JPH0351832B2 - - Google Patents
Info
- Publication number
- JPH0351832B2 JPH0351832B2 JP58236980A JP23698083A JPH0351832B2 JP H0351832 B2 JPH0351832 B2 JP H0351832B2 JP 58236980 A JP58236980 A JP 58236980A JP 23698083 A JP23698083 A JP 23698083A JP H0351832 B2 JPH0351832 B2 JP H0351832B2
- Authority
- JP
- Japan
- Prior art keywords
- component
- polyester
- ester
- glycol
- mol
- 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
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 43
- 229920000728 polyester Polymers 0.000 claims description 21
- 229920000642 polymer Polymers 0.000 claims description 21
- 238000012545 processing Methods 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- 239000002202 Polyethylene glycol Substances 0.000 claims description 14
- 229920001223 polyethylene glycol Polymers 0.000 claims description 14
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 12
- KKEYFWRCBNTPAC-UHFFFAOYSA-N terephthalic acid group Chemical group C(C1=CC=C(C(=O)O)C=C1)(=O)O KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 12
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 8
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- -1 alkali metal sulfonic acid salt compound Chemical class 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 7
- 229910052783 alkali metal Inorganic materials 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 2
- 238000000034 method Methods 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000004744 fabric Substances 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 4
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 4
- 229920001225 polyester resin Polymers 0.000 description 4
- 239000004645 polyester resin Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000000295 fuel oil Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000001632 sodium acetate Substances 0.000 description 3
- 235000017281 sodium acetate Nutrition 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- YZTJKOLMWJNVFH-UHFFFAOYSA-N 2-sulfobenzene-1,3-dicarboxylic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1S(O)(=O)=O YZTJKOLMWJNVFH-UHFFFAOYSA-N 0.000 description 1
- VSAWBBYYMBQKIK-UHFFFAOYSA-N 4-[[3,5-bis[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-2,4,6-trimethylphenyl]methyl]-2,6-ditert-butylphenol Chemical compound CC1=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C1CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 VSAWBBYYMBQKIK-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- QLZHNIAADXEJJP-UHFFFAOYSA-N Phenylphosphonic acid Chemical compound OP(O)(=O)C1=CC=CC=C1 QLZHNIAADXEJJP-UHFFFAOYSA-N 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940121375 antifungal agent Drugs 0.000 description 1
- 239000003429 antifungal agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
Landscapes
- Polyesters Or Polycarbonates (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Description
本発明は水分散性のポリエステル系加工剤に関
するものである。
合成繊維の汚れ防止法として、従来からフツ素
樹脂加工、撥水、撥油加工、帯電防止加工など数
多くの方法が試みられている。また、汚れを防ぐ
というよりも、汚れを落ちやすくするというSR
（soil release）加工も提案されている。本発明の
目的は、優れたSR性を有し、かつ滑脱抵抗性の
高いポリエステル系加工剤を提供することにあ
る。
ポリエステル繊維のSR加工剤としては、ポリ
エステルセグメントとポリエチレングリコールセ
グメントを共重合せしめて得られるポリエステル
系樹脂が有効であることは以前から知られている
が、このポリエステル系樹脂には、滑脱抵抗性が
低いという欠点があつた。本発明者らは、優れた
SR性および水分散性を保持したまま十分な滑脱
抵抗性を与えうるポリエステル系加工剤を開発す
るべく鋭意検討した結果、本発明に到達したもの
である。
すなわち、本発明はエステル形成性スルホン酸
アルカリ金属塩化合物を必須成分として含むジカ
ルボン酸成分とグリコール成分とからなるポリエ
ステルセグメントにポリエチレングリコールを共
重合せしめてなるポリエステルエーテル共重合体
であつて、ポリエステルセグメントの組成が、
(1) エステル形成性スルホン酸アルカリ金属塩化
合物が、全酸成分に対して30〜50モル％
