JPS63282307A - Production of rayon having excellent dyeability - Google Patents
Production of rayon having excellent dyeabilityInfo
- Publication number
- JPS63282307A JPS63282307A JP11228387A JP11228387A JPS63282307A JP S63282307 A JPS63282307 A JP S63282307A JP 11228387 A JP11228387 A JP 11228387A JP 11228387 A JP11228387 A JP 11228387A JP S63282307 A JPS63282307 A JP S63282307A
- Authority
- JP
- Japan
- Prior art keywords
- polyethyleneimine
- aqueous solution
- viscose
- rayon
- spinning
- 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
- 229920000297 Rayon Polymers 0.000 title claims abstract description 46
- 239000002964 rayon Substances 0.000 title claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 229920002873 Polyethylenimine Polymers 0.000 claims abstract description 63
- 238000009987 spinning Methods 0.000 claims abstract description 36
- 239000007864 aqueous solution Substances 0.000 claims abstract description 31
- 239000003945 anionic surfactant Substances 0.000 claims abstract description 12
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 10
- 125000000129 anionic group Chemical group 0.000 claims abstract description 5
- 230000001112 coagulating effect Effects 0.000 claims abstract description 5
- 230000001172 regenerating effect Effects 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 abstract description 7
- 239000004094 surface-active agent Substances 0.000 abstract description 7
- 239000002202 Polyethylene glycol Substances 0.000 abstract description 4
- 229920001223 polyethylene glycol Polymers 0.000 abstract description 4
- 239000000243 solution Substances 0.000 abstract description 4
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 abstract description 3
- ZPIRTVJRHUMMOI-UHFFFAOYSA-N octoxybenzene Chemical compound CCCCCCCCOC1=CC=CC=C1 ZPIRTVJRHUMMOI-UHFFFAOYSA-N 0.000 abstract description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 abstract description 3
- 238000000034 method Methods 0.000 description 13
- 238000005345 coagulation Methods 0.000 description 10
- 230000015271 coagulation Effects 0.000 description 10
- 230000008929 regeneration Effects 0.000 description 10
- 238000011069 regeneration method Methods 0.000 description 10
- 229920002678 cellulose Polymers 0.000 description 9
- 239000001913 cellulose Substances 0.000 description 9
- -1 sulfuric acid ester salts Chemical class 0.000 description 7
- 239000000980 acid dye Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000975 dye Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000008234 soft water Substances 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 4
- SJEYSFABYSGQBG-UHFFFAOYSA-M Patent blue Chemical compound [Na+].C1=CC(N(CC)CC)=CC=C1C(C=1C(=CC(=CC=1)S([O-])(=O)=O)S([O-])(=O)=O)=C1C=CC(=[N+](CC)CC)C=C1 SJEYSFABYSGQBG-UHFFFAOYSA-M 0.000 description 4
- 238000004043 dyeing Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 3
- 239000005518 polymer electrolyte Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920003043 Cellulose fiber Polymers 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229920006317 cationic polymer Polymers 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 210000002268 wool Anatomy 0.000 description 2
- 239000012991 xanthate Substances 0.000 description 2
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- 229920006318 anionic polymer Polymers 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000440 effect on coagulation Effects 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 238000009940 knitting Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- GSGDTSDELPUTKU-UHFFFAOYSA-N nonoxybenzene Chemical compound CCCCCCCCCOC1=CC=CC=C1 GSGDTSDELPUTKU-UHFFFAOYSA-N 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 239000004627 regenerated cellulose Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000009991 scouring Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000009182 swimming Effects 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000002166 wet spinning Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Artificial Filaments (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は衣料用、インテリア全般、寝装、産業資材用等
の用途に使用可能な染色性の優れたレーヨンに関するも
のである。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a rayon with excellent dyeability that can be used for clothing, interior decoration in general, bedding, industrial materials, and the like.
（従来の技術）
セルローズ系繊維は酸性染料と直接の親和性を有してい
ないため酸性染料による染色は不可能であり、再生セル
ローズ繊維、いわゆるレーヨンが酸性染料と親和性の強
い羊毛と混紡または交織編され、その後、染色される場
合、レーヨンサイドおよび羊毛サイドは各々の適性染料
によシ個別浴または同浴の染色操作によシ染色１色合せ
が行なわれているのが実状で、煩雑であると同時に多大
の費用と処理時間を要している。(Prior art) Cellulose fibers do not have a direct affinity for acid dyes, so it is impossible to dye them with acid dyes.Regenerated cellulose fibers, so-called rayon, are blended or blended with wool, which has a strong affinity for acid dyes. When knitting is mixed and knitted and then dyed, the rayon side and wool side are dyed in separate baths with appropriate dyes, or in the same bath, dyeing is performed in one color, which is complicated. At the same time, it requires a large amount of cost and processing time.
