JPS6142027B2 - - Google Patents
Info
- Publication number
- JPS6142027B2 JPS6142027B2 JP54037931A JP3793179A JPS6142027B2 JP S6142027 B2 JPS6142027 B2 JP S6142027B2 JP 54037931 A JP54037931 A JP 54037931A JP 3793179 A JP3793179 A JP 3793179A JP S6142027 B2 JPS6142027 B2 JP S6142027B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- water
- hydroxyethyl
- bis
- polyester resin
- 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
Links
- 229920002472 Starch Polymers 0.000 claims description 23
- 229920001225 polyester resin Polymers 0.000 claims description 23
- 239000004645 polyester resin Substances 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 19
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical class OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 18
- 235000019698 starch Nutrition 0.000 claims description 17
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 15
- -1 alkali metal salts Chemical class 0.000 claims description 14
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 11
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 10
- QPKOBORKPHRBPS-UHFFFAOYSA-N bis(2-hydroxyethyl) terephthalate Chemical compound OCCOC(=O)C1=CC=C(C(=O)OCCO)C=C1 QPKOBORKPHRBPS-UHFFFAOYSA-N 0.000 claims description 10
- 239000008107 starch Substances 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 8
- 239000002202 Polyethylene glycol Substances 0.000 claims description 7
- 229910052783 alkali metal Inorganic materials 0.000 claims description 7
- ULCGAWLDXLEIIR-UHFFFAOYSA-N bis(2-hydroxyethyl) benzene-1,3-dicarboxylate Chemical compound OCCOC(=O)C1=CC=CC(C(=O)OCCO)=C1 ULCGAWLDXLEIIR-UHFFFAOYSA-N 0.000 claims description 7
- 229920001223 polyethylene glycol Polymers 0.000 claims description 7
- CARJPEPCULYFFP-UHFFFAOYSA-N 5-Sulfo-1,3-benzenedicarboxylic acid Chemical class OC(=O)C1=CC(C(O)=O)=CC(S(O)(=O)=O)=C1 CARJPEPCULYFFP-UHFFFAOYSA-N 0.000 claims description 4
- 150000007513 acids Chemical class 0.000 claims description 2
- 239000003292 glue Substances 0.000 description 17
- 229920000728 polyester Polymers 0.000 description 16
- 239000000835 fiber Substances 0.000 description 15
- 239000000047 product Substances 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 229920000742 Cotton Polymers 0.000 description 10
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 10
- 238000005406 washing Methods 0.000 description 10
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 7
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 6
- 239000004753 textile Substances 0.000 description 6
- 239000000443 aerosol Substances 0.000 description 5
- 238000006068 polycondensation reaction Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 230000002209 hydrophobic effect Effects 0.000 description 3
- QQVIHTHCMHWDBS-UHFFFAOYSA-L isophthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC(C([O-])=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-L 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000004513 sizing Methods 0.000 description 3
- YXTFRJVQOWZDPP-UHFFFAOYSA-M sodium;3,5-dicarboxybenzenesulfonate Chemical compound [Na+].OC(=O)C1=CC(C(O)=O)=CC(S([O-])(=O)=O)=C1 YXTFRJVQOWZDPP-UHFFFAOYSA-M 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 2
- 239000001639 calcium acetate Substances 0.000 description 2
- 229960005147 calcium acetate Drugs 0.000 description 2
- 235000011092 calcium acetate Nutrition 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920002689 polyvinyl acetate Polymers 0.000 description 2
- 239000011118 polyvinyl acetate Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000009955 starching Methods 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 125000001174 sulfone group Chemical group 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229920002261 Corn starch Polymers 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 229920000881 Modified starch Polymers 0.000 description 1
- 239000004368 Modified starch Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000008120 corn starch Substances 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005108 dry cleaning Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 235000019426 modified starch Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- HHDOORYZQSEMGM-UHFFFAOYSA-L potassium;oxalate;titanium(4+) Chemical compound [K+].[Ti+4].[O-]C(=O)C([O-])=O HHDOORYZQSEMGM-UHFFFAOYSA-L 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- UOULCEYHQNCFFH-UHFFFAOYSA-M sodium;hydroxymethanesulfonate Chemical compound [Na+].OCS([O-])(=O)=O UOULCEYHQNCFFH-UHFFFAOYSA-M 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 229940100445 wheat starch Drugs 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
Landscapes
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Description
【発明の詳細な説明】
本発明は新規な洗濯糊組成物に関する。更に詳
しくは、洗濯糊として従来から使用されていた澱
粉やポリビニルアルコールの欠点を除去した新し
い洗濯仕上用糊剤に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel laundry starch compositions. More specifically, the present invention relates to a new laundry finishing glue that eliminates the drawbacks of starch and polyvinyl alcohol that have been conventionally used as laundry glue.
