TWI724154B - Fiber treatment agent, method for manufacturing fiber processed product, and fiber processed product - Google Patents
Fiber treatment agent, method for manufacturing fiber processed product, and fiber processed product Download PDFInfo
- Publication number
- TWI724154B TWI724154B TW106112401A TW106112401A TWI724154B TW I724154 B TWI724154 B TW I724154B TW 106112401 A TW106112401 A TW 106112401A TW 106112401 A TW106112401 A TW 106112401A TW I724154 B TWI724154 B TW I724154B
- Authority
- TW
- Taiwan
- Prior art keywords
- fiber
- treatment agent
- fiber treatment
- unsaturated monomer
- meth
- Prior art date
Links
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
- D06M15/27—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof of alkylpolyalkylene glycol esters of unsaturated carboxylic acids
-
- 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
- D06M15/356—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
Description
本發明係關於對纖維可賦予阻燃性及防鏽性的纖維處理劑、使用該纖維處理劑的纖維加工品之製造方法及使用該纖維加工品之製造方法所得之纖維加工品。 The present invention relates to a fiber processing agent capable of imparting flame retardancy and rust resistance to fibers, a method for manufacturing a fiber processed product using the fiber processing agent, and a fiber processed product obtained using the method for manufacturing the fiber processed product.
近年來對於使用於建築材料或家電、電子材料、汽車等車輛內裝材等用途的纖維加工品之難燃化被要求著。又，對於如此纖維加工品，作為物性提高劑及接著劑，廣泛使用含有合成樹脂及各種添加劑之纖維處理劑。欲得到如前述之難燃纖維加工品，於纖維賦予阻燃性或防鏽性的纖維處理劑被期待。如此纖維處理劑之開發正進行者。 In recent years, there has been a demand for flame-retardant fiber processed products used in construction materials, home appliances, electronic materials, automobile interior materials, and other applications. In addition, for such processed fiber products, fiber treatment agents containing synthetic resins and various additives are widely used as physical property improvers and adhesives. In order to obtain the flame-retardant fiber processed product as described above, a fiber treatment agent that imparts flame retardancy or rust resistance to the fiber is expected. The development of such a fiber treatment agent is in progress.
一般作為將纖維進行難燃化的方法，主要可舉出於纖維處理劑添加阻燃劑的方法。作為如此阻燃劑，例如已知有紅磷或磷酸鹽、三氧化銻、氫氧化鋁、氫氧化 鎂等無機系阻燃劑；五溴聯苯基、八溴聯苯基、十溴聯苯基等鹵素系阻燃劑；磷酸胍、三苯基磷酸鹽、胺基磺酸等非鹵素阻燃劑等。 Generally, as a method of making fibers flame-retardant, a method of adding a flame retardant to a fiber treatment agent is mainly cited. As such flame retardants, for example, red phosphorus or phosphate, antimony trioxide, aluminum hydroxide, and hydroxide are known. Inorganic flame retardants such as magnesium; halogen flame retardants such as pentabromobiphenyl, octabrombiphenyl, and decabrombiphenyl; non-halogen flame retardants such as guanidine phosphate, triphenyl phosphate, and aminosulfonic acid剂 etc.
然而，這些阻燃劑一般與纖維處理劑中之合成樹脂的相溶性上有著問題，對於纖維加工品的阻燃劑成分有時會引起分離、沈澱及嗆人的現象。 However, these flame retardants generally have problems with the compatibility of synthetic resins in fiber treatment agents, and the flame retardant components of fiber processed products sometimes cause separation, precipitation, and choking.
且，對於含有合成樹脂之纖維處理劑，期待使用這些阻燃劑時，如此纖維處理劑不僅對於纖維加工品賦予阻燃性，對於強度或質地、防鏽性等纖維加工品的其他各種物性亦不會有壞影響。然而，一般為了對纖維加工品賦予阻燃性時必須添加多量阻燃劑，故成為阻礙纖維加工品之物性的原因。 In addition, for fiber treatment agents containing synthetic resins, when these flame retardants are expected to be used, such fiber treatment agents not only impart flame retardancy to processed fiber products, but also provide various other physical properties of fiber processed products such as strength, texture, and rust resistance. There will be no bad effects. However, it is generally necessary to add a large amount of flame retardant in order to impart flame retardancy to processed fiber products, which is a cause of hindering the physical properties of processed fiber products.
特別為無機系阻燃劑缺乏難燃化性能，對纖維處理劑必須多量地添加，故因與合成樹脂等其他添加劑成分的比重差而容易產生沈澱物。又，使用無機系阻燃劑的纖維加工品中，有著亦容易使質地變硬的問題。 In particular, the inorganic flame retardant lacks inflammability performance and must be added in a large amount to the fiber treatment agent. Therefore, it is easy to generate deposits due to the difference in specific gravity with other additive components such as synthetic resin. In addition, fiber processed products using inorganic flame retardants also have a problem that they tend to harden their texture.
另一方面，鹵素系阻燃劑因具有優良難燃化性能，對纖維處理劑添加少量即可。由此得知使用含有這些之纖維處理劑對於進行加工的纖維加工品之物性的影響為少。然而，因含有如氯或溴之鹵素元素，燃燒使用這些的纖維加工品時，恐怕會產生稱為二噁英或鹵化氫的有害物質，在以EU各國為主的世界各國已重新規定其規制或使用方式。 On the other hand, halogen-based flame retardants have excellent flame retardancy properties, so a small amount of fiber treatment agent may be added. From this, it is understood that the use of fiber processing agents containing these has little effect on the physical properties of processed fiber processed products. However, due to the presence of halogen elements such as chlorine or bromine, when these fiber processed products are burned and used, hazardous substances called dioxins or hydrogen halides may be generated. Countries around the world, mainly EU countries, have re-regulated their regulations. Or how to use it.
非鹵素系阻燃劑與鹵素系阻燃劑比較，因具 有優良安全性，故以磷系為主的多數阻燃劑被檢討。然而，磷系阻燃劑的難燃化性能必須比鹵素系的阻燃劑更低且需要使用比較多量。因此，含有磷系阻燃劑之纖維處理劑會降低使用該纖維處理劑進行加工之纖維加工品的物性。例如水溶性磷系阻燃劑的潮解性高，外觀上可使樹脂可塑化，故成為降低使用此等纖維加工品之強度、質地的原因。又，油溶性磷系阻燃劑亦藉由樹脂可塑化或對纖維處理劑表面的滲出(Bleeding)，不僅使強度、質地降低，亦成為在使用該纖維處理劑之纖維加工品產生發黏性或嗆人之原因。 Comparing non-halogen flame retardant with halogen flame retardant, it has With excellent safety, most flame retardants mainly based on phosphorus have been reviewed. However, the flame retardancy of the phosphorus-based flame retardant must be lower than that of the halogen-based flame retardant and a relatively large amount must be used. Therefore, the fiber treatment agent containing the phosphorus-based flame retardant reduces the physical properties of the fiber processed product processed with the fiber treatment agent. For example, water-soluble phosphorus-based flame retardants have high deliquescent properties and can plasticize the resin in appearance, which is the cause of reducing the strength and texture of processed fiber products. In addition, the oil-soluble phosphorus flame retardant is also plasticized by the resin or bleeding on the surface of the fiber treatment agent, which not only reduces the strength and texture, but also becomes sticky in the fiber processing product using the fiber treatment agent. Or choking.
又，作為對纖維賦予防鏽性的方法，主要可舉出於纖維處理劑添加防鏽劑之方法。例如已知有亞硝酸鹽、鉻酸鹽、磷酸鹽、矽酸鹽等無機系防鏽劑；烷基磺酸或苯磺酸之鋇鹽、鋇皂、有機胺之羧酸鹽、安息香酸鹽等有機系防鏽劑。 In addition, as a method of imparting anti-rust properties to fibers, a method of adding an anti-rust agent to a fiber treatment agent is mainly cited. For example, there are known inorganic rust inhibitors such as nitrite, chromate, phosphate, silicate; barium salt of alkyl sulfonic acid or benzene sulfonic acid, barium soap, carboxylate of organic amine, benzoate And other organic rust inhibitors.
無機系防鏽劑與有機系防鏽劑相比較，因具有優良防鏽性，故多被討論。然而，一般而言，於無機系防鏽劑中含有對人體有害的物質，恐怕對環境造成影響。例如雖已知亞硝酸鹽顯示高防鏽性，但被指出對人體之有害性，故要求無亞硝酸之防鏽劑。又雖已知鉻酸鹽亦顯示同様高防鏽性，但含有重金屬，故與亞硝酸鹽同様地對人體具有有害性且在該處理過程中有著排水規制等，於現今避免使用。 Compared with organic rust inhibitors, inorganic rust inhibitors are often discussed because of their superior rust resistance. However, in general, inorganic rust inhibitors contain substances harmful to the human body, which may affect the environment. For example, although nitrite is known to show high rust resistance, it is pointed out that it is harmful to the human body, so nitrite-free rust inhibitors are required. Although it is known that chromate also shows high rust resistance, but contains heavy metals, it is harmful to the human body as nitrite and has drainage regulations during the treatment process, so it is avoided nowadays.
有機系防鏽劑為欲解如在前述無機系防鏽劑 被指摘對人體有害性或環境負荷之課題者，而廣泛地被使用。作為顯示高防鏽性的有機系防鏽劑，例如已知有烷基磺酸或苯磺酸之鋇鹽、鋇皂等，但近年來有指出鋇鹽對人體造成有害性，故對於該使用方式在歐美有著規制。烷基琥珀酸半酯、烯基琥珀酸半酯等各種羧酸酯雖顯示一定防鏽性，但並非充分。另一方面，已知安息香酸鹽顯示防鏽性，亦使用於汽車引擎用的預防冷凍卻液之添加劑等。又，一般而言，安息香酸鹽對於人體之影響為輕微，有著使用於食品保存料等，與無機系防鏽劑相比其環境負荷較低的優點。然而，一般有機系防鏽劑為可燃性，使用此等之纖維處理劑時，成為降低纖維加工品阻燃性之原因。 The organic rust inhibitor is the inorganic rust inhibitor as mentioned above. Those who have been accused of harmfulness to the human body or environmental impact, and are widely used. As organic rust inhibitors showing high rust resistance, for example, barium salts of alkyl sulfonic acid or benzene sulfonic acid, barium soap, etc. are known, but in recent years, it has been pointed out that barium salts are harmful to the human body. The way is regulated in Europe and America. Although various carboxylic acid esters such as alkyl succinic acid half ester and alkenyl succinic acid half ester show certain anti-rust properties, they are not sufficient. On the other hand, it is known that benzoate has anti-rust properties, and is also used as an additive to prevent freezing liquid in automobile engines. In addition, generally speaking, benzoate has a slight effect on the human body, and it has the advantage of being used in food preservation materials, etc., and having a lower environmental load than inorganic rust inhibitors. However, general organic rust inhibitors are flammable, and when these fiber treatment agents are used, it becomes a cause of reducing the flame retardancy of processed fiber products.
例如於專利文獻1所揭示的具有磷酸基或亞磷酸基骨架之不飽和單體、丙烯酸系不飽和單體與乙酸乙烯基單體經共聚合的非鹵素系阻燃性樹脂組成物已被提案，但使用該阻燃性樹脂組成物的加工品其強度、剛軟性並未令人満足，期待物性能進一步地提高。 For example, a non-halogen flame-retardant resin composition in which an unsaturated monomer having a phosphoric acid group or a phosphorous acid group skeleton, an acrylic unsaturated monomer and a vinyl acetate monomer are copolymerized as disclosed in Patent Document 1 has been proposed However, the strength and rigidity of processed products using the flame-retardant resin composition are not satisfactory, and further improvement of the properties is expected.