そのため、レーヨンに対し、酸性染料への親和性を付与
することは大きな意義があり、その方法としてポリエチ
レンイミンなどアミノ基、イミノ基を有する高分子重合
体を利用し、改質する方法が提案されている。たとえば
持分１１１Ｂ４８−２３８３４号ではポリエチレンイミ
ン水溶液中にレーヨンを浸漬処理する方法、また特公昭
３５−９６７７号および特公昭３５−１６７１４号の各
号ではポリエチレンイミン等の水溶液をレーヨン紡糸用
原液（以下ビスコースと略す）Ｋ混和し、常法によシ紡
糸浴で凝固再生しレーヨンを得る方法などがある。Therefore, it is of great significance to impart affinity for acid dyes to rayon, and a method of modifying it using a high molecular weight polymer having amino and imino groups, such as polyethyleneimine, has been proposed. ing. For example, Chiken No. 111B48-23834 describes a method of immersing rayon in an aqueous polyethyleneimine solution, and Japanese Patent Publication No. 35-9677 and Japanese Patent Publication No. 35-16714 disclose an aqueous solution of polyethyleneimine, etc. There is a method of obtaining rayon by mixing K (abbreviated as "Coase") and coagulating and regenerating it in a conventional spinning bath.
しかしながら、前者の場合は後処理による改質であシ、
操作が煩雑なこととともに、後処理ゆえに改質剤である
ポリエチレンイミンとレーヨンとの結合の強さに懸念が
ある。後者の場合はレーヨンのダル糸を作る場合の手法
がそのまま適用され、煩雑さはなくなシ、製造に関して
は非常に優位な方法であるが１本発明者らの追試で、該
改質レーヨンを得ようとした所、紡糸工程での凝固再生
の不良に起因するとみられるビスカス（繊維状の塊状物
、膠着物）が多発し、該改質レーヨンを安定して製造す
ることは困難であった。However, in the former case, modification by post-treatment is required;
In addition to the complicated operations, there are concerns about the strength of the bond between the modifier polyethyleneimine and rayon due to the post-treatment. In the latter case, the method used to make dull rayon yarn is applied as is, and it is not complicated and is a very advantageous method in terms of production. When trying to obtain modified rayon, a large amount of viscous (fibrous lumps, agglomerates) appeared due to poor coagulation and regeneration during the spinning process, making it difficult to stably produce the modified rayon. .
（問題点を解決するための平膜）
本発明者らは、製造に関して優位な方法であるポリエチ
レンイミン水溶液をビスコースに添加し。(Flat membrane for solving problems) The present inventors added a polyethyleneimine aqueous solution to viscose, which is an advantageous method for manufacturing.
レーヨンを改質する方法において、前述の問題点を解決
するため鋭意検討を重ねた結果、約１０，０００以上の
分子ｉｔヲ持つポリエチレンイミンの水溶液にアニオン
性およびノニオン性の界面活性剤を分散、溶解すること
で前処理し、該ポリエチレンイミン水溶液をビスコース
に添加し、混和することにより、紡糸工程でビスカスが
多発する問題が改善されることを見出し５本発明を完成
するに至った。As a result of extensive research in order to solve the aforementioned problems in the method of modifying rayon, we discovered that anionic and nonionic surfactants were dispersed in an aqueous solution of polyethyleneimine, which has a molecular weight of about 10,000 or more. The present inventors have discovered that by pre-treating by dissolving the polyethyleneimine aqueous solution, adding the polyethyleneimine aqueous solution to viscose, and mixing the polyethyleneimine solution, the problem of frequent generation of viscose during the spinning process can be improved, and the present invention has been completed.
ポリエチレンイミンはその構造中に第１．第２゜第３級
のアミン窒素を含むカチオン性の高分子電解質であシ水
に対し、如何なる割合でも溶は合う。Polyethyleneimine has a primary molecule in its structure. It is a cationic polymer electrolyte containing 2.degree. and tertiary amine nitrogen and is soluble in water at any ratio.
またポリエチレンイミンの水溶液からは常温、常圧下で
ポリエチレンイミンを乾燥することが出来ず、水との結
合力が非常に強い性質を示す。Furthermore, polyethyleneimine cannot be dried from an aqueous solution of polyethyleneimine at room temperature and under normal pressure, and exhibits a very strong bonding force with water.
