甲基)丙烯酸異𦯉酯、甲基丙烯酸環己酯，更佳為甲基丙烯酸異𦯉酯。 就所獲得之纖維製品之撥水性及質地之觀點而言，非氟系聚合物中之上述(C2)之單體之構成比率相對於構成非氟系聚合物之單體成分之總量，較佳為1～30質量%，更佳為3～25質量%，進而較佳為5～20質量%。 上述(C3)之單體係未經取代之碳數1～4之1價鏈狀烴基直接鍵結於酯部分之酯鍵之甲基丙烯酸酯單體。作為碳數1～4之鏈狀烴基，較佳為碳數1～2之直鏈烴基及碳數3～4之支鏈烴基。作為碳數1～4之鏈狀烴基，例如可列舉甲基、乙基、正丙基、異丙基、正丁基、第三丁基等。作為具體之化合物，可列舉甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸正丙酯、甲基丙烯酸異丙酯、甲基丙烯酸正丁酯、甲基丙烯酸異丁酯、甲基丙烯酸第三丁酯。該等單體可單獨使用1種，亦可將2種以上組合使用。其中，就可提高所獲得之纖維製品之耐久撥水性之方面而言，較佳為甲基丙烯酸甲酯、甲基丙烯酸異丙酯、甲基丙烯酸第三丁酯，更佳為甲基丙烯酸甲酯。 就所獲得之纖維製品之撥水性及質地之觀點而言，非氟系聚合物中之上述(C3)之單體之構成比率相對於構成非氟系聚合物之單體成分之總量，較佳為1～30質量%，更佳為3～25質量%，進而較佳為5～20質量%。 上述(C4)之單體係1分子內具有3個以上之聚合性不飽和基之(甲基)丙烯酸酯單體。於本實施形態中，較佳為上述通式(C-4)中之T為(甲基)丙烯醯氧基之1分子內具有3個以上之(甲基)丙烯醯氧基之多官能之(甲基)丙烯酸酯單體。於式(C-4)中，p個T可相同，亦可不同。作為具體之化合物，例如可列舉乙氧基化異三聚氰酸三丙烯酸酯、四羥甲基甲烷四丙烯酸酯、四羥甲基甲烷四甲基丙烯酸酯、三羥甲基丙烷三丙烯酸酯、三羥甲基丙烷三甲基丙烯酸酯、季戊四醇三丙烯酸酯、季戊四醇三甲基丙烯酸酯、二季戊四醇六丙烯酸酯、二季戊四醇六甲基丙烯酸酯等。該等單體可單獨使用1種，亦可將2種以上組合使用。其中，就可提高所獲得之纖維製品之耐久撥水性之方面而言，更佳為四羥甲基甲烷四丙烯酸酯及乙氧基化異三聚氰酸三丙烯酸酯。 就所獲得之纖維製品之撥水性及質地之觀點而言，非氟系聚合物中之上述(C4)之單體之構成比率相對於構成非氟系聚合物之單體成分之總量，較佳為1～30質量%，更佳為3～25質量%，進而較佳為5～20質量%。 上述(C5)之單體具有具備選自由氯基及溴基所組成之群中之至少1種官能基與羥基之碳數3～6之1價鏈狀飽和烴基。於上述(C5)之單體中，R11 為氫或甲基。就所獲得之纖維製品之耐久撥水性之方面而言，R11 較佳為甲基。 R12 為具有選自由氯基及溴基所組成之群中之至少1種官能基與羥基之碳數3～6之1價鏈狀飽和烴基。鏈狀飽和烴基可為直鏈狀，亦可為支鏈狀。於鏈狀飽和烴基為直鏈狀之情形時，所獲得之纖維製品之耐久撥水性變得更優異。就所獲得之纖維製品之耐久撥水性之方面而言，鏈狀飽和烴基之碳數較佳為3～4，更佳為3。 就所獲得之纖維製品之耐久撥水性之方面而言，上述鏈狀飽和烴基較佳為具有一個或者兩個氯基及一個羥基，更佳為具有一個氯基及一個羥基。又，就所獲得之纖維製品之耐久撥水性之方面而言，鏈狀飽和烴基進而較佳為於β位(鍵結於CH2 =CR11 (CO)O-之碳原子之相鄰之碳原子)具有羥基。作為具體之上述鏈狀飽和烴基，例如可列舉3-氯-2-羥基丙基、3-氯-2-羥基丁基、5-氯-2-羥基戊基、3-氯-2-羥基-2-甲基丙基及3-溴-2-羥基丙基。 作為具體之(C5)之單體，例如可列舉(甲基)丙烯酸3-氯-2-羥基丙酯、(甲基)丙烯酸3-氯-2-羥基丁酯、(甲基)丙烯酸5-氯-2-羥基戊酯及(甲基)丙烯酸3-溴-2-羥基丙酯。其中，就可提高所獲得之纖維製品之耐久撥水性之方面而言，較佳為(甲基)丙烯酸3-氯-2-羥基丙酯，更佳為甲基丙烯酸3-氯-2-羥基丙酯。 就所獲得之纖維製品之耐久撥水性之方面而言，非氟系聚合物中之上述(C5)之單體之構成比率相對於構成非氟系聚合物之單體成分之總量，較佳為1～30質量%，更佳為3～25質量%，進而較佳為5～20質量%。 就所獲得之纖維製品之撥水性及質地之觀點而言，非氟系聚合物中之上述(C)成分之單體之合計構成比率相對於構成非氟系聚合物之單體成分之總量，較佳為1～30質量%，更佳為3～25質量%，進而較佳為5～20質量%。 非氟系撥水劑所包含之非氟系聚合物除可含有(A)成分、(B)成分及(C)成分以外，亦可於無損本發明之效果之範圍內含有可與該等共聚合之單官能之單體(D)(以下，亦稱為「(D)成分」)。 作為上述(D)之單體，例如可列舉(甲基)丙烯醯嗎啉、(A)成分及(C)成分以外之具有烴基之(甲基)丙烯酸酯、(甲基)丙烯酸、反丁烯二酸酯、順丁烯二酸酯、反丁烯二酸、順丁烯二酸、(甲基)丙烯醯胺、N-羥甲基丙烯醯胺、乙烯醚類、乙烯酯類、乙烯、苯乙烯等不含氟之(E)成分以外之乙烯系單體等。再者，(A)成分及(C)成分以外之具有烴基之(甲基)丙烯酸酯可於烴基具有乙烯基、羥基、胺基、環氧基及異氰酸基、封端異氰酸基等取代基，亦可具有四級銨基等可與交聯劑反應之基以外之取代基，亦可具有醚鍵、酯鍵、醯胺鍵或胺基甲酸酯鍵等。作為(A)成分及(C)成分以外之(甲基)丙烯酸酯，例如可列舉丙烯酸甲酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸苄酯、乙二醇二(甲基)丙烯酸酯等。其中，就可提高所獲得之纖維製品對塗層之剝離強度之方面而言，更佳為(甲基)丙烯醯嗎啉。 就所獲得之纖維製品之撥水性及質地之觀點而言，非氟系聚合物中之上述(D)成分之單體之構成比率相對於構成非氟系聚合物之單體成分之總量，較佳為10質量%以下。 就可提高所獲得之纖維製品之耐久撥水性之方面而言，非氟系撥水劑所包含之非氟系聚合物較佳為具有選自由可與交聯劑反應之羥基、胺基、羧基、環氧基及異氰酸基所組成之群中之至少1種官能基。異氰酸基亦可形成經封端化劑保護之封端異氰酸基。又，就亦可提高所獲得之纖維製品之質地之方面而言，非氟系聚合物較佳為具有胺基。 就可提高所獲得之纖維製品之撥水性與對塗層之剝離強度之方面而言，非氟系撥水劑所包含之非氟系聚合物較佳為除(A)成分以外，亦含有氯乙烯及偏二氯乙烯中之至少任1種單體(E)(以下，亦稱為「(E)成分」)作為單體成分。 就所獲得之纖維製品之撥水性與對塗層之剝離強度之方面而言，本實施形態中所使用之氯乙烯及偏二氯乙烯中之至少任1種單體(E)較佳為氯乙烯。 就可提高所獲得之纖維製品對塗層之剝離強度之觀點而言，非氟系聚合物中之上述(E)成分之單體之構成比率相對於構成非氟系聚合物之單體成分之總量，較佳為1～45質量%，更佳為3～40質量%，進而較佳為5～35質量%。 亦可視需要於本實施形態之撥水劑組合物中添加添加劑等。作為添加劑，可列舉其他撥水劑、交聯劑、抗菌防臭劑、阻燃劑、抗靜電劑、柔軟劑、抗皺劑等。 繼而，對包含非氟系聚合物之非氟系撥水劑之製造方法進行說明。 包含非氟系聚合物之非氟系撥水劑可利用自由基聚合法進行製造。又，該自由基聚合法之中，就所獲得之撥水劑之性能及環境之方面而言，較佳為利用乳化聚合法或分散聚合法進行聚合。 例如，可藉由於介質中使上述通式(A-1)所表示之(甲基)丙烯酸酯單體(A)進行乳化聚合或分散聚合而獲得非氟系聚合物。更具體而言，例如向介質中添加(A)成分及視需要之上述(B)成分、上述(C)成分、上述(D)成分及上述(E)成分、以及乳化輔助劑或分散輔助劑，並使該混合液乳化或分散而獲得乳化物或分散物。可藉由向所獲得之乳化物或分散物中添加聚合起始劑而使聚合反應開始，從而使單體及反應性乳化劑進行聚合。再者，作為使上述混合液乳化或分散之方法，可列舉均質攪拌機、高壓乳化機或超音波等。 作為上述乳化輔助劑或分散輔助劑等(以下，亦稱為「乳化輔助劑等」)，可使用上述反應性乳化劑(B)以外之選自非離子界面活性劑、陽離子界面活性劑、陰離子界面活性劑、及兩性界面活性劑中之1種以上。乳化輔助劑等之含量相對於總單體100質量份，較佳為0.5～30質量份，更佳為1～20質量份，進而較佳為1～10質量份。若上述乳化輔助劑等之含量未達0.5質量份，則與乳化輔助劑等之含量處於上述範圍之情形時相比較，有混合液之分散穩定性降低之傾向，若乳化輔助劑等之含量超過30質量份，則與乳化輔助劑等之含量處於上述範圍之情形時相比較，有所獲得之非氟系聚合物之撥水性降低之傾向。 作為乳化聚合或分散聚合之介質，較佳為水，亦可視需要將水與有機溶劑混合。作為此時之有機溶劑，只要為可與水混合之有機溶劑，則並無特別限制，例如可列舉甲醇或乙醇等醇類、乙酸乙酯等酯類、丙酮或甲基乙基酮等酮類、二乙醚等醚類等、丙二醇、二丙二醇、三丙二醇等乙二醇類。再者，水與有機溶劑之比率並無特別限定。 作為上述聚合起始劑，可適當使用偶氮系、過氧化物系或氧化還原系等之公知之聚合起始劑。聚合起始劑之含量相對於總單體100質量份，較佳為聚合起始劑為0.01～2質量份。若聚合起始劑之含量為上述範圍，則可高效率地製造重量平均分子量為10萬以上之非氟系聚合物。 又，於聚合反應中，為了調整分子量，亦可使用十二烷基硫醇、第三丁醇等鏈轉移劑。鏈轉移劑之含量相對於總單體100質量份，較佳為0.3質量份以下，更佳為0.1質量份以下。若鏈轉移劑之含量超過0.3質量份，則有會導致分子量降低，而難以高效率地製造重量平均分子量為10萬以上之非氟系聚合物之傾向。 再者，為了調整分子量，亦可使用聚合禁止劑。藉由添加聚合禁止劑，可容易地獲得具有所需之重量平均分子量之非氟系聚合物。 聚合反應之溫度較佳為20℃～150℃。若溫度未達20℃，則與溫度處於上述範圍之情形時相比較，有聚合變得不充分之傾向，若溫度超過150℃，則存在難以控制反應熱之情形。 於聚合反應中，所獲得之非氟系聚合物之重量平均分子量可藉由上述聚合起始劑、鏈轉移劑、聚合禁止劑之含量之增減而進行調整，105℃下之熔融黏度可藉由多官能單體之含量及聚合起始劑之含量之增減而進行調整。再者，於使105℃下之熔融黏度降低之情形時，只要使具有2個以上之可聚合之官能基之單體之含量減少或者使聚合起始劑之含量增加即可。 就組合物之儲存穩定性及操作性之觀點而言，藉由乳化聚合或分散聚合而獲得之聚合物乳化液或分散液中之非氟系聚合物之含量相對於乳化液或分散液之總量，較佳為設為10～50質量%，更佳為設為20～40質量%。 本實施形態之非氟系撥水劑組合物可藉由將上述本實施形態之撥水助劑與上述非氟系撥水劑進行混合而製造。 就所獲得之纖維製品之耐久撥水性之方面而言，本實施形態之非氟系撥水劑組合物中之上述通式(1)所表示之有機改性聚矽氧之調配量較佳為1～10質量%，更佳為3～7質量%。 又，就所獲得之纖維製品之耐久撥水性之方面而言，本實施形態之非氟撥水劑組合物中之上述通式(1)所表示之有機改性聚矽氧之調配量相對於非氟系聚合物100質量份，較佳為1～50質量份，更佳為3～30質量份，進而較佳為10～25質量份。 對本實施形態之撥水性纖維製品之製造方法進行說明。 本實施形態之撥水性纖維製品係藉由利用包含上述非氟系撥水劑組合物之處理液對纖維製品進行處理而獲得。作為該纖維製品之素材，並無特別限制，可列舉棉、麻、絹、羊毛等天然纖維、嫘縈、乙酸酯等半合成纖維、尼龍、聚酯、聚胺基甲酸酯、聚丙烯等合成纖維及該等之複合纖維、混紡纖維等。纖維製品之形態亦可為纖維、絲、布、梭織物、編織物、衣料品形態之布、地毯、不織布、紙等任一形態。 作為利用上述處理液對纖維製品進行處理之方法，例如可列舉浸漬、噴霧、塗佈等加工方法或基於清潔法之加工方法等。又，於非氟系撥水劑組合物含有水之情形時，較佳為於附著於纖維製品後為了將水去除而使之乾燥。 又，較佳為於利用本實施形態之非氟系撥水劑組合物對纖維製品進行處理後適當進行熱處理。溫度條件並無特別限制，若使用本實施形態之非氟系撥水劑組合物，則可藉由100～130℃之溫和之條件而使纖維製品表現出充分良好之撥水性。溫度條件亦可為130℃以上(較佳為200℃)之高溫處理，於此情形時，可較使用氟系撥水劑之先前之情形時縮短處理時間。因此，根據本實施形態之撥水性纖維製品，熱所導致之纖維製品之變質被抑制，撥水處理時之纖維製品之質地變得柔軟，並且可於溫和之熱處理條件即低溫固化條件下對纖維製品賦予充分之撥水性。 尤其於欲提高耐久撥水性之情形時，較佳為利用如下方法對纖維製品進行撥水加工，該方法包括：利用包含非氟系撥水劑組合物之處理液對纖維製品進行處理之上述步驟，及使羥甲基三聚氰胺、具有1個以上之異氰酸基或封端異氰酸基之化合物所代表之交聯劑附著於纖維製品後對其進行加熱之步驟。進而，於欲進一步提高耐久撥水性之情形時，非氟系撥水劑組合物較佳為包含使具有可與上述交聯劑反應之官能基之單體共聚合而成之非氟系聚合物。 作為具有1個以上之異氰酸基之化合物，可列舉丁基異氰酸酯、苯基異氰酸酯、三異氰酸酯、萘異氰酸酯等單異氰酸酯、甲苯二異氰酸酯、二苯甲烷二異氰酸酯、四甲基苯二甲基二異氰酸酯、氫化二苯甲烷二異氰酸酯等二異氰酸酯及作為該等之異氰尿酸酯環之三量體、三羥甲基丙烷加成物體。又，作為具有1個以上之封端異氰酸基之化合物，可列舉利用封端化劑對上述具有異氰酸基之化合物之異氰酸基進行保護之化合物。作為此時使用之封端化劑，可列舉二級或三級醇類、活性亞甲基化合物、酚類、肟類、內醯胺類等有機系封端化劑或重亞硫酸鈉、重亞硫酸鉀等重亞硫酸鹽。上述交聯劑可單獨使用1種，亦可將複數種組合。 交聯劑例如可藉由將被處理物(纖維製品)浸漬於將交聯劑溶解於有機溶劑中或乳化分散於水中而成之處理液中，並對附著於被處理物之處理液進行乾燥之方法而附著於被處理物。並且，藉由對附著於被處理物之交聯劑進行加熱，可進行交聯劑與被處理物及非氟系聚合物之反應。為了使交聯劑之反應充分地進行而更有效地提高洗滌耐久性，此時之加熱可於110～180℃下進行1～5分鐘。交聯劑之附著及加熱之步驟亦可與利用包含上述撥水劑組合物之處理液進行處理之步驟同時地進行。於同時地進行之情形時，例如使含有撥水劑組合物及交聯劑之處理液附著於被處理物，並將水去除後，進而對附著於被處理物之交聯劑進行加熱。於考慮到撥水加工步驟之簡單化或熱量之削減、經濟性之情形時，較佳為與撥水劑組合物之處理步驟同時地進行。 又，若過度使用交聯劑，則有損害質地之虞。上述交聯劑相對於被處理物(纖維製品)，較佳為以0.1～50質量%之量使用，尤佳為以0.1～10質量%之量使用。 以如上方式獲得之本實施形態之撥水性纖維製品即便於在室外長期使用之情形時，亦可充分地發揮撥水性，又，上述撥水性纖維製品未使用氟系化合物，因此可製成對環境無害者。 本實施形態之撥水性纖維製品可對特定之部分進行塗佈加工。作為塗佈加工，可列舉運動用途或戶外用途下之透濕防水加工或防風加工等。作為加工方法，例如於透濕防水加工之情形時，可藉由將包含胺基甲酸酯樹脂或丙烯酸系樹脂等與介質之塗佈液塗佈於經撥水處理之纖維製品之單面並進行乾燥而進行加工。 以上，對本發明之適當之實施形態進行了說明，但本發明並不限定於上述實施形態。 例如，於製造非氟系聚合物之情形時，於上述實施形態中，係藉由自由基聚合進行聚合反應，但亦可藉由照射如紫外線、電子束、γ射線之游離輻射等之光聚合進行聚合反應。 又，於本發明中，係將非氟系撥水劑組合物處理於纖維製品而製成撥水性纖維製品，但作為經非氟系撥水劑組合物處理之製品，亦可不限纖維製品用途而為金屬、玻璃、樹脂等之物品。 又，於此情形時，使非氟系撥水劑組合物附著於上述物品之方法或撥水劑之附著量可根據被處理物之種類等任意決定。 [實施例] 以下，藉由實施例進一步對本發明進行說明，但本發明並不受該等實施例任何限制。 ＜撥水助劑之製備＞ (合成例1) 向具備攪拌機、溫度計、回流冷卻機、氮氣導入管及滴加漏斗之反應容器中加入SiH基當量為63.2 g/mol、聚合度為50之甲基氫聚矽氧63.2 g，使氮氣流動，於溫度成為65℃之前一面進行加熱一面進行混合直至成為均勻。作為矽氫化觸媒，將氯化鉑(IV)之乙二醇單丁醚-甲苯混合溶液以相對於體系內之反應物而鉑濃度成為5 ppm之方式添加。於反應物之溫度成為120℃時，滴加1莫耳之1-十二烯168.3 g，並於120℃下使之反應6小時。加成反應完成之確認係藉由進行所獲得之有機改性聚矽氧之FT-IR分析，並確認源自甲基氫聚矽氧之SiH基之吸收光譜消失而進行。如此，獲得上述通式(1)中之a為0、b為50、R22 為甲基、R23 為十二烷基、R30 、R31 、R32 、R33 、R34 及R35 為甲基之有機改性聚矽氧。進而，向所獲得之有機改性聚矽氧20質量份中添加碳數12～14之支鏈高級醇之環氧乙烷9莫耳加成物3質量份並進行混合。繼而，將水77質量份一面逐次少量添加一面進行混合，使之乳化於水中而獲得聚矽氧乳化物。 (合成例2) 使用1莫耳之1-己烯84.2 g代替1莫耳之1-十二烯168.3g，除此以外，以與合成例1相同之方式獲得有機改性聚矽氧及聚矽氧乳化物。再者，獲得有機改性聚矽氧之上述通式(1)中之a為0、b為50、R22 為甲基、R23 為己基、R30 、R31 、R32 、R33 、R34 及R35 為甲基之有機改性聚矽氧。 (合成例3) 使用1莫耳之1-十八烯252.5 g代替1莫耳之1-十二烯168.3g，除此以外，以與合成例1相同之方式獲得有機改性聚矽氧及聚矽氧乳化物。再者，獲得有機改性聚矽氧之通式(1)之a為0、b為50、R22 為甲基、R23 為十八烷基、R30 、R31 、R32 、R33 、R34 及R35 為甲基之有機改性聚矽氧。 (合成例4) 使用0.5莫耳之1-十二烯84.2 g、及0.5莫耳之α-甲基苯乙烯59.1 g代替1莫耳之1-十二烯168.3 g，除此以外，以與合成例1相同之方式獲得有機改性聚矽氧及聚矽氧乳化物。再者，獲得有機改性聚矽氧之通式(1)之a為0、b為50、R22 為甲基、R23 為十二烷基或甲基苯乙烯基、R30 、R31 、R32 、R33 、R34 及R35 為甲基之有機改性聚矽氧。 (合成例5) 使用0.5莫耳之1-十二烯84.2 g、及0.5莫耳之1-十八烯126.2 g代替1莫耳之1-十二烯168.3 g，除此以外，以與合成例1相同之方式獲得有機改性聚矽氧及聚矽氧乳化物。再者，獲得有機改性聚矽氧之通式(1)之a為0、b為50、R22 為甲基、R23 為十二烷基或十八烷基、R30 、R31 、R32 、R33 、R34 及R35 為甲基之有機改性聚矽氧。 (合成例6) 使用SiH基當量為140.5 g/mol、聚合度為50之二甲基矽氧烷與甲基氫矽氧烷之共聚物140.5 g代替SiH基當量為63.2 g/mol、聚合度為50之甲基氫聚矽氧63.2 g，除此以外，以與合成例1相同之方式獲得有機改性聚矽氧及聚矽氧乳化物。再者，獲得有機改性聚矽氧之通式(1)之a為25、b為25、R20 及R21 為甲基、R22 為甲基、R23 為十二烷基、R30 、R31 、R32 、R33 、R34 及R35 為甲基之有機改性聚矽氧。 (合成例7) 向氫化聚矽氧(商品名：KF-99，信越化學工業股份有限公司製造)20質量份中添加碳數12～14之支鏈高級醇之環氧乙烷9莫耳加成物3質量份並進行混合。繼而，將水77質量份一面逐次少量添加一面進行混合，使之乳化於水中而獲得聚矽氧乳化物。 (合成例8) 使用二甲基改性聚矽氧(商品名：KF-96H-30萬cs，信越化學工業股份有限公司製造)代替氫化聚矽氧，除此以外，以與合成例7相同之方式獲得聚矽氧乳化物。 ＜聚合物分散液之調整＞ 將具有表1～6所示之組成(表中，數值表示(g))之混合液按以下所示之順序進行聚合而獲得聚合物分散液。 (合成例9) 向500 mL燒瓶中加入丙烯酸硬脂酯60 g、Noigen XL-100(第一工業製藥股份有限公司製造，聚氧伸烷基支鏈癸醚，HLB＝14.7)2 g、Noigen XL-60(第一工業製藥股份有限公司製造，聚氧伸烷基支鏈癸醚，HLB＝12.5)2 g、硬脂基二甲胺鹽酸鹽3 g、三丙二醇25 g及水207.70 g，於45℃下混合攪拌而製成混合液。對該混合液照射超音波而使總單體乳化分散。繼而，將偶氮雙(異丁基脒)二鹽酸鹽0.3 g添加至混合液中，於氮氣環境下以60℃使之自由基聚合6小時，獲得聚合物濃度20質量%之非氟系聚合物分散液。 (合成例10～36) 使用表1～6所記載之材料，除此以外，以與合成例9相同之方式進行聚合，分別獲得表7～10所示之聚合物濃度之非氟系聚合物分散液。 再者，關於合成例9～36中所獲得之聚合物分散液中之各聚合物，利用氣相層析儀(GC-15APTF，島津製作所(股)製造)確認到均為總單體之98%以上進行聚合。 表1～6所示之材料之詳細內容如下所述。 Latemul PD-420(花王股份有限公司製造，聚氧伸烷基烯基醚，HLB＝12.6) Latemul PD-430(花王股份有限公司製造，聚氧伸烷基烯基醚，HLB＝14.4) 腰果酚之環氧乙烷12.5莫耳加成物(HLB＝12.9，表中，表示為「腰果酚12.5EO」) 腰果酚之環氧乙烷8.3莫耳加成物(HLB＝11.0，表中，表示為「腰果酚8.3EO」) 蓖麻油之環氧乙烷42莫耳加成物(HLB＝13.3，表中，表示為「蓖麻油42EO」) 蓖麻油之環氧乙烷30莫耳加成物(HLB＝11.7，表中，表示為「蓖麻油30EO」) 表中之「C8含氟基之丙烯酸酯」係由下述通式(III)： [化18]
Figure TW201803964AD00018
所表示且n之平均值成為8之混合物(再者，於該混合物中混合有n為6、8、10、12、14之化合物)。 對上述所獲得之聚合物分散液及利用以下所示之方法獲得之聚合物進行評價。 (聚合物之物性評價) 向合成例9～36中所獲得之聚合物分散液50 g中添加丙酮500 mL，藉此使聚合物與乳化劑分離並對聚合物進行濾取，使該聚合物於25℃下減壓乾燥24小時。以如下方式對所獲得之聚合物進行評價。將結果示於表7～10。 (1)熔融黏度之測定方法 針對上述所獲得之聚合物，使用高架式流變儀CFT-500(島津製作所(股)製造)，向安裝有模具(長度10 mm，直徑1 mm)之汽缸內加入聚合物1 g，於105℃下保持6分鐘，並藉由柱塞施加100 kg・f/cm2 之負載後測定105℃下之熔融黏度。 (2)重量平均分子量之測定方法 針對上述所獲得之聚合物，藉由GPC(Gel Permeation Chromatograph，凝膠滲透層析)裝置(Tosoh(股)製造之GPC「HLC-8020」)，於管柱溫度40℃、流量1.0 ml/min之條件下使用四氫呋喃對溶離液進行測定，並以標準聚苯乙烯換算計測定重量平均分子量。再者，管柱係將Tosoh(股)製造之商品名TSK-GEL G5000HHR、G4000HHR、G3000HHR之3根連接並安裝。 ＜撥水劑組合物之調整＞ (實施例1～37及比較例1～9) 將合成例1～8中所獲得之撥水助劑(聚矽氧乳化物)與合成例9～36中所獲得之聚合物分散液以表11～15所記載之質量比進行混合，製成撥水劑組合物。 對上述所獲得之撥水劑組合物進行評價。 (纖維製品之撥水性評價) 依據JIS L 1092(1998)之噴霧法將淋浴水溫設為27℃進行試驗。於本試驗中，將進行染色後之聚酯100%布或尼龍100%布於將實施例及比較例之撥水劑組合物以聚合物之含量成為3質量%之方式利用水進行稀釋而成之處理液中進行浸漬處理(拾取率60質量%)後，於130℃下乾燥2分鐘，進而於表7～10所示般之條件下進行熱處理，對所獲得之布之撥水性進行評價。結果係藉由目視以下述等級進行評價。再者，於特性略微良好之情形時對等級附上「+」，於特性略微較差之情形時對等級附上「-」。將結果示於表16～22。 撥水性：狀態 5：表面不存在附著濕潤者 4：表面略微顯示出附著濕潤者 3：表面局部顯示出濕潤者 2：表面顯示出濕潤者 1：整個表面顯示出濕潤者 0：正背兩面完全顯示出濕潤者 (纖維製品之質地評價) 質地係使用將進行染色後之聚酯100%布於將實施例及比較例之撥水劑組合物以聚合物之含量成為3質量%之方式利用水進行稀釋而成之處理液中進行浸漬處理(拾取率60質量%)後，於130℃下乾燥2分鐘，進而於170℃下熱處理30秒所得者而進行評價。結果係藉由操作以下述所示之5個等級進行評價。將結果示於表16～22。 1：硬～5：柔軟 (纖維製品之耐久撥水性評價) 依據JIS L 1092(1998)之噴霧法將淋浴水溫設為27℃進行試驗。於本試驗中，以與上述撥水性評價方法相同之方式對將進行染色後之聚酯100%布於以聚合物之含量成為3質量%、UNIKA RESIN 380-K(交聯劑，Union化學工業股份有限公司製造，三羥甲基三聚氰胺樹脂)之含量成為0.3質量%及UNIKA CATALYST 3-P(界面活性劑，Union化學工業股份有限公司製造，胺基醇鹽酸鹽)之含量成為0.2質量%之方式將實施例及比較例之撥水劑組合物及上述各藥劑利用水進行稀釋而成之處理液中進行浸漬處理(拾取率60質量%)後，於130℃下乾燥2分鐘，進而於170℃下熱處理60秒而獲得之布(L-0)，及將基於JIS L 0217(1995)之103法之洗滌進行10次(L-10)後之布之撥水性進行評價。又，於尼龍100%布之情形時，亦將熱處理溫度自170℃變成160℃，除此以外，以與聚酯100%布之情形時相同之方式進行評價。將結果示於表16～22。 (纖維製品對塗層之剝離強度) 依據JIS K 6404-5(1999)進行試驗。於本試驗中，將於將進行染色後之尼龍100%布於將實施例及比較例之撥水劑組合物以聚合物含量成為3質量%之方式利用水進行稀釋而成之處理液中進行浸漬處理(拾取率60質量%)後，於130℃下乾燥2分鐘，進而於160℃下熱處理30秒而獲得者設為基布。使用熱壓接裝置，將熱熔接著帶(SANKASEI股份有限公司製造之「MELCO TAPE」)以150℃熱壓接於該所獲得之基布1分鐘，利用Autograph(AG-IS，島津製作所(股)製造)測定基布與接縫膠帶之層間之剝離強度。將夾具之移動速度以100 mm/min進行牽拉，將應力之平均值設為剝離強度[N/inch]。將結果示於表16～22。 [表1] [表2] [表3] [表4] [表5] [表6] [表7] [表8] [表9] [表10] [表11] [表12] [表13] [表14] [表15] [表16] [表17] [表18] [表19] [表20] [表21] [表22] 確認到對實施例1～37之撥水劑組合物進行處理後之纖維製品即便於未進行熱處理之情形時，亦發揮與先前之氟系撥水劑(比較例7)及僅使用上述通式(1)所表示之有機改性聚矽氧(比較例8)之情形時同等以上之撥水性，耐久撥水性優異且質地亦良好。 又，確認到對實施例1～37之撥水劑組合物進行處理後之纖維製品發揮與使用不包含上述通式(1)所表示之有機改性聚矽氧之撥水劑組合物(比較例9)之情形時同等以上之撥水性，耐久撥水性優異，對樹脂塗層之剝離強度更優異。 比較例1～6之撥水劑組合物使用上述通式(1)所表示之有機改性聚矽氧以外之聚矽氧，具有耐久撥水性尤其較差之傾向。 [產業上之可利用性] 根據本發明，可提供一種可提高非氟系撥水劑之耐久撥水性之撥水助劑及包含其之非氟系撥水劑組合物。The water-repellent auxiliary agent for the non-fluorine-based water-repellent agent of this embodiment includes an organic modified polysiloxane represented by the following general formula (1). In addition, in the following general formula (1), the structural units may be alternately arranged regardless of whether they are block or random. [Chemical 5]
Figure TW201803964AD00005