(2) 全酸成分の70〜50モル％はテレフタル酸およ
び／又はイソフタル酸またはそれらのエステル
形成性誘導体であり、テレフタル酸成分とイソ
フタル酸成分のモル比が100／０〜０／100
(3) グリコール成分の50モル％以上がエチレング
ルコールおよび／又は１，４−ブタンジオール
であり、分子量800〜3000のポリエチレングリ
コールが生成ポリマーに対して10〜20重量％含
有されてなることを特徴とするポリエステル系
加剤である。
本発明において用いられるエステル形成性スル
ホン酸アルカリ金属化合物の好ましいものとして
は５−ナトリウムスルホイソフタル酸、５−カリ
ウムスルホイソフタル酸およびそれらのエステル
形成性誘導体（例えばジメチルエステル、ジエチ
ルエステル、ジフエニルエステル等）が挙げられ
る。エステル形成性スルホン酸アルカリ金属塩化
合物は全酸成分に対して30〜50モル％の範囲内で
ある必要があり、30モル％よりも少ないと生成ポ
リマーの水分散性が低下し、逆に50モル％よりも
多く使用するとポリマーの重合が極めて困難にな
るため、不適当である。
全酸成分の70〜50モル％はテレフタル酸およ
び／又はイソフタル酸、またはそれらのエステル
形成性誘導体が用いられる。テレフタル酸成分と
イソフタル酸成分のモル比については特に制限は
なく100／０〜０／100の範囲において有効である
が、生成ポリエステル系加工剤のSR性能から特
に100／０〜50／50の範囲が好ましい。
本発明において用いられるグリコール成分とし
ては、エチレングリコール、１，２−プロパンジ
オール、１，３−プロパンジオール、１，２−ブ
タンジオール、１，４−ブタンジオール、１，６
−ヘキサンジオール、ジエチレングリコールなど
が挙げられる。このうち、エチレングリコールお
よび／又は１，４−ブタンジオールをグリコール
成分に対して50モル％以上使用することが必要で
ある。他のグリコール成分が50モル％以上になる
と分散性又は加工布の耐洗濯性が低下する傾向が
ある。
本発明において用いられるポリエチレングリコ
ールの分子量は800〜3000が必要であり、その添
加量は生成ポリマーに対して12〜20重量％の範囲
内である。分子量80以下の低分子量ポリエチレン
グリコールでは、重合時において反応系外に留出
されやすく目的とする組成のポリマーが得られに
くいばかりか、SR性能が低下する。ポリエチレ
ングリコールの生成ポリマーに対する添加量が12
重量％以下ではSR性能が十分でなく、20重量％
以上では滑脱抵抗性が低下する。
本発明におけるポリエステルエーテル共重合体
の製造は従来から知られているポリエステルエー
テルの製造方法に従つて行なわれる。例えば、各
酸成分のアルキルエステルとグリコール成分とを
適当な触媒（たとえばチタン化合物など）の存在
下でエステル交換を行なう。次いで所定量のポリ
エチレングリコールを添加、減圧下で重縮合反応
を行なう方法、ポリエステルオリゴマーを製造し
これとポリエチレングリコールを反応させる方
法、比較的高分子量のポリエステルをポリエチレ
ングリコールの存在下解重合させながら反応させ
る方法等が挙げられる。ポリエチレングリコール
を添加する際又はそれ以前に少量の酸化防止剤を
同時に加えると良いポリマーが得られる場合があ
る。
ポリエステルエーテル共重合体は、還元比粘度
（溶媒フエノール／１，１，２，２−テトラクロ
ロエタン３／２重量比、ポリマー濃度２ｇ／、
温度30℃で測定）が通常0.1以上であることが好
ましい。
本発明によるポリエステル系樹脂は、水分散
性、SR性に優れ、また滑脱抵抗性が高いという
特徴を有し、ポリエステル繊維のSR加工剤、成
形品の表面改質剤等として適している。また、コ
ーテイング樹脂中に配合して塗面の表面性質を改
良することもできる。本発明による加工剤は吸尽
法のほか、パツド、スプレー、塗布、転写等の手
段により付与した後熱処理する方法により用いら
れる。加工にあたり、加工剤の親和性または固着
性を改良するため加工剤液中に塩類、PH調節剤を
添加したり、場合によつては安定性を改善するた
め少量の保護膠質や活性剤を添加することもでき
る。また、本発明による加工剤は所望により他の
加工剤たとえば撥油加工剤、金属酸化物コロイ
ド、架橋剤、帯電防止剤、抗菌剤、防黴剤、難撚
剤、その他加工剤を適宜同浴または別浴で使用す
ることができる。
以下に実施例をあげて本発明の効果をさらに詳
細に説明する。なお、得られたポリエステル系樹
脂は次の試験方法によつて評価された。また実施
例中の％および部はことわらない限り重量基準で
ある。
試験布：ポリエステル加工糸織物
試験条件
●加工条件
Ａ吸尽法：加工剤（10％水分散液）10％owf、酢
酸（90％）、0.6ml／、酢酸ナトリウム0.3
ｇ／、浴比１：20、130℃30分
●洗濯条件
洗剤２ｇ／、試料と洗剤液比１：50、40℃で
15分間
●SR性…SRM（Ｂ重油法）試料にＢ重油を１滴
落とし、24時間室温放置した後洗濯し、洗濯後
のＢ重油の除去性を調べる。判定は１〜５級で
あり、５級は完全除去を示す。
●吸水性…JIS Ｌ−1096−1979 6.26、1.A（滴下
法）に準じる。
●引き抜き強度…JIS Ｌ−1096−1979−6.21、
（糸引き抜きＡ法）に準じる。試験機シヨツパ
ー使用。引き抜き速度５cm／秒。
実施例 １
撹拌機、温度計、メタノール流出管を取り付け
た反応器に、テレフタル酸ジメチル（DMT）
252部、５−ナトリウムスルホイソフタル酸ジメ
チル（SDM）207部、エチレングリコール（EG）
337部、酢酸ナトリウム2.87部、酢酸亜鉛0.20部
（2.5％EG溶液）、および三酸化アンチモン0.20部
（1.0％EG溶液）をとり、撹拌しながら徐々に昇
温する。所定量のメタノールが留出した後（内温
220℃）フエニルホスホン酸0.20部（5.0％EG溶
液）を加えて撹拌する。
得られた反応混合物と分子量2000のポリエチレ
ングリコール（PEG）100部および１，３，５−
トリメチル−２，４，６−トリス（３，５−ジ−
ｔ−ブチル−４−ヒドロキシベンジル）ベンゼン
1.1部を内温220℃のオートクレーブに仕込む。次
いで撹拌しながら徐々に減圧にし、30分間で１mm
Ｈｇ以下とする。この間温度を250℃まで昇温さ
せる。その温度で１時間反応させた後、窒素ガス
で常圧にもどし、オートクレーブ底部の細孔より
ポリマーを取り出す。得られたポリマーの還元比
粘度（ηsp／ｃ）は、0.14であつた。該ポリマー
をポリマーＡとする。
実施例 ２
実施例１と同様にして組成の異なるポリマーを
作製した。得られたポリマーの組成および還元比
粘度を第１表に示す。
The present invention relates to a water-dispersible polyester processing agent. Many methods have been tried to prevent stains on synthetic fibers, including fluororesin treatment, water repellency, oil repellency treatment, and antistatic treatment. Also, rather than preventing dirt, SR makes it easier to remove dirt.
(soil release) processing has also been proposed. An object of the present invention is to provide a polyester processing agent that has excellent SR properties and high slip resistance. It has long been known that polyester resin obtained by copolymerizing polyester segments and polyethylene glycol segments is effective as an SR processing agent for polyester fibers, but this polyester resin has poor slip resistance. It had the disadvantage of being low. The inventors have discovered an excellent