又，例如於專利文獻2中雖揭示使用阻燃性樹脂組成物之加工品，但未揭示有關防鏽性。期待可得到兼具阻燃性與防鏽性之加工品的纖維處理劑。 Also, for example, Patent Document 2 discloses a processed product using a flame-retardant resin composition, but does not disclose the rust resistance. It is expected that a fiber treatment agent that has both flame retardancy and anti-rust properties can be obtained.
[專利文獻1]日本特開平7-18028號公報 [Patent Document 1] Japanese Patent Application Laid-Open No. 7-18028
[專利文獻2]日本專利第5669363號公報 [Patent Document 2] Japanese Patent No. 5669363
因此，本發明為提供可得到同時具有優良阻燃性及防鏽性之處理加工品的纖維處理劑。又，本發明之其他目的為使用該纖維處理劑的纖維加工品之製造方法及使用該纖維加工品之製造方法所得的纖維加工品。 Therefore, the present invention is to provide a fiber treatment agent that can obtain processed products having excellent flame retardancy and rust resistance at the same time. In addition, another object of the present invention is a method of manufacturing a fiber processed product using the fiber processing agent and a fiber processed product obtained using the method of manufacturing the fiber processed product.
即，本發明係關於以下[1]~[11]。 That is, the present invention relates to the following [1] to [11].
[1]其為含有含磷不飽和單體(A)與聚合性不飽和單體(B)之共聚物(P)、防鏽劑(C)與阻燃劑(D)的纖維處理劑，前述聚合性不飽和單體(B)為含有(甲基)丙烯酸烷基酯不飽和單體(b1)與選自由(甲基)丙烯酸及衣康酸所成群的至少一種不飽和單體(b2)者為特徴之纖維處理劑。 [1] It is a fiber treatment agent containing a copolymer (P) of a phosphorus-containing unsaturated monomer (A) and a polymerizable unsaturated monomer (B), a rust inhibitor (C), and a flame retardant (D), The aforementioned polymerizable unsaturated monomer (B) contains an alkyl (meth)acrylate unsaturated monomer (b1) and at least one unsaturated monomer selected from the group consisting of (meth)acrylic acid and itaconic acid ( b2) is a special fiber treatment agent.
[2]前述含磷不飽和單體(A)為含有具有磷酸基或亞磷酸基之單體(a1)的上述[1]所記載的纖維處理劑。 [2] The phosphorus-containing unsaturated monomer (A) is the fiber treatment agent described in [1] above containing a monomer (a1) having a phosphoric acid group or a phosphorous acid group.
[3]具有前述磷酸基或亞磷酸基之單體(a1)為含有酸．磷氧基聚氧烷二醇單(甲基)丙烯酸酯之上述[2]所記載的纖維處理劑。 [3] The monomer (a1) having the aforementioned phosphoric acid group or phosphorous acid group contains an acid. The fiber treatment agent described in the above [2] of phosphoroxypolyoxyalkylene glycol mono(meth)acrylate.
[4]前述防鏽劑(C)為含有胺之羧酸鹽、安息香酸鹽的上述[1]~[3]中任一所記載的纖維處理劑。 [4] The rust inhibitor (C) is the fiber treatment agent described in any one of [1] to [3] containing amine carboxylate and benzoate.
[5]前述阻燃劑(D)為含有磷之上述[1]~[4]中任一所 記載的纖維處理劑。 [5] The aforementioned flame retardant (D) is any one of the above [1] ~ [4] containing phosphorus The described fiber treatment agent.
[6]含有前述聚合性不飽和單體(B)對於共聚物(P)中之全單體為40質量%以上的上述[1]~[5]中任一所記載的纖維處理劑。 [6] The fiber treatment agent described in any one of the above [1] to [5] containing 40% by mass or more of the polymerizable unsaturated monomer (B) with respect to all monomers in the copolymer (P).
[7]含有前述防鏽劑(C)對於全纖維處理劑為0.1~15質量%的上述[1]~[6]中任一所記載的纖維處理劑。 [7] The fiber treatment agent described in any one of [1] to [6] containing 0.1 to 15% by mass of the rust inhibitor (C) to the total fiber treatment agent.
[8]含有前述阻燃劑(D)對於全纖維處理劑為0.1~70質量%之上述[1]~[7]中任一所記載的纖維處理劑。 [8] The fiber treatment agent described in any one of [1] to [7] containing 0.1 to 70% by mass of the flame retardant (D) to the total fiber treatment agent.
[9]纖維處理劑中之磷原子量為0.01~30質量%之上述[1]~[8]中任一所記載的纖維處理劑。 [9] The fiber treatment agent described in any one of [1] to [8] above, in which the phosphorus atomic weight in the fiber treatment agent is 0.01 to 30% by mass.
[10]具有使用上述[1]~[9]中任一所記載的纖維處理劑處理纖維基材，得到纖維加工品之步驟的纖維加工品之製造方法。 [10] A method for manufacturing a fiber processed product having a step of treating a fiber base material with the fiber processing agent described in any one of [1] to [9] to obtain a fiber processed product.
[11]乾燥後的上述[1]~[9]中任一所記載的纖維處理劑之附著量對於纖維基材100質量份而言為50~100質量份之纖維加工品。 [11] After drying, the adhesion amount of the fiber treatment agent described in any one of [1] to [9] is 50 to 100 parts by mass of the fiber processed product with respect to 100 parts by mass of the fiber base material.
以本發明之纖維處理劑進行處理的加工品具有優良阻燃性，且同時具有優良的防鏽性。藉由使用該纖維處理劑的纖維加工品之製造方法所得的纖維加工品同時具有阻燃性及防鏽性，故可作為家電、電子材料、汽車內裝材用途之纖維用素材適用。 The processed product treated with the fiber treatment agent of the present invention has excellent flame retardancy and at the same time has excellent rust resistance. The fiber processed product obtained by the method of manufacturing fiber processed product using the fiber treatment agent has both flame retardancy and rust resistance, so it can be used as a fiber material for home appliances, electronic materials, and automotive interior materials.
以下詳細說明本發明。 The present invention will be described in detail below.
本發明之纖維處理劑含有含磷不飽和單體(A)與聚合性不飽和單體(B)之共聚物(P)、防鏽劑(C)及阻燃劑(D)。 The fiber treatment agent of the present invention contains a copolymer (P) of a phosphorus-containing unsaturated monomer (A) and a polymerizable unsaturated monomer (B), a rust inhibitor (C), and a flame retardant (D).
有關本實施的形態之纖維處理劑，對於經處理的加工品同時具有優良的阻燃性與防鏽性雙方，作為纖維用之難燃處理劑為有用，可適用於各種纖維上。 The fiber treatment agent of the aspect of this embodiment has both excellent flame retardancy and rust resistance for processed processed products, is useful as a flame retardant treatment agent for fibers, and can be applied to various fibers.
其中，本說明書中之「~」表示在「~」之記載前的值以上，在「~」之記載後的值以下的意思。 Among them, "~" in this manual means more than the value before the description of "~" and below the value after the description of "~".
又，於本說明書中之「(甲基)丙烯酸酯」等記載與「丙烯酸酯及/或甲基丙烯酸酯」等同義。 In addition, the description of "(meth)acrylate" etc. in this specification is synonymous with "acrylate and/or methacrylate".
有關本發明之共聚物(P)為聚合含磷不飽和單體(A)與聚合性不飽和單體(B)而得之共聚物。 The copolymer (P) related to the present invention is a copolymer obtained by polymerizing a phosphorus-containing unsaturated monomer (A) and a polymerizable unsaturated monomer (B).
於本發明中所使用的含磷不飽和單體(A)若為於分子中含有乙烯性不飽和鍵與磷原子者即可，並無特別限制。 The phosphorus-containing unsaturated monomer (A) used in the present invention is not particularly limited as long as it contains an ethylenic unsaturated bond and a phosphorus atom in the molecule.
作為前述含磷不飽和單體(A)之具體例子，可舉出二 甲基乙烯基膦酸酯、二乙基乙烯基膦酸酯、二苯基乙烯基膦酸酯、二苯基乙烯基膦酸酯、二甲基(1,2-二苯基-乙烯基)膦酸酯、二甲基-p-乙烯基苯甲基膦酸酯、二乙基-p-乙烯基苯甲基膦酸酯、二苯基-p-乙烯基苯甲基膦氧化物、9,10-二氫-9-氧雜-10-膦菲-10-氧化物-10-p-乙烯基苯甲基、酸‧磷氧基乙基(甲基)丙烯酸酯、2-丙烯醯氧基乙基酸磷酸酯、二苯基-2-甲基丙烯醯氧乙基磷酸酯、(甲基)丙烯醯基．氧基乙基酸磷酸酯．單乙醇胺酯、酸‧磷氧基聚氧乙二醇單(甲基)丙烯酸酯及酸‧磷氧基聚氧丙二醇(甲基)丙烯酸酯以及這些金屬鹽、銨鹽及胺鹽等。這些化合物可單獨使用或亦可作為二種以上之混合物使用。 As specific examples of the aforementioned phosphorus-containing unsaturated monomer (A), two Methyl vinyl phosphonate, diethyl vinyl phosphonate, diphenyl vinyl phosphonate, diphenyl vinyl phosphonate, dimethyl (1,2-diphenyl-vinyl) Phosphonate, dimethyl-p-vinyl benzyl phosphonate, diethyl-p-vinyl benzyl phosphonate, diphenyl-p-vinyl benzyl phosphine oxide, 9 ,10-Dihydro-9-oxa-10-phosphinphenanthrene-10-oxide-10-p-vinylbenzyl, acid‧phosphooxyethyl (meth)acrylate, 2-propenyloxy Ethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate, (meth)acryloyl. Oxyethyl acid phosphate. Monoethanolamine ester, acid‧phosphooxypolyoxyethylene glycol mono(meth)acrylate and acid‧phosphooxypropyleneglycol (meth)acrylate and these metal salts, ammonium salts and amine salts, etc. These compounds can be used alone or as a mixture of two or more kinds.
作為前述含磷不飽和單體(A)，以具有磷酸基或亞磷酸基之單體(a1)為佳。作為具有前述磷酸基或亞磷酸基之單體(a1)，例如可舉出一般式(1)：
(式中，R1及R2各獨立表示氫或碳數1~3的烷基；Y表示羥基、碳數1~3的烷基或碳數1~3的烷基酯基；Z表示氫 原子、羥基、碳數1~3的烷基或碳數1~3的烷基酯基；n為1~20的整數)所示化合物以及該化合物之金屬鹽、銨鹽及胺鹽等。這些化合物可單獨使用或亦可以二種以上的混合物方式使用。R1、R2、Y、Z各以氫或甲基為佳。又，n以1~3為佳。 (In the formula, R 1 and R 2 each independently represent hydrogen or an alkyl group with 1 to 3 carbons; Y represents a hydroxyl group, an alkyl group with 1 to 3 carbons or an alkyl ester group with 1 to 3 carbons; Z represents hydrogen Atom, hydroxyl group, C1-C3 alkyl group or C1-C3 alkyl ester group; n is an integer of 1-20) and the metal salt, ammonium salt and amine salt of the compound. These compounds can be used alone or in a mixture of two or more kinds. R 1 , R 2 , Y, and Z are each preferably hydrogen or methyl. Also, n is preferably 1~3.
