JPH0350776B2 - - Google Patents
Info
- Publication number
- JPH0350776B2 JPH0350776B2 JP58084628A JP8462883A JPH0350776B2 JP H0350776 B2 JPH0350776 B2 JP H0350776B2 JP 58084628 A JP58084628 A JP 58084628A JP 8462883 A JP8462883 A JP 8462883A JP H0350776 B2 JPH0350776 B2 JP H0350776B2
- Authority
- JP
- Japan
- Prior art keywords
- flame
- retardant polyester
- polyester molded
- group
- molded product
- 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.)
- Expired - Lifetime
Links
- 229920000728 polyester Polymers 0.000 claims description 33
- 239000003063 flame retardant Substances 0.000 claims description 29
- 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 claims description 28
- 239000007795 chemical reaction product Substances 0.000 claims description 19
- 150000001875 compounds Chemical class 0.000 claims description 17
- 239000000047 product Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
- -1 alkylene terephthalate Chemical compound 0.000 claims description 13
- 238000002844 melting Methods 0.000 claims description 11
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims description 8
- 239000011574 phosphorus Substances 0.000 claims description 8
- 229920000768 polyamine Polymers 0.000 claims description 7
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 125000003700 epoxy group Chemical group 0.000 claims description 4
- 150000003944 halohydrins Chemical class 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- 239000002202 Polyethylene glycol Substances 0.000 description 8
- 229920001223 polyethylene glycol Polymers 0.000 description 8
- 229920000139 polyethylene terephthalate Polymers 0.000 description 7
- 239000005020 polyethylene terephthalate Substances 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000000835 fiber Substances 0.000 description 6
- 239000012943 hotmelt Substances 0.000 description 6
- 238000000465 moulding Methods 0.000 description 6
- 239000004744 fabric Substances 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 4
- 239000004202 carbamide Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- GKQPCPXONLDCMU-CCEZHUSRSA-N lacidipine Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1C1=CC=CC=C1\C=C\C(=O)OC(C)(C)C GKQPCPXONLDCMU-CCEZHUSRSA-N 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 description 1
- SEFYJVFBMNOLBK-UHFFFAOYSA-N 2-[2-[2-(oxiran-2-ylmethoxy)ethoxy]ethoxymethyl]oxirane Chemical compound C1OC1COCCOCCOCC1CO1 SEFYJVFBMNOLBK-UHFFFAOYSA-N 0.000 description 1
- ZAXCZCOUDLENMH-UHFFFAOYSA-N 3,3,3-tetramine Chemical compound NCCCNCCCNCCCN ZAXCZCOUDLENMH-UHFFFAOYSA-N 0.000 description 1
- MMINFSMURORWKH-UHFFFAOYSA-N 3,6-dioxabicyclo[6.2.2]dodeca-1(10),8,11-triene-2,7-dione Chemical compound O=C1OCCOC(=O)C2=CC=C1C=C2 MMINFSMURORWKH-UHFFFAOYSA-N 0.000 description 1
- WSQZNZLOZXSBHA-UHFFFAOYSA-N 3,8-dioxabicyclo[8.2.2]tetradeca-1(12),10,13-triene-2,9-dione Chemical compound O=C1OCCCCOC(=O)C2=CC=C1C=C2 WSQZNZLOZXSBHA-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 150000001767 cationic compounds Chemical class 0.000 description 1
- 238000009990 desizing Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- GKIPXFAANLTWBM-UHFFFAOYSA-N epibromohydrin Chemical compound BrCC1CO1 GKIPXFAANLTWBM-UHFFFAOYSA-N 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- QQVIHTHCMHWDBS-UHFFFAOYSA-L isophthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC(C([O-])=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-L 0.000 description 1