The present invention was arrived at as a result of extensive research aimed at developing a polyester-based finishing agent that can provide sufficient slip resistance while maintaining SR properties and water dispersibility. That is, the present invention provides a polyester ether copolymer obtained by copolymerizing polyethylene glycol with a polyester segment consisting of a dicarboxylic acid component containing an ester-forming alkali metal sulfonic acid salt compound as an essential component and a glycol component. (1) The ester-forming sulfonic acid alkali metal salt compound is 30 to 50 mol% of the total acid component. (2) The total acid component is 70 to 50 mol% of terephthalic acid and/or isophthalic acid or These are ester-forming derivatives, and the molar ratio of terephthalic acid component to isophthalic acid component is 100/0 to 0/100. (3) 50 mol% or more of the glycol component is ethylene glycol and/or 1,4-butanediol. This is a polyester additive characterized by containing polyethylene glycol having a molecular weight of 800 to 3000 in an amount of 10 to 20% by weight based on the produced polymer. Preferred examples of the ester-forming alkali metal sulfonate compounds used in the present invention include 5-sodium sulfoisophthalic acid, 5-potassium sulfoisophthalic acid, and ester-forming derivatives thereof (e.g., dimethyl ester, diethyl ester, diphenyl ester, etc.). ). The ester-forming sulfonic acid alkali metal salt compound must be present in the range of 30 to 50 mol% based on the total acid components; if it is less than 30 mol%, the water dispersibility of the resulting polymer will decrease; If it is used in an amount greater than mol %, polymerization of the polymer becomes extremely difficult, and therefore it is unsuitable. Terephthalic acid and/or isophthalic acid, or ester-forming derivatives thereof, are used for 70 to 50 mol% of the total acid component. There is no particular restriction on the molar ratio of the terephthalic acid component and the isophthalic acid component, and a range of 100/0 to 0/100 is effective, but a range of 100/0 to 50/50 is particularly recommended due to the SR performance of the polyester processing agent produced. is preferred. Glycol components used in the present invention include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,4-butanediol, 1,6
-Hexanediol, diethylene glycol, etc. Among these, it is necessary to use ethylene glycol and/or 1,4-butanediol in an amount of 50 mol% or more based on the glycol component. If the content of other glycol components exceeds 50 mol%, the dispersibility or wash resistance of the processed fabric tends to decrease. The molecular weight of polyethylene glycol used in the present invention is required to be 800 to 3000, and the amount added is within the range of 12 to 20% by weight based on the produced polymer. Low molecular weight polyethylene glycol with a molecular weight of 80 or less is easily distilled out of the reaction system during polymerization, making it difficult to obtain a polymer with the desired composition, and also reduces SR performance. The amount of polyethylene glycol added to the produced polymer is 12
SR performance is insufficient below 20% by weight.