作為具有前述磷酸基或亞磷酸基之單體(a1)的具體例子，可舉出酸．磷氧基聚氧烷二醇單(甲基)丙烯酸酯。更具體可舉出酸‧磷氧基乙基(甲基)丙烯酸酯、2-丙烯醯氧基乙基酸磷酸鹽、2-甲基丙烯醯氧基乙基酸磷酸鹽、酸‧磷氧基聚氧乙二醇單(甲基)丙烯酸酯及酸‧磷氧基聚氧丙二醇(甲基)丙烯酸酯等。這些化合物可單獨使用或亦可以二種以上的混合物方式使用。其中由每1分子的磷含有量高的觀點來看，以酸‧磷氧基乙基(甲基)丙烯酸酯為佳。 As a specific example of the monomer (a1) having the aforementioned phosphoric acid group or phosphorous acid group, an acid can be cited. Phosphoroxylated polyoxyalkylene glycol mono(meth)acrylate. More specifically, acid ‧ phosphoroxy ethyl (meth) acrylate, 2-acryloxy ethyl phosphate, 2-methacryloxy ethyl phosphate, acid ‧ phosphoroxy Polyoxyethylene glycol mono(meth)acrylate and acid ‧ phosphoroxy propylene glycol (meth)acrylate, etc. These compounds can be used alone or in a mixture of two or more kinds. Among them, from the viewpoint of high phosphorus content per molecule, acid ‧ phosphooxyethyl (meth)acrylate is preferred.
前述含磷不飽和單體(A)對於含磷不飽和單體(A)與聚合性不飽和單體(B)之共聚物(P)中的全單體而言，使用20質量%~60質量%之範圍為佳，以使用23~50質量%的範圍為較佳，以使用26質量%~40質量%的範圍為更佳。若在20質量%以上時，以本纖維處理劑進行處理的加工品之阻燃性為充分，若在60質量%以下時聚合會安定，有著使用本纖維處理劑之加工品的強度或耐熱黃變性不會降低之傾向。 The aforementioned phosphorus-containing unsaturated monomer (A) is used for all monomers in the copolymer (P) of phosphorus-containing unsaturated monomer (A) and polymerizable unsaturated monomer (B), using 20% by mass to 60% The range of mass% is preferable, the range of 23-50 mass% is more preferable, and the range of 26 mass %-40 mass% is more preferable. If it is 20% by mass or more, the flame retardancy of processed products treated with this fiber treatment agent is sufficient, and if it is less than 60% by mass, the polymerization will be stable and have the strength or heat resistance of processed products using this fiber treatment agent. Denaturation does not reduce the tendency.
又，前述含磷不飽和單體(A)的聚合比例對於含磷不飽和單體(A)、聚合性不飽和單體(B)與共聚物(P)，使由(A)成分與(B)成分中之磷原子量及含磷不飽和單體(A) 的分子量所計算的磷原子含有量成為3~13質量%下可適宜決定。若考慮到阻燃性賦予與共聚物(P)之聚合安定性、加工品中之物性表現的平衡，聚合成磷含有量成為3~10質量%者為佳。若比3質量%多時，共聚物(P)本身的阻燃性會充分故作為纖維處理劑的阻燃性為充分，若未達13質量%時，共聚物(P)之聚合為安定。 In addition, the polymerization ratio of the aforementioned phosphorus-containing unsaturated monomer (A) is such that the phosphorus-containing unsaturated monomer (A), the polymerizable unsaturated monomer (B) and the copolymer (P) are composed of (A) component and ( B) Phosphorus atomic weight and phosphorus-containing unsaturated monomers in the ingredients (A) The phosphorus atom content calculated by the molecular weight of, can be appropriately determined when it is 3 to 13% by mass. Considering the balance between the flame retardancy imparting and the polymerization stability of the copolymer (P) and the physical properties in the processed product, the content of the polymerized phosphorus is preferably 3-10% by mass. If it is more than 3% by mass, the flame retardancy of the copolymer (P) itself will be sufficient, so the flame retardancy as a fiber treatment agent is sufficient. If it is less than 13% by mass, the polymerization of the copolymer (P) will be stable.
本發明中所使用的聚合性不飽和單體(B)為於分子中具有乙烯性不飽和鍵，表現聚合性，可與前述含磷不飽和單體(A)進行共聚合者即可，並無特別限制。又，亦可為複數種類的單體。 The polymerizable unsaturated monomer (B) used in the present invention has an ethylenic unsaturated bond in the molecule, exhibits polymerizability, and can be copolymerized with the aforementioned phosphorus-containing unsaturated monomer (A), and There are no special restrictions. In addition, it may be a plurality of types of monomers.
作為前述聚合性不飽和單體(B)，例如可舉出丙烯酸、甲基丙烯酸、富馬酸、馬來酸及這些酯類；(甲基)丙烯醯胺及其衍生物；苯乙烯及其衍生物；乙烯基酯；N取代馬來醯亞胺化合物；衣康酸、巴豆酸、鄰苯二甲酸及這些酯類及這些金屬鹽、銨鹽等。 Examples of the aforementioned polymerizable unsaturated monomer (B) include acrylic acid, methacrylic acid, fumaric acid, maleic acid and these esters; (meth)acrylamide and its derivatives; styrene and its derivatives Derivatives; vinyl esters; N-substituted maleimide compounds; itaconic acid, crotonic acid, phthalic acid and these esters and these metal salts, ammonium salts, etc.
又，作為前述聚合性不飽和單體(B)的具體例子，可舉出甲基(甲基)丙烯酸酯、乙基(甲基)丙烯酸酯、丙基(甲基)丙烯酸酯、丁基(甲基)丙烯酸酯、2-乙基己基(甲基)丙烯酸酯、烯丙基(甲基)丙烯酸酯、乙二醇二(甲基)丙烯酸酯、甲氧基乙基(甲基)丙烯酸酯、丁氧基乙基(甲基)丙烯酸酯、二甲基胺基乙基(甲基)丙烯酸酯、二乙基胺基乙基(甲基)丙烯酸酯、羥基乙基(甲基)丙烯酸酯、 羥基丙基(甲基)丙烯酸酯、羥基丁基(甲基)丙烯酸酯、乙二醇單(甲基)丙烯酸酯、聚乙二醇單(甲基)丙烯酸酯、聚丙二醇單(甲基)丙烯酸酯、聚四甲二醇單(甲基)丙烯酸酯、聚乙二醇聚四甲二醇單(甲基)丙烯酸酯、聚丙二醇聚四甲二醇單(甲基)丙烯酸酯、縮水甘油基(甲基)丙烯酸酯、甲基縮水甘油基(甲基)丙烯酸酯、3,4-環氧環己基甲基(甲基)丙烯酸酯、乙烷二醇二(甲基)丙烯酸酯、丙烷二醇二(甲基)丙烯酸酯、丁二醇二(甲基)丙烯酸酯、己二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、二丙二醇二(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、二羥甲基三環癸烷二(甲基)丙烯酸酯、異冰片基(甲基)丙烯酸酯、苯氧基聚乙二醇(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯等(甲基)丙烯酸酯；二甲基富馬酸酯、二乙基富馬酸酯、二丁基富馬酸酯、二-(2-乙基己基)富馬酸酯等富馬酸酯；馬來酸二甲酯、馬來酸二乙酯、馬來酸二丁酯、二-(2-乙基己基)馬來酸酯等馬來酸酯；甲基丙烯醯胺；N-甲基(甲基)丙烯醯胺、N-乙基(甲基)丙烯醯胺、N-丁基(甲基)丙烯醯胺、N-丙基(甲基)丙烯醯胺等(甲基)丙烯醯胺衍生物；甲氧基苯乙烯、乙氧基苯乙烯乙烯基安息香酸、乙烯基安息香酸甲酯、乙烯基苯甲基乙酸酯、羥基苯乙烯、二乙烯基苯等苯乙烯衍生物；乙酸乙烯酯；丙酸乙烯酯、己酸乙烯酯、癸酸乙烯酯、月桂酸乙烯酯、硬脂酸乙烯酯等乙烯基酯類；甲基馬來醯亞胺、乙基馬來醯亞胺、異丙基馬來醯亞胺、環己基馬來醯亞胺、苯基馬來醯 亞胺、苯甲基馬來醯亞胺、萘馬來醯亞胺等N取代馬來醯亞胺化合物；單甲基衣康酸酯、二甲基衣康酸酯、單乙基衣康酸酯、二乙基衣康酸酯、單丁基衣康酸酯、二丁基衣康酸酯等衣康酸酯；甲基巴豆酸酯、乙基巴豆酸酯、丁基巴豆酸酯等巴豆酸酯；二甲基鄰苯二甲酸酯、二乙基鄰苯二甲酸酯、二丙基鄰苯二甲酸酯、二丁基鄰苯二甲酸酯、二己基鄰苯二甲酸酯等鄰苯二甲酸酯等，這些可單獨或組合二種以上後使用。 In addition, specific examples of the aforementioned polymerizable unsaturated monomer (B) include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and butyl (meth)acrylate. Meth)acrylate, 2-ethylhexyl (meth)acrylate, allyl (meth)acrylate, ethylene glycol di(meth)acrylate, methoxyethyl (meth)acrylate , Butoxyethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, hydroxyethyl (meth)acrylate , Hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, ethylene glycol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth) Acrylate, polytetramethylene glycol mono(meth)acrylate, polyethylene glycol polytetramethylene glycol mono(meth)acrylate, polypropylene glycol polytetramethylene glycol mono(meth)acrylate, glycidol (Meth)acrylate, methylglycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl(meth)acrylate, ethanediol di(meth)acrylate, propane Glycol di(meth)acrylate, butanediol di(meth)acrylate, hexanediol di(meth)acrylate, diethylene glycol di(meth)acrylate, dipropylene glycol di(meth) )Acrylate, trimethylolpropane tri(meth)acrylate, dimethyloltricyclodecane di(meth)acrylate, isobornyl (meth)acrylate, phenoxy polyethylene glycol (Meth) acrylate, pentaerythritol tetra (meth) acrylate and other (meth) acrylates; dimethyl fumarate, diethyl fumarate, dibutyl fumarate, di-( 2-ethylhexyl) fumarate and other fumarates; dimethyl maleate, diethyl maleate, dibutyl maleate, di-(2-ethylhexyl) maleate And other maleic acid esters; methacrylamide; N-methyl(meth)acrylamide, N-ethyl(meth)acrylamide, N-butyl(meth)acrylamide, N- Propyl (meth)acrylamide and other (meth)acrylamide derivatives; methoxystyrene, ethoxystyrene vinyl benzoic acid, vinyl methyl benzoate, vinyl benzyl acetic acid Esters, hydroxystyrene, divinylbenzene and other styrene derivatives; vinyl acetate; vinyl propionate, vinyl caproate, vinyl decanoate, vinyl laurate, vinyl stearate and other vinyl esters ; Methyl maleimide, ethyl maleimide, isopropyl maleimide, cyclohexyl maleimide, phenyl maleimide N-substituted maleimide compounds such as imine, benzyl maleimide, naphthalene maleimide, etc.; monomethyl itaconate, dimethyl itaconate, monoethyl itaconate Esters, diethyl itaconate, monobutyl itaconate, dibutyl itaconate and other itaconates; methyl crotonate, ethyl crotonate, butyl crotonate and other crotons Esters; dimethyl phthalate, diethyl phthalate, dipropyl phthalate, dibutyl phthalate, dihexyl phthalate Phthalates such as esters, etc., can be used alone or in combination of two or more kinds.