- 238000009940 knitting Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000009991 scouring Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- MNCGMVDMOKPCSQ-UHFFFAOYSA-M sodium;2-phenylethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 MNCGMVDMOKPCSQ-UHFFFAOYSA-M 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Landscapes
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Description
本発明は熱溶融性難燃ポリエステル成形物の耐
久性親水、制電加工法に関するものであり、その
目的は、熱溶融性難燃ポリエステル成形物の難燃
性を低下させることなく耐久性親水・制電加工を
行うにある。
従来、ポリエステル成形物の耐久性制電加工と
しては、スチレンスルホン酸ナトリウム塩、メタ
クリ酸ポリエチレングリコールエステル等の重合
体や、アクリルアミドから誘導された下式の如き
カチオン性化合物の重合体が用いられていた。
一方、熱溶融性ポリエステル成形品に難燃性を
付与するためには、リン、ハロゲン、硫黄等の元
素を含有する化合物を重縮合、混合紡糸、後加工
等によつて導入または付与する方法も種々検討さ
れているが、繊維物性等から導入量に限界がある
ため、多くの難燃化も接炎または着火部分の熱溶
融落下による自己消化性を目的としている。そし
て、このような熱溶融性難燃ポリエステル成形物
に上述の各種ビニル重合体から成る制電加工剤を
付与すると難燃性が大きく低下し、折角付与され
た難燃性も失われてしまうという欠点を有してい
た。これらビニル重合体を用いたときの難燃性低
下の理由は明らかでないが、接炎または着火した
周囲部に存在するビニル重合体の一部が三次元結
合によつて不融化するために熱溶融性難燃ポリエ
ステルの熱溶融落下性を妨げるためと考えられ
る。このようなことから、熱溶融性難燃ポリエス
テル成形物の耐久性親水・制電加工法としてポリ
エチレングリコールとポリエチレンテレフタレー
トのブロツクコポリマーの如き親水化剤の付与も
検討されているが、このようなノニオン化合物で
は親水制は付与されても制電性の効果は不充分で
あり、更にポリエチレングリコール系制電剤は日
光照射に対して耐久性が劣ることから耐久性が不
充分であつた。
本発明者らは、熱溶融性難燃ポリエステル成形
物の耐久性親水・制電加工における上記欠点を解
決し、すぐれた難燃性・親水・制電加工製品を得
るべく鋭意研究の結果、本発明の方法に到達した
ものである。
すなわち、本発明は、リン含有エステル形成性
化合物を共重合した熱溶融性を有する難燃ポリエ
ステル成形物を、ポリオキシアルキレン単位含有
ポリアミンとハロヒドリン基および／またはエポ
キシ基含有化合物との反応生成物(A)およびアルカ
リ性化合物(B)を含む処理液により処理することを
特徴とする難燃ポリエステル成形物の処理方法で
ある。
本発明の方法による時は、熱溶融性難燃ポリエ
ステル成形物の難燃性を低下させることなく、し
かも耐久性にすぐれた親水・制電加工品を得るこ
とが出来る。
更におどろくべきことは、本発明における熱溶
融難燃ポリエステル成形物に本親水・制電加工を
行つたものと難燃制を有しない通常の熱溶融性ポ
リエチレンテレフタレートに同様加工を行つたも
のについて、制電性効果の耐久性を比較するとき
前者が著しくすぐれていることである。この理由
は明らかでないが、リン含有エステル形成性化合
物を共重合したポリエステル成形物の表面状態が
変化しており、上記親水・制電加工剤との接着性
が向上するか、もしくは難燃剤成分と親水・制電
加工剤との接着性が改善されるものと考えられ
る。
本発明でいう熱溶融性を有するポリエステル難
燃ポリエステル成形物とは、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、ポリエ
チレンテレフタレート・イソフタレート・ポリシ
クロヘキサンジメチレンテレフタレート、ポリエ
チレンテレフタレート・ブチレンテレフタレート
のようなアルキレンテレフタレートを主たる繰返
し単位とするポリエステルに、リンを含有する難
燃剤を重縮合によつて導入して得られる糸条物、
編織物、不織布、合成紙、敷物、スパンボンド、
フイルム、その他成形品等が例示される。リン含
有エステル形成性化合物を共重合した難燃ポリエ
ステルのうち、下記式〔〕で示されるカルボン
酸を酸成分の一部として共重合したポリエステル
が特に好ましい。
（但し、Ｒ，R1は同じかまたは相異なる基で水
素原子、ハロゲン原子または炭素数６以下の炭化
水素基、R2，R3は同じかまたは相異なる基で水
素原子、炭素数７以下の炭化水素基または（−
R4O）rHで示される基を示す。またR4はエチレ
ン、プロピレンまたはブチレン基を、ｒは１〜10
の整数、ｌ、ｍは０または１〜４の整数、ｎは
０、１または２である。）
リン含有量は通常500〜１万PPm程度が好まし
い。
本発明において用いられる制電加工剤として
は、ポリオキシアルキレン単位含有ポリアミンと
ハロヒドリン基および／またはエポキシ基含有化
合物と反応生成物が挙げられるが、ポリオキシア
ルキレンジアミン、ポリオキシアルキレングリコ
ールにエピハロヒドリンを反応させて得られるポ
リオキシアルキレンビスハロヒドリンエーテルと
ジエチレントリアミン、ジプロピレントリアミ
ン、トリプロピレンテトラミンのようなポリアミ
ンを反応させて得られる生成物等のポリオキシア
ルキレン単位含有ポリアミンとハロヒドリン基、
エポキシ基、エポキシ前駆体基をもつ化合物、た
とえばエピクロルヒドリン、エピブロムヒドリ
ン、エチレングリコールビスハロヒドリン、グリ
センポリハロヒドリン、ビスハロヒドリンエーテ
ル・ジクロログリセリン、ジエチレングリコール
ジハロヒドリン、ポリエチレングリコールジハロ
ヒドリン、ジグリシジルエーテル、エチレングリ
コールジグリシジルエーテル、グリセトリンポリ
グリシジルエーテル、ジエチレングリコールジグ
リシジルエーテル等との反応生成物が特に好まし
い。該反応生成物はアルカリ性化合物の存在によ
り硬化し繊維表面に硬化的に固着される。かくし
て得られた反応生成物たる制電加工剤を熱溶融性
難燃ポリエステル成形物に付与するに際しては、
アルカリ性化合物を含む水溶液中で加熱処理する
か、またはアルカリ性化合物を含む水溶液をポリ
エステル成形物に任意の手段たとえばパツド法で
付与し、ドライ、キユアを行う等の方法がある。
この際、本反応生成物とアルカリ性物質の他に尿
素または尿素系化合物を併用するとよい。処理条
件について説明すると、水溶液中での加熱処理法
においては、反応生成物を0.5〜５％owf、アルカ
リ性物質としてたとえば水酸化アルカリを１〜30
ｇ／含む水溶液とし、この処理浴中へ被処理ポ
リエステル成形物を入れて加温し、90〜100℃で
20〜30分保持した後、冷却、洗浄し、乾燥、セツ
トを行う。またパツド法においては、通常反応生
成物の10〜15ｇ／、アルカリ物質としてたとえ
ば炭酸アルカリ10〜50ｇ／、尿素10〜100ｇ／
を含む水溶液によるパツドし過剰の処理液を絞
液した後100〜130℃で乾燥後、150〜180℃で３〜
30秒熱処理を行う。この後洗浄し、再び乾燥、セ
ツトを行う。かくして得られる処理物、例えば織
物の難燃性は例えば消防法に定められたコイル法
等でテストしても、本来その織物のもつ難燃性は
