JPH03221581A - Flame retardant, water-and-oil repellent of solvent type - Google Patents
Flame retardant, water-and-oil repellent of solvent typeInfo
- Publication number
- JPH03221581A JPH03221581A JP1728090A JP1728090A JPH03221581A JP H03221581 A JPH03221581 A JP H03221581A JP 1728090 A JP1728090 A JP 1728090A JP 1728090 A JP1728090 A JP 1728090A JP H03221581 A JPH03221581 A JP H03221581A
- Authority
- JP
- Japan
- Prior art keywords
- water
- oil
- flame
- oil repellent
- retardant
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000005871 repellent Substances 0.000 title claims abstract description 29
- 239000003063 flame retardant Substances 0.000 title claims abstract description 27
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 230000002940 repellent Effects 0.000 title claims abstract description 25
- 239000002904 solvent Substances 0.000 title claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 39
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 12
- 229920001577 copolymer Polymers 0.000 claims abstract description 11
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims abstract description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 239000000178 monomer Substances 0.000 abstract description 14
- 238000007334 copolymerization reaction Methods 0.000 abstract description 12
- 239000000835 fiber Substances 0.000 abstract description 11
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 abstract description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052794 bromium Inorganic materials 0.000 abstract description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 5
- -1 polyethylene terephthalate Polymers 0.000 description 5
- 229950011008 tetrachloroethylene Drugs 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 239000004753 textile Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000004677 Nylon Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920001778 nylon Polymers 0.000 description 3
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 2
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 2
- JRONWTIJVLNAET-UHFFFAOYSA-N C(CCC)C1CCC(CC1)OC(=O)OOC1CCC(CC1)CCCC Chemical compound C(CCC)C1CCC(CC1)OC(=O)OOC1CCC(CC1)CCCC JRONWTIJVLNAET-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 2
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- 229920002972 Acrylic fiber Polymers 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- MWMBMDKWXVQCHY-UHFFFAOYSA-N C.OC(=O)C=C Chemical compound C.OC(=O)C=C MWMBMDKWXVQCHY-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- LXEKPEMOWBOYRF-UHFFFAOYSA-N [2-[(1-azaniumyl-1-imino-2-methylpropan-2-yl)diazenyl]-2-methylpropanimidoyl]azanium;dichloride Chemical compound Cl.Cl.NC(=N)C(C)(C)N=NC(C)(C)C(N)=N LXEKPEMOWBOYRF-UHFFFAOYSA-N 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
- Fireproofing Substances (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、ソルベント型難燃性撥水撥油剤に関する。更
に詳しくは、処理対象である難燃性繊維製品の難燃性を
低下させることなく、撥水撥油性を付与乃至向上せしめ
るソルベント型難燃性撥水撥油剤に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a solvent type flame retardant water and oil repellent. More specifically, the present invention relates to a solvent-type flame-retardant water- and oil-repellent agent that imparts or improves water- and oil-repellency without reducing the flame retardancy of flame-retardant textile products to be treated.
〔従来の技術〕および〔発明が解決しようとする課題〕
近年、災害事故による被害の増大に伴い、ホテル、旅館
、学校、病院などの建物で使用されるカーテン、カーペ
ットなどのインテリア材料は、消防法により防炎規制さ
れている。しかしながら、こうした用途に用いられる場
合には、難燃性がすぐれているだけでは満足されず、日
常の使用上から撥水性や撥油性を兼ね備えた製品の出現
が待望されている。[Prior art] and [Problem to be solved by the invention]
In recent years, with the increase in damage caused by disasters and accidents, interior materials such as curtains and carpets used in buildings such as hotels, inns, schools, and hospitals are regulated as flame retardant under the Fire Service Act. However, when used in such applications, it is not enough to have excellent flame retardancy alone, and there is a long-awaited emergence of products that have both water and oil repellency for everyday use.