衣料あるいはその他の家庭用繊維製品は、その
種類に応じてランドリーあるいはドライクリーニ
ングによつて汚れを除去するとともに糊付、柔軟
加工等の仕上げがなされる。本発明はこのうちの
ランドリーによつて汚れを落とし、仕上げ加工の
行なわれる繊維製品の仕上げ用糊剤に関するもの
であるが、ランドリー即ち、水を用いて洗濯する
ものとしては綿製品、レーヨンその他の再生繊維
製品、またはこれらとポリエステル繊維との混紡
品に多く利用されている。しかし、その中でもポ
リエステル繊維との混紡品、例えば綿35%−ポリ
エステル繊維65%の混紡品は広くワイシヤツ地、
ブラウス地として使われており、洗濯後比較的し
わになり難い性質上綿単独製品に比し比較的アイ
ロン仕上げを簡略化し得る長所を有している。し
かし、その反面ポリエステル繊維は疎水性繊維で
あるため油性汚れを付着し易いこと、静電気を発
生し易いこと及び洗濯糊として澱粉系の糊を使用
しても接着性が乏しく仕上げ加工が思わしくない
こと等の欠点を有している。このような現状にか
んかみ、主としてポリエステル繊維−綿混紡糸織
物用の洗濯仕上げ糊剤について鋭意研究した結
果、限定された水溶性ポリエステル樹脂とデンプ
ンまたはビニルアルコールとを併用することによ
り極めて優れた洗濯仕上げ用糊剤が得られること
を見出した。ワイシヤツ、ブラウス等の洗濯仕上
げは、専門業者いわゆる洗濯屋の加工賃の高騰と
ポリエステル繊維−綿混紡糸織物の普及が相まつ
て家庭での洗濯仕上げが増えており、そのため家
庭で容易に処理できる糊剤の要望が強くなつてい
る。このような観点から洗濯用糊剤に要望される
性質としては前述したポリエステル繊維との接着
性がよいこと、静電気防止能が優れていることの
ほか、適度の柔軟性を有すること、糊液が安定で
必要なだけ使用し、保存のできるもの、再洗濯時
の脱落性のよいものなどの要求特性を満たすもの
でなければならない。このような要求特性を満た
すものとして(A)平均分子量600〜6000のポリエチ
レングリコールを5〜40重量%(B)ビス(β−ヒド
ロキシエチル)テレフタレートとビス(β−ヒド
ロキシエチル)イソフタレートとの重量比が95:
5〜70:30である二塩基酸のエチレングリコール
エステルの混合物40〜75重量%(C)5−スルホイソ
フタル酸のアルカリ金属塩3〜15重量%及び(D)エ
チレングリコールまたはプロピレングリコール0
〜30重量%とを共重縮合して得られる水溶性ポリ
エステル樹脂をデンプンおよび/またはポリビニ
ルアルコールと混合することにより、これらの特
性を満たす極めて優れた洗濯糊が得られたのであ
る。デンプンやポリビニルアルコールは綿製品に
は優れた糊剤であつてもポリエステル繊維−綿混
紡品にとつては接着性が不足したり、静電防止能
が劣つたりするため柔軟剤を添加したり、ポリ酢
酸ビニル系重合体あるいは無水マレイン酸系共重
合体やアクリル酸エステル系共重合体を併用する
方法が知られているが、ポリ酢酸ビニル系重合体
はそれ自身水溶性でないため洗濯時の脱落性が悪
く汚れと共に残留し易いこと、また無水マレイン
酸系共重合体やアクリル酸エステル系共重合体で
不飽和カルボン酸を共重合し、それをアルカリ金
属塩やアミン塩として水溶性とした共重合体は一
見水溶性も良く、従つて洗濯性も良いようである
が、実際には洗濯時水中のカルシウムやマグネシ
ウムイオンあるいは鉄分を選択的に吸着し、共重
合体自身が不溶化すると共に疎水性繊維であるポ
リエステル繊維に強固に吸着し、油性汚れと共に
脱落不良となつて糊付け−洗濯を繰り返すと段々
と黄ばんで来る欠点を有する。これに反して本発
明の水溶液性ポリエステル樹脂はデンプンやポリ
ビニルアルコールと併用して接着性を高めめると
同時に適度の柔軟性を与え肌ざわりが良いのみな
らず静電気防止能を有し、且つ、不飽和カルボン
酸を共重合した弱酸性基によるイオン性の共重合
体と異なり、水中のカルシウム塩やマグネシウム
塩によつても不溶化しないため繰り返し使用して
も糊剤の残留、蓄積がなく、汚れ落ちの極めて良
い糊剤を与えるものである。この汚れ落ち性を極
めて良くするために、本発明に使用する水溶性ポ
リエステル樹脂としてはその構成成分の(A)として
平均分子量600〜6000のポリエチレングリコール
を5〜40重量%含有することが必要であつて、分
子量が600未満のもののみであつたり、5重量%
未満であれば水溶性が不足し、且つ、水溶性ポリ
エステル樹脂が硬くもろいため、糊付仕上げした
繊維製品の風合が粗硬となつて好ましくない。逆
にポリエチレングリコールの平均分子量が6000以
上であつたり、40重量%以上となると繊維との親
和性が劣り糊付効果が不足して好ましくない。次
に(B)成分としてはビス(β−ヒドロキシエチル)
テレフタレートとビス(β−ヒドロキシエチル)
イソフタレートとが重量比で95:5〜70:30であ
る二塩基酸成分が40〜75重量%必要である。水溶
性ポリエステル樹脂を合成するに際して、各成分
即ち(A)〜(D)成分が比較的低温で溶融混合して均一
混合物となつた上で重縮合反応が進行することが
必要で、そのため二塩基酸成分としてテレフタル
酸またはイソフタル酸のビスエチレングリコール
エステル即ちビス(β−ヒドロキシエチル)テレ
フタレートまたはビス(β−ヒドロキシエチル)
イソフタレートが必要であつて、テレフタル酸ま
たはイソフタル酸そのものでは均一な重縮合反応
物が得られず好ましくないのである。テレフタル
酸、イソフタル酸またはそれらのメチルエステ
ル、エチルエステル等から出発する場合にはあら
かじめエチレングリコールでエステル化もしくは
エステル交換してビス(β−ヒドロキシエチル)
テレフタレートまたはビス(β−ヒドロキシエチ
ル)イソフタレートとした後、他の成分と重縮合
反応を行なうことが出来る。同時に二塩基酸成分
としてビス(β−ヒドロキシエチル)テレフタレ
ートのみを用いた場合は、水溶性ポリエステル樹
脂ひいてはこれを配合した洗濯糊が粗硬となつて
糊付けした繊維製品の肌ざわりが悪く最も嫌われ
るものである。そのためにビス(β−ヒドロキシ
エチル)テレフタレートにビス(β−ヒドロキシ
エチル)イソフタレートを95:5〜70:30の比で
混合し重縮合することによりビス(β−ヒドロキ
シエチル)テレフタレートのみの時にみられた粗
硬性が悪くなり、極めて風合の良好な樹脂となつ
たのである。一方ビス(β−ヒドロキシエチル)
イソフタレートが逆に70:30より多くなれば重縮
合反応が阻害され樹脂としての効果、即ち、繊維
との接着性や保型性が不足するのみでなく、水溶
性が不良となり再洗濯時の脱落性が不良となつて
洗濯−糊付けを繰り返す間に着色の原因となる。
(C)成分である5−スルホイソフタル酸のアルカリ
金属塩は(A)成分と相まつてポリエステル樹脂の水
溶性を高めるに必要である。3〜15重量%より少
なければ水溶性が不足し、逆に多ければ親水性が
過剰となり繊維特に疎水性の繊維との親和性即ち
接着性が不足する。5−スルホイソフタル酸のア