全く阻害されることがないばかりでなく、制電性
の耐久性も極めて優れていた。このように本反応
生成物が熱溶融性難燃ポリエステル成形物の難燃
性を低下させない理由としては、反応生成物中に
含まれる窒素の作用およびポリエーテル鎖やポリ
アミン鎖の熱分解が容易に進み、非溶融性の物質
形成がないため等によるものと推定される。
次に、実施例により本発明の効果を説明する。
なお、実施例中の部および％は重量基準である。
反応生成物Ａ
分子量1000のポリエチレングリコールのビスク
ロルヒドリンエーテルにジプロピレントリアミン
を反応させ得られたポリエチレングリコールポリ
アミンにエピクロルヒドリンを反応させた。こう
して得られた反応生成物を反応生成物Ａとした。
反応生成物Ｂ
分子量600のポリエチレングリコールのビスク
ロルヒドリンエーテル80部と13.2部のジプロピレ
ントリアミンを反応させ、この反応物に更に分子
量600のポリエチレングリコールのビスクロルヒ
ドリンエーテル160部を反応させて反応生成物Ｂ
を得た。
実施例 １
ボリエステルの酸成分として式(A)で表わされる
カルボン酸をリンとして約4000PPm共重合した
ポリエチレンテレフタレートを常法による紡糸、
延伸して繊維（150d−48f）を製造した。
この繊維を平織物にし、常法に従つて糊抜、精
練を行つた後、第１表に示す浴組成の水溶液中に
よりパツドし、絞り率40％で絞液後90℃で乾燥
し、160℃で２分キユアを行つた。更に60℃の温
水（ノイゲンHC：（第１工業製薬社ノニオン活
性剤）１ｇ／含有）中で10分間洗浄した。この
後充分温洗、水洗を行い、乾燥、セツト（170℃、
20秒）した。かくして得た織物の難燃性、制電性
を第１表に示した。なお、通常のポリエチレンテ
レフタレート繊維（150d−48f）よりなるタフタ
について同様テストした結果も示した。
The present invention relates to a durable hydrophilic and antistatic processing method for heat-melting flame-retardant polyester moldings, and its purpose is to provide durable hydrophilic and anti-static processing for heat-melting flame-retardant polyester moldings without reducing the flame retardancy. To perform anti-static processing. Conventionally, polymers such as sodium styrene sulfonate and polyethylene glycol methacrylate ester, and polymers of cationic compounds derived from acrylamide such as the following formula have been used for durable antistatic finishing of polyester moldings. Ta. On the other hand, in order to impart flame retardancy to hot-melt polyester molded products, there are also methods of introducing or imparting compounds containing elements such as phosphorus, halogen, and sulfur through polycondensation, mixed spinning, post-processing, etc. Various studies have been conducted, but since there is a limit to the amount introduced due to the physical properties of the fibers, most flame retardants aim at self-extinguishing properties due to heat melting and falling of the flame contact or ignited part. It is said that if an antistatic finishing agent made of the various vinyl polymers mentioned above is applied to such hot-melt flame-retardant polyester molded products, the flame retardance will be greatly reduced, and the flame retardance that was painstakingly imparted will also be lost. It had drawbacks. The reason for the decrease in flame retardancy when these vinyl polymers are used is not clear, but some of the vinyl polymers present in the surrounding areas that come in contact with flame or ignite become infusible due to three-dimensional bonding, so they melt under heat. This is thought to be because it impedes the thermal melting properties of the flame-retardant polyester. For this reason, the addition of a hydrophilic agent such as a block copolymer of polyethylene glycol and polyethylene terephthalate is being considered as a durable hydrophilic and antistatic processing method for hot-melt flame-retardant polyester moldings. Although the compound imparts hydrophilic properties, the antistatic effect is insufficient, and polyethylene glycol-based antistatic agents have insufficient durability because they have poor durability against sunlight irradiation. The present inventors have conducted intensive research to solve the above-mentioned drawbacks in durable hydrophilic and antistatic processing of heat-melting flame-retardant polyester moldings and to obtain products with excellent flame retardancy, hydrophilicity, and antistatic