従来は、かかるインテリア材料に難燃性と撥水撥油性と
を同時に付与せんとする場合には、難燃性繊維製品をフ
ッ素系撥水撥油剤で処理することが試みられてきた。し
かるに、かかるフッ素系撥水撥油剤での処理は、高度な
撥水撥油性を付与し得るものの（２種類の某社製品では
、共に撥油性６゜撥水性１００）、難燃性繊維製品が本
来有している難燃性を著しく低下させ、後記難燃性評価
試験では全焼するような事態に至る程である。Conventionally, in order to impart flame retardancy and water/oil repellency to such interior materials at the same time, attempts have been made to treat flame retardant textile products with fluorine-based water/oil repellents. However, although treatment with such a fluorine-based water and oil repellent can impart a high degree of water and oil repellency (two types of products from a certain company both have an oil repellency of 6° and a water repellency of 100), flame-retardant textile products are The flame retardancy it possesses is significantly reduced, and in the flame retardant evaluation test described below, it even causes a complete fire.
そこで、難燃性繊維の融点以下の温度範囲で、特定の融
解流動温度を有する撥水剤を用いて、難燃性繊維製品が
本来有する難燃性を低下させることなく、撥水性を付与
する方法が、特公昭６０−１７１７０号公報に記載され
ている。しかしながら、かかる処理方法は難燃性は維持
させるものの、十分な撥水性を付与させるものではない
。Therefore, water repellency can be imparted to flame-retardant fiber products without reducing their inherent flame retardancy by using a water-repellent agent that has a specific melting and flow temperature in a temperature range below the melting point of flame-retardant fibers. The method is described in Japanese Patent Publication No. 60-17170. However, although this treatment method maintains flame retardancy, it does not impart sufficient water repellency.
本発明の目的は、風乾（室温乾燥）や低温での熱処理（
１００℃以下）であるいはスプレータイプの処理で、高
度な撥水撥油性を付与できるソルベント型であって、処
理対象である難燃性繊維製品が本来有する難燃性を低下
させることなく、撥水撥油性を付与乃至向上せしめるソ
ルベント型難燃性撥水撥油剤を提供することにある。The purpose of the present invention is to perform air drying (room temperature drying) and low temperature heat treatment (
It is a solvent type that can impart a high degree of water and oil repellency at temperatures below 100°C or by spray-type treatment. An object of the present invention is to provide a solvent type flame retardant water and oil repellent that imparts or improves oil repellency.
かかる本発明の目的は、一般式Ｒｆ （ＣＨ２）ｎ０ｃ
ＯｃＲ＝ＣＨ２（ここで、Ｒｆは炭素数６〜■２のパー
フルオロアルキル基であり、Ｒは水素原子またはメチル
基であり、ｎは１〜４の整数である）で表わされるパー
フルオロアルキル基含有アクリレートを４０〜８０重量
％、また臭素含有単量体を２０〜５０重量％それぞれ共
重合させた共重合体を撥水撥油成分としてなるソルベン
ト型難燃性撥水撥油剤によって遠戚される。Such an object of the present invention is the general formula Rf (CH2)n0c
A perfluoroalkyl group represented by OcR=CH2 (where Rf is a perfluoroalkyl group having 6 to 2 carbon atoms, R is a hydrogen atom or a methyl group, and n is an integer of 1 to 4) It is distantly related to solvent-type flame-retardant water and oil repellents whose water and oil repellent components are copolymerized by copolymerizing 40 to 80% by weight of acrylates and 20 to 50% by weight of bromine-containing monomers. Ru.
上記一般式で表わされるパーフルオロアルキル基含有ア
クリレートとしては、単一化合物ばかりではなく混合物
、特に種々の炭素数のパーフルオロアルキル基を有する
化合物の混合物なども用いられる。As the perfluoroalkyl group-containing acrylate represented by the above general formula, not only a single compound but also a mixture, particularly a mixture of compounds having perfluoroalkyl groups having various numbers of carbon atoms, can be used.