[In formula (1), R 20 , R twenty one And R twenty two Each independently represents a hydrogen atom, a methyl group, an ethyl group, or an alkoxy group having 1 to 4 carbon atoms, and R twenty three A hydrocarbon group having 8 to 40 carbon atoms or an alkyl group having 3 to 22 carbon atoms having an aromatic ring, R 30 , R 31 , R 32 , R 33 , R 34 And R 35 Each independently represents a hydrogen atom, a methyl group, an ethyl group, an alkoxy group having 1 to 4 carbon atoms, a hydrocarbon group having 8 to 40 carbon atoms or an alkyl group having 3 to 22 carbon atoms, and a represents 0 or more Integer, b is an integer of 1 or more, (a + b) is 10 to 200, and when a is 2 or more, there are plural Rs 20 And R twenty one They can be the same or different. When b is 2 or more, there are plural Rs. twenty two And R twenty three It may be the same or different.] In the organically modified polysiloxane of this embodiment, the alkoxy group having the carbon number of 1 to 4 may be linear or branched. Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. In terms of industrial ease of manufacture and availability, R 20 , R twenty one And R twenty two Preferably they are each independently a hydrogen atom or a methyl group, and more preferably a methyl group. Examples of the hydrocarbon group having 8 to 40 carbon atoms having an aromatic ring include an aralkyl group having 8 to 40 carbon atoms, a group represented by the following general formula (2) or (3), and the like. [Chemical 6]
Figure TW201803964AD00006
[In formula (2), R 40 Represents an alkylene group having 2 to 6 carbon atoms, and R 41 Represents a single bond or an alkylene group having 1 to 4 carbon atoms, and c represents an integer from 0 to 3; when c is 2 or 3, there are plural Rs 41 It may be the same or different.] The above-mentioned alkylene group may be linear or branched. [Chemical 7]
Figure TW201803964AD00007
[In formula (3), R 42 Represents an alkylene group having 2 to 6 carbon atoms, and R 43 Represents a single bond or an alkylene group having 1 to 4 carbon atoms, and d represents an integer from 0 to 3; when d is 2 or 3, there are plural R's 43 It may be the same or different.] The above-mentioned alkylene group may be linear or branched. Examples of the aralkyl group having 8 to 40 carbon atoms include phenylethyl, phenylpropyl, phenylbutyl, phenylpentyl, phenylhexyl, and naphthylethyl. Among them, phenylethyl and phenylpropyl are preferred in terms of industrially easy production and availability. In the group represented by the above general formula (2), in terms of industrially easy production and easy access, R 40 An alkylene group having 2 to 4 carbon atoms is preferred, and c is preferably 0 or 1, and more preferably 0. In the group represented by the above general formula (3), in terms of industrially easy production and easy access, R 42 An alkylene group having 2 to 4 carbon atoms is preferred, and d is preferably 0 or 1, and more preferably 0. As the hydrocarbon group having 8 to 40 carbon atoms having an aromatic ring, in terms of being easily manufactured industrially and easily available, the arylalkyl group having 8 to 40 carbon atoms and the general formula (2) are preferable. The base is more preferably an aralkyl group having 8 to 40 carbon atoms in terms of improving the water repellency of the obtained fiber product. The alkyl group having 3 to 22 carbon atoms may be linear or branched. Examples of the alkyl group having 3 to 22 carbon atoms include hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, myristyl, cetyl, and stearyl. As the alkyl group having 3 to 22 carbon atoms, in terms of improving the water repellency of the obtained fiber product, an alkyl group having 8 to 20 carbon atoms is preferred, and an alkyl group having 12 to 18 carbon atoms is more preferred. In the organic modified polysiloxane of this embodiment, R 30 , R 31 , R 32 , R 33 , R 34 And R 35 They are each independently a hydrogen atom, a methyl group, an ethyl group, an alkoxy group having 1 to 4 carbon atoms, a hydrocarbon group having 8 to 40 carbon atoms having an aromatic ring, or an alkyl group having 3 to 22 carbon atoms. In terms of industrial ease of manufacture and availability, R 30 , R 31 , R 32 , R 33 , R 34 And R 35 It is preferably a hydrogen atom, a methyl group, an ethyl group, or an alkoxy group having 1 to 4 carbon atoms, each of which is more preferably a methyl group. In the organic modified polysiloxane of this embodiment, a is an integer of 0 or more. In terms of industrially easy manufacture, easy acquisition, and better peel strength of the obtained fiber product from the resin coating, a is preferably 40 or less, and more preferably 30 or less. In the organically modified polysiloxane of this embodiment, (a + b) is 10 to 200. In terms of industrially easy production and easy availability, (a + b) is preferably from 20 to 100, more preferably from 40 to 60. When (a + b) is within the above-mentioned range, there is a tendency that the production or handling of the polysiloxane itself becomes easy. The organic modified polysiloxane of this embodiment can be synthesized by a conventionally known method. The organically modified polysiloxane of this embodiment can be obtained, for example, by subjecting an aromatic compound having a vinyl group and / or an α-olefin to a polysiloxy group having a SiH group by a hydrosilylation reaction. Examples of the polysiloxane having a SiH group include methylhydropolysiloxane having a polymerization degree of 10 to 200, or a copolymer of dimethylsiloxane and methylhydrosiloxane. Among these, methyl hydride polysiloxane is preferable from the point that it is industrially easy to manufacture and obtain. The aromatic compound having a vinyl group becomes R in the general formula (1). twenty three A compound derived from a hydrocarbon group having 8 to 40 carbon atoms in an aromatic ring. Examples of the aromatic compound having a vinyl group include styrene, α-methylstyrene, vinylnaphthalene, allylphenyl ether, allylnaphthyl ether, allyl-p-cumenebenzene Ether, allyl-o-phenylphenyl ether, allyl-tris (phenylethyl) -phenyl ether, allyl-tris (2-phenylpropyl) phenyl ether, and the like. The α-olefin is R in the general formula (1) twenty three A compound derived from an alkyl group having 3 to 22 carbon atoms. Examples of the α-olefin include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, and 1-undecene. , 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and other α-olefins having 3 to 22 carbon atoms. The hydrosilylation reaction is also carried out by reacting the aromatic compound having a vinyl group and the α-olefin stepwise or one-time with a polysiloxane having the SiH group in the presence of a catalyst, if necessary. The amount of the polysiloxy group having a SiH group, the aromatic compound having a vinyl group, and the α-olefin used for the hydrosilylation reaction can be appropriately selected according to the SiH group equivalent or number average molecular weight of the polysiloxy group having a SiH group, respectively. Examples of the catalyst used in the hydrosilylation reaction include compounds such as platinum and palladium. Among them, platinum compounds are preferred. Examples of the platinum compound include platinum (IV) chloride. The reaction conditions for the hydrosilylation reaction are not particularly limited and can be appropriately adjusted. The reaction temperature is, for example, 10 to 200 ° C, and preferably 50 to 150 ° C. The reaction time may be 3 to 12 hours when the reaction temperature is, for example, 50 to 150 ° C. The hydrosilylation reaction is preferably performed under an inert gas environment. Examples of the inert gas include nitrogen and argon. Although the reaction proceeds without a solvent, a solvent may be used. Examples of the solvent include dioxane, methyl isobutyl ketone, toluene, xylene, and butyl acetate. The non-fluorine-based water-repellent composition of this embodiment will be described. The non-fluorine-based water-repellent composition of this embodiment includes the water-repellent auxiliary agent and the non-fluorine-based water-repellent agent of the above-mentioned embodiment. The above non-fluorine-based fibers are excellent in storage stability and can impart sufficient water repellency to fiber products and the like even without heat treatment, thereby obtaining water-repellent fiber products with excellent texture and water repellency. It is preferable that the water agent contains a structural unit derived from a (meth) acrylate monomer (A) represented by the following general formula (A-1) (hereinafter, also referred to as "(A) component"). Fluoropolymer. [Chemical 8]
Figure TW201803964AD00008
[In formula (A-1), R 1 Represents hydrogen or methyl, R 2 Denotes a monovalent hydrocarbon group having 12 or more carbon atoms which may have a substituent] Here, the "(meth) acrylate" means "acrylate" or a corresponding "methacrylate", and "(A The same meaning applies to "acrylic acid", "(meth) acrylamide", and the like. The (meth) acrylic acid ester monomer (A) represented by the general formula (A-1) used in this embodiment has a monovalent hydrocarbon group having 12 or more carbon atoms which may have a substituent. The hydrocarbon group may be linear or branched, may be a saturated hydrocarbon group, may be an unsaturated hydrocarbon group, and may further have an alicyclic or aromatic ring. Among these, a linear one is preferable, and a linear alkyl group is more preferable. In this case, the water repellency becomes more excellent. When a monovalent hydrocarbon group having 12 or more carbon atoms has a substituent, examples of the substituent include a hydroxyl group, an amino group, a carboxyl group, an epoxy group, an isocyanate group, a blocked isocyanate group, and a (methyl) group. One or more of acryloxy and the like. In this embodiment, in the general formula (A-1), R 2 An unsubstituted hydrocarbon group is preferred. The carbon number of the hydrocarbon group is preferably 12 to 24. When the carbon number is less than 12, when a non-fluorine-based polymer is attached to a fiber product or the like, sufficient water repellency cannot be exhibited. On the other hand, if the carbon number exceeds 24, the texture of the fiber product tends to become coarser when the non-fluorine-based polymer is attached to the fiber product than when the carbon number is in the above range. . The carbon number of the hydrocarbon group is more preferably 12 to 21. When the carbon number is within this range, water repellency and texture are particularly excellent. The hydrocarbon group is particularly preferably a linear alkyl group having 12 to 18 carbon atoms. Examples of the component (A) include stearyl (meth) acrylate, cetyl (meth) acrylate, lauryl (meth) acrylate, dodecyl (meth) acrylate, and (meth) ) Myristyl acrylate, pentadecyl (meth) acrylate, heptadecyl (meth) acrylate, undecyl (meth) acrylate, eicosyl (meth) acrylate, Twenty-one alkyl (meth) acrylate, behenyl (meth) acrylate, hexadecyl (meth) acrylate, and tridecyl (meth) acrylate. The component (A) may have at least one functional group selected from the group consisting of a hydroxyl group, an amine group, a carboxyl group, an epoxy group, and an isocyanate group that can react with a crosslinking agent. In this case, the durability and water repellency of the obtained fiber product can be further improved. Isocyanate groups can also form blocked isocyanate groups protected by a blocking agent. When the component (A) has an amine group, the texture of the obtained fiber product can be further improved. The (A) component is preferably a monofunctional (meth) acrylate monomer having one polymerizable unsaturated group in one molecule. The said (A) component may be used individually by 1 type, and may be used in combination of 2 or more