properties. This method of invention has been achieved. That is, the present invention provides a heat-melting flame-retardant polyester molded product copolymerized with a phosphorus-containing ester-forming compound, a reaction product of a polyoxyalkylene unit-containing polyamine and a halohydrin group-containing compound and/or an epoxy group-containing compound ( This is a method for treating a flame-retardant polyester molded article, characterized in that it is treated with a treatment liquid containing A) and an alkaline compound (B). When the method of the present invention is used, it is possible to obtain a hydrophilic and antistatic product with excellent durability without reducing the flame retardancy of the hot-melt flame-retardant polyester molded product. What is even more surprising is that the hot-melt flame-retardant polyester molded product of the present invention is subjected to this hydrophilic/antistatic treatment, and the conventional hot-melt flame-retardant polyethylene terephthalate without flame retardant is treated in the same manner. When comparing the durability of the antistatic effect, the former is significantly superior. The reason for this is not clear, but the surface condition of the polyester molded product copolymerized with the phosphorus-containing ester-forming compound has changed, and the adhesion with the above-mentioned hydrophilic/antistatic finishing agent has improved, or the flame retardant component has improved. It is thought that the adhesiveness with the hydrophilic/antistatic finishing agent is improved. In the present invention, flame-retardant polyester molded products having heat-melting properties are mainly repeating alkylene terephthalates such as polyethylene terephthalate, polybutylene terephthalate, polyethylene terephthalate/isophthalate/polycyclohexane dimethylene terephthalate, and polyethylene terephthalate/butylene terephthalate. A yarn material obtained by introducing a phosphorus-containing flame retardant into a polyester unit by polycondensation,
Knitted fabrics, non-woven fabrics, synthetic paper, rugs, spunbond,
Examples include films and other molded products. Among flame-retardant polyesters copolymerized with a phosphorus-containing ester-forming compound, polyesters copolymerized with a carboxylic acid represented by the following formula [] as part of the acid component are particularly preferred. (However, R and R 1 are the same or different groups, such as a hydrogen atom, a halogen atom, or a hydrocarbon group having 6 or less carbon atoms, and R 2 and R 3 are the same or different groups, such as a hydrogen atom, or a hydrocarbon group having 7 or less carbon atoms. hydrocarbon group or (−
R 4 O) represents a group represented by rH. Also, R 4 is ethylene, propylene or butylene group, r is 1 to 10
, l and m are 0 or an integer of 1 to 4, and n is 0, 1 or 2. ) The phosphorus content is usually preferably about 500 to 10,000 PPm. Examples of the antistatic finishing agent used in the present invention include reaction products of polyoxyalkylene unit-containing polyamines, halohydrin group- and/or epoxy group-containing compounds, and polyoxyalkylene diamines, polyoxyalkylene glycols, and epihalohydrin reaction products. A polyoxyalkylene unit-containing polyamine such as a product obtained by reacting a polyoxyalkylene bishalohydrin ether obtained by reacting with a polyamine such as diethylene triamine, dipropylene triamine, or tripropylene tetramine, and a halohydrin group,