前述聚合性不飽和單體(B)之中，特別由以本纖維處理劑處理所得的纖維加工品中之阻燃性表現的觀點來看，以同時使用(甲基)丙烯酸烷基酯不飽和單體(b1)及(甲基)丙烯酸及衣康酸所成群的至少一種不飽和單體(b2)為佳。使用(甲基)丙烯酸烷基酯不飽和單體(b1)時，由使用本發明之纖維處理劑處理的纖維加工品中之阻燃劑(D)成分之耐滲出性提高的層面來看為佳。若使用選自由(甲基)丙烯酸及衣康酸所成群的至少一種不飽和單體(b2)時，由使用本發明之纖維處理劑處理的纖維加工品之防鏽性提高的層面來看為佳。 Among the aforementioned polymerizable unsaturated monomers (B), in particular, from the standpoint of flame retardancy performance in fiber processed products treated with this fiber treatment agent, the simultaneous use of unsaturated alkyl (meth)acrylate The monomer (b1) and at least one unsaturated monomer (b2) grouped by (meth)acrylic acid and itaconic acid are preferred. When the alkyl (meth)acrylate unsaturated monomer (b1) is used, it can be seen from the aspect that the flame retardant (D) component in the fiber processing product treated with the fiber processing agent of the present invention improves the bleed-out resistance. good. If at least one unsaturated monomer (b2) selected from the group consisting of (meth)acrylic acid and itaconic acid is used, it can be seen from the aspect that the rust resistance of the fiber processed product treated with the fiber treatment agent of the present invention is improved Better.
(甲基)丙烯酸烷基酯不飽和單體(b1)的烷基以碳數1~5的烷基者為佳。作為具體例子可舉出甲基(甲基)丙烯酸酯、乙基(甲基)丙烯酸酯、丙基(甲基)丙烯酸酯、丁基(甲基)丙烯酸酯等，其中由阻燃性表現的觀點來看以甲基(甲 基)丙烯酸酯、乙基(甲基)丙烯酸酯為佳。這些可單獨或組合二種以上後使用。 The alkyl group of the alkyl (meth)acrylate unsaturated monomer (b1) is preferably an alkyl group having 1 to 5 carbon atoms. Specific examples include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, etc., among which are represented by flame retardancy From the viewpoint of methyl (A Ethyl) acrylate and ethyl (meth)acrylate are preferred. These can be used alone or in combination of two or more kinds.
又，可進一步使用其他(甲基)丙烯酸烷基酯不飽和單體(b1)。作為具體例子，可舉出2-乙基己基(甲基)丙烯酸酯、烯丙基(甲基)丙烯酸酯、乙二醇二(甲基)丙烯酸酯、甲氧基乙基(甲基)丙烯酸酯、丁氧基乙基(甲基)丙烯酸酯、二甲基胺基乙基(甲基)丙烯酸酯、二乙基胺基乙基(甲基)丙烯酸酯等，這些可單獨或組合二種以上後使用。 In addition, other unsaturated monomers (b1) of alkyl (meth)acrylate may be further used. Specific examples include 2-ethylhexyl (meth)acrylate, allyl (meth)acrylate, ethylene glycol di(meth)acrylate, and methoxyethyl (meth)acrylate. Ester, butoxyethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, etc., these can be singly or in combination of two Use after the above.
選自由(甲基)丙烯酸及衣康酸所成群的至少一種不飽和單體(b2)使用於提高本發明之纖維處理劑的阻燃性。其中亦由不損失聚合的安定性，且可提高共聚物(P)中之含有量的層面來看，以丙烯酸為佳。 At least one unsaturated monomer (b2) selected from the group consisting of (meth)acrylic acid and itaconic acid is used to improve the flame retardancy of the fiber treatment agent of the present invention. Among them, from the perspective of not losing the stability of the polymerization and increasing the content of the copolymer (P), acrylic acid is preferred.
又，並用選自由(甲基)丙烯酸及衣康酸所成群的至少一種不飽和單體(b2)，亦可使用具有選自由(甲基)丙烯酸及衣康酸所成群以外的羧基之不飽和單體。作為具有選自由(甲基)丙烯酸及衣康酸所成群以外的羧基之不飽和單體的具體例子，可舉出富馬酸、馬來酸、巴豆酸等，這些可單獨或組合二種以上後使用。 In addition, at least one unsaturated monomer (b2) selected from the group consisting of (meth)acrylic acid and itaconic acid is used in combination, and one having a carboxyl group other than the group selected from (meth)acrylic acid and itaconic acid may also be used. Unsaturated monomers. Specific examples of the unsaturated monomer having a carboxyl group other than the group of (meth)acrylic acid and itaconic acid include fumaric acid, maleic acid, crotonic acid, etc., and these may be singly or in combination of two kinds Use after the above.
前述聚合性不飽和單體(B)對於含於纖維處理劑之含磷不飽和單體(A)與聚合性不飽和單體(B)的共聚物 (P)中之全單體而言，該合計為40質量%以上使用量者為佳，以50質量%~80質量%的使用量者為較佳。 The aforementioned polymerizable unsaturated monomer (B) is a copolymer of the phosphorus-containing unsaturated monomer (A) and the polymerizable unsaturated monomer (B) contained in the fiber treatment agent For all monomers in (P), the total amount used is 40% by mass or more, and the amount used is 50% to 80% by mass.
若為40質量%以上時，本發明之纖維處理劑的聚合為穩定，若在80質量%以下時，使用本發明之纖維處理劑處理的纖維加工品之阻燃性有充分之傾向。 If it is 40% by mass or more, the polymerization of the fiber treatment agent of the present invention is stable, and if it is less than 80% by mass, the flame retardancy of the fiber processed product treated with the fiber treatment agent of the present invention tends to be sufficient.
對於聚合性不飽和單體(B)，(甲基)丙烯酸烷基酯不飽和單體(b1)及選自由(甲基)丙烯酸及衣康酸所成群的至少一種不飽和單體(b2)之合計量以90質量%以上為佳，較佳為95質量%以上，更佳為100質量%。 Regarding the polymerizable unsaturated monomer (B), the alkyl (meth)acrylate unsaturated monomer (b1) and at least one unsaturated monomer (b2) selected from the group consisting of (meth)acrylic acid and itaconic acid The total amount of) is preferably 90% by mass or more, preferably 95% by mass or more, and more preferably 100% by mass.
對於聚合性不飽和單體(B)，(甲基)丙烯酸烷基酯不飽和單體(b1)及選自由(甲基)丙烯酸及衣康酸所成群的至少一種不飽和單體(b2)的質量比(b1/b2)例如以96/4~4/96為佳，以79/21~21/79為較佳，以75/25~30/70為更佳。該範圍內時，使用本發明之纖維處理劑處理的纖維加工品中之阻燃劑(D)成分的耐滲出性有提高的傾向。又，使用本發明之纖維處理劑處理的纖維加工品之阻燃性或防鏽性有提高的傾向。 Regarding the polymerizable unsaturated monomer (B), the alkyl (meth)acrylate unsaturated monomer (b1) and at least one unsaturated monomer (b2) selected from the group consisting of (meth)acrylic acid and itaconic acid The mass ratio (b1/b2) of) is preferably 96/4~4/96, preferably 79/21~21/79, and more preferably 75/25~30/70. When it is within this range, the bleed-out resistance of the flame retardant (D) component in the fiber processed product treated with the fiber processing agent of the present invention tends to be improved. In addition, the flame retardancy or rust resistance of processed fiber products treated with the fiber treatment agent of the present invention tends to be improved.
本發明之纖維處理劑所含的含磷不飽和單體(A)與聚合性不飽和單體(B)的共聚物(P)可使用懸浮聚合法、乳化聚合法、溶液聚合法、塊狀聚合法等公知共聚合方法而製造。又，亦可由連續式聚合法或階段式聚合法進行製造。 The copolymer (P) of the phosphorus-containing unsaturated monomer (A) and the polymerizable unsaturated monomer (B) contained in the fiber treatment agent of the present invention can use suspension polymerization, emulsion polymerization, solution polymerization, or block It is produced by a known copolymerization method such as a polymerization method. In addition, it can also be produced by a continuous polymerization method or a stepwise polymerization method.
於本發明中所使用的防鏽劑(C)若以本發明之纖維處理劑進行處理的加工品之阻燃性無顯著損害者即可，並無特別限制。 The rust inhibitor (C) used in the present invention is not particularly limited as long as the flame retardancy of the processed product treated with the fiber treatment agent of the present invention is not significantly impaired.
作為前述防鏽劑(C)之具體例子，可舉出單及二異丙基胺亞硝酸鹽、單及二環己基胺亞硝酸鹽、三乙基胺亞硝酸鹽、吡啶亞硝酸鹽、苯胺亞硝酸鹽等亞硝酸鹽；烷基琥珀酸半酯、烯基琥珀酸半酯等各種羧酸酯；二環己基銨水楊酸鹽、二環己基銨環己烷羧酸酯、環己基胺環己烷羧酸酯、二環己基銨丙烯酸酯、環己基胺丙烯酸酯及這些胺基甲酸鹽、環烷烴酸鹽、辛基酸鹽等胺之羧酸鹽；乙基嗎啉安息香酸鹽、二及單環己基胺安息香酸鹽、單乙醇胺安息香酸鹽、安息香酸鈉等安息香酸鹽；各種鉻酸鹽；磷酸鹽；矽酸鹽；磺酸鹽等，其中亦由環境負荷、使用規制或有效率防鏽性表現之觀點來看，以胺的羧酸鹽或安息香酸鹽為佳。這些化合物可單獨或組合二種以上使用。 Specific examples of the aforementioned rust inhibitor (C) include mono- and diisopropylamine nitrite, mono- and dicyclohexylamine nitrite, triethylamine nitrite, pyridine nitrite, and aniline. Nitrite and other nitrites; alkyl succinic acid half ester, alkenyl succinic acid half ester and various carboxylic acid esters; dicyclohexylammonium salicylate, dicyclohexylammonium cyclohexane carboxylate, cyclohexylamine Cyclohexane carboxylate, dicyclohexyl ammonium acrylate, cyclohexyl amine acrylate and amine carboxylates such as amino formate, cycloalkane acid and octyl acid; ethylmorpholine benzoate , Di- and monocyclohexylamine benzoate, monoethanolamine benzoate, sodium benzoate and other benzoates; various chromates; phosphates; silicates; sulfonates, etc., which are also regulated by environmental load and use Or from the viewpoint of effective rust prevention performance, amine carboxylate or benzoate is preferred. These compounds can be used alone or in combination of two or more kinds.