type. In terms of the durable water repellency of the obtained fiber product, the (A) component is preferably a combination of an acrylate monomer (a1) and a methacrylate monomer (a2). The ratio of the mass of the (a1) component to the mass of the (a2) component (a1) / (a2) is preferably 30/70 to 90/10, more preferably 40/60 to 85/15, and even more preferably It is 50/50 to 80/20. When (a1) / (a2) falls within the above range, the durable water repellency of the obtained fiber product becomes more favorable. When (a1) / (a2) exceeds 90/10 or when it does not reach 30/70, there is a tendency that the water repellency of the obtained fiber product is reduced. In terms of the water repellency and durable water repellency of the obtained fiber product, the total composition ratio of the monomers of the component (A) in the non-fluorine-based polymer relative to the monomer components of the non-fluoro-based polymer The total amount is preferably 50 to 100% by mass, more preferably 55 to 97% by mass, and still more preferably 60 to 95% by mass. The weight average molecular weight of the non-fluorine-based polymer is preferably 100,000 or more. If the weight average molecular weight is less than 100,000, the water repellency of the obtained fiber product tends to be insufficient. Furthermore, the weight average molecular weight of the non-fluorine-based polymer is more preferably 500,000 or more. In this case, the obtained fiber product can exert water repellency more fully. The upper limit of the weight average molecular weight of the non-fluorine-based polymer is preferably about 5 million. In this embodiment, the melt viscosity at 105 ° C of the non-fluorine-based polymer is preferably 1,000 Pa · s or less. If the melt viscosity at 105 ° C exceeds 1,000 Pa · s, the texture of the obtained fiber product tends to become coarse. In addition, if the melt viscosity of the non-fluorine-based polymer is too high, when the non-fluorine-based polymer is emulsified or dispersed to form a water-repellent composition, the non-fluorine-based polymer may be precipitated or precipitated. The storage stability of the water repellent composition tends to decrease. The melt viscosity at 105 ° C is more preferably 500 Pa · s or less. In this case, the obtained fiber products and the like sufficiently exhibit water repellency, and the texture becomes more excellent. The "melt viscosity at 105 ° C" refers to the use of an overhead rheometer (for example, CFT-500 manufactured by Shimadzu Corporation) to add non-fluorine-based polymerization to a cylinder equipped with a mold (length 10 mm and diameter 1 mm). 1 g of material, hold at 105 ° C for 6 minutes, and apply 100 kg · f / cm through the plunger 2 The viscosity at the time of measurement after the load. When the weight average molecular weight of the non-fluorine-based polymer is equal, the higher the blending ratio of the non-fluorine-based (meth) acrylate monomer, the higher the water repellency of the attached fiber product tends to be. In addition, by copolymerizing a copolymerizable non-fluorine-based monomer, properties such as durability of water repellency and texture of the adhered fiber product can be improved. In terms of improving the water repellency of the obtained fiber product, and the emulsification stability of the non-fluorine-based polymer during emulsification polymerization or dispersion polymerization, and in the composition after the polymerization, the non-fluorine-based polymer is preferably removed. (A) In addition to the component, it also contains a compound selected from (B1) a compound represented by the following general formula (I-1) having an HLB of 7 to 18, and (B2) a HLB of the following general formula (II-1) having an HLB of 7 to 18 ) And at least one of the compounds represented by (B3) and (B3) HLB of 7 to 18 is a compound obtained by adding an alkylene oxide having 2 to 4 carbon atoms to a fat or oil having a hydroxyl group and a polymerizable unsaturated group. Agent (B) (hereinafter, also referred to as "(B) component") as a monomer component. [Chemical 9]
Figure TW201803964AD00009
[In formula (I-1), R 3 Represents hydrogen or methyl, X represents a straight or branched alkylene group having 1 to 6 carbon atoms, Y 1 Represents a divalent group containing an alkyleneoxy group having 2 to 4 carbon atoms] [Chem. 10]
Figure TW201803964AD00010
[In formula (II-1), R 4 A monovalent unsaturated hydrocarbon group having 13 to 17 carbon atoms having a polymerizable unsaturated group, Y 2 Represents a divalent group containing an alkyleneoxy group having 2 to 4 carbon atoms] The so-called "reactive emulsifier" refers to a radically reactive emulsifying dispersant, that is, having one or more polymerizable unsaturated groups in the molecule The surfactant can be copolymerized with (meth) acrylate-like monomers. The "HLB" refers to an HLB value calculated by the Griffin method in which the ethylenoxy group is regarded as a hydrophilic group, and all other groups are regarded as lipophilic groups. The HLB of the compounds (B1) to (B3) used in this embodiment is 7 to 18, and the emulsification stability of the non-fluorine-based polymer at the time of emulsion polymerization or dispersion polymerization and the composition after polymerization (hereinafter (Referred to as emulsification stability for short), preferably from 9 to 15. Furthermore, in terms of storage stability of the non-fluorine-based water-repellent agent, it is more preferable to use a combination of two or more reactive emulsifiers (B) having different HLBs within the above range. In the reactive emulsifier (B1) represented by the general formula (I-1) used in this embodiment, R 3 It is hydrogen or methyl, and in terms of copolymerizability with the component (A), methyl is more preferred. X is a linear or branched alkylene group having 1 to 6 carbon atoms. In terms of the emulsification stability of the non-fluorine-based polymer of this embodiment, a linear alkylene group having 2 to 3 carbon atoms is more preferred. base. Y 1 It is a divalent group containing an alkyleneoxy group having 2 to 4 carbon atoms. About Y 1 The kind, combination, and addition number of the alkyleneoxy group in can be appropriately selected within the range of the above-mentioned HLB. When there are two or more kinds of alkyleneoxy groups, these may have a block addition structure or a random addition structure. The compound represented by the general formula (I-1) is preferably a compound represented by the following general formula (I-2). [Chemical 11]
Figure TW201803964AD00011
[In formula (I-2), R 3 Represents hydrogen or methyl, X represents a linear or branched alkylene group having 1 to 6 carbon atoms, A 1 O represents an alkyleneoxy group having 2 to 4 carbon atoms, and m can be selected as appropriate within the above-mentioned HLB range. Specifically, it is preferably an integer from 1 to 80. When m is 2 or more, m A's 1 O may be the same or different] In the compound represented by the general formula (I-2), R 3 It is hydrogen or methyl, and in terms of copolymerizability with the component (A), methyl is more preferred. X is a linear or branched alkylene group having 1 to 6 carbon atoms. In terms of emulsification stability of a non-fluorine-based polymer, a linear alkylene group having 2 to 3 carbon atoms is more preferred. A 1 O is an alkyleneoxy group having 2 to 4 carbon atoms. A 1 The type and combination of O and the number of m can be appropriately selected within a range of the above-mentioned HLB. In terms of emulsion stability of a non-fluorine-based polymer, m is preferably an integer of 1 to 80, and more preferably an integer of 1 to 60. When m is 2 or more, m A's 1 O can be the same or different. Also, in A 1 When O is two or more types, these may have a block addition structure or a random addition structure. The reactive emulsifier (B1) represented by the general formula (I-2) can be obtained by a conventionally known method, and is not particularly limited. In addition, it can be easily obtained from commercially available products, and examples thereof include "Latemul PD-420", "Latemul PD-430", and "Latemul PD-450" manufactured by Kao Corporation. In the reactive emulsifier (B2) represented by the general formula (II-1) used in this embodiment, R 4 Examples of monovalent unsaturated hydrocarbon groups having 13 to 17 carbon atoms having polymerizable unsaturated groups include tridecenyl, tridecadienyl, tetradecenyl, tetradecadienyl, and fifteen Carboalkenyl, pentadecadienyl, pentatrienyl, heptadecenyl, heptadecenyl, heptadecenyl, and the like. In terms of emulsion stability of non-fluorine-based polymers, R 4 More preferably, it is a monovalent unsaturated hydrocarbon group having 14 to 16 carbon atoms. Y 2 It is a divalent group containing an alkyleneoxy group having 2 to 4 carbon atoms. Y 2 The type, combination, and addition number of the alkyleneoxy group in the above can be appropriately selected within a range of the above-mentioned HLB. When there are two or more kinds of alkyleneoxy groups, these may have a block addition structure or a random addition structure. In terms of emulsification stability of a non-fluorine-based polymer, an alkyleneoxy group is more preferably an ethyloxy group. The compound represented by the general formula (II-1) is preferably a compound represented by the following general formula (II-2). [Chemical 12]
Figure TW201803964AD00012
[In formula (II-2), R 4 A monovalent unsaturated hydrocarbon group having 13 to 17 carbon atoms having a polymerizable unsaturated group, A 2 O represents an alkyleneoxy group having 2 to 4 carbon atoms, and n can be selected as appropriate within the above-mentioned HLB range. Specifically, an integer of 1 to 50 is preferred. When n is 2 or more, n A 2 O may be the same or different] R in the compound represented by the general formula (II-2) 4 Examples of the same as R in the general formula (II-1) 4 The same. A 2 O is an alkyleneoxy group having 2 to 4 carbon atoms. In terms of emulsification stability of non-fluorine-based polymers, A 2 The type and combination of O and the number of n can be appropriately selected within the above-mentioned range of HLB. In terms of emulsification stability of non-fluorine-based polymers, A 2 O is more preferably an ethyl ethoxy group, n is preferably an integer of 1 to 50, more preferably an integer of 5 to 20, and even more preferably an integer of 8 to 14. When n is 2 or more, n A's 2 O can be the same or different. Also, in A 2 When O is two or more types, these may have a block addition structure or a random addition structure. The reactive emulsifier (B2) represented by the general formula (II-2) used in this embodiment can be synthesized by adding an alkylene oxide to a corresponding phenol having an unsaturated hydrocarbon group by a known method, It is not particularly limited. For example, it can be synthesized by using alkali catalysts such as caustic soda and caustic potassium to add a specific amount of alkylene oxide at 120 to 170 ° C under pressure. The corresponding phenols having an unsaturated hydrocarbon group include, in addition to industrially pure products or mixtures, those that are extracted and refined from plants and the like and exist as pure products or mixtures. For example, 3- [8 (Z), 11 (Z), 14-pentadecatrienyl] phenol, 3- [8 (Z), 11 (Z) -pentadecenyl] phenol, 3- [8 (Z) -pentadecenyl] phenol, 3- [11 (Z) -pentadecenyl] phenol, and the like. The reactive emulsifier (B3) used in this embodiment is a compound obtained by adding an alkylene oxide having 2 to 4 carbon atoms to an oil having a hydroxyl group and a polymerizable unsaturated group with an HLB of 7 to 18. Examples of fats and oils having a hydroxyl group and a polymerizable unsaturated group may include hydroxyl unsaturated fatty acids (palmitoleic acid, oleic acid, linoleic acid, α-linolenic acid, arachidonic acid, and eicosapentaene). Acid, docosapentaenoic acid, etc.) of mono- or diglycidyl fatty acids, containing at least 1 type of hydroxy unsaturated fatty acid (ricinoleic acid, ricinoleic acid, 2-hydroxydocosatrienoic acid, etc.) Triglycerides of fatty acids. In terms of emulsification stability of a non-fluorine-based polymer, an alkylene oxide adduct of triglyceride containing at least one type of hydroxy unsaturated fatty acid and fatty acid is preferred, and castor oil (including ricinoleic acid) is more preferred. The fatty acid triglyceride) has an alkylene oxide adduct having 2 to 4 carbon atoms, and is more preferably an ethylene oxide adduct of castor oil. Furthermore, the addition mole number of the alkylene oxide can be appropriately selected within a range of the above-mentioned HLB. In terms of emulsification stability of the non-fluorine-based polymer, it is more preferably 20 to 50 moles, and more preferably It is 25 to 45 moles. When there are two or more kinds of alkylene oxides, these may have a block addition structure or a random addition structure. The reactive emulsifier (B3) used in this embodiment can be synthesized by adding an alkylene oxide to a fat or oil having a hydroxyl group and a polymerizable unsaturated group by a conventionally known method, and is not particularly limited. For example, it can be synthesized by adding a specific amount of alkylene oxide to castor oil, which is a triglyceride containing ricinoleic acid fatty acid, at 120 to 170 ° C under pressure using an alkali catalyst such as caustic soda and caustic potassium. From the viewpoint of improving the water repellency of the obtained fiber product and the emulsification stability of the non-fluorine-based polymer during emulsification polymerization or dispersion polymerization and in the composition after polymerization, the above-mentioned ( B) The composition ratio of the monomers of the component is preferably 0.5 to 20% by mass, more preferably 1 to 15% by mass, and still more preferably 3 to 10 with respect to the total amount of the monomer components constituting the non-fluorine-based polymer. quality%. In terms of improving the durable water repellency of the obtained fiber product, the non-fluorine-based polymer contained in the non-fluorine-based water-repellent agent is preferably selected from the following (C1) in addition to the component (A) , (C2), (C3), (C4), and (C5) at least one second (meth) acrylate monomer (C) (hereinafter, also referred to as "C component") in the group Monomer composition. (C1) (meth) acrylic acid ester monomer represented by the following general formula (C-1) other than (C5)
Figure TW201803964AD00013
[In formula (C-1), R 5 Represents hydrogen or methyl, R 6 A monovalent chain having a carbon number of 1 to 11 having at least one functional group selected from the group consisting of a hydroxyl group, an amine group, a carboxyl group, an epoxy group, an isocyanate group, and a (meth) acryloxy group A hydrocarbon group in which the number of (meth) acrylic fluorenyloxy groups in the molecule is 2 or less] (C2) a (meth) acrylate monomer represented by the following general formula (C-2) [Chem. 14]
Figure TW201803964AD00014
[In formula (C-2), R 7 Represents hydrogen or methyl, R 8 Represents a monovalent cyclic hydrocarbon group having 1 to 11 carbon atoms which may have a substituent] (C3) a methacrylate monomer represented by the following general formula (C-3) [Chem. 15]
Figure TW201803964AD00015
[In formula (C-3), R 9 Represents an unsubstituted monovalent chain hydrocarbon group having 1 to 4 carbon atoms] (C4) (meth) acrylic acid ester monomer represented by the following general formula (C-4) [Chem. 16]
Figure TW201803964AD00016
[In formula (C-4), R 10 Represents hydrogen or methyl, p represents an integer of 2 or more, S represents a (p + 1) -valent organic group, and T represents a monovalent organic group having a polymerizable unsaturated group] (C5) represented by the following general formula (C-5) (Meth) acrylate monomers [Chem. 17]
Figure TW201803964AD00017
[In formula (C-5), R 11 Represents hydrogen or methyl, R 12 It represents a monovalent chain saturated hydrocarbon group having at least one functional group selected from the group consisting of a chloro group and a bromo group, and a monovalent chain hydrocarbon group having 3 to 6 carbon atoms in the hydroxyl group. A monovalent chain hydrocarbon group having 1 to 11 carbon atoms in at least one functional group in the group consisting of a hydroxyl group, an amino group, a carboxyl group, an epoxy group, an isocyanate group, and a (meth) acryloxy group, and the above ( C5) other (meth) acrylate monomers. In terms of reacting with a crosslinking agent, the monovalent chain hydrocarbon group having 1 to 11 carbon atoms is preferably selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, an epoxy group, and an isocyanate group. At least one functional group. When a non-fluorine-based polymer containing a monomer (C1) having a base capable of reacting with these cross-linking agents is processed together with a cross-linking agent in a fiber product, it is possible to maintain the obtained fiber product. Improves water repellency with texture. The isocyanate group may also be a blocked isocyanate group protected by a blocking agent. The chain hydrocarbon group may be linear or branched, and may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. The chain hydrocarbon group may further have a substituent in addition to the above-mentioned functional group. Among them, a linear and / or saturated hydrocarbon group is preferred in terms of improving the durability of the obtained fiber product. Specific monomers of (C1) include 2-hydroxyethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, glycidyl (meth) acrylate, and isocyanate 1,1 -Bis (propenyloxymethyl) ethyl ester and the like. These monomers may be used individually by 1 type, and may be used in combination of 2 or more type. Among these, in terms of improving the durable water repellency of the obtained fiber product, 2-hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, and 1,1-bis isocyanate are preferred. (Acryloxymethyl) ethyl ester. Furthermore, from the point which can improve the texture of the obtained fiber product, dimethylaminoethyl (meth) acrylate is preferable. From the viewpoint of the water repellency and texture of the obtained fiber product, the composition ratio of the monomer (C1) in the non-fluorine-based polymer to the total amount of the monomer components constituting the non-fluorine-based polymer is smaller than It is preferably 1 to 30% by mass, more preferably 3 to 25% by mass, and still more preferably 5 to 20% by mass. The (meth) acrylic acid ester monomer having a monovalent cyclic hydrocarbon group having 1 to 11 carbon atoms as the (C2) mono-system ester portion, and examples of the cyclic hydrocarbon group include an iso group, a cyclohexyl group, and a dicyclohexyl group. Cyclopentyl and others. These cyclic hydrocarbon groups may have a substituent such as an alkyl group. Among them, when the substituent is a hydrocarbon group, the total number of carbons of the substituent and the cyclic hydrocarbon group is selected to be a hydrocarbon group of 11 or less. From the viewpoint of improving the durability of water repellency, the cyclic hydrocarbon group is preferably directly bonded to an ester bond. The cyclic hydrocarbon group may be alicyclic or aromatic, and in the case of alicyclic, it may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. Specific examples of the monomer include iso (meth) acrylate, cyclohexyl (meth) acrylate, and dicyclopentyl (meth) acrylate. These monomers may be used individually by 1 type, and may be used in combination of 2 or more type. Among these, in terms of improving the durability and water repellency of the obtained fiber product, iso (meth) acrylic acid iso (158665) ester and cyclohexyl methacrylate, and more preferably isomethacrylate 158665; ester. From the viewpoint of the water repellency and texture of the obtained fiber product, the composition ratio of the monomer (C2) in the non-fluorine-based polymer relative to the total amount of the monomer components constituting the non-fluorine-based polymer is smaller than It is preferably 1 to 30% by mass, more preferably 3 to 25% by mass, and still more preferably 5 to 20% by mass. The monovalent unsubstituted monovalent chain hydrocarbon group having 1 to 4 carbon atoms in the above (C3) is a methacrylate monomer having an ester bond directly bonded to an ester portion. The chain hydrocarbon group having 1 to 4 carbon atoms is preferably a linear hydrocarbon group having 1 to 2 carbon atoms and a branched hydrocarbon group having 3 to 4 carbon atoms. Examples of the chain hydrocarbon group having 1 to 4 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, and third butyl. Specific compounds include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, and methacrylic acid. Third butyl ester. These monomers may be used individually by 1 type, and may be used in combination of 2 or more type. Among these, in terms of improving the durable water repellency of the obtained fiber product, methyl methacrylate, isopropyl methacrylate, and third butyl methacrylate are more preferable, and methyl methacrylate is more preferable. ester. From the viewpoint of the water repellency and texture of the obtained fiber product, the composition ratio of the monomer (C3) in the non-fluorine-based polymer relative to the total amount of the monomer components constituting the non-fluorine-based polymer is smaller than It is preferably 1 to 30% by mass, more preferably 3 to 25% by mass, and still more preferably 5 to 20% by mass. The (C4) (meth) acrylate monomer having three or more polymerizable unsaturated groups in one molecule of the single system. In this embodiment, it is preferred that T in the general formula (C-4) is a polyfunctional one having (meth) acryloxy groups having 3 (meth) acryloxy groups in one molecule. (Meth) acrylate monomer. In formula (C-4), p Ts may be the same or different. Specific examples of the compound include ethoxylated isotricyanic acid triacrylate, tetramethylolmethane tetraacrylate, tetramethylolmethane tetramethacrylate, trimethylolpropane triacrylate, Trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, and the like. These monomers may be used individually by 1 type, and may be used in combination of 2 or more type. Among these, in terms of improving the durable water repellency of the obtained fiber product, tetramethylolmethane tetraacrylate and ethoxylated isotricyanate triacrylate are more preferable. From the viewpoint of the water repellency and texture of the obtained fiber product, the composition ratio of the monomer (C4) in the non-fluorine-based polymer relative to the total amount of monomer components constituting the non-fluorine-based polymer It is preferably 1 to 30% by mass, more preferably 3 to 25% by mass, and still more preferably 5 to 20% by mass. The monomer (C5) has a monovalent chain saturated hydrocarbon group having at least one functional group selected from the group consisting of a chloro group and a bromo group and a carbon number of 3 to 6 of a hydroxyl group. In the monomer of (C5) above, R 11 Is hydrogen or methyl. In terms of the durable water repellency of the obtained fiber products, R 11 Methyl is preferred. R 12 It is a monovalent chain saturated hydrocarbon group having at least one functional group selected from the group consisting of a chlorine group and a bromo group and a carbon number of 3 to 6 and a hydroxyl group. The linear saturated hydrocarbon group may be linear or branched. When the linear saturated hydrocarbon group