Compounds with epoxy groups or epoxy precursor groups, such as epichlorohydrin, epibromohydrin, ethylene glycol bishalohydrin, glycene polyhalohydrin, bishalohydrin ether/dichloroglycerin, diethylene glycol dihalohydrin, polyethylene glycol dihalohydrin, etc. Particularly preferred are reaction products with lohydrin, diglycidyl ether, ethylene glycol diglycidyl ether, glycetrin polyglycidyl ether, diethylene glycol diglycidyl ether, and the like. The reaction product is cured by the presence of the alkaline compound and fixed to the fiber surface in a curing manner. When applying the antistatic finishing agent, which is the reaction product thus obtained, to the heat-melting flame-retardant polyester molded article,
There are methods such as heat treatment in an aqueous solution containing an alkaline compound, or applying an aqueous solution containing an alkaline compound to a polyester molded article by any means such as a pad method, followed by drying and curing.
At this time, in addition to the reaction product and the alkaline substance, urea or a urea-based compound may be used in combination. To explain the treatment conditions, in the heat treatment method in an aqueous solution, the reaction product is 0.5 to 5% owf , and the alkaline substance, such as alkali hydroxide, is 1 to 30% owf.
The polyester molded article to be treated is placed in this treatment bath and heated at 90 to 100℃.
After holding for 20 to 30 minutes, cool, wash, dry, and set. In addition, in the PAD method, the reaction product is usually 10 to 15 g/alkaline substance, such as alkali carbonate 10 to 50 g/, urea 10 to 100 g/
After padding with an aqueous solution containing
Perform heat treatment for 30 seconds. After that, wash, dry and set again. Even if the flame retardancy of the thus obtained treated product, such as a textile, is tested using the coil method stipulated in the Fire Service Act, the flame retardancy of the textile is not inhibited at all; The electrical durability was also extremely excellent. The reason why this reaction product does not reduce the flame retardancy of heat-melting flame-retardant polyester moldings is that the reaction product contains nitrogen and the polyether chains and polyamine chains are easily thermally decomposed. This is presumed to be due to the fact that there is no formation of non-melting substances. Next, the effects of the present invention will be explained using examples.
Note that parts and percentages in the examples are based on weight. Reaction Product A Bischlorohydrin ether of polyethylene glycol having a molecular weight of 1000 was reacted with dipropylene triamine, and the resulting polyethylene glycol polyamine was reacted with epichlorohydrin. The reaction product thus obtained was designated as reaction product A. Reaction product B 80 parts of bischlorohydrin ether of polyethylene glycol with a molecular weight of 600 is reacted with 13.2 parts of dipropylene triamine, and this reaction product is further reacted with 160 parts of bischlorohydrin ether of polyethylene glycol with a molecular weight of 600. Reaction product B
I got it. Example 1 Polyethylene terephthalate, which was copolymerized with about 4000 PPm of carboxylic acid represented by formula (A) as the acid component of the polyester, was spun by a conventional method.