本發明之纖維處理劑中，防鏽劑(C)的含有量以0.1~15質量%為佳，以0.5~10質量%為較佳，以1~5質量%為更佳。比0.1質量%少時，以本發明之纖維處理劑處理的加工品之防鏽性會降低，比15質量%多時，纖維處理劑的乾燥性會降低，有阻礙經該纖維處理劑處理所得之纖維加工品的物性，或該纖維加工品的處理性降低之傾向。又，若在該範圍時，使用於本發明之纖維處理劑的經處理之加工品的防鏽性不會降低，藉由並用下述適量阻燃劑 時，亦可使加工品之阻燃性不會降低。 In the fiber treatment agent of the present invention, the content of the rust inhibitor (C) is preferably 0.1-15% by mass, preferably 0.5-10% by mass, and more preferably 1-5% by mass. When it is less than 0.1% by mass, the rust resistance of processed products treated with the fiber treatment agent of the present invention will decrease, and when it is more than 15% by mass, the drying property of the fiber treatment agent will decrease, which hinders the treatment of the fiber treatment agent. The physical properties of the processed fiber products, or the tendency of the processing properties of the processed fiber products to decrease. In addition, if it is in this range, the rust resistance of the processed processed product used in the fiber treatment agent of the present invention will not decrease. By using the following appropriate amount of flame retardant in combination At the same time, the flame retardancy of the processed product will not be reduced.
使用於本發明的阻燃劑(D)若可混合於纖維處理劑中者即可，並無特別限制。 The flame retardant (D) used in the present invention is not particularly limited as long as it can be mixed with the fiber treatment agent.
作為前述阻燃劑(D)之具體例子，可舉出胍磷酸鹽、三苯基磷酸鹽、甲酚二苯基磷酸鹽、三甲酚磷酸鹽、三二甲苯基磷酸鹽、參(t-丁基化苯基)磷酸鹽、參(i-丙基化苯基)磷酸鹽、2-乙基己基二苯基磷酸鹽、紅磷、1,3-亞苯基雙(二苯基磷酸鹽)、1,3-亞苯基雙(二二甲苯基磷酸鹽)、雙酚A雙(二苯基磷酸鹽)及這些金屬鹽等磷系阻燃劑；三氧化銻、四氧化銻、五氧化銻、銻蘇打、氫氧化鋁、氫氧化鎂等無機系阻燃劑；三聚氰胺氰脲酸酯等氮系阻燃劑；五溴聯苯基、八溴聯苯基、十溴聯苯基等鹵素系阻燃劑等。其中亦由環境負荷低且有效率地表現阻燃性之觀點來看，使用含有磷的阻燃劑者為佳。這些化合物可單獨或組合二種以上使用。 Specific examples of the aforementioned flame retardant (D) include guanidine phosphate, triphenyl phosphate, cresol diphenyl phosphate, tricresol phosphate, trixylyl phosphate, ginseng (t-butyl phosphate) (I-propylated phenyl) phosphate, ginseng (i-propylated phenyl) phosphate, 2-ethylhexyl diphenyl phosphate, red phosphorus, 1,3-phenylene bis (diphenyl phosphate) , 1,3-phenylene bis (xylyl phosphate), bisphenol A bis (diphenyl phosphate) and these metal salts and other phosphorus-based flame retardants; antimony trioxide, antimony tetraoxide, pentoxide Antimony, antimony soda, aluminum hydroxide, magnesium hydroxide and other inorganic flame retardants; melamine cyanurate and other nitrogen-based flame retardants; pentabromobiphenyl, octabrombiphenyl, decabrombiphenyl and other halogens Department of flame retardants, etc. Among them, from the viewpoint of low environmental load and efficient performance of flame retardancy, it is preferable to use a flame retardant containing phosphorus. These compounds can be used alone or in combination of two or more kinds.
本發明之纖維處理劑中，阻燃劑(D)之含有量以0.1~70質量%為佳，以0.5~50質量%為較佳，以1~30質量%為更佳。若為0.1質量%以上時，以本發明之纖維處理劑處理的加工品之阻燃性變的充分，若在70質量%以下時，使用本發明之纖維處理劑處理所得之纖維加工品中之嗆人或黏沾感等亦有被抑制的傾向。 In the fiber treatment agent of the present invention, the content of the flame retardant (D) is preferably 0.1 to 70% by mass, preferably 0.5 to 50% by mass, and more preferably 1 to 30% by mass. If it is 0.1% by mass or more, the flame retardancy of processed products treated with the fiber treatment agent of the present invention becomes sufficient, and if it is less than 70% by mass, among the processed fiber products treated with the fiber treatment agent of the present invention Choking or stickiness also tends to be suppressed.
本發明之纖維處理劑中，阻燃劑(D)的含有量為以與 防鏽劑(C)之含有量的合計40質量%以下者為佳。若在40質量%以下時，有滲出受到抑制之傾向，又藉由使用本發明之纖維處理劑進行處理所得之纖維加工品中，有嗆人或黏沾感等受到抑制之傾向。 In the fiber treatment agent of the present invention, the content of the flame retardant (D) is as follows The content of the rust inhibitor (C) is preferably 40% by mass or less in total. If it is 40% by mass or less, the exudation tends to be suppressed, and the processed fiber product obtained by treatment with the fiber treatment agent of the present invention tends to be choked or sticky.
本發明之纖維處理劑中的合計磷原子之含有量以0.01~30質量%為佳，以0.05~25質量%者為較佳，以0.1~20質量%者為更佳。若在0.01質量%以上時，藉由本發明之纖維處理劑進行處理的加工品之阻燃性會充分，若在30質量%以下時，藉由使用本發明之纖維處理劑進行處理所得之纖維加工品中，有嗆人或黏沾感等受到抑制之傾向。 The total content of phosphorus atoms in the fiber treatment agent of the present invention is preferably 0.01-30% by mass, preferably 0.05-25% by mass, and more preferably 0.1-20% by mass. If it is 0.01% by mass or more, the flame retardancy of processed products treated with the fiber treatment agent of the present invention will be sufficient, and if it is less than 30% by mass, the fiber processing obtained by treatment with the fiber treatment agent of the present invention In the product, there is a tendency for choking or stickiness to be suppressed.
藉由自由基聚合得到含磷不飽和單體(A)與聚合性不飽和單體(B)的共聚物(P)時，聚合在起始劑存在下進行。在該聚合反應所使用的自由基聚合起始劑若為可啟始自由基聚合者即可，並無特別限定，可使用通常使用的過氧化物或偶氮化合物。例如作為該具體例子，可舉出過硫酸鈉、過硫酸鉀、過硫酸銨、過氧化氫、苯甲醯基過氧化物、二枯基過氧化物、二異丙基過氧化物、二-t-丁基過氧化物、t-丁基過氧苯甲酸酯、t-己基過氧苯甲酸酯、t-丁基過氧-2-乙基己酸酯、t-己基過氧-2-乙基己酸酯、1,1-雙(t-丁基過氧)-3,3,5-三甲基環己烷、2,5-二甲基-2,5-雙(t-丁基 過氧)己基-3,3-異丙基氫過氧化物、t-丁基氫過氧化物、二枯基氫過氧化物、乙醯過氧化物、雙(4-t-丁基環己基)過氧二碳酸酯、二異丙基過氧二碳酸酯、異丁基過氧化物、3,3,5-三甲基己醯基過氧化物、月桂基過氧化物、1,1-雙(t-己基過氧)-3,3,5-三甲基環己烷、偶氮二異丁腈、偶氮二羧醯胺等，配合反應可使用適當還原劑。起始劑的使用量對於共聚物(P)中的含磷不飽和單體(A)及聚合性不飽和單體(B)之合計100質量份而言以0.01~20質量份為佳，以0.1~10質量份為更佳。 When the copolymer (P) of the phosphorus-containing unsaturated monomer (A) and the polymerizable unsaturated monomer (B) is obtained by radical polymerization, the polymerization is carried out in the presence of an initiator. The radical polymerization initiator used in the polymerization reaction is not particularly limited as long as it can initiate radical polymerization, and generally used peroxides or azo compounds can be used. For example, as the specific example, sodium persulfate, potassium persulfate, ammonium persulfate, hydrogen peroxide, benzyl peroxide, dicumyl peroxide, diisopropyl peroxide, di- t-butyl peroxide, t-butylperoxybenzoate, t-hexylperoxybenzoate, t-butylperoxy-2-ethylhexanoate, t-hexylperoxy- 2-ethylhexanoate, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5-bis(t -Butyl Peroxy)hexyl-3,3-isopropyl hydroperoxide, t-butyl hydroperoxide, dicumyl hydroperoxide, acetyl peroxide, bis(4-t-butylcyclohexyl) ) Peroxy dicarbonate, diisopropyl peroxy dicarbonate, isobutyl peroxide, 3,3,5-trimethylhexyl peroxide, lauryl peroxide, 1,1- Bis(t-hexylperoxy)-3,3,5-trimethylcyclohexane, azobisisobutyronitrile, azodicarboxamide, etc., suitable reducing agents can be used for the reaction. The amount of the initiator used is preferably 0.01-20 parts by mass for the total of 100 parts by mass of the phosphorus-containing unsaturated monomer (A) and polymerizable unsaturated monomer (B) in the copolymer (P). 0.1-10 parts by mass is more preferable.
於本發明之纖維處理劑中所含的含磷不飽和單體(A)與聚合性不飽和單體(B)之共聚物(P)藉由乳化聚合法進行製造時，在界面活性劑的存在下進行。作為界面活性劑，可使用一般市售的負離子性界面活性劑、非離子性界面活性劑、陽離子性界面活性劑及共聚合性界面活性劑。又，這些界面活性劑可單獨或組合二種類以上使用。所使用的界面活性劑量對於含磷不飽和單體(A)及聚合性不飽和單體(B)的合計而言以0.01~30質量份為佳，以0.1~20質量份為更佳。且，由聚合安定性之觀點來看，同様地可將水溶性(甲基)丙烯酸樹脂、水溶性(甲基)丙烯酸酯樹脂、聚氧乙烯烷基醚等水溶性高分子作為保護膠體使用。又，這些保護膠體與是否有皂化度、平均聚合度、變性無關下可使用，但平均聚合度由聚合安定性、製品黏度之觀點來看以 200~2，400為佳，皂化度由聚合安定性之觀點來看以80%~100%者為佳。又，這些保護膠體之使用量雖無特別限制，但由聚合安定性之觀點來看，對於含磷不飽和單體(A)及聚合性不飽和單體(B)之合計100質量份而言，以1~100質量份為佳，以10~30質量份為更佳。 When the copolymer (P) of the phosphorus-containing unsaturated monomer (A) and the polymerizable unsaturated monomer (B) contained in the fiber treatment agent of the present invention is produced by the emulsion polymerization method, the surface active agent Existence. As the surfactant, generally commercially available anionic surfactants, nonionic surfactants, cationic surfactants, and copolymerizable surfactants can be used. In addition, these surfactants can be used alone or in combination of two or more kinds. The amount of surfactant used is preferably 0.01-30 parts by mass, and more preferably 0.1-20 parts by mass for the total of the phosphorus-containing unsaturated monomer (A) and the polymerizable unsaturated monomer (B). In addition, from the viewpoint of polymerization stability, water-soluble polymers such as water-soluble (meth)acrylic resins, water-soluble (meth)acrylate resins, and polyoxyethylene alkyl ethers can also be used as protective colloids. In addition, these protective colloids can be used regardless of the presence or absence of saponification degree, average degree of polymerization, and denaturation. However, the average degree of polymerization is based on the viewpoint of polymerization stability and product viscosity. 200~2,400 is better, and the degree of saponification is preferably 80%~100% from the viewpoint of polymerization stability. Also, although the amount of these protective colloids used is not particularly limited, from the viewpoint of polymerization stability, it is based on a total of 100 parts by mass of the phosphorus-containing unsaturated monomer (A) and the polymerizable unsaturated monomer (B) , Preferably 1-100 parts by mass, more preferably 10-30 parts by mass.