is linear, the durable water repellency of the obtained fiber product becomes more excellent. In terms of the durable water repellency of the obtained fiber product, the carbon number of the chain-saturated hydrocarbon group is preferably 3 to 4, and more preferably 3. In terms of the durable water repellency of the obtained fiber product, the aforementioned chain saturated hydrocarbon group preferably has one or two chlorine groups and one hydroxyl group, and more preferably has one chlorine group and one hydroxyl group. Moreover, in terms of the durable water repellency of the obtained fiber product, the chain-like saturated hydrocarbon group is further preferably at the β position (bonded to CH 2 = CR 11 (The carbon atom adjacent to (CO) O-) has a hydroxyl group. Specific examples of the chain saturated hydrocarbon group include 3-chloro-2-hydroxypropyl, 3-chloro-2-hydroxybutyl, 5-chloro-2-hydroxypentyl, and 3-chloro-2-hydroxy- 2-methylpropyl and 3-bromo-2-hydroxypropyl. Specific monomers of (C5) include, for example, 3-chloro-2-hydroxypropyl (meth) acrylate, 3-chloro-2-hydroxybutyl (meth) acrylate, 5- (meth) acrylate 5- Chloro-2-hydroxypentyl ester and 3-bromo-2-hydroxypropyl (meth) acrylate. Among these, in terms of improving the durable water repellency of the obtained fiber product, 3-chloro-2-hydroxypropyl (meth) acrylate is preferred, and 3-chloro-2-hydroxy methacrylate is more preferred. Propyl ester. In terms of the durable water repellency of the obtained fiber product, the composition ratio of the above-mentioned (C5) monomer in the non-fluorine-based polymer is preferably relative to the total amount of the monomer components constituting the non-fluorine-based polymer. It is 1 to 30% by mass, more preferably 3 to 25% by mass, and even more preferably 5 to 20% by mass. From the viewpoint of the water repellency and texture of the obtained fiber product, the total composition ratio of the monomers of the component (C) in the non-fluorine-based polymer relative to the total amount of the monomer components constituting the non-fluorine-based polymer. It is preferably 1 to 30% by mass, more preferably 3 to 25% by mass, and still more preferably 5 to 20% by mass. The non-fluorine-based polymer contained in the non-fluorine-based water repellent may contain (A) component, (B) component, and (C) component, and may also be contained in a range that does not impair the effect of the present invention. Polymerized monofunctional monomer (D) (hereinafter, also referred to as "(D) component"). Examples of the monomer of (D) include (meth) acrylic morpholine, (meth) acrylic acid esters (meth) acrylic acid esters, (meth) acrylic acid, and tetrabutylene having hydrocarbon groups other than (meth) acrylic morpholine Maleic acid esters, maleic acid esters, fumaric acid, maleic acid, (meth) acrylamide, N-hydroxymethylacrylamide, vinyl ethers, vinyl esters, ethylene And vinyl monomers other than the fluorine-free (E) component such as styrene. Furthermore, the (meth) acrylate having a hydrocarbon group other than the (A) component and the (C) component may have a vinyl group, a hydroxyl group, an amine group, an epoxy group, an isocyanate group, and a blocked isocyanate group in the hydrocarbon group. Such substituents may have a substituent other than a group capable of reacting with a cross-linking agent such as a quaternary ammonium group, and may have an ether bond, an ester bond, a amide bond, or a urethane bond. Examples of the (meth) acrylate other than the (A) component and the (C) component include methyl acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, and ethylene glycol di (Meth) acrylates and the like. Among these, in terms of improving the peel strength of the obtained fiber product to the coating layer, (meth) acrylic morpholine is more preferable. From the viewpoint of the water repellency and texture of the obtained fiber product, the composition ratio of the monomers of the component (D) in the non-fluorine-based polymer relative to the total amount of the monomer components constituting the non-fluorine-based polymer, It is preferably 10% by mass or less. In terms of improving the durable water repellency of the obtained fiber product, the non-fluorine-based polymer contained in the non-fluorine-based water-repellent agent preferably has a hydroxyl group, an amine group, and a carboxyl group selected from a group capable of reacting with a crosslinking agent. At least one type of functional group in the group consisting of 1, 3, epoxy groups and isocyanate groups. Isocyanate groups can also form blocked isocyanate groups protected by a blocking agent. Moreover, it is preferable that a non-fluorine type polymer has an amine group from the point which can also improve the texture of the obtained fiber product. In terms of improving the water-repellency of the obtained fiber product and the peeling strength to the coating layer, the non-fluorine-based polymer contained in the non-fluorine-based water-repellent agent preferably contains chlorine in addition to the component (A). At least one of monomers (E) (hereinafter, also referred to as "(E) component") in ethylene and vinylidene chloride is used as a monomer component. In terms of the water repellency of the obtained fiber product and the peeling strength to the coating layer, at least one of the monomers (E) of vinyl chloride and vinylidene chloride used in this embodiment is preferably chlorine. Ethylene. From the viewpoint of improving the peel strength of the obtained fiber product to the coating layer, the composition ratio of the monomer of the component (E) in the non-fluorine-based polymer relative to the monomer component of the non-fluorine-based polymer The total amount is preferably 1 to 45% by mass, more preferably 3 to 40% by mass, and still more preferably 5 to 35% by mass. If necessary, additives and the like may be added to the water-repellent composition of this embodiment. Examples of the additives include other water-repellent agents, cross-linking agents, antibacterial deodorants, flame retardants, antistatic agents, softeners, and anti-wrinkle agents. Next, a method for producing a non-fluorine-based water-repellent agent containing a non-fluorine-based polymer will be described. A non-fluorine-based water repellent containing a non-fluorine-based polymer can be produced by a radical polymerization method. In addition, in this radical polymerization method, in terms of the performance and environment of the obtained water-repellent agent, it is preferred to perform polymerization by an emulsion polymerization method or a dispersion polymerization method. For example, a non-fluorine-based polymer can be obtained by subjecting the (meth) acrylate monomer (A) represented by the general formula (A-1) to emulsion polymerization or dispersion polymerization in a medium. More specifically, for example, the component (A) and the above-mentioned (B) component, the (C) component, the (D) component, and the (E) component, and an emulsifying aid or a dispersing aid are added to the medium as necessary. And emulsifying or dispersing the mixed solution to obtain an emulsion or dispersion. The polymerization reaction can be started by adding a polymerization initiator to the obtained emulsion or dispersion, thereby polymerizing the monomer and the reactive emulsifier. Examples of the method for emulsifying or dispersing the mixed liquid include a homomixer, a high-pressure emulsifier, and an ultrasonic wave. As the above-mentioned emulsifying adjuvant, dispersion adjuvant, etc. (hereinafter also referred to as "emulsifying adjuvant" etc.), a non-ionic surfactant, a cationic surfactant, and an anion other than the reactive emulsifier (B) may be used. One or more of a surfactant and an amphoteric surfactant. The content of the emulsifying adjuvant and the like is preferably 0.5 to 30 parts by mass, more preferably 1 to 20 parts by mass, and still more preferably 1 to 10 parts by mass based on 100 parts by mass of the total monomer. If the content of the above-mentioned emulsifying adjuvant is less than 0.5 parts by mass, the dispersion stability of the mixed liquid tends to be lower than when the content of the above-mentioned emulsifying adjuvant is in the above range. 30 parts by mass tends to decrease the water repellency of the obtained non-fluorinated polymer compared with the case where the content of the emulsifying adjuvant is in the above range. As a medium for emulsion polymerization or dispersion polymerization, water is preferred, and water and an organic solvent may be mixed as necessary. The organic solvent at this time is not particularly limited as long as it is an organic solvent that can be mixed with water. Examples of the organic solvent include alcohols such as methanol and ethanol, esters such as ethyl acetate, and ketones such as acetone and methyl ethyl ketone. , Ethers such as diethyl ether, ethylene glycol such as propylene glycol, dipropylene glycol, and tripropylene glycol. The ratio of water to organic solvent is not particularly limited. As said polymerization initiator, well-known polymerization initiators, such as an azo system, a peroxide system, and a redox system, can be used suitably. The content of the polymerization initiator is preferably from 0.01 to 2 parts by mass relative to 100 parts by mass of the total monomer. When the content of the polymerization initiator is in the above range, a non-fluorine-based polymer having a weight average molecular weight of 100,000 or more can be efficiently produced. In addition, in the polymerization reaction, in order to adjust the molecular weight, a chain transfer agent such as dodecyl mercaptan and third butanol may be used. The content of the chain transfer agent is preferably 0.3 parts by mass or less, and more preferably 0.1 parts by mass or less with respect to 100 parts by mass of the total monomer. When the content of the chain transfer agent exceeds 0.3 parts by mass, the molecular weight may decrease, and it is difficult to efficiently produce a non-fluorine-based polymer having a weight average molecular weight of 100,000 or more. Furthermore, in order to adjust the molecular weight, a polymerization inhibitor may be used. By adding a polymerization inhibitor, a non-fluorine-based polymer having a desired weight average molecular weight can be easily obtained. The temperature of the polymerization reaction is preferably 20 ° C to 150 ° C. If the temperature is less than 20 ° C, the polymerization tends to be insufficient compared to when the temperature is in the above range. If the temperature exceeds 150 ° C, it may be difficult to control the heat of reaction. In the polymerization reaction, the weight-average molecular weight of the obtained non-fluorine-based polymer can be adjusted by increasing or decreasing the contents of the above-mentioned polymerization initiator, chain transfer agent, and polymerization inhibitor. It is adjusted by increasing or decreasing the content of the polyfunctional monomer and the content of the polymerization initiator. When the melt viscosity at 105 ° C is reduced, the content of the monomer having two or more polymerizable functional groups may be reduced or the content of the polymerization initiator may be increased. From the standpoint of storage stability and operability of the composition, the content of the non-fluorine-based polymer in the polymer emulsion or dispersion obtained by emulsion polymerization or dispersion polymerization relative to the total of the emulsion or dispersion The amount is preferably 10 to 50% by mass, and more preferably 20 to 40% by mass. The non-fluorine-based water-repellent composition of the present embodiment can be produced by mixing the water-repellent auxiliary agent of the above-mentioned embodiment with the