また、臭素含有単量体としては、かかるパーフルオロア
ルキル基含有アクリレートと共重合性を有するアクリレ
ート化合物、ビニル化合物、ビニリデン化合物などが用
いられ、それらのいくつかの例は次に示される。Further, as the bromine-containing monomer, acrylate compounds, vinyl compounds, vinylidene compounds, etc. which are copolymerizable with such perfluoroalkyl group-containing acrylates are used, and some examples thereof are shown below.
ＣＨ２＝ｃＲＣＯＯＱ（’）内
Ｃ）Ｉ２＝ＣＲＣＯＯ（ＣＨ２）イ（］（８ｒ）１−’
ＣＨ２＝ＣＲａ）Ｏ（ＣＨ２ＣＨ２０）ｚイ（］（Ｂｒ
）”−閂Ｌ
ＣＨ，＝α侶「
ｃＨ２＝ＣＢｒ２
ソルベント型難燃性撥水撥油剤の撥水撥油成分を形成す
る共重合体は、パーフルオロアルキル基含有アクリレー
トを４０〜８０重量対、好ましくは４０〜６０重量２の
割合で共重合せしめている。共重合割合がこれ以下では
、十分なる撥水撥油性の付与が行われず、一方これ以上
の割合で共重合させると、難燃性繊維製品の難燃性保持
が困難となる。CH2=cRCOOQ(') C) I2=CRCOO(CH2)i(](8r)1-'
CH2=CRa)O(CH2CH20)zi(](Br
)”-bar L CH,=α group “cH2=CBr2 The copolymer forming the water and oil repellent component of the solvent-type flame retardant water and oil repellent contains 40 to 80 parts by weight of perfluoroalkyl group-containing acrylate, Preferably, the copolymerization ratio is 40 to 60% by weight.If the copolymerization ratio is less than this, sufficient water and oil repellency will not be imparted, while if the copolymerization ratio is higher than this, flame retardancy will be It becomes difficult to maintain the flame retardancy of textile products.
また、含臭素単量体は、共重合体中に２０〜５０重量％
、好ましくは２５〜４０重量％の割合で共重合せしめて
いる。共重合割合がこれ以下では、難燃性繊維製品の難
燃性の保持が困難となり、一方これ以上の割合で共重合
させると、十分なる撥水撥油性を付与することができな
い。なお、これらの共重合割合は、用いられた共単量体
の重量割合でもあり。In addition, the bromine-containing monomer is contained in the copolymer in an amount of 20 to 50% by weight.
, preferably in a proportion of 25 to 40% by weight. If the copolymerization ratio is less than this, it will be difficult to maintain the flame retardancy of the flame-retardant fiber product, while if the copolymerization ratio is higher than this, sufficient water and oil repellency cannot be imparted. Note that these copolymerization ratios are also the weight ratios of the comonomers used.
１００％共重合反応が進行しているとの前提に立ってい
る。This is based on the assumption that 100% copolymerization reaction has proceeded.
共重合体中には、本発明の目的とする難燃性および撥水
撥油性を実質的に低下させない範囲内において、他の共
単量体、例えば塩化ビニル、塩化ビニリデン、ベンジル
（メタ）アクリレート、シクロヘキシル（メタンアクリ
レート、ラウリル（メタ）アクリレート、ステアリル（
メタ）アクリレート、アクリロニトリル、アクリルアミ
ド、酢酸ビニル、スチレンなどのビニル化合物またはビ
ニリデン化合物、あるいはＮ−メチロール（メタ）アク
リルアミド、Ｎ−メチロールアクリルアミドブチルエー
テル、Ｎ−ブトキシ（メタ）アクリルアミド、２−ヒド
ロキシ（メタ）アクリレート、２−ヒドロキシプロピル
（メタ〉アクリレートなどの架橋性基含有単量体などを
１種類以上共重合させることができる。The copolymer may contain other comonomers, such as vinyl chloride, vinylidene chloride, benzyl (meth)acrylate, within a range that does not substantially reduce the flame retardancy and water/oil repellency that are the objectives of the present invention. , cyclohexyl (methane acrylate, lauryl (meth)acrylate, stearyl (
Vinyl compounds or vinylidene compounds such as meth)acrylate, acrylonitrile, acrylamide, vinyl acetate, styrene, or N-methylol(meth)acrylamide, N-methylolacrylamide butyl ether, N-butoxy(meth)acrylamide, 2-hydroxy(meth)acrylate , 2-hydroxypropyl(meth)acrylate, or other crosslinkable group-containing monomers may be copolymerized.