Above this level, the slip resistance decreases. The polyester ether copolymer in the present invention is produced according to a conventionally known method for producing polyester ether. For example, the alkyl ester of each acid component and the glycol component are transesterified in the presence of a suitable catalyst (eg, a titanium compound, etc.). Next, a predetermined amount of polyethylene glycol is added, followed by a polycondensation reaction under reduced pressure, a method in which a polyester oligomer is produced and this is reacted with polyethylene glycol, and a method in which a relatively high molecular weight polyester is reacted while being depolymerized in the presence of polyethylene glycol. For example, the method of A good polymer may be obtained if a small amount of antioxidant is added at the same time or before adding the polyethylene glycol. The polyester ether copolymer has a reduced specific viscosity (solvent phenol/1,1,2,2-tetrachloroethane 3/2 weight ratio, polymer concentration 2 g/,
(measured at a temperature of 30°C) is preferably 0.1 or more. The polyester resin according to the present invention has excellent water dispersibility, SR properties, and high slip resistance, and is suitable as an SR processing agent for polyester fibers, a surface modifier for molded products, and the like. It can also be blended into coating resins to improve the surface properties of coated surfaces. In addition to the exhaustion method, the processing agent according to the present invention can be used by a method in which it is applied by means such as padding, spraying, coating, or transfer, and then heat-treated. During processing, salts and PH regulators are added to the processing agent solution to improve the affinity or adhesion of the processing agent, and in some cases, small amounts of protective colloids and activators are added to improve stability. You can also. Furthermore, the processing agent according to the present invention may be optionally mixed with other processing agents such as oil repellent finishing agents, metal oxide colloids, crosslinking agents, antistatic agents, antibacterial agents, antifungal agents, twist retardants, and other processing agents. Or it can be used in a separate bath. The effects of the present invention will be explained in more detail with reference to Examples below. The obtained polyester resin was evaluated by the following test method. Further, % and parts in the examples are based on weight unless otherwise specified. Test fabric: Polyester processed yarn fabric Test conditions Processing conditions A Exhaustion method: Processing agent (10% aqueous dispersion) 10% owf, acetic acid (90%), 0.6ml/, sodium acetate 0.3
g/, bath ratio 1:20, 130℃ 30 minutes ●Washing conditions detergent 2g/, sample and detergent liquid ratio 1:50, 40℃
15 minutes●SR property...SRM (B heavy oil method) Drop one drop of B heavy oil onto the sample, leave it at room temperature for 24 hours, wash it, and check the removability of B heavy oil after washing. The evaluation is from grade 1 to grade 5, with grade 5 indicating complete removal. ●Water absorption…According to JIS L-1096-1979 6.26, 1.A (dropping method). ●Pull-out strength…JIS L-1096-1979-6.21,
(According to thread pulling method A). Uses testing machine Schottspur. Pulling speed 5cm/sec. Example 1 Dimethyl terephthalate (DMT) was added to a reactor equipped with a stirrer, a thermometer, and a methanol outflow tube.
252 parts, 5-sodium dimethyl sulfoisophthalate (SDM) 207 parts, ethylene glycol (EG)
Take 337 parts of sodium acetate, 2.87 parts of sodium acetate, 0.20 parts of zinc acetate (2.5% EG solution), and 0.20 parts of antimony trioxide (1.0% EG solution), and gradually raise the temperature while stirring. After a predetermined amount of methanol has been distilled out (inner temperature
(220℃) Add 0.20 part of phenylphosphonic acid (5.0% EG solution) and stir. The resulting reaction mixture and 100 parts of polyethylene glycol (PEG) with a molecular weight of 2000 and 1,3,5-
Trimethyl-2,4,6-tris(3,5-di-
t-Butyl-4-hydroxybenzyl)benzene
Place 1.1 part into an autoclave with an internal temperature of 220℃. Then, while stirring, gradually reduce the pressure to 1mm in 30 minutes.