ルカリ金属塩とはスルホン基のアルカリ金属、主
としてナトリウム、カリウム塩でイソフタル酸は
遊離の酸である。スルホン基を導入せず、カルボ
キシル基を残存せしめたポリエステル樹脂もアル
カリ金属とすることにより水溶性とすることが出
来るが、カルボキシル基の塩によつて水溶性とし
たものは水中の多価金属、例えばカルシウム、マ
グネシウム、鉄等により不溶化し、洗濯を繰り返
す間に黄変を起こし極めて好ましくない欠点を有
する。また同時にスルホン基の導入により静電気
防止能も有し、極めてよい性質を具備する。次に
(D)成分としてのエチレングリコールまたはプロピ
レングリコールは水溶性ポリエステル樹脂の重合
度調整や繊維との親和性を良くするため30重量%
を越えない範囲で共重縮合する。これが30重量%
以上となると水溶性が不足する等の欠点が現われ
好ましくない。これらの(A)〜(D)成分より水溶性ポ
リエステル樹脂を製造するに当つては、酸成分と
アルコール成分とがモル比で1:1付近になるよ
うに調整することが好ましいが、エチレングリコ
ールまたはプロピレングリコールは揮発性である
ため過剰に配合した上で重縮合反応中に溜去し、
結果的に酸成分とアルコール成分とを1:1付近
のポリエステル樹脂とすることができる。これら
の(A)〜(D)成分を混合加熱溶融し、必要に応じてエ
ステル化触媒、例えばリン酸、ポリリン酸、亜リ
ン酸、パラトルエンスルホン酸、酢酸チタネート
等を添加し、常圧または減圧下で温度200〜300℃
にて反応せしめて、水溶性ポリエステル樹脂を得
る。 Depending on the type of clothing or other household textile products, dirt is removed by laundry or dry cleaning, and finishes such as starching and softening are applied. The present invention relates to a finishing sizing agent for textile products that are cleaned and finished in the laundry room. It is often used in recycled fiber products or blended products with polyester fibers. However, among them, blends with polyester fibers, such as 35% cotton and 65% polyester fibers, are widely used in white shirt fabrics,
It is used as a blouse fabric, and because it is relatively resistant to wrinkles after washing, it has the advantage that it can be ironed relatively easily compared to products made only of cotton. However, on the other hand, since polyester fiber is a hydrophobic fiber, it easily attracts oil-based stains, generates static electricity, and even when starch-based glue is used as a laundry glue, it has poor adhesion and poor finishing. It has the following disadvantages. In view of this current situation, we have conducted intensive research into washing finishing glues mainly for polyester fiber-cotton blended yarn fabrics, and have found that extremely excellent washing results can be obtained by using a limited amount of water-soluble polyester resin in combination with starch or vinyl alcohol. It has been found that a finishing paste can be obtained. Clothes, blouses, etc. are being washed at home more and more due to the rise in processing fees for specialized laundry shops and the spread of polyester fiber-cotton blended yarn fabrics. There is a growing demand for drugs. From this point of view, the properties required for laundry starches include good adhesion to polyester fibers, excellent antistatic properties, as well as appropriate flexibility and the ability to absorb size liquid. It must meet the required characteristics, such as being stable, able to be used as much as necessary, able to be stored, and easily falling off when rewashed. To meet these required properties, (A) 5 to 40% by weight of polyethylene glycol with an average molecular weight of 600 to 6000, (B) the weight of bis(β-hydroxyethyl) terephthalate and bis(β-hydroxyethyl) isophthalate. Ratio is 95:
5-70:30 mixture of ethylene glycol esters of dibasic acids 40-75% by weight (C) 3-15% by weight of alkali metal salts of 5-sulfoisophthalic acid and (D) 0 ethylene glycol or propylene glycol