共重合反応は、重合開始剤の存在下に、約４０〜１２０
℃で溶液重合法によって行われる。反応溶媒としては、
例えば１，１．１− トリクロロエタン、パークロロエ
チレン、トリクロロトリフルオロエタンナトのハロゲン
化炭化水素、トルエン、キシレンなどの芳香族炭化水素
、酢酸エチル、酢酸ブチルなどのエステル、アセトン、
メチルエチルケトンなどのケトンなどが用いられる。The copolymerization reaction is carried out in the presence of a polymerization initiator at approximately 40 to 120
It is carried out by solution polymerization method at ℃. As a reaction solvent,
For example, halogenated hydrocarbons such as 1,1.1-trichloroethane, perchloroethylene, and trichlorotrifluoroethanato, aromatic hydrocarbons such as toluene and xylene, esters such as ethyl acetate and butyl acetate, acetone,
Ketones such as methyl ethyl ketone are used.
ソルベント型難燃性撥水撥油剤の使用に際しては、この
ようにして得られた固形分濃度約１５〜５゜重量Ｉの溶
液重合液を、パークロロエチレンなどの撥水撥油剤溶媒
で約０．２５〜２重量２程度迄希釈することが行われる
。When using a solvent-type flame-retardant water and oil repellent, the solution polymerization solution obtained in this manner with a solid content concentration of about 15 to 5 degrees by weight I is mixed with a water and oil repellent solvent such as perchloroethylene to It is diluted to about .25 to 2 weight.
このソルベント型難燃性撥水撥油剤によって処理される
難燃性繊維製品としては、ポリエステル系繊維（ポリエ
チレンテレフタレート、ポリブチレンテレフタレートな
ど）、ポリアミド系繊維（４−ナイロン、６−ナイロン
、６，６−ナイロンなど）、アクリル系繊維、ポリオレ
フィン系繊維など、あるいはこれらの繊維と綿などとの
混紡繊維の難燃化処理された各種製品などが挙げられる
。Flame-retardant fiber products treated with this solvent-type flame-retardant water and oil repellent include polyester fibers (polyethylene terephthalate, polybutylene terephthalate, etc.), polyamide fibers (4-nylon, 6-nylon, 6,6 - nylon, etc.), acrylic fibers, polyolefin fibers, etc., and various products made of blended fibers of these fibers and cotton etc., which have been treated to be flame retardant.
本発明により、処理対象であるＭＭ性織繊維製品難燃性
を低下させることなく、撥水撥油性を付与乃至向上せし
めたソルベント型難燃性撥水撥油剤が提供される。The present invention provides a solvent-type flame-retardant water- and oil-repellent agent that imparts or improves water- and oil-repellency without reducing the flame-retardancy of MM woven fiber products to be treated.
次に、実施例について本発明を説明する。 Next, the present invention will be explained with reference to examples.