本發明之纖維處理劑中，在不損害本發明之效果的範圍下，可添加填充劑、防腐劑、著色劑、消泡劑、發泡劑、分散劑、乳化劑、流動性調整劑、可塑劑、pH調整劑、各種油劑等添加劑。 In the fiber treatment agent of the present invention, fillers, preservatives, coloring agents, defoamers, foaming agents, dispersants, emulsifiers, fluidity regulators, plasticizers can be added within the range that does not impair the effects of the present invention. Additives such as additives, pH adjusters, and various oils.
又，於本發明之纖維處理劑中，在不損害本發明之效果的範圍下，可含有其他樹脂乳膠或溶液樹脂、環氧樹脂、胺基甲酸酯樹脂等各種樹脂組成物作為黏合劑。 In addition, the fiber treatment agent of the present invention may contain various resin compositions such as other resin emulsions or solution resins, epoxy resins, and urethane resins as binders within a range that does not impair the effects of the present invention.
使用於本發明之纖維處理劑的製造之溶劑可為水或一般使用的有機溶劑。例如作為該具體例子，可舉出甲醇、乙醇、丙醇、異丙醇、丁醇等醇類；乙酸乙酯、乙酸異丙基、溶纖劑乙酸酯、丁基溶纖劑乙酸酯等乙二醇單烷基醚乙酸酯類、二乙二醇單甲基醚乙酸酯、卡必醇乙酸酯、丁基卡必醇乙酸酯等二乙二醇單烷基醚乙酸酯類、丙二醇單 烷基醚乙酸酯類、二丙二醇單烷基醚乙酸酯類等乙酸酯類；乙二醇二烷基醚類、甲基卡必醇、乙基卡必醇、丁基卡必醇等二乙二醇二烷基醚類、三乙二醇二烷基醚類、丙二醇二烷基醚類、二丙二醇二烷基醚類、甲基醚、乙基醚、1,4-二噁烷、四氫呋喃等醚類；丙酮、甲基乙基酮、甲基異丁基酮、環己酮等酮類；苯、甲苯、二甲苯、己烷、辛烷、癸烷等烴類；石油醚、石腦油、氫化石腦油、溶劑石腦油等石油系溶劑；乳酸甲酯、乳酸乙酯、乳酸丁酯等乳酸酯類；二甲基甲醯胺；N-甲基吡咯啶酮等。這些水、有機溶劑可單獨或組合二種以上使用。 The solvent used in the manufacture of the fiber treatment agent of the present invention may be water or a commonly used organic solvent. For example, the specific examples include alcohols such as methanol, ethanol, propanol, isopropanol, and butanol; ethyl acetate, isopropyl acetate, cellosolve acetate, butyl cellosolve acetate, etc. Glycol monoalkyl ether acetates, diethylene glycol monomethyl ether acetate, carbitol acetate, butyl carbitol acetate and other diethylene glycol monoalkyl ether acetates, Propylene Glycol Mono Alkyl ether acetates, dipropylene glycol monoalkyl ether acetates and other acetates; ethylene glycol dialkyl ethers, methyl carbitol, ethyl carbitol, butyl carbitol and other diethyl esters Glycol dialkyl ethers, triethylene glycol dialkyl ethers, propylene glycol dialkyl ethers, dipropylene glycol dialkyl ethers, methyl ether, ethyl ether, 1,4-dioxane, tetrahydrofuran Ethers; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; hydrocarbons such as benzene, toluene, xylene, hexane, octane, decane, etc.; petroleum ether, naphtha Petroleum solvents such as oil, hydrogenated naphtha, and solvent naphtha; lactate esters such as methyl lactate, ethyl lactate, and butyl lactate; dimethylformamide; N-methylpyrrolidone, etc. These water and organic solvents can be used alone or in combination of two or more kinds.
本說明書中，所謂纖維為含有各種纖維及由這些混紡品所成的不織布、織物、編物等。又，作為該纖維，例如可舉出木綿、麻、絹、羊毛、膠原纖維、丙烯酸纖維、纖維素系纖維、聚醯亞胺纖維、聚醯胺醯亞胺纖維、人造絲(Rayon)纖維、尼龍纖維、維尼纖維、聚酯纖維、聚丙烯纖維、聚氯乙烯纖維、聚乙烯纖維、聚甲基亞苯基異鄰苯二醯胺纖維、芳醯基纖維、聚芳酯纖維、聚四氟伸乙基纖維、聚苯並咪唑纖維、聚醚醚酮纖維、聚伸苯基硫化物纖維及由這些混紡品所成的不織布、織物、編物等。 In this specification, the term "fiber" refers to non-woven fabrics, woven fabrics, woven fabrics, etc., including various fibers and blended products. Moreover, as the fiber, for example, wood wool, hemp, silk, wool, collagen fiber, acrylic fiber, cellulose fiber, polyimide fiber, polyimide fiber, rayon (Rayon) fiber, Nylon fiber, Vinnie fiber, polyester fiber, polypropylene fiber, polyvinyl chloride fiber, polyethylene fiber, polymethylphenylene isophthalamide fiber, aramid fiber, polyarylate fiber, polytetrafluoroethylene Ethylene fiber, polybenzimidazole fiber, polyether ether ketone fiber, polyphenylene sulfide fiber, and non-woven fabrics, fabrics, knitted fabrics, etc. made of these blends.
作為藉由本發明之纖維處理劑處理纖維(基材)，製造 纖維加工品的方法，並無特別限制，可採用各種公知方法。例如作為將本發明之纖維處理劑塗布於纖維進行處理的方法，可舉出直接塗佈法、噴霧塗布法、輥塗機法、槽塗機方法、刮刀塗佈法、印刷法、滾筒轉印法等。又，例如作為將纖維浸漬於本發明之纖維處理劑而進行處理的方法，可舉出臥式滾筒法、金屬輥法、絲網輸送法、表格方法等。 As a fiber (substrate) treated by the fiber treatment agent of the present invention, manufacture The method of the fiber processed product is not particularly limited, and various known methods can be adopted. For example, as a method of applying the fiber treatment agent of the present invention to fibers for processing, there are direct coating method, spray coating method, roll coater method, slot coater method, knife coating method, printing method, roller transfer Law and so on. In addition, for example, as a method of immersing fibers in the fiber treatment agent of the present invention and treating them, a horizontal roller method, a metal roller method, a screen conveying method, a table method, etc. can be mentioned.
例如，將如不織布的纖維藉由本發明之纖維處理劑進行處理時的加工方法，可舉出噴霧塗布法、印刷法、滾筒轉印法、臥式滾筒法、金屬輥法、絲網輸送法、表格方法等。又，例如將如織物之纖維藉由本發明之纖維處理劑進行處理時的加工方法，可舉出直接塗佈法、噴霧塗布法、輥塗機法、槽塗機方法、刮刀塗佈法等。又，將纖維形成薄片狀後做成網路(web)，將該織網進一步接著或者交織使其布形化時，前述纖維處理可對織網化前之纖維進行，或亦可將纖維藉由各種方法進行織網化後進行。前述纖維織網化方法可無特別限制下採用各種公知方法，例如可舉出空氣鋪設法等。 For example, processing methods when fibers such as non-woven fabrics are treated with the fiber treatment agent of the present invention include spray coating method, printing method, roller transfer method, horizontal roller method, metal roller method, screen conveying method, Form method, etc. Moreover, for example, the processing method when a fiber such as a fabric is treated with the fiber treatment agent of the present invention includes a direct coating method, a spray coating method, a roll coater method, a slot coater method, and a knife coating method. In addition, when the fibers are formed into a sheet shape and then made into a web, and the web is further connected or interwoven to form a cloth, the aforementioned fiber treatment may be performed on the fibers before the web is formed, or the fibers may be borrowed After weaving the net by various methods. Various well-known methods can be used for the said fiber weaving method without a restriction|limiting in particular, For example, an air laying method etc. are mentioned.
對於各種纖維基材之纖維處理劑的使用量雖取決於基材本身的阻燃性，但以樹脂附著量(乾燥附著的纖維處理劑後之附著量)成為10~200質量份/100質量份的量為佳，成為30~150質量份/100質量份的量為較佳，成為50~100質量份/100質量份的量為更佳。若在10質量份/100質量份以上時，使用本發明之纖維處理劑而得的纖維加工 品之阻燃性及防鏽性會充分，若比200質量份/100質量份更多時，使用本發明之纖維處理劑而得之纖維加工品的強度、質地之降低會有受到抑制之傾向。乾燥可藉由送風乾燥，亦可藉由減壓乾燥，更可藉由加壓乾燥。又，亦可進行加熱。於乾燥時加熱時，溫度為乾燥時進行加熱情況的溫度，其範圍以50~250℃為佳，以80~190℃為較佳。加熱溫度若過低時，與乾燥的時間有關，可能會造成乾燥不充分。加熱溫度若過高時，可能會引起變質。 Although the amount of fiber treatment agent used for various fiber substrates depends on the flame retardancy of the substrate itself, the resin adhesion amount (the adhesion amount after drying the adhered fiber treatment agent) becomes 10~200 parts by mass/100 parts by mass The amount is preferably 30 to 150 parts by mass/100 parts by mass, and more preferably 50 to 100 parts by mass/100 parts by mass. If it is 10 parts by mass/100 parts by mass or more, the fiber processing obtained by using the fiber treatment agent of the present invention The flame retardancy and rust resistance of the product will be sufficient. If it is more than 200 parts by mass/100 parts by mass, the decrease in the strength and texture of the fiber processed product obtained by using the fiber treatment agent of the present invention will be suppressed. . Drying can be dried by blowing air, can also be dried by reduced pressure, and can be dried by pressure. In addition, heating may also be performed. When heating during drying, the temperature is the temperature under which heating is performed during drying, and the range is preferably from 50 to 250°C, and more preferably from 80 to 190°C. If the heating temperature is too low, it is related to the drying time and may cause insufficient drying. If the heating temperature is too high, it may cause deterioration.
本發明之纖維加工品可使用本發明之纖維加工品的製造方法而得。樹脂附著量(乾燥後之纖維處理劑的附著量)對於纖維(基材)而言為50~100質量份/100質量份，以成為10~200質量份/100質量份的量為佳，以成為30~150質量份/100質量份的量為較佳，以成為50~100質量份/100質量份的量為更佳。在10質量份/100質量份以上時，本發明之纖維加工品的阻燃性及防鏽性為充分，在200質量份/100質量份以下時，本發明之纖維加工品的強度、質地之降低有受到抑制之傾向。 The processed fiber product of the present invention can be obtained by using the method for producing processed fiber product of the present invention. The resin adhesion amount (the adhesion amount of the fiber treatment agent after drying) to the fiber (base material) is 50-100 parts by mass/100 parts by mass, preferably 10 to 200 parts by mass/100 parts by mass, The amount is preferably 30 to 150 parts by mass/100 parts by mass, and more preferably 50 to 100 parts by mass/100 parts by mass. When it is 10 parts by mass/100 parts by mass or more, the flame retardancy and rust resistance of the processed fiber product of the present invention are sufficient, and when it is less than 200 parts by mass/100 parts by mass, the strength and texture of the processed fiber product of the present invention are Decrease tends to be restrained.
本發明之纖維加工品為可活化兼具的優良阻燃性與防鏽性等而適用於種種領域。例如本發明之纖維加工品可適用於電子材料用緩衝材、家電用緩衝材、汽車內裝緩衝材等。 The fiber processed product of the present invention is activatable and has excellent flame retardancy and rust resistance, etc., and is suitable for various fields. For example, the fiber processed product of the present invention can be applied to cushioning materials for electronic materials, cushioning materials for household appliances, and automotive interior cushioning materials.