By mixing a water-soluble polyester resin obtained by copolycondensation of ~30% by weight with starch and/or polyvinyl alcohol, an extremely excellent laundry paste that satisfies these properties was obtained. Although starch and polyvinyl alcohol are excellent sizing agents for cotton products, they lack adhesion and have poor antistatic properties for polyester fiber-cotton blends, so softeners may be added. It is known to use polyvinyl acetate-based polymers, maleic anhydride-based copolymers, and acrylic ester-based copolymers in combination, but polyvinyl acetate-based polymers themselves are not water-soluble, so they are difficult to wash during washing. It has poor removability and tends to remain with dirt, and it also copolymerizes unsaturated carboxylic acids with maleic anhydride copolymers and acrylic ester copolymers and makes them water-soluble as alkali metal salts and amine salts. At first glance, copolymers have good water solubility and therefore seem to have good washability, but in reality, they selectively adsorb calcium, magnesium ions, or iron in water during washing, making the copolymers themselves insoluble and hydrophobic. It strongly adsorbs to polyester fiber, which is a polyester fiber, and has the disadvantage that it becomes difficult to fall off along with oily stains and gradually yellows when pasting and washing are repeated. On the other hand, the aqueous polyester resin of the present invention can be used in combination with starch or polyvinyl alcohol to increase adhesion, give appropriate flexibility, and not only feel good on the skin, but also have antistatic properties. Unlike ionic copolymers with weak acidic groups copolymerized with saturated carboxylic acids, they do not become insolubilized by calcium salts or magnesium salts in water, so there is no glue residue or accumulation even after repeated use, and stains are removed. It provides an extremely good adhesive. In order to extremely improve this stain removal property, the water-soluble polyester resin used in the present invention must contain 5 to 40% by weight of polyethylene glycol with an average molecular weight of 600 to 6000 as its constituent component (A). Only those with a molecular weight of less than 600, 5% by weight
If it is less than this, the water solubility will be insufficient and the water-soluble polyester resin will be hard and brittle, so the texture of the pasted textile product will be rough and hard, which is not preferable. On the other hand, if the average molecular weight of polyethylene glycol is 6,000 or more or 40% by weight or more, the affinity with fibers will be poor and the sizing effect will be insufficient, which is undesirable. Next, as component (B), bis(β-hydroxyethyl)
Terephthalate and bis(β-hydroxyethyl)