non-fluorine-based water-repellent agent. In terms of the durable water repellency of the obtained fiber product, the blending amount of the organic modified polysiloxane represented by the general formula (1) in the non-fluorine-based water repellent composition of the present embodiment is preferably 1 to 10 mass%, more preferably 3 to 7 mass%. In terms of the durable water repellency of the obtained fiber product, the amount of the organically modified polysiloxane represented by the general formula (1) in the non-fluorine water repellent composition of the present embodiment is relative to The non-fluorine-based polymer is 100 parts by mass, preferably 1 to 50 parts by mass, more preferably 3 to 30 parts by mass, and even more preferably 10 to 25 parts by mass. The manufacturing method of the water-repellent fiber product of this embodiment is demonstrated. The water-repellent fiber product of this embodiment is obtained by treating a fiber product with a treatment liquid containing the non-fluorine-based water-repellent composition. The material of the fiber product is not particularly limited, and examples thereof include natural fibers such as cotton, hemp, silk, and wool, semi-synthetic fibers such as rayon, acetate, nylon, polyester, polyurethane, and polypropylene And other synthetic fibers, such as composite fibers and blended fibers. The form of the fiber product may be any form of fiber, silk, cloth, woven fabric, knitted fabric, cloth in the form of clothing, carpet, non-woven fabric, paper, and the like. Examples of the method for treating the fiber product by using the treatment liquid include processing methods such as dipping, spraying, and coating, and processing methods based on a cleaning method. In the case where the non-fluorine-based water-repellent composition contains water, it is preferred that the non-fluorine-based water-repellent composition is dried after being attached to the fiber product in order to remove the water. In addition, it is preferred that the non-fluorine-based water-repellent composition of the present embodiment be used for heat treatment as appropriate after the fiber product is treated. The temperature condition is not particularly limited. If the non-fluorine-based water-repellent composition of this embodiment is used, the fiber product can exhibit sufficiently good water-repellency under mild conditions of 100 to 130 ° C. The temperature condition can also be a high temperature treatment of 130 ° C or higher (preferably 200 ° C). In this case, the processing time can be shortened compared to the previous case where a fluorine-based water repellent is used. Therefore, according to the water-repellent fiber product of this embodiment, the deterioration of the fiber product caused by heat is suppressed, the texture of the fiber product during the water-repellent treatment becomes soft, and the fiber can be treated under mild heat treatment conditions, that is, low-temperature curing conditions. The product imparts sufficient water repellency. Especially when it is desired to improve the durability of water repellency, it is preferable to perform water repellent processing on the fiber product by the following method. The method includes the above steps of processing the fiber product by using a treatment liquid containing a non-fluorine-based water repellent composition. , And a step of heating the methylol melamine, a crosslinking agent represented by a compound having more than one isocyanate group or a blocked isocyanate group, and then heating the fiber product. Furthermore, when it is desired to further improve the durability of water repellency, the non-fluorine-based water-repellent composition preferably contains a non-fluorine-based polymer obtained by copolymerizing a monomer having a functional group capable of reacting with the crosslinking agent. . Examples of the compound having one or more isocyanate groups include monoisocyanates such as butyl isocyanate, phenyl isocyanate, triisocyanate, and naphthalene isocyanate, toluene diisocyanate, diphenylmethane diisocyanate, and tetramethylxylylene dimethionate. Diisocyanates such as isocyanate, hydrogenated diphenylmethane diisocyanate, and the tritrim and trimethylolpropane addition objects of these isocyanurate rings. Examples of the compound having one or more blocked isocyanate groups include compounds in which an isocyanate group of the compound having an isocyanate group is protected by a blocking agent. Examples of the end-capping agent used at this time include organic end-capping agents such as secondary or tertiary alcohols, active methylene compounds, phenols, oximes, and lactams, or sodium bisulfite and bisulfite. Potassium and other bisulfites. These crosslinking agents may be used individually by 1 type, and may be used in combination of multiple types. The cross-linking agent can be, for example, immersed in a treatment liquid (fiber product) in a treatment liquid obtained by dissolving the cross-linking agent in an organic solvent or emulsified and dispersed in water, and drying the treatment liquid adhering to the treatment object. Method to adhere to the object. In addition, by heating the cross-linking agent attached to the object to be processed, the cross-linking agent can react with the object to be processed and the non-fluorine-based polymer. In order to allow the reaction of the cross-linking agent to proceed sufficiently and to improve the washing durability more effectively, the heating at this time may be performed at 110 to 180 ° C. for 1 to 5 minutes. The steps of attaching and heating the crosslinking agent may be performed simultaneously with the step of treating with the treatment liquid containing the water-repellent composition described above. In the case where they are performed at the same time, for example, a treatment liquid containing a water-repellent composition and a cross-linking agent is attached to the object to be treated, the water is removed, and then the cross-linking agent attached to the object is heated. In consideration of simplification of the water-repellent processing step, reduction of heat, and economic efficiency, it is preferably performed simultaneously with the processing step of the water-repellent composition. In addition, if the crosslinking agent is used excessively, the texture may be damaged. The crosslinking agent is preferably used in an amount of 0.1 to 50% by mass, and more preferably used in an amount of 0.1 to 10% by mass based on the object to be treated (fiber product). The water-repellent fiber product of this embodiment obtained in the above manner can sufficiently exert water repellency even when it is used for a long time outdoors. Moreover, the above water-repellent fiber product does not use a fluorine-based compound, so it can be made to the environment. Harmless. The water-repellent fiber product of this embodiment can be applied to a specific portion. Examples of the coating process include moisture-permeable waterproof processing or wind-proof processing for sports or outdoor applications. As a processing method, for example, in the case of moisture-permeable and water-repellent processing, a coating liquid containing a urethane resin or an acrylic resin and a medium may be applied to one side of a water-repellent fiber product and It is dried and processed. As mentioned above, although suitable embodiment of this invention was described, this invention is not limited to the said embodiment. For example, in the case of manufacturing a non-fluorine-based polymer, in the above embodiment, the polymerization reaction is performed by radical polymerization, but it may also be photopolymerized by irradiation with free radiation such as ultraviolet rays, electron beams, and gamma rays. Polymerization is performed. Moreover, in the present invention, a non-fluorine-based water-repellent composition is treated with a fiber product to produce a water-repellent fiber product. However, as a product treated with a non-fluorine-based water-repellent composition, the use of the fiber product is not limited It is metal, glass, resin, etc. In this case, the method of attaching the non-fluorine-based water-repellent composition to the article or the amount of water-repellent agent can be arbitrarily determined according to the type of the object to be treated. [Examples] Hereinafter, the present invention will be further described by examples, but the present invention is not limited by these examples. <Preparation of water repellent assistant> (Synthesis Example 1) A reaction vessel equipped with a stirrer, a thermometer, a reflux cooler, a nitrogen introduction tube, and a dropping funnel was charged with a SiH group equivalent of 63.2 g / mol and a polymerization degree of 50 63.2 g of hydrogen-based polysilicon, nitrogen was allowed to flow, and the mixture was heated and mixed until the temperature became 65 ° C until it became homogeneous. As the hydrosilylation catalyst, a mixed solution of ethylene glycol monobutyl ether-toluene of platinum (IV) chloride was added so that the platinum concentration became 5 ppm with respect to the reactants in the system. When the temperature of the reactant became 120 ° C, 168.3 g of 1-mole 1-dodecene was added dropwise, and reacted at 120 ° C for 6 hours. Confirmation of completion of the addition reaction was performed by performing FT-IR analysis of the obtained organic modified polysiloxane and confirming that the absorption spectrum of the SiH group derived from methylhydrogen polysiloxane has disappeared. In this way, it is obtained that a in the general formula (1) is 0, b is 50, and R is twenty two Methyl, R twenty three Dodecyl, R 30 , R 31 , R 32 , R 33 , R 34 And R 35 It is a methyl modified organic silicone. Further, 3 parts by mass of a 9-mole ethylene oxide adduct of a branched higher alcohol having 12 to 14 carbon atoms was added to 20 parts by mass of the obtained organic modified polysiloxane and mixed. Then, 77 parts by mass of water was added in small amounts one by one and mixed, and emulsified in water to obtain a polysiloxane emulsion. (Synthesis Example 2) An organic modified polysiloxane and a polysiloxane were obtained in the same manner as in Synthesis Example 1 except that 84.2 g of 1-mole 1-hexene was used instead of 168.3 g of 1-mole-1-dodecene. Silicone emulsion. Furthermore, in the above general formula (1) to obtain an organic modified polysiloxane, a is 0, b is 50, and R is twenty two Methyl, R twenty three Hexyl, R 30 , R 31 , R 32 , R 33 , R 34 And R 35 It is a methyl modified organic silicone. (Synthesis Example 3) Except that 252.5 g of 1 mole of 1-octadecene was used instead of 168.3 g of 1 mole of 1-dodecene, 1% of organic modified polysiloxane was obtained in the same manner as in Synthesis Example 1. Polysiloxane emulsion. In addition, in the general formula (1) to obtain the organic modified polysiloxane, a is 0, b is 50, and R is twenty two Methyl, R twenty three Octadecyl, R 30 , R 31 , R 32 , R 33 , R 34 And R 35 It is a methyl modified organic silicone. (Synthesis Example 4) In addition to using 84.2 g of 1-dodecene of 0.5 mol and 59.1 g of α-methylstyrene of 0.5 mol, instead of 168.3 g of 1-dodecene of 1 mol, In the same manner as in Synthesis Example 1, an organic modified polysiloxane and a polysiloxane emulsion were obtained. In addition, in the general formula (1) to obtain the organic modified polysiloxane, a is 0, b is 50, and R is twenty two Methyl, R twenty three Dodecyl or methylstyryl, R 30 , R 31 , R 32 , R 33 , R 34 And R 35 It is a methyl modified organic silicone. (Synthesis Example 5) In addition to 0.5 mole of 1-dodecene 84.2 g and 0.5 mole of 1-octadecene 126.2 g were used instead of 1 mole of 1-dodecene 168.3 g. In the same manner as in Example 1, an organic modified polysiloxane and a polysiloxane emulsion were obtained. In addition, in the general formula (1) to obtain the organic modified polysiloxane, a is 0, b is 50, and R is twenty two Methyl, R twenty three Dodecyl or octadecyl, R 30 , R 31 , R 32 , R 33 , R 34 And R 35 It is a methyl modified organic silicone. (Synthesis Example 6) Instead of a SiH group equivalent of 63.2 g / mol and a degree of polymerization, a copolymer of 140.5 g of a dimethylsiloxane and methylhydrosiloxane having a SiH group equivalent of 140.5 g / mol and a degree of polymerization of 50 was used. An organically modified polysiloxane and a polysiloxane emulsion were obtained in the same manner as in Synthesis Example 1 except that 63.2 g of methylhydrogenpolysiloxane was 50. Furthermore, a of the general formula (1) to obtain the organic modified polysiloxane is 25, b is 25, and R is 20 And R twenty one Methyl, R twenty two Methyl, R twenty three Dodecyl, R 30 , R 31 , R 32 , R 33 , R 34 And R 35 It is a methyl modified organic silicone. (Synthesis Example 7) To 20 parts by mass of hydrogenated polysiloxane (trade name: KF-99, manufactured by Shin-Etsu Chemical Industry Co., Ltd.) was added 9 mol of ethylene oxide, a branched higher alcohol having 12 to 14 carbon atoms. 