以下使用實施例及比較例對本發明做進一步說明，但本發明並未受限於實施例及比較例。 The following examples and comparative examples are used to further illustrate the present invention, but the present invention is not limited to the examples and comparative examples.
將離子交換水150g放入1L的五口可分離燒瓶中，一邊攪拌一邊加熱至80℃。將酸性磷酸聚氧乙二醇單甲基丙烯酸酯(共榮公司化學股份有限公司製的輕酯P-1M，磷含有量15質量%)60g、甲基甲基丙烯酸酯36g、乙基丙烯酸酯36g、丙烯酸18g、十二烷基苯磺酸蘇打1.5g、聚氧乙烯烷基醚7.5g、離子交換水150g均勻地乳化。於可分離燒瓶中添加過硫酸鉀0.2g，開始進行單體乳化物的滴入時表示反應開始。單體乳化物經4小時添加於可分離燒瓶內，同時亦將3%過流酸鉀水溶液30g經4小時添加。單體乳化物之添加終了後，在80℃進行2小時攪拌，使反應終了。冷卻可分離燒瓶內，添加30%氫氧化鈉水溶液8g，中和系統內。 Put 150 g of ion-exchanged water into a 1L five-neck separable flask, and heat to 80°C while stirring. 60 g of acidic phosphoric acid polyoxyethylene glycol monomethacrylate (light ester P-1M manufactured by Kyoei Chemical Co., Ltd., phosphorus content 15% by mass), 36 g of methacrylate, and ethyl acrylate 36 g, 18 g of acrylic acid, 1.5 g of dodecyl benzene sulfonic acid soda, 7.5 g of polyoxyethylene alkyl ether, and 150 g of ion exchange water are uniformly emulsified. 0.2 g of potassium persulfate was added to the separable flask, and when the dripping of the monomer emulsion started, the reaction started. The monomer emulsion was added to the separable flask over 4 hours, and 30 g of a 3% overcurrent potassium acid aqueous solution was added over 4 hours. After the addition of the monomer emulsion was completed, stirring was performed at 80°C for 2 hours to complete the reaction. Cool the separable flask and add 8g of 30% sodium hydroxide aqueous solution to neutralize the system.
其後，一邊攪拌，一邊添加以離子交換水20g稀釋的阻燃劑多聚磷酸銨(鈴裕股份有限公司製之FCP-770，磷含有量24%)20g、以離子交換水10g稀釋的防鏽劑羧基苯並三唑(城北化學工業股份有限公司製之CBT-1)10g，加入離子交換水10g。添加阻燃劑與防鏽劑完成後，進行1小時攪拌，調製出纖維處理劑1。其組成如表1所示。 After that, while stirring, 20g of flame retardant ammonium polyphosphate (FCP-770 manufactured by Suzuhiro Co., Ltd., 24% phosphorus content) diluted with 20g of ion-exchanged water, and 20g of flame retardant diluted with 10g of ion-exchanged water were added. 10g of rust agent carboxybenzotriazole (CBT-1 manufactured by Chengbei Chemical Industry Co., Ltd.) was added to 10g of ion-exchanged water. After the addition of the flame retardant and the rust inhibitor is completed, stirring is performed for 1 hour to prepare a fiber treatment agent 1. Its composition is shown in Table 1.
使用所得之纖維處理劑1，以後述方法製作出纖維加工品。將所得之纖維加工品的物性評估藉由後述評估方法進行。該評估結果如表4所示。 Using the obtained fiber treatment agent 1, a fiber processed product was produced by the method described later. The physical property evaluation of the obtained fiber processed product was performed by the evaluation method mentioned later. The evaluation results are shown in Table 4.
除表1與表2所示組成以外，進行與實施例1之同様方法調製，調製出纖維處理劑2~12。 Except for the compositions shown in Table 1 and Table 2, the preparation was carried out in the same manner as in Example 1 to prepare fiber treatment agents 2-12.
且，表1與表2中之各成分的詳細內容如以下所示。 In addition, the details of each component in Table 1 and Table 2 are as follows.
．二苯基-2-甲基丙烯醯氧乙基磷酸鹽：大八化學工業股份有限公司製之MR-260，磷含有量8% . Diphenyl-2-methacryloyloxyethyl phosphate: MR-260 manufactured by Daha Chemical Industry Co., Ltd., with a phosphorus content of 8%
．1-[N,N-雙(2-乙基己基)胺基甲基]苯並三唑：城北化學工業股份有限公司製之BT-LX . 1-[N,N-bis(2-ethylhexyl)aminomethyl]benzotriazole: BT-LX manufactured by Chengbei Chemical Industry Co., Ltd.
．三苯基磷酸鹽：大八化學工業股份有限公司製之TPP，磷含有量10% . Triphenyl phosphate: TPP made by Dahachi Chemical Industry Co., Ltd., with a phosphorus content of 10%
．聚乙烯醇：股份有限公司Kuraray製之PVA205(皂化度86.5~89.0%，平均聚合度500) . Polyvinyl alcohol: PVA205 manufactured by Kuraray Co., Ltd. (saponification degree 86.5~89.0%, average polymerization degree 500)
使用所得之纖維處理劑2~12，藉由後述方法製作纖維加工品。將所得之纖維加工品的物性評估以後述評估方法進行。該評估結果如表4所示。 Using the obtained fiber treatment agents 2 to 12, a fiber processed product was produced by the method described later. The physical property evaluation of the obtained fiber processed product was performed by the evaluation method mentioned later. The evaluation results are shown in Table 4.
除表3所示組成以外，進行與實施例1之同様方法調製，調製出纖維處理劑13~18。 Except for the composition shown in Table 3, it was prepared in the same manner as in Example 1 to prepare fiber treatment agents 13 to 18.
使用所得之纖維處理劑13~18，藉由後述方法製作出 纖維加工品。將所得之纖維加工品的物性評估藉由後述評估方法進行。該評估結果如表5所示。 Using the obtained fiber treatment agents 13~18, it is produced by the method described below Fiber processing products. The physical property evaluation of the obtained fiber processed product was performed by the evaluation method mentioned later. The evaluation results are shown in Table 5.
使用在實施例1~12及比較例1~6所得之纖維處理劑，製作出纖維加工品。進行所得之纖維加工品的物性評估。纖維加工品之製作及評估依據下述方法進行。 The fiber processing agents obtained in Examples 1 to 12 and Comparative Examples 1 to 6 were used to produce processed fiber products. The physical properties of the obtained fiber processed products were evaluated. The production and evaluation of fiber processed products are carried out according to the following methods.
本發明之實施例、比較例中之纖維基材如以下所示。 The fiber substrates in the examples and comparative examples of the present invention are as follows.
(1)纖維 (1) Fiber
聚酯-纖維素不織布 Polyester-cellulose non-woven fabric
(2)基重 35g/m2 (2) Basis weight 35g/m 2
(3)厚度 200μm (3) Thickness 200μm
將在實施例1~12及比較例1~6所得之纖維處理劑各使用離子交換水，將固體成分稀釋至15質量%後，將基材纖維浸漬在纖維處理劑中。其後，將浸漬纖維處理劑的基材纖維以2根軋輥擠壓、熱風式乾燥機在130℃進行10分鐘乾燥。纖維處理劑之附著量對於纖維重量而言為40~50質量%。 The fiber treatment agents obtained in Examples 1 to 12 and Comparative Examples 1 to 6 were each diluted with ion-exchanged water to 15% by mass, and then the base fiber was immersed in the fiber treatment agent. Thereafter, the base fiber impregnated with the fiber treatment agent was squeezed with two rolls and dried at 130°C for 10 minutes with a hot-air dryer. The adhesion amount of the fiber treatment agent is 40-50% by mass with respect to the fiber weight.
預先精秤所定量試料於乾淨的鋁皿(高度約17mm，口徑約40mm)，使用感度0.5mg以下直讀式天秤進行精秤後，內溫調整在105℃±2℃之乾燥機內放置1小時。乾燥後的試料在乾燥器內冷卻至室溫後，以同一直讀式天秤進行精秤，以下式子算出固體成分。 Preliminarily weigh the quantitative sample in a clean aluminum dish (height: about 17mm, diameter: about 40mm), use a direct-reading balance with a sensitivity of 0.5 mg or less for precision weighing, adjust the internal temperature and place it in a dryer at 105℃±2℃1 hour. After the dried sample is cooled to room temperature in the desiccator, it is finely weighed with the same direct-reading balance, and the solid content is calculated by the following formula.
固體成分(%)=乾燥後的試料重量(g)/原試料重量(g)×100 Solid content (%) = dry sample weight (g) / original sample weight (g) × 100
可使用比色定量法、ICP發光分析等任一方法，例如可藉由元素分析求得磷原子之含有量。 Any method such as colorimetric quantification and ICP emission analysis can be used. For example, the content of phosphorus atoms can be determined by elemental analysis.
對於纖維加工品之燃燒性、防鏽性、滲出進行評估。 Evaluate the flammability, rust resistance, and exudation of processed fiber products.
(1)阻燃性 (1) Flame retardancy
將纖維加工品製作後在23℃及50%RH之條件下靜置12小時以上的試驗體，依據UL-94垂直燃燒試驗(V-0、V-1、V-2規格)，進行燃燒試驗。試驗片之尺寸為長度127mm，寬度12.7mm。對於5片試驗片，各進行點燃火焰2次，合計進行10次，測定消滅火焰時間之平均秒數及最大秒數而進行判定。 After the fabricated product is made, the test body that is left to stand for more than 12 hours under the conditions of 23°C and 50%RH is subjected to a burning test according to the UL-94 vertical burning test (V-0, V-1, V-2 specifications) . The size of the test piece is 127 mm in length and 12.7 mm in width. For the 5 test pieces, the flame was ignited twice for each, and the flame was ignited for a total of 10 times, and the average number of seconds and the maximum number of seconds for the flame-extinguishing time were measured for determination.
UL-94垂直燃燒性試驗(V) UL-94 vertical flammability test (V)
V-0：5片試驗片之第一次與第二次點燃火焰所得之合計燃燒時間為50秒以內，且最大燃燒時間為10秒以內，並無因燃燒所造成的材料滴下。 V-0: The total burning time of the first and second flame ignition of 5 test pieces is within 50 seconds, and the maximum burning time is within 10 seconds, and there is no material dripping due to burning.
V-1：5片試驗片的第一次與第二次之點燃火焰所得之合計燃燒時間為250秒以內，且最大燃燒時間為30秒以內，並無因燃燒所造成的材料滴下。 V-1: The total burning time of the first and second flame ignition of 5 test pieces is within 250 seconds, and the maximum burning time is within 30 seconds, and there is no material dripping due to burning.
V-2：5片試驗片的第一次與第二次之點燃火焰所得之合計燃燒時間為250秒以內，且最大燃燒時間為30秒以內。 V-2: The total burning time of the first and second flame ignition of 5 test pieces is within 250 seconds, and the maximum burning time is within 30 seconds.