Hg or less. During this time, the temperature is raised to 250°C. After reacting at that temperature for 1 hour, the pressure is returned to normal using nitrogen gas, and the polymer is taken out from the pores at the bottom of the autoclave. The reduced specific viscosity (η sp /c) of the obtained polymer was 0.14. This polymer is referred to as Polymer A. Example 2 Polymers with different compositions were produced in the same manner as in Example 1. Table 1 shows the composition and reduced specific viscosity of the obtained polymer.
【表】【table】
【表】
実施例 ３
第１表に示したポリマーを用いて、吸尽法によ
りポリエステル加工糸織物を加工した。得られた
加工布のSR性、吸水性、引き抜き強度の測定結
果を第２表に示す。
ポリマーａは分散性が悪く、吸尽法により加工
することができなかつた。
ポリマーｂは耐洗濯性が悪かつた。この理由
は、SDMの量が多いため、重合中に急激な粘度
上昇が超り、十分に反応が進んでいないことや、
親水性が大きくなりすぎたためと考えられる。
ポリマーｃはSR性、吸水性は良好であつたが、
引き抜き強度（滑脱抵抗）が低い。
ポリマーｄはSRMおよび吸水性が低く、未加
工布に近い値を示した。又ポリマーの分散性も十
分ではなかつた。[Table] Example 3 Using the polymers shown in Table 1, a polyester processed yarn fabric was processed by an exhaustion method. Table 2 shows the measurement results of the SR properties, water absorption properties, and pull-out strength of the obtained processed fabrics. Polymer a had poor dispersibility and could not be processed by the exhaustion method. Polymer b had poor washing resistance. The reason for this is that due to the large amount of SDM, the viscosity increases rapidly during polymerization, and the reaction does not proceed sufficiently.
This is thought to be because the hydrophilicity became too large. Polymer c had good SR properties and water absorption, but
Low pull-out strength (slip resistance). Polymer d had low SRM and water absorption, showing values close to those of the untreated fabric. Also, the dispersibility of the polymer was not sufficient.
【表】【table】
Claims (1)
合物を必須成分として含むジカルボン酸成分とグ
リコール成分とからなるポリエステルセグメント
にポリエチレングリコールを共重合せしめてなる
ポリエステルエーテル共重合体であつて、ポリエ
ステルセグメントの組成が、 (1) エステル形成性スルホン酸アルカリ金属塩化
合物が、全酸成分に対して30〜50モル％ (2) 全酸成分の70〜50モル％は、テレフタル酸お
よび／又はイソフタルル酸、またはそれらのエ
ステル形成性誘導体であり、テレフタル酸成分
とイソフタル酸成分のモル比が100／０〜０／
100 (3) グリコール成分の50モル％以上がエチレング
リコールおよび／又は１，４−ブタンジオール
であり、分子量800〜3000のポリエチレングリ
コールが生成ポリマーに対して12〜20重量％含
有されてなることを特徴とするポリエステル系
加工剤。[Scope of Claims] 1. A polyester ether copolymer obtained by copolymerizing polyethylene glycol with a polyester segment consisting of a dicarboxylic acid component containing an ester-forming alkali metal sulfonic acid salt compound as an essential component and a glycol component, The composition of the polyester segment is as follows: (1) The ester-forming alkali metal sulfonic acid salt compound is 30 to 50 mol% of the total acid component (2) 70 to 50 mol% of the total acid component is terephthalic acid and/or Isophthalic acid or an ester-forming derivative thereof, with a molar ratio of terephthalic acid component and isophthalic acid component of 100/0 to 0/
100 (3) 50 mol% or more of the glycol component is ethylene glycol and/or 1,4-butanediol, and polyethylene glycol with a molecular weight of 800 to 3000 is contained in an amount of 12 to 20% by weight based on the resulting polymer. Characteristic polyester processing agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58236980A JPS60127324A (en) | 1983-12-14 | 1983-12-14 | Polyester-based processing agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58236980A JPS60127324A (en) | 1983-12-14 | 1983-12-14 | Polyester-based processing agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60127324A JPS60127324A (en) | 1985-07-08 |
| JPH0351832B2 true JPH0351832B2 (en) | 1991-08-08 |
Family
ID=17008605
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58236980A Granted JPS60127324A (en) | 1983-12-14 | 1983-12-14 | Polyester-based processing agent |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60127324A (en) |
-
1983
- 1983-12-14 JP JP58236980A patent/JPS60127324A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60127324A (en) | 1985-07-08 |
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