3 parts by mass of the product were mixed. Then, 77 parts by mass of water was added in small amounts one by one and mixed, and emulsified in water to obtain a polysiloxane emulsion. (Synthesis Example 8) A dimethyl-modified polysiloxane (trade name: KF-96H-300,000 cs, manufactured by Shin-Etsu Chemical Industry Co., Ltd.) was used in place of the hydrogenated polysiloxane except that it was the same as in Synthesis Example 7 The way to obtain polysiloxane emulsion. <Adjustment of Polymer Dispersion Liquid> A polymer dispersion liquid was obtained by polymerizing a mixed liquid having a composition shown in Tables 1 to 6 (in the table, the numerical value (g)) in the order shown below. (Synthesis Example 9) In a 500 mL flask, 60 g of stearyl acrylate, Noigen XL-100 (manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd., polyoxyalkylene branched chain decyl ether, HLB = 14.7), 2 g, Noigen XL-60 (manufactured by Daiichi Kogyo Co., Ltd., polyoxyalkylene branched decyl ether, HLB = 12.5) 2 g, 3 g stearyl dimethylamine hydrochloride, 25 g tripropylene glycol, and 207.70 g water , And mixed at 45 ° C to prepare a mixed solution. This mixture was irradiated with ultrasonic waves to emulsify and disperse the total monomer. Next, 0.3 g of azobis (isobutylphosphonium) dihydrochloride was added to the mixed solution, and radical polymerization was performed at 60 ° C. for 6 hours under a nitrogen environment to obtain a non-fluorine-based polymer having a polymer concentration of 20% by mass. Polymer dispersion. (Synthesis Examples 10 to 36) Except that the materials described in Tables 1 to 6 were used, polymerization was performed in the same manner as in Synthesis Example 9 to obtain non-fluorine polymers having the polymer concentrations shown in Tables 7 to 10, respectively. Dispersions. Furthermore, each polymer in the polymer dispersion liquids obtained in Synthesis Examples 9 to 36 was confirmed to be 98% of the total monomers using a gas chromatograph (GC-15APTF, manufactured by Shimadzu Corporation). % Or more polymerization. The details of the materials shown in Tables 1 to 6 are as follows. Latemul PD-420 (manufactured by Kao Corporation, polyoxyalkylene alkenyl ether, HLB = 12.6) Latemul PD-430 (manufactured by Kao Corporation, polyoxyalkylene alkenyl ether, HLB = 14.4) cardanol 12.5 moles of ethylene oxide (HLB = 12.9, shown in the table as "cardanol 12.5EO") ethylene oxide 8.3 moles of cardanol (HLB = 11.0, in the table, shows "Cardanol 8.3EO") Ethylene oxide 42 mol adduct of castor oil (HLB = 13.3, shown in the table as "castor oil 42EO") Ethylene oxide 30 mol adduct of castor oil (HLB = 11.7, shown in the table as "castor oil 30EO") The "C8 fluorine-containing acrylate" in the table is represented by the following general formula (III):
Figure TW201803964AD00018
A mixture in which the average value of n is 8 (in addition, a compound in which n is 6, 8, 10, 12, 14 is mixed in the mixture). The polymer dispersion obtained above and the polymer obtained by the method shown below were evaluated. (Evaluation of the physical properties of the polymer) 500 mL of acetone was added to 50 g of the polymer dispersion obtained in Synthesis Examples 9 to 36, thereby separating the polymer from the emulsifier and filtering the polymer to obtain the polymer. It was dried under reduced pressure at 25 ° C for 24 hours. The obtained polymer was evaluated in the following manner. The results are shown in Tables 7 to 10. (1) Measurement method of melt viscosity For the polymer obtained above, an overhead rheometer CFT-500 (manufactured by Shimadzu Corporation) was used in a cylinder equipped with a mold (length 10 mm, diameter 1 mm). Add 1 g of polymer, hold it at 105 ° C for 6 minutes, and apply 100 kg · f / cm with a plunger 2 After the load, the melt viscosity at 105 ° C was measured. (2) Method for measuring weight average molecular weight For the polymer obtained above, a GPC (Gel Permeation Chromatograph, gel permeation chromatography) device (GPC "HLC-8020" manufactured by Tosoh Co., Ltd.) was used on a column The eluate was measured using tetrahydrofuran at a temperature of 40 ° C and a flow rate of 1.0 ml / min, and the weight average molecular weight was measured in terms of standard polystyrene. In addition, the pipe string is connected to and installed by three TSK-GEL G5000HHR, G4000HHR, and G3000HHR trade names manufactured by Tosoh Co., Ltd. <Adjustment of Water Repellent Composition> (Examples 1 to 37 and Comparative Examples 1 to 9) The water repellent additives (polysiloxane emulsions) obtained in Synthesis Examples 1 to 8 and Synthesis Examples 9 to 36 were used The obtained polymer dispersion was mixed at the mass ratios shown in Tables 11 to 15 to prepare a water-repellent composition. The water repellent composition obtained above was evaluated. (Evaluation of water repellency of fiber products) The test was performed by setting the shower water temperature to 27 ° C according to the spray method according to JIS L 1092 (1998). In this test, 100% of polyester or 100% of nylon after dyeing is used to dilute the water-repellent composition of the examples and comparative examples with water so that the polymer content becomes 3% by mass. The treatment liquid was immersed (60% by mass pick-up), and then dried at 130 ° C for 2 minutes, and then heat-treated under the conditions shown in Tables 7 to 10 to evaluate the water repellency of the obtained cloth. The results were evaluated visually on the following scale. Furthermore, "+" is attached to the rank when the characteristics are slightly better, and "-" is attached to the rank when the characteristics are slightly worse. The results are shown in Tables 16 to 22. Water repellency: State 5: There is no wet and adherent on the surface 4: Wet slightly adhered to the surface 3: Wet partially displayed on the surface 2: Wet on the surface 1: Wet on the entire surface 0: Both sides of the front and back are completely Wet person (texture evaluation of the fiber product) The texture uses 100% of the polyester after dyeing, and the water-repellent composition of the examples and comparative examples is used so that the polymer content becomes 3% by mass. The dilute treatment liquid was subjected to an immersion treatment (pickup rate of 60% by mass), and then dried at 130 ° C for 2 minutes and further heat-treated at 170 ° C for 30 seconds to evaluate. The results were evaluated by operation at five levels shown below. The results are shown in Tables 16 to 22. 1: Hard to 5: Flexible (evaluation of durable water repellency of fiber products) The spray water method according to JIS L 1092 (1998) was used to test the shower water temperature at 27 ° C. In this test, 100% of the polyester after dyeing was distributed in the same manner as the water repellency evaluation method described above, with a polymer content of 3% by mass, UNIKA RESIN 380-K (crosslinking agent, Union Chemical Industry Co., Ltd., trimethylol melamine resin) content was 0.3% by mass and UNIKA CATALYST 3-P (surfactant, manufactured by Union Chemical Industry Co., Ltd., amine alcohol hydrochloride) was 0.2 mass% In the method, the water-repellent composition of the examples and comparative examples and the above-mentioned respective agents were diluted with water, and then subjected to an immersion treatment (pickup rate: 60% by mass), and then dried at 130 ° C for 2 minutes, The cloth (L-0) obtained by heat treatment at 170 ° C for 60 seconds, and the water repellency of the cloth after washing 10 times (L-10) based on the 103 method of JIS L 0217 (1995) were evaluated. In the case of 100% nylon cloth, the heat treatment temperature was changed from 170 ° C to 160 ° C. The evaluation was performed in the same manner as in the case of 100% polyester cloth. The results are shown in Tables 16 to 22. (Peel strength of the fiber product against the coating layer) The test was performed in accordance with JIS K 6404-5 (1999). In this test, 100% of nylon after dyeing is applied to a treatment liquid obtained by diluting the water-repellent composition of the examples and comparative examples with water so that the polymer content becomes 3% by mass. After the immersion treatment (pickup rate: 60% by mass), it was dried at 130 ° C. for 2 minutes, and further heat-treated at 160 ° C. for 30 seconds to obtain a base fabric. Using a thermocompression bonding device, a thermofusion tape ("MELCO TAPE" manufactured by SANKASEI Co., Ltd.) was thermocompression-bonded to the obtained base cloth at 150 ° C for 1 minute, and Autograph (AG-IS, Shimadzu Corporation (stock) Manufacture)) The peel strength between the base fabric and the seam tape was measured. The moving speed of the jig was pulled at 100 mm / min, and the average value of the stress was taken as the peel strength [N / inch]. The results are shown in Tables 16 to 22. [Table 1] [Table 2] [Table 3] [Table 4] [Table 5] [Table 6] [Table 7] [Table 8] [Table 9] [Table 10] [Table 11] [Table 12] [Table 13] [Table 14] [Table 15] [Table 16] [Table 17] [Table 18] [Table 19] [Table 20] [Table 21] [Table 22] The water-repellent agents of Examples 1 to 37 were confirmed After the composition is processed, the fiber product exhibits the same effect as the previous fluorine-based water-repellent agent (Comparative Example 7) and uses only the organic modified polysiloxane represented by the general formula (1) even when the fiber product is not heat-treated. (Comparative Example 8) In the case of the same or higher water repellency, the water repellency is excellent and the texture is also good. In addition, it was confirmed that the fiber products treated with the water-repellent composition of Examples 1 to 37 exhibited and used the water-repellent composition that did not contain the organic modified polysiloxane represented by the general formula (1) (comparison) In the case of Example 9), the water repellency is equal to or higher than the above, and the water repellency is excellent, and the peeling strength to the resin coating is more excellent. The water-repellent composition of Comparative Examples 1 to 6 uses a polysiloxane other than the organic modified polysiloxane represented by the above-mentioned general formula (1), and tends to have particularly poor water repellency. [Industrial Applicability] According to the present invention, it is possible to provide a water-repellent auxiliary agent capable of improving the durable water repellency of a non-fluorine-based water-repellent agent and a non-fluorine-based water-repellent agent composition containing the same.