(2)防鏽性 (2) Rust resistance
加工品製作後，將在23℃且50%RH之條件下靜置12小時以上的試驗體剪裁成縱：50mm，橫：70mm，密著於黃銅(縱：120mm，橫：30mm，厚度：0.1mm)的主面上，在60℃且95%RH之條件下靜置14天，確認有無黃銅表面的鏽。於表4與5中之評估結果如以下所示。 After the processed product is produced, the test body that has been left to stand at 23°C and 50%RH for more than 12 hours is cut into length: 50mm, width: 70mm, and adhered to brass (length: 120mm, width: 30mm, thickness: On the main surface of 0.1mm), let it stand for 14 days under the conditions of 60°C and 95%RH to confirm whether there is rust on the brass surface. The evaluation results in Tables 4 and 5 are shown below.
有產生鏽：× Rust: ×
無產生鏽：○ No rust: ○
(3)滲出 (3) Exudation
加工品製作後，將在23℃且50%RH的條件下靜置12小時以上的試驗體剪裁成縱：50mm，橫：70mm，以濾紙(縱：100mm，橫：60mm，No.2、東洋濾紙股份有限公司製)夾住，在60℃且95%RH之條件下靜置5天，確認有無加工品表面之滲出。 After the processed product is produced, the test body that has been allowed to stand at 23°C and 50%RH for more than 12 hours is cut into length: 50mm, width: 70mm, with filter paper (length: 100mm, width: 60mm, No. 2, Toyo (Made by Filter Paper Co., Ltd.) and let it stand for 5 days under the conditions of 60°C and 95%RH to check whether there is any exudation on the surface of the processed product.
對於表4與5，評估結果如以下所示。 For Tables 4 and 5, the evaluation results are shown below.
有滲出：× There is oozing: ×
無滲出：○ No oozing: ○
由表4之結果得知，對於藉由本發明之纖維處理劑(實施例1~12)進行處理的纖維加工品，其阻燃性、防鏽性皆同時優良。又得知對於滲出亦充分地被抑制。 From the results in Table 4, it is known that the processed fiber products treated with the fiber treatment agent of the present invention (Examples 1 to 12) have excellent flame retardancy and rust resistance at the same time. It is also known that the exudation is sufficiently suppressed.
相對於此，如表5所示得知，使用未含有阻燃劑(D)的纖維處理劑時(比較例1)，其阻燃性並不充分。得知使用未含有含磷不飽和單體(A)，且添加阻燃劑(D)至纖維處理劑中的磷量成為2.6%的纖維處理劑時(比較例2)，在60℃且95%RH之條件下引起顯著滲出。得知使用未含含磷不飽和單體(A)，且添加阻燃劑(D)至纖維處理劑中之磷量成為1.4%的纖維處理劑時(比較例3)，其阻燃性並不充分。得知使用未含防鏽劑(C)的纖維處理劑時(比較例4)，在60℃且95%RH的條件下，其防鏽性並不充分。得知使用未含有將具有選自由(甲基)丙烯酸及衣康酸所成群的至少一種羧基之不飽和單體(b2)作為聚合性不飽和單體(B)成分的纖維處理劑時(比較例5)，其顯著引起滲出。 In contrast, as shown in Table 5, when a fiber treatment agent that does not contain the flame retardant (D) is used (Comparative Example 1), the flame retardancy is insufficient. It is known that when using a fiber treatment agent that does not contain the phosphorus-containing unsaturated monomer (A), and the flame retardant (D) is added to the phosphorus content of the fiber treatment agent to become 2.6% (Comparative Example 2), the temperature is at 60°C and 95% Causes significant exudation under the condition of %RH. It is known that when a fiber treatment agent that does not contain a phosphorus-containing unsaturated monomer (A) and the amount of phosphorus in the fiber treatment agent becomes 1.4% by adding the flame retardant (D) to the fiber treatment agent (Comparative Example 3), its flame retardancy is insufficient. It was found that when a fiber treatment agent containing no rust inhibitor (C) was used (Comparative Example 4), its rust resistance was insufficient under the conditions of 60° C. and 95% RH. It is known that when using a fiber treatment agent that does not contain an unsaturated monomer (b2) having at least one carboxyl group selected from the group consisting of (meth)acrylic acid and itaconic acid as the polymerizable unsaturated monomer (B) component ( Comparative Example 5), which significantly caused exudation.
得知使用未含有將(甲基)丙烯酸烷基酯不飽和單體 (b1)作為聚合性不飽和單體(B)成分的纖維處理劑時(比較例6)，其防鏽性並不充分。 It is known that the use of unsaturated monomers that do not contain alkyl (meth)acrylate (b1) When used as a fiber treatment agent of the polymerizable unsaturated monomer (B) component (Comparative Example 6), the rust resistance is insufficient.
本發明之纖維處理劑為，經處理的纖維加工品為具有優良阻燃性，或在高濕度條件下具有優良防鏽性，特適用於纖維處理上。又，使用本發明之纖維處理劑的纖維加工品之製造方法為，可製造出具有優良阻燃性、防鏽性之各種纖維加工品，藉由使用該纖維加工品之製造方法，可製造出具有優良的阻燃性、防鏽性之纖維加工品。而藉由使用該纖維加工品，可製造出具有優良阻燃性、防鏽性之電子材料用緩衝材、家電用緩衝材、汽車內裝緩衝材等。 The fiber treatment agent of the present invention is that the processed fiber processed product has excellent flame retardancy, or has excellent rust resistance under high humidity conditions, and is particularly suitable for fiber treatment. In addition, the method for manufacturing fiber processed products using the fiber processing agent of the present invention is to produce various fiber processed products with excellent flame retardancy and rust resistance. By using the manufacturing method of the fiber processed product, it is possible to manufacture Fiber processed products with excellent flame retardancy and rust resistance. And by using this fiber processed product, it is possible to manufacture cushioning materials for electronic materials, cushioning materials for home appliances, and automotive interior cushioning materials with excellent flame retardancy and rust resistance.
Claims (10)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016082714 | 2016-04-18 | ||
| JP2016-082714 | 2016-04-18 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| TW201809402A TW201809402A (en) | 2018-03-16 |
| TWI724154B true TWI724154B (en) | 2021-04-11 |
Family
ID=60116864
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW106112401A TWI724154B (en) | 2016-04-18 | 2017-04-13 | Fiber treatment agent, method for manufacturing fiber processed product, and fiber processed product |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP7012007B2 (en) |
| CN (1) | CN108603332A (en) |
| TW (1) | TWI724154B (en) |
| WO (1) | WO2017183535A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115726186B (en) * | 2021-08-31 | 2024-12-03 | 山东双圆生物科技有限公司 | Biological enzyme-containing waste cloth decoloring agent, preparation method, treating agent and application |
| CN114874393B (en) * | 2022-06-13 | 2024-04-16 | 中铁上海工程局集团市政环保工程有限公司 | Flame-retardant phosphorus-containing acrylic acid salt core-shell emulsion and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010113796A1 (en) * | 2009-03-31 | 2010-10-07 | 昭和高分子株式会社 | Resin composition and processed paper or fiber product treated therewith |
| JP2012089375A (en) * | 2010-10-20 | 2012-05-10 | Teijin Techno Products Ltd | Synthetic fiber for small-diameter electric wire cord |
| WO2013047652A1 (en) * | 2011-09-28 | 2013-04-04 | 豊田合成株式会社 | Coating material for airbag base fabric, and airbag base fabric |
| CN103510379A (en) * | 2012-06-14 | 2014-01-15 | （株）宇宙染色 | Method for applying conductivity to nylon fiber |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03243344A (en) * | 1990-02-21 | 1991-10-30 | Kanzaki Paper Mfg Co Ltd | Rustproofing sheet |
| CA2485826C (en) * | 2003-10-21 | 2016-06-28 | Integrated Marketing Solutions | Corrosion inhibiting protective sleeves |
| US20070135551A1 (en) * | 2005-12-12 | 2007-06-14 | Nissin Chemical Industry Co., Ltd. | Coating composition and vehicle interior material |
| JP6210327B2 (en) * | 2013-09-27 | 2017-10-11 | 豊田合成株式会社 | Airbag base fabric paint, airbag base fabric and manufacturing method thereof |
| CN103911860B (en) * | 2013-12-27 | 2016-03-30 | 宁波市江东林清环保科技有限公司 | A kind of artificial fibre fire-proof flame-retarded agent |
-
2017
- 2017-04-12 JP JP2018513129A patent/JP7012007B2/en active Active
- 2017-04-12 WO PCT/JP2017/014965 patent/WO2017183535A1/en active Application Filing
- 2017-04-12 CN CN201780010003.5A patent/CN108603332A/en active Pending
- 2017-04-13 TW TW106112401A patent/TWI724154B/en active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010113796A1 (en) * | 2009-03-31 | 2010-10-07 | 昭和高分子株式会社 | Resin composition and processed paper or fiber product treated therewith |
| JP2012089375A (en) * | 2010-10-20 | 2012-05-10 | Teijin Techno Products Ltd | Synthetic fiber for small-diameter electric wire cord |
| WO2013047652A1 (en) * | 2011-09-28 | 2013-04-04 | 豊田合成株式会社 | Coating material for airbag base fabric, and airbag base fabric |
| CN103510379A (en) * | 2012-06-14 | 2014-01-15 | （株）宇宙染色 | Method for applying conductivity to nylon fiber |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108603332A (en) | 2018-09-28 |
| JPWO2017183535A1 (en) | 2019-02-21 |
| TW201809402A (en) | 2018-03-16 |
| JP7012007B2 (en) | 2022-01-27 |
| WO2017183535A1 (en) | 2017-10-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR102064933B1 (en) | Non-halogen flame retardant polymers | |
| JP5669363B2 (en) | Resin composition and paper or fiber processed product treated with the same | |
| CN100526381C (en) | Aqueous flame retardant resin composition | |
| JP2018510227A (en) | Aqueous dispersion containing multistage polymer and coating composition containing the same | |
| CN101580619B (en) | Polyvinyl ester dispersions and their application | |
| JP5847177B2 (en) | Sound reduction material with emulsion polymer stabilized with protective colloid | |
| JP5992050B2 (en) | Non-halogen flame retardant as a coating for fiber filtration media | |
| EP1739109A1 (en) | Flame retardant polymer emulsion | |
| TWI778076B (en) | Copolymer, resin composition, treatment agent and processed product | |
| US20190119424A1 (en) | Water-based polymer dispersions comprising hydrophobic antimony-free flame retardants | |
| TWI724154B (en) | Fiber treatment agent, method for manufacturing fiber processed product, and fiber processed product | |
| KR101861018B1 (en) | Dye transfer inhibitor composition and wall papering method using the same | |
| KR20220044992A (en) | Blend of polyacrylic latex and polyvinyl acetate latex | |
| US20200048473A1 (en) | Resin emulsion for damping paint, damping paint, and method for producing resin emulsion for damping paint | |
| JP4354999B2 (en) | Aqueous emulsion composition and processed paper or fiber processed with the same | |
| EP3176187B1 (en) | Formaldehyde-free thermally curable polymers | |
| JP6128290B1 (en) | Resin composition for fiber processing and fabric using the same | |
| JP2015227396A (en) | Resin composition for vibration damping material | |
| US20190375867A1 (en) | Formaldehyde-free thermally curable polymers | |
| JP2005320463A (en) | Water-based flame-retardant resin emulsion and method for producing the same | |
| JP2013049858A (en) | Coating composition for vehicular interior material, and vehicular interior material | |
| JPWO2020032063A1 (en) | Aqueous dispersion, its production method, coating composition and coating film | |
| WO2020142111A1 (en) | Acrylic resin with internal plasticizer | |
| JP2014028899A (en) | Finishing agent for coating film |