A dibasic acid component having a weight ratio of 95:5 to 70:30 with isophthalate is required in an amount of 40 to 75% by weight. When synthesizing a water-soluble polyester resin, it is necessary to melt and mix each component (A) to (D) at a relatively low temperature to form a homogeneous mixture before the polycondensation reaction proceeds. Bisethylene glycol ester of terephthalic acid or isophthalic acid, i.e. bis(β-hydroxyethyl) terephthalate or bis(β-hydroxyethyl) as acid component.
Isophthalate is necessary, and terephthalic acid or isophthalic acid itself is not preferred because a homogeneous polycondensation reaction product cannot be obtained. When starting from terephthalic acid, isophthalic acid, or their methyl esters, ethyl esters, etc., they are esterified or transesterified with ethylene glycol to form bis(β-hydroxyethyl).
After forming terephthalate or bis(β-hydroxyethyl) isophthalate, a polycondensation reaction can be performed with other components. At the same time, if only bis(β-hydroxyethyl) terephthalate is used as the dibasic acid component, the water-soluble polyester resin and the laundry starch containing it will become coarse and hard, resulting in poor texture of the textile products to which they are pasted, which is the most disliked problem. It is. For this purpose, by mixing bis(β-hydroxyethyl) terephthalate and bis(β-hydroxyethyl) isophthalate in a ratio of 95:5 to 70:30 and polycondensing, only bis(β-hydroxyethyl) terephthalate can be used. This resulted in a resin with an extremely good texture. On the other hand, bis(β-hydroxyethyl)
On the other hand, if the isophthalate ratio exceeds 70:3, the polycondensation reaction will be inhibited and the resin will not only have insufficient adhesion to fibers and shape retention, but will also have poor water solubility, making it difficult to wash when rewashed. The shedding property becomes poor, which causes discoloration during repeated washing and gluing.
Component (C), an alkali metal salt of 5-sulfoisophthalic acid, is necessary in combination with component (A) to increase the water solubility of the polyester resin. If it is less than 3 to 15% by weight, the water solubility will be insufficient, and if it is more than 3% by weight, the hydrophilicity will be excessive and the affinity for fibers, especially hydrophobic fibers, will be insufficient. The alkali metal salt of 5-sulfoisophthalic acid is an alkali metal salt of a sulfonic group, mainly sodium or potassium salt, and isophthalic acid is a free acid. Polyester resins in which no sulfone groups are introduced and carboxyl groups remain can also be made water-soluble by adding an alkali metal to them, but polyester resins made water-soluble by using salts of carboxyl groups can absorb polyvalent metals in water, For example, it is insolubilized by calcium, magnesium, iron, etc., and yellows during repeated washing, which is an extremely undesirable drawback. At the same time, it also has antistatic ability due to the introduction of a sulfone group, and has extremely good properties. next
Ethylene glycol or propylene glycol as component (D) is 30% by weight in order to adjust the degree of polymerization of water-soluble polyester resin and improve affinity with fibers.