実施例
パーフルオロアルキルエチルアクリレートＣ，Ｆ２，４
．ＣＣＨ２ＣＨ２０ＣＯＣＨ＝ＣＨ２（： ６．８．１
０．１２の混合物で平均９）［ＦＡＡ］、 ２，４．６
−ドリブロモフエニルメタクリレート（第一工業製薬製
品ピロガード５Ｒ−８０４）［ＢＰＭＡ］、インプロピ
リデンビス（３，５−ジブロモ−４−メタクリロキシフ
ェニル）［ＰＢＭＡＰ］、塩化ビニリデン［νＤＣＱコ
、ベンジルメタクリレート［ＢｚＭＡコ、シクロへキシ
ルメタクリレート［ＣＨＭＡ］、 Ｎ−メチロールアク
リルアミドブチルエーテル［ＭＡＡＢＥ］の各所定量（
表１にｇ単位で示される）およびビス（４−ブチルシク
ロヘキシル）パーオキシカーボネート２ｇ、パークロロ
エチレン２９３．４ｇを、容量５００ｍ Ｑの冷却管付
きガラス製反応容器内に仕込み、窒素ガス気流下で攪拌
した後昇温させ、 ５０℃で１２時間共重合反応させて
、それぞれ固形分濃度約２５．０重量％のソルベント型
難燃性撥水撥油剤Ａ−４（Ａ−Ｆ：実施例、Ｇ−Ｊ：比
較例）を得た。また、撥水撥油剤Ｊは、ビス（４−ブチ
ルシクロヘキシル）パーオキシカーボネートおよびパー
クロロエチレンを用いずに、ｎ−ドデシルメルカプタン
０．４ｇ、ノニオン界面活性剤（花王製品エマルゲン９
３０）６．０ｇ、メチルエチルケトン６３．０ｇ、蒸留
水２３０．４ｇおよびアゾビスイソブチロアミジン２塩
酸塩２．０ｇを用い、７０℃で４時間共重合反応させて
得られた。Example perfluoroalkylethyl acrylate C,F2,4
．． CCH2CH20COCH=CH2(: 6.8.1
Average 9) [FAA], 2,4.6 in a mixture of 0.12
-dribromophenyl methacrylate (Daiichi Kogyo Seiyaku Pyroguard 5R-804) [BPMA], inpropylidene bis(3,5-dibromo-4-methacryloxyphenyl) [PBMAP], vinylidene chloride [νDCQ, benzyl methacrylate [ Predetermined amounts of BzMA, cyclohexyl methacrylate [CHMA], and N-methylol acrylamide butyl ether [MAABE] (
(shown in g in Table 1), 2 g of bis(4-butylcyclohexyl) peroxycarbonate, and 293.4 g of perchloroethylene were charged into a glass reaction vessel with a cooling tube of 500 m Q capacity, and heated under a nitrogen gas stream. After stirring, the temperature was raised, and a copolymerization reaction was carried out at 50°C for 12 hours to obtain solvent-type flame-retardant water and oil repellents A-4 (A-F: Examples, G -J: Comparative Example) was obtained. In addition, water and oil repellent J contains 0.4 g of n-dodecyl mercaptan and a nonionic surfactant (Kao product Emulgen 9) without using bis(4-butylcyclohexyl) peroxycarbonate or perchloroethylene.
30), 63.0 g of methyl ethyl ketone, 230.4 g of distilled water, and 2.0 g of azobisisobutyramidine dihydrochloride were copolymerized at 70° C. for 4 hours.