無no

Claims (10)

一種撥水助劑，其係非氟系撥水劑用之撥水助劑，且包含下述通式(1)所表示之有機改性聚矽氧， [化1]
Figure TW201803964AC00001
[式(1)中，R20 、R21 及R22 分別獨立地表示氫原子、甲基、乙基或碳數1～4之烷氧基，R23 表示具有芳香族環之碳數8～40之烴基或碳數3～22之烷基，R30 、R31 、R32 、R33 、R34 及R35 分別獨立地表示氫原子、甲基、乙基、碳數1～4之烷氧基、具有芳香族環之碳數8～40之烴基或碳數3～22之烷基，a表示0以上之整數，b表示1以上之整數，(a＋b)為10～200，於a為2以上之情形時，存在有複數個之R20 及R21 可分別相同，亦可不同，於b為2以上之情形時，存在有複數個之R22 及R23 可分別相同，亦可不同]。A water-repellent auxiliary agent, which is a water-repellent auxiliary agent for a non-fluorine-based water-repellent agent, and contains an organic modified polysiloxane represented by the following general formula (1), [化 1]
Figure TW201803964AC00001
[In formula (1), R 20 , R 21, and R 22 each independently represent a hydrogen atom, a methyl group, an ethyl group, or an alkoxy group having 1 to 4 carbon atoms, and R 23 represents an 8 to 6 carbon atom having an aromatic ring. A hydrocarbon group of 40 or an alkyl group having 3 to 22 carbon atoms, and R 30 , R 31 , R 32 , R 33 , R 34, and R 35 each independently represent a hydrogen atom, a methyl group, an ethyl group, and an alkyl group having 1 to 4 carbon atoms An oxygen group, a hydrocarbon group having 8 to 40 carbon atoms or an alkyl group having 3 to 22 carbon atoms having an aromatic ring, a represents an integer of 0 or more, b represents an integer of 1 or more, (a + b) is 10 to 200, and a is In the case of 2 or more, a plurality of R 20 and R 21 may be the same or different, and when b is 2 or more, the R 22 and R 23 may be the same or different. ]. 一種非氟系撥水劑組合物，其包含如請求項1之撥水助劑與非氟系撥水劑。A non-fluorine-based water repellent composition comprising the water-repellent auxiliary agent according to claim 1 and a non-fluorine-based water-repellent agent. 如請求項2之非氟系撥水劑組合物，其中上述非氟系撥水劑包含具有源自下述通式(A-1)所表示之(甲基)丙烯酸酯單體(A)之結構單元之非氟系聚合物， [化2]
Figure TW201803964AC00002
[式(A-1)中，R1 表示氫或甲基，R2 表示亦可具有取代基之碳數12以上之1價烴基]。The non-fluorine-based water-repellent composition according to claim 2, wherein the above-mentioned non-fluorine-based water-repellent agent comprises a polymer having a (meth) acrylic acid ester monomer (A) derived from the following general formula (A-1) Non-fluorinated polymer of structural unit, [Chem 2]
Figure TW201803964AC00002
[In the formula (A-1), R 1 represents hydrogen or a methyl group, and R 2 represents a monovalent hydrocarbon group having 12 or more carbon atoms which may have a substituent]. 如請求項3之非氟系撥水劑組合物，其中上述非氟系聚合物進而含有源自選自(B1)HLB為7～18之下述通式(I-1)所表示之化合物、(B2)HLB為7～18之下述通式(II-1)所表示之化合物、及(B3)HLB為7～18之對具有羥基及聚合性不飽和基之油脂加成碳數2～4之環氧烷而成之化合物中之至少1種反應性乳化劑(B)之結構單元， [化3]
Figure TW201803964AC00003
[式(I-1)中，R3 表示氫或甲基，X表示碳數1～6之直鏈或者支鏈之伸烷基，Y1 表示包含碳數2～4之伸烷基氧基之2價基] [化4]
Figure TW201803964AC00004
[式(II-1)中，R4 表示具有聚合性不飽和基之碳數13～17之1價不飽和烴基，Y2 表示包含碳數2～4之伸烷基氧基之2價基]。The non-fluorine-based water-repellent composition according to claim 3, wherein the non-fluorine-based polymer further comprises a compound derived from the following general formula (I-1) selected from (B1) HLB of 7 to 18, (B2) A compound represented by the following general formula (II-1) having an HLB of 7 to 18, and (B3) an addition carbon number of 2 or more to an oil or fat having a hydroxyl group and a polymerizable unsaturated group with an HLB of 7 to 18 The structural unit of at least one reactive emulsifier (B) in the compound made of alkylene oxide of [4]
Figure TW201803964AC00003
[In the formula (I-1), R 3 represents hydrogen or a methyl group, X represents a linear or branched alkylene group having 1 to 6 carbon atoms, and Y 1 represents an alkylene oxide group having 2 to 4 carbon atoms. 2-valent base] [Chemical 4]
Figure TW201803964AC00004
[In formula (II-1), R 4 represents a monovalent unsaturated hydrocarbon group having 13 to 17 carbon atoms having a polymerizable unsaturated group, and Y 2 represents a divalent group containing an alkyleneoxy group having 2 to 4 carbon atoms. ]. 如請求項3或4之非氟系撥水劑組合物，其中上述非氟系聚合物進而含有源自氯乙烯及偏二氯乙烯中之至少任1種單體(E)之結構單元。The non-fluorine-based water-repellent composition according to claim 3 or 4, wherein the non-fluorine-based polymer further contains a structural unit derived from at least any one of monomers (E) in vinyl chloride and vinylidene chloride. 如請求項2之非氟系撥水劑組合物，其中上述非氟系撥水劑包含使包含下述通式(A-1)所表示之(甲基)丙烯酸酯單體(A)之乳化物或分散物乳化聚合或分散聚合而成之非氟系聚合物， [化5]
Figure TW201803964AC00005
[式(A-1)中，R1 表示氫或甲基，R2 表示亦可具有取代基之碳數12以上之1價烴基]。The non-fluorine-based water-repellent composition according to claim 2, wherein the non-fluorine-based water-repellent agent comprises emulsifying a (meth) acrylate monomer (A) containing the (meth) acrylate monomer represented by the following general formula (A-1) Polymers or dispersions of non-fluorinated polymers, [Chem. 5]
Figure TW201803964AC00005
[In the formula (A-1), R 1 represents hydrogen or a methyl group, and R 2 represents a monovalent hydrocarbon group having 12 or more carbon atoms which may have a substituent]. 如請求項6之非氟系撥水劑組合物，其中上述乳化物或上述分散物進而包含選自(B1)HLB為7～18之下述通式(I-1)所表示之化合物、(B2)HLB為7～18之下述通式(II-1)所表示之化合物、及(B3)HLB為7～18之對具有羥基及聚合性不飽和基之油脂加成碳數2～4之環氧烷而成之化合物中之至少1種反應性乳化劑(B)， [化6]
Figure TW201803964AC00006
[式(I-1)中，R3 表示氫或甲基，X表示碳數1～6之直鏈或者支鏈之伸烷基，Y1 表示包含碳數2～4之伸烷基氧基之2價基] [化7]
Figure TW201803964AC00007
[式(II-1)中，R4 表示具有聚合性不飽和基之碳數13～17之1價不飽和烴基，Y2 表示包含碳數2～4之伸烷基氧基之2價基]。The non-fluorine-based water-repellent composition according to claim 6, wherein the emulsion or the dispersion further comprises a compound represented by the following general formula (I-1) selected from (B1) an HLB of 7 to 18, ( B2) A compound represented by the following general formula (II-1) having an HLB of 7 to 18, and (B3) an addition carbon number of 2 to 4 to an oil or fat having a hydroxyl group and a polymerizable unsaturated group with an HLB of 7 to 18 At least one type of reactive emulsifier (B) in compounds made of alkylene oxide, [Chem. 6]
Figure TW201803964AC00006
[In the formula (I-1), R 3 represents hydrogen or a methyl group, X represents a linear or branched alkylene group having 1 to 6 carbon atoms, and Y 1 represents an alkylene oxide group having 2 to 4 carbon atoms. 2-valent base] [Chem. 7]
Figure TW201803964AC00007
[In formula (II-1), R 4 represents a monovalent unsaturated hydrocarbon group having 13 to 17 carbon atoms having a polymerizable unsaturated group, and Y 2 represents a divalent group containing an alkyleneoxy group having 2 to 4 carbon atoms. ]. 如請求項6或7之非氟系撥水劑組合物，其中上述乳化物或上述分散物進而包含氯乙烯及偏二氯乙烯中之至少任1種單體(E)。The non-fluorine-based water-repellent composition according to claim 6 or 7, wherein the emulsion or the dispersion further contains at least any one of monomers (E) of vinyl chloride and vinylidene chloride. 如請求項3至8中任一項之非氟系撥水劑組合物，其中上述有機改性聚矽氧之含量相對於上述非氟系聚合物100質量份為1～50質量份。The non-fluorine-based water-repellent composition according to any one of claims 3 to 8, wherein the content of the organically modified polysiloxane is 1 to 50 parts by mass relative to 100 parts by mass of the non-fluorine-based polymer. 一種撥水性纖維製品之製造方法，其具備利用包含如請求項2至9中任一項之非氟系撥水劑組合物之處理液對纖維製品進行處理之步驟。A method for producing a water-repellent fiber product, comprising the step of treating the fiber product with a treatment liquid containing a non-fluorine-based water-repellent composition according to any one of claims 2 to 9.
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