Copolycondensate within a range not exceeding . This is 30% by weight
If it is more than that, disadvantages such as insufficient water solubility will appear, which is not preferable. When producing a water-soluble polyester resin from these components (A) to (D), it is preferable to adjust the molar ratio of the acid component to the alcohol component to be around 1:1. Or, since propylene glycol is volatile, it is added in excess and distilled off during the polycondensation reaction.
As a result, the polyester resin can have a ratio of acid component and alcohol component of around 1:1. These components (A) to (D) are mixed and melted by heating, and if necessary, an esterification catalyst such as phosphoric acid, polyphosphoric acid, phosphorous acid, p-toluenesulfonic acid, acetate titanate, etc. is added, and the mixture is heated at normal pressure or Temperature 200-300℃ under reduced pressure
A water-soluble polyester resin is obtained.
本発明の洗濯糊組成物の他の成分であるデンプ
ンやポリビニルアルコールは特に限定する必要は
ないが、取り扱い易さ、経日的安定性、あるいは
エアゾール製品とした場合のエアゾール粒子の大
きさ等からデンプンとしてはコーンスターチ、小
麦デンプン等の生デンプンも使用し得るが、これ
らから誘導した酸化、ばい焼等による可溶性デン
プン、エステル化デンプン、エーテル化デンプ
ン、ヒドロキシ化デンプン等が好ましく、ポリビ
ニルアルコールとしては重合度500〜2300程度、
鹸化度80%以上のものが好ましい。これらのデン
プン、ポリビニルアルコールは適宜2種もしくは
それ以上混合して使用することが出来るが、水溶
性ポリエステル樹脂とデンプンおよび/またはポ
リビニルアルコールとの混合比は通常50:50〜
5:95程度、即ち水溶性ポリエステル樹脂は全糊
剤成分中半分以下5重量%以上で十分である。ま
た、このような洗濯糊組成物を使用するに当つ
て、本発明の思想に反しない程度において油剤成
分を併用したり、防腐防かび剤を添加しても良
く、また繊維製品を糊付けするに当つて全体を浸
漬し絞つても良く、エアゾール製品にして部分的
に付与してもよい。また、本発明の洗濯糊組成物
は詳述した如く、ポリエステル繊維混紡品に対し
て特にその優秀さが発揮されるのであるが、その
他の綿単独製品にあつても何ら遜色なく、ランド
リー即ち水洗いする繊維製品ならば広く使用し得
るものである。 Starch and polyvinyl alcohol, which are other components of the laundry glue composition of the present invention, do not need to be particularly limited, but may be affected by factors such as ease of handling, stability over time, and the size of aerosol particles when used as an aerosol product. Raw starches such as corn starch and wheat starch can be used as the starch, but soluble starches derived from these by oxidation, roasting, etc., esterified starches, etherified starches, hydroxylated starches, etc. are preferable, and as polyvinyl alcohol, polymerized starches degree 500~2300 degree,
A saponification degree of 80% or more is preferred. These starches and polyvinyl alcohols can be used as a mixture of two or more types, but the mixing ratio of water-soluble polyester resin and starch and/or polyvinyl alcohol is usually 50:50 to 50:50.
It is sufficient to use the water-soluble polyester resin in an amount of about 5:95, that is, 5% by weight or more, which is less than half of the total glue component. In addition, when using such a laundry starch composition, an oil component or a preservative and fungicide may be added to the extent that it does not contradict the idea of the present invention, and it is also suitable for pasting textile products. The entire product may be immersed and squeezed, or it may be applied partially as an aerosol product. In addition, as described in detail, the laundry starch composition of the present invention is particularly effective for polyester fiber blended products, but it is no inferior to other cotton products as well. It can be widely used as long as it is a textile product.