表１
撥水撥油剤 」易 □Ｍ ツルｆ 百１ｃＩＩＩ 敗
Ｍ □Ｍ 髪人里Ａ ４２．５ ２１．３ −
２１．３ １０．７Ｂ −
−１６，０１６，ＯＣ２９，３−−１１，０１１，Ｏ
Ｄ ＃ ３９．１ − − ７．１
７．１Ｅ ４８．９ − − ２
．２ ２．２Ｆ ２０．０ １．３
２１．３ １０．７Ｇ ３０．０４８．９ −
− ８．５ ８．４Ｈ４２，５１２，６−２１
，３９，７９，７Ｉ ３５．０２１．３ −
２７．７ ７．３ − ４．３Ｊ
−２１，３ｔｒ −ｎ得られた各
ソルベント型難燃性撥水撥油剤を、固形分濃度が所定濃
度になるようにパークロロエチレンで希釈し、希釈液中
に試験布［市販難燃性ポリエステルカーテン布：日本防
災協会防炎規格（イ）合格品コを５秒間浸漬し、十分に
マングルで絞ってから、８０℃で５分間乾燥した後、次
の各試験を行った。Table 1 Water and oil repellent 'Yi □M Tsuru f 101cIII Defeated M □M Hair Hitori A 42.5 21.3 -
21.3 10.7B -
-16,016,OC29,3--11,011,OD #39.1 - - 7.1
7.1E 48.9 - - 2
．． 2 2.2F 20.0 1.3
21.3 10.7G 30.048.9 -
- 8.5 8.4H42,512,6-21
,39,79,7I 35.021.3 −
27.7 7.3 - 4.3J
-21,3tr -n Each of the obtained solvent-type flame-retardant water and oil repellents was diluted with perchlorethylene so that the solid content concentration became a predetermined concentration, and the test cloth [commercially available flame-retardant polyester Curtain cloth: A product that passed Japan Disaster Prevention Association Fire Retardant Standards (A) was immersed for 5 seconds, thoroughly squeezed with a mangle, dried at 80° C. for 5 minutes, and then subjected to the following tests.
難燃性評価： ＪＩＳ Ｌ−１０９１Ａ−１法（４５”
ミクロバーナ＠）撥水性評価： ＡＡＴＣＣ−ＴＭ−
２２−１９８５撥油性評価： ＡＡＴＣＣ−ＴＭ−１１
８−１９８３試験結果は、撥水撥油剤共重合体中の含Ｆ
単量体（パーフルオロアルキル基含有アクリレート）お
よび含Ｂｒ単量体の含有率と共に、次の表２に示される
６なお、Ｎｏ、１４は、未処理の難燃性ポリエステルカ
ーテン布である。Flame retardancy evaluation: JIS L-1091A-1 method (45”
Microburner @) Water repellency evaluation: AATCC-TM-
22-1985 Oil repellency evaluation: AATCC-TM-11
8-1983 test results are based on the F content in water and oil repellent copolymers.
The contents of the monomer (perfluoroalkyl group-containing acrylate) and the Br-containing monomer are shown in Table 2 below.No. 14 is an untreated flame-retardant polyester curtain cloth.
（以下余白） 撥水撥油剤 見亀恩４東刃 ０．２５ ０．５０ １．００ ２．００ １．００ ２１．８ ３０．７ ４３．５ ３５．８ ３０．０ ４０．０ ５０．０ ２１．８ ５０、Ｏ １２，９ ２１，８ 表２ 以上の結果から、次のようなことがいえる。(Margin below) Water and oil repellent Mikion 4 East Blade 0.25 0.50 1.00 2.00 1.00 21.8 30.7 43.5 35.8 30.0 40.0 50.0 21.8 50, O 12,9 21,8 Table 2 From the above results, the following can be said.
（１）Ｎｏ１〜９（実施例）に示される如く、含Ｆ単量
体を４０〜８０重量２の範囲内でかつ含Ｂｒ単量体を２
０〜５０重量２の範囲内でそれぞれ共重合させた共重合
体よりなる撥水撥油剤で処理した市販難燃性ポリエステ
ル布は、難燃性を低下させることなく、良好な撥水撥油
性を発現している。(1) As shown in Nos. 1 to 9 (Example), the F-containing monomer is in the range of 40 to 80% by weight, and the Br-containing monomer is in the range of 2 to 80% by weight.
Commercially available flame-retardant polyester fabric treated with a water- and oil-repellent agent made of a copolymer copolymerized within the range of 0 to 50 weight 2 exhibits good water- and oil-repellency without reducing flame retardancy. It is manifesting.