Fibers (150d-48f) were produced by drawing. This fiber was made into a plain weave, and after desizing and scouring in accordance with conventional methods, it was padded in an aqueous solution having the bath composition shown in Table 1, squeezed at a squeezing rate of 40%, and dried at 90°C. Cure was carried out for 2 minutes at ℃. Furthermore, it was washed for 10 minutes in 60°C warm water (containing 1 g/Neugen HC (nonionic activator from Daiichi Kogyo Seiyaku Co., Ltd.)). After that, wash thoroughly at warm temperature, rinse with water, dry, and set (170℃,
20 seconds). The flame retardancy and antistatic properties of the fabric thus obtained are shown in Table 1. The results of a similar test on taffeta made of ordinary polyethylene terephthalate fiber (150d-48f) are also shown.
【表】
難燃ポリエステル織物に本発明の方法を施した
とき難燃性の低下もなく、制電性がえられた。ま
た制電性の耐久性は通常ポリエステル識物に処理
したときと比較して著しく改善された。
実施例 ２
実施例１と同様の難燃ポリエステル糸（150d
−48f）をテキスチユアード加工し、加工糸とし
た。この糸をフライスに編立てた後常法により精
練を行つた。この後第２表に示す処理浴処方によ
り、実施例１と同じ工程条件で加工した。なお通
常のポリエステル糸（150d−48f）も同様加工糸
にし、フライスに編立てた後、実施例と同様に精
練および加工した。[Table] When the method of the present invention was applied to flame-retardant polyester fabrics, antistatic properties were obtained without any decrease in flame retardancy. Furthermore, the durability of antistatic properties was significantly improved compared to when ordinary polyester materials were treated. Example 2 Flame-retardant polyester yarn (150d
-48f) was textured and processed into processed yarn. After knitting this yarn into a milling cutter, it was refined by a conventional method. Thereafter, processing was carried out under the same process conditions as in Example 1 using the processing bath formulation shown in Table 2. Note that ordinary polyester yarn (150d-48f) was similarly processed, knitted into a milling cutter, and then refined and processed in the same manner as in the examples.
【表】
実施例 ３
難燃ポリエステル「東洋紡ハイム」（東洋紡績
社リン系難燃改質）の短繊維織物を反応生成物
A5％、Na2CO30.5％、尿素３％を含む水溶液で
実施例２と同条件で処理したところ、制電性にす
ぐれた難燃性織物が得られた。[Table] Example 3 Short fiber fabric of flame-retardant polyester “Toyobo Heim” (phosphorus-based flame-retardant modified by Toyobo Co., Ltd.) was used as a reaction product.
When treated with an aqueous solution containing 5% A, 0.5% Na 2 CO 3 and 3% urea under the same conditions as in Example 2, a flame-retardant fabric with excellent antistatic properties was obtained.
Claims (1)
熱溶融性を有する難燃ポリエステル成形物を、ポ
リオキシアルキレン単位含有ポリアミンとハロヒ
ドリン基および／またはエポキシ基含有化合物と
の反応生成物(A)およびアルカリ性化合物(B)を含む
処理液により処理することを特徴とする難燃ポリ
エステル成形物の処理方法。 ２ 難燃ポリエステル成形物が式〔〕で示され
る酸成分を共重合せしめてなるアルキレンテレフ
タレート系ポリエステル成形物である特許請求範
囲の第１項記載の難燃ポリエステル成形物の処理
方法。 （但し、Ｒ，R1は同じかまたは相違なる基で水
素原子、ハロゲン原子または炭素数６以下の炭化
水素基、R2，R3は同じかまたは相異なる基で水
素原子、炭素数７以下の炭化水素基または
（R4O）rHで示される基を示す。またR4はエチレ
ン、プロピレン、またはブチレン基を、ｒは１〜
10の整数、ｌ、ｍは０または１〜４の整数、ｎは
０，１または２である。）[Scope of Claims] 1. A heat-melting flame-retardant polyester molded product copolymerized with a phosphorus-containing ester-forming compound is a reaction product of a polyoxyalkylene unit-containing polyamine and a halohydrin group- and/or epoxy group-containing compound. A method for treating a flame-retardant polyester molded article, the method comprising treating a flame-retardant polyester molded article with a treatment liquid containing (A) and an alkaline compound (B). 2. The method for treating a flame-retardant polyester molded product according to claim 1, wherein the flame-retardant polyester molded product is an alkylene terephthalate-based polyester molded product obtained by copolymerizing an acid component represented by the formula []. (However, R and R 1 are the same or different groups such as a hydrogen atom, a halogen atom, or a hydrocarbon group having 6 or less carbon atoms, and R 2 and R 3 are the same or different groups such as a hydrogen atom or a hydrocarbon group having 7 or less carbon atoms. represents a hydrocarbon group or a group represented by (R 4 O) rH. R 4 represents ethylene, propylene, or butylene group, and r represents 1 to 1.