次に実施例をあげて更に詳細に説明する。 Next, a more detailed explanation will be given with reference to examples.
実施例 1
次の原料組成にて水溶性ポリエステル樹脂(A)を
合成する。Example 1 A water-soluble polyester resin (A) was synthesized using the following raw material composition.
ビス(β−ヒドロキシエチル)テレフタレート
1000g(41.7重量%)
ビス(β−ヒドロキシエチル)イソフタレート
400〃(16.7〃)
ポリエチレングリコール(分子量2000)
300〃(12.5〃)
5−スルホイソフタル酸ナトリウム
300〃(12.5〃)
エチレングリコール 400〃(16.7〃)
酢酸カルシウム 1〃
上記の水溶性ポリエステル樹脂(A)を用いて次の
組成の糊剤を調合した。Bis(β-hydroxyethyl) terephthalate
1000g (41.7% by weight) Bis(β-hydroxyethyl)isophthalate
400〃(16.7〃) Polyethylene glycol (molecular weight 2000)
300〃(12.5〃) Sodium 5-sulfoisophthalate
300〃(12.5〃) Ethylene glycol 400〃(16.7〃) Calcium acetate 1〃 A glue having the following composition was prepared using the above water-soluble polyester resin (A).
化工デンプン 7 %
水溶性ポリエステル系糊剤(A) 3 〃
パラオキシ安息香酸メチル 0.5〃
この糊剤溶液を更に20倍に稀釈し、綿ブラウス
に糊付けしたところ、腰のあるしかもしなやかな
仕上りとなり、また洗濯により完全に脱落し、汚
れ落ちも良好であつた。Modified starch 7% Water-soluble polyester glue (A) 3 Methyl paraoxybenzoate 0.5 When this glue solution was further diluted 20 times and glued to a cotton blouse, it had a firm yet supple finish. It completely fell off after washing, and stain removal was also good.
実施例 2
次の原料組成にて水溶性ポリエステル樹脂(B)を
合成する。Example 2 A water-soluble polyester resin (B) was synthesized using the following raw material composition.
ビス(β−ヒドロキシエチル)テレフタレート
1000g(48.8重量%)
ビス(β−ヒドロキシエチル)イソフタレート
200〃(14.4〃)
ポリエチレングリコール(分子量4000)
400〃(19.5〃)
5−スルホイソフタル酸ナトリウム
200〃(9.8〃)
プロピレングリコール 250〃(12.2〃)
修酸チタニウムカリウム 1〃
上記の水溶性ポリエステル樹脂(B)を用いて次の
組成の糊剤を調合した。Bis(β-hydroxyethyl) terephthalate
1000g (48.8% by weight) Bis(β-hydroxyethyl)isophthalate
200〃(14.4〃) Polyethylene glycol (molecular weight 4000)
400〃(19.5〃) Sodium 5-sulfoisophthalate
200〃(9.8〃) Propylene glycol 250〃(12.2〃) Titanium potassium oxalate 1〃 A glue having the following composition was prepared using the above water-soluble polyester resin (B).
ポリビニルアルコール(重合度1700) 3 %
水溶性ポリエステル系糊剤(B) 0.6〃
この糊剤溶液を更に水で10倍に稀釈し、ポリエ
ステル/綿(65/35)混のワイシヤツに糊付けし
たところ、腰のあるしかも滑りのよい仕上りとな
つた。また冬期の乾燥期においても静電気の発生
はみられなかつた。また洗濯−糊付け−着用を20
回繰り返したが汚れ落ちも良く、白度の低下も殆
んどみられなかつた。Polyvinyl alcohol (degree of polymerization 1700) 3% Water-soluble polyester glue (B) 0.6 This glue solution was further diluted 10 times with water and glued onto a polyester/cotton (65/35) mixed dress shirt. It has a firm yet smooth finish. Furthermore, no static electricity was observed even during the dry winter season. In addition, washing - starching - wearing 20
After repeated use several times, stains were removed well and there was almost no decrease in whiteness.
実施例 3
次の原料組成にて水溶性ポリエステル樹脂(C)を
合成する。Example 3 A water-soluble polyester resin (C) was synthesized using the following raw material composition.