（２）＆１０（比較例）に示される如く、含Ｆ単量体が
４０重量％以下でしか共重合されていない共重合体より
なる撥水撥油剤では、満足される撥水撥油性が得られず
、またＮＱＩＩ（比較例）に示される如く、含Ｂｒ単量
体が２０重量％以下でしか共重合されていない共重合体
よりなる撥水撥油剤では、防災規格（イ）に合格する難
燃性が維持できない。As shown in (2) & 10 (comparative example), a water and oil repellent made of a copolymer in which the F-containing monomer is copolymerized in an amount of 40% by weight or less can provide satisfactory water and oil repellency. In addition, as shown in NQII (comparative example), water and oil repellents made of copolymers in which Br-containing monomers are copolymerized at less than 20% by weight pass the disaster prevention standard (a). Flame retardancy cannot be maintained.
（３）更↓こ、ＮＯ３２〜］３（比較例）に示される如
く、同し共重合割合で含Ｆ単量体と含Ｂｒ単量体とを共
重合させた共重合体よりなる撥水撥油剤にあっては、界
面活性剤を含有していないもの（Ｎα１２）の方が含有
しているもの（Ｎα１３）よりも、難燃性、撥水撥泊性
共に良好である。(3) As shown in 3 (comparative example), a water repellent made of a copolymer obtained by copolymerizing an F-containing monomer and a Br-containing monomer at the same copolymerization ratio. Regarding oil repellents, those that do not contain a surfactant (Nα12) have better flame retardancy and water and repellency than those that do contain a surfactant (Nα13).
Claims (1)
ここで、Ｒｆは炭素数６〜１２のパーフルオロアルキル
基であり、Ｒは水素原子またはメチル基であり、ｎは１
〜４の整数である）で表わされるパーフルオロアルキル
基含有アクリレートを４０〜８０重量％、また臭素含有
単量体を２０〜５０重量％それぞれ共重合させた共重合
体を撥水撥油成分としてなるソルベント型難燃性撥水撥
油剤。1. General formula Rf(CH_2)nOCOCR=CH_2(
Here, Rf is a perfluoroalkyl group having 6 to 12 carbon atoms, R is a hydrogen atom or a methyl group, and n is 1
A copolymer obtained by copolymerizing 40 to 80% by weight of perfluoroalkyl group-containing acrylate represented by Solvent type flame retardant water and oil repellent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1728090A JP2787243B2 (en) | 1990-01-26 | 1990-01-26 | Solvent type flame retardant water and oil repellent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1728090A JP2787243B2 (en) | 1990-01-26 | 1990-01-26 | Solvent type flame retardant water and oil repellent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03221581A true JPH03221581A (en) | 1991-09-30 |
| JP2787243B2 JP2787243B2 (en) | 1998-08-13 |
Family
ID=11939569
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1728090A Expired - Lifetime JP2787243B2 (en) | 1990-01-26 | 1990-01-26 | Solvent type flame retardant water and oil repellent |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2787243B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002072727A1 (en) * | 2001-03-09 | 2002-09-19 | Daikin Industries, Ltd. | Water-and-oil repellant composition with improved suitability for cold cure |
| JP2014129532A (en) * | 2008-09-15 | 2014-07-10 | Daikin Ind Ltd | Water and oil repellent composition |
-
1990
- 1990-01-26 JP JP1728090A patent/JP2787243B2/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002072727A1 (en) * | 2001-03-09 | 2002-09-19 | Daikin Industries, Ltd. | Water-and-oil repellant composition with improved suitability for cold cure |
| US7217760B2 (en) | 2001-03-09 | 2007-05-15 | Daikin Industries, Ltd. | Water-and-oil repellant composition with improved suitability for cold cure |
| JP2014129532A (en) * | 2008-09-15 | 2014-07-10 | Daikin Ind Ltd | Water and oil repellent composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2787243B2 (en) | 1998-08-13 |
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