An integer of 10, l and m are 0 or an integer of 1 to 4, and n is 0, 1 or 2. )
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58084628A JPS59210949A (en) | 1983-05-13 | 1983-05-13 | Method for treating flame-retardant polyester molding |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58084628A JPS59210949A (en) | 1983-05-13 | 1983-05-13 | Method for treating flame-retardant polyester molding |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59210949A JPS59210949A (en) | 1984-11-29 |
| JPH0350776B2 true JPH0350776B2 (en) | 1991-08-02 |
Family
ID=13835940
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58084628A Granted JPS59210949A (en) | 1983-05-13 | 1983-05-13 | Method for treating flame-retardant polyester molding |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59210949A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2525512B2 (en) * | 1990-11-29 | 1996-08-21 | 矢崎総業株式会社 | Switch terminals and connectors with switch terminals |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61215780A (en) * | 1985-03-20 | 1986-09-25 | ユニチカ株式会社 | Cloth processing method |
| JPH04352876A (en) * | 1991-05-30 | 1992-12-07 | Teijin Ltd | Fabric for flameproof sheet |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4941438A (en) * | 1972-08-30 | 1974-04-18 | ||
| JPS5271571A (en) * | 1975-12-11 | 1977-06-15 | Toray Industries | Synthetic fiber or film of fusible high polymer * treated to nonninflammable and method of manufacture thereof |
-
1983
- 1983-05-13 JP JP58084628A patent/JPS59210949A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4941438A (en) * | 1972-08-30 | 1974-04-18 | ||
| JPS5271571A (en) * | 1975-12-11 | 1977-06-15 | Toray Industries | Synthetic fiber or film of fusible high polymer * treated to nonninflammable and method of manufacture thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2525512B2 (en) * | 1990-11-29 | 1996-08-21 | 矢崎総業株式会社 | Switch terminals and connectors with switch terminals |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59210949A (en) | 1984-11-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US3897584A (en) | Rendering fibrous material flame retardant with cyan amide/halomethyl phosphonic acid systems | |
| EP0155834B1 (en) | Flame-proof fiber product | |
| CA1205607A (en) | Mild-cure formaldehyde-free durable-press finishing of cotton textiles with glyoxal and glycols | |
| US4311760A (en) | Method for applying mercaptoalkyl-containing polydiorganosiloxanes to textile fibers | |
| US3620826A (en) | Process for improving soiling characteristics of hydrophobic textile material | |
| US3577270A (en) | Process for rendering cellulosic fibers flame resistant | |
| JPH04202895A (en) | Bulky cellulosic sheet | |
| JPS61296178A (en) | Flame-proof processing of cellulosic fiber material | |
| US4296165A (en) | Antistatic natural and synthetic textile materials which have been treated with salts of orthophosphoric or polyphosphoric acid | |
| JPH0350776B2 (en) | ||
| US3512920A (en) | Wrinkle resistant fabric | |
| KR102050566B1 (en) | Flameproof method of cellulose fabric, and RAYON goods manufactured of cellulose fabric of the same | |
| JPS6254811B2 (en) | ||
| KR101024974B1 (en) | Production Method of Flame Retardant Textile with Outstanding Laundry Durability | |
| KR101985106B1 (en) | Flameproof method of blended yarn goods having aramid fibers, and Blended yarn goods manufactured of the same | |
| EP0325610B1 (en) | Flame-resistant cotton blend fabrics | |
| EP1549796B1 (en) | Flame-retardant fabrics | |
| Harris et al. | Flame resistant cotton fabrics prepared by radiation‐initiated polymerization with vinyl phosphonate oligomer and N‐methylolacrylamide | |
| JPS6134283A (en) | Flame-proof processing of fabric containing polyester fiber | |
| JP3900705B2 (en) | Cellulosic fiber-containing fabric | |
| US2975077A (en) | Shrinkproofing textiles with polyepoxides and hydrazine | |
| JP3385389B2 (en) | Natural cellulose fiber having pleating property, fiber product thereof, and production method thereof | |
| JP2600663B2 (en) | Flame retardant fiber composite | |
| JPH07145562A (en) | Water-repellent flame-retardant polyester fiber and its production | |
| JPS6047952B2 (en) | How to prevent polyester from pilling |