ビス(β−ヒドロキシエチル)テレフタレート
1000g(57.1重量%)
ビス(β−ヒドロキシエチル)イソフタレート
300〃(17.1〃)
ポリエチレングリコール(分子量1000)
300〃(17.1〃)
5−スルホイソフタル酸ナトリウム
150〃(8.6〃)
酢酸カルシウム 1〃
上記の水溶性ポリエステル樹脂(C)を用いて次の
組成のエアゾール型糊剤を製合しる。Bis(β-hydroxyethyl) terephthalate
1000g (57.1% by weight) Bis(β-hydroxyethyl)isophthalate
300〃(17.1〃) Polyethylene glycol (molecular weight 1000)
300〃(17.1〃) Sodium 5-sulfoisophthalate
150〃(8.6〃) Calcium acetate 1〃 Prepare an aerosol type glue having the following composition using the water-soluble polyester resin (C) above.
ポリビニルアルコール(重合度500) 4g
水溶性ポリエステル系糊剤(C) 1〃
水 95〃
ジメチルエーテル 150〃
このエアゾール型糊剤をポリエステル/綿
(65/35)混のワイシヤツの襟及び袖口にスプレ
ーし糊付けしたところ、適度の硬さを有する仕上
りとなり汚れ落ちも極めて良好であつた。Polyvinyl alcohol (degree of polymerization 500) 4g Water-soluble polyester glue (C) 1〃 Water 95〃 Dimethyl ether 150〃 Spray this aerosol type glue on the collar and cuffs of a dress shirt made of polyester/cotton (65/35) blend. As a result, the finish had a suitable hardness and stain removal was also extremely good.
Claims (1)
コールを5〜40重量%(B)ビス(β−ヒドロキシエ
チル)テレフタレートとビス(β−ヒドロキシエ
チル)イソフタレートとの重量比が95:5〜70:
30である二塩基酸のエチレングリコールエステル
の混合物40〜75重量%(C)5−スルホイソフタル酸
のアルカリ金属塩3〜15重量%及び(D)エチレング
リコールまたはプロピレングリコール0〜30重量
%とを共重縮合して得られる水溶性ポリエステル
樹脂をデンプンおよび/またはポリビニルアルコ
ールと併用してなる洗濯糊組成物。1 (A) 5 to 40% by weight of polyethylene glycol with an average molecular weight of 600 to 6000 (B) The weight ratio of bis(β-hydroxyethyl) terephthalate to bis(β-hydroxyethyl) isophthalate is 95:5 to 70:
30 to 75% by weight of a mixture of ethylene glycol esters of dibasic acids (C) 3 to 15% by weight of alkali metal salts of 5-sulfoisophthalic acid and (D) 0 to 30% by weight of ethylene glycol or propylene glycol. A laundry paste composition comprising a water-soluble polyester resin obtained by copolycondensation in combination with starch and/or polyvinyl alcohol.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP3793179A JPS55132775A (en) | 1979-03-28 | 1979-03-28 | Washing size composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP3793179A JPS55132775A (en) | 1979-03-28 | 1979-03-28 | Washing size composition |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS55132775A JPS55132775A (en) | 1980-10-15 |
JPS6142027B2 true JPS6142027B2 (en) | 1986-09-18 |
Family
ID=12511291
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP3793179A Granted JPS55132775A (en) | 1979-03-28 | 1979-03-28 | Washing size composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS55132775A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007308813A (en) * | 2006-05-16 | 2007-11-29 | Nicca Chemical Co Ltd | Oligomer removing agent for polyester-based fiber material |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA1190695A (en) * | 1981-05-14 | 1985-07-16 | George J. Stockburger | Anionic textile treating compositions |
JPS61296180A (en) * | 1985-06-21 | 1986-12-26 | 東京コパル化学株式会社 | Antistatic agent for clothings |
-
1979
- 1979-03-28 JP JP3793179A patent/JPS55132775A/en active Granted
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007308813A (en) * | 2006-05-16 | 2007-11-29 | Nicca Chemical Co Ltd | Oligomer removing agent for polyester-based fiber material |
JP4614912B2 (en) * | 2006-05-16 | 2011-01-19 | 日華化学株式会社 | Oligomer remover for polyester fiber materials |
Also Published As
Publication number | Publication date |
---|---|
JPS55132775A (en) | 1980-10-15 |
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