ポリエチレンイミン水溶液をビスコースに添加し、紡糸
浴で凝固再生し、改質レーヨンを得ようとした場合にビ
スカスが多発した原因は、前述したポリエチレンイミン
の特性より、ビスコース中のセルロースザンテートの凝
固再生において、遅延作用があったと考えられ、一方ビ
スコース中のセルローズザンテートは陰イオン性の高分
子電解質であり、カチオン性のポリエチレンイミンとの
相互作用があり、その点も凝固再生を遅延させる方向に
繋がったものと思われる。When an attempt was made to obtain modified rayon by adding a polyethyleneimine aqueous solution to viscose and coagulating and regenerating it in a spinning bath, the reason for the large amount of viscose produced was due to the cellulose xanthate in the viscose, based on the properties of polyethyleneimine mentioned above. It is thought that there was a delaying effect on coagulation and regeneration.On the other hand, cellulose xanthate in viscose is an anionic polymer electrolyte and interacts with cationic polyethyleneimine, which also delays coagulation and regeneration. This seems to have led to this.
本発明者らは、この凝固再生の遅延作用に着目し、その
改良を進めた結果、本発明に至ったものである。従って
、本発明は約１０，０００以上の分子量を持つポリエチ
レンイミンの水溶液にアニオン性およびノニオン性の界
面活性剤を分散、溶解してポリエチレンイミンのイオン
性を中和した水溶液をビスコースに添加、混和し、紡糸
浴にて凝固再生すること罠より、染色性の優れたレーヨ
ンを得る製造方法に関するものである。The present inventors focused on this retarding effect of coagulation and regeneration, and as a result of their efforts to improve the effect, they arrived at the present invention. Therefore, the present invention involves dispersing and dissolving anionic and nonionic surfactants in an aqueous solution of polyethyleneimine having a molecular weight of about 10,000 or more to neutralize the ionicity of polyethyleneimine, and adding an aqueous solution to viscose. The present invention relates to a manufacturing method for producing rayon with excellent dyeability by mixing and coagulating and regenerating it in a spinning bath.
以下に本発明のレーヨン製造方法を説明する。The rayon manufacturing method of the present invention will be explained below.
本発明に用いられるビスコースはあらかじめ。The viscose used in the present invention is prepared in advance.
濾過された紡糸直前の組成がセルローズ濃度およびアル
カリ濃度がそれぞれ８．４〜１０．０％、５．０〜６．
３のものを用いる。The filtered composition immediately before spinning has a cellulose concentration and an alkali concentration of 8.4 to 10.0% and 5.0 to 6.0%, respectively.
3 is used.
ポリエチレンイミン水溶液に利用するポリエチレンイミ
ンの分子量は１０，０００以上、１００，０００以下の
ものが望ましい、特に凝固再生時にレーヨン中への歩留
シを考慮すれば３０，０００以上のものがより望ましく
１分子量がより高い、すなわち１００．０００以上のポ
リエチレンイミンでは水溶液粘度が著しく上昇し、希釈
して使用するにも凝固再生の点より限界°があシ、脱泡
などのノ・ンドリング面で不適となり、また分子量の大
きいことによる効果も見出せ々いので好ましくない。The molecular weight of the polyethyleneimine used in the polyethyleneimine aqueous solution is preferably 10,000 or more and 100,000 or less, and more preferably 30,000 or more, especially considering the retention in rayon during coagulation and regeneration. Polyethyleneimine with a higher molecular weight, i.e., 100,000 or more, has a marked increase in aqueous solution viscosity, and even when used diluted, there is a limit to coagulation and regeneration, making it unsuitable in terms of non-driving such as defoaming. Moreover, it is not preferable because the effect of having a large molecular weight cannot be seen.
一方、ポリエチレンイミンの分子量が１０，０００未満
になると凝固再生時に凝固浴中に溶は出し。On the other hand, if the molecular weight of polyethyleneimine is less than 10,000, it will dissolve into the coagulation bath during coagulation and regeneration.
歩留りが悪く、染色性の改良の効果が小さい。The yield is poor and the effect of improving dyeability is small.
ポリエチレンイミン水溶液中のポリエチレンイミンの濃
度はビスコースに添加した場合の可紡性の面からはなる
べく高濃度が良く、ノ１ンドリングの容易さ、脱泡の面
からは粘度の低い低濃度が望ましい、これらの点より７
〜２０％の濃度が望ましい。The concentration of polyethyleneimine in the polyethyleneimine aqueous solution is preferably as high as possible from the viewpoint of spinnability when added to viscose, and a low concentration with low viscosity is desirable from the viewpoint of ease of rolling and defoaming. , from these points 7
A concentration of ~20% is desirable.
以上の分子量、組成のポリエチレンイミンの水溶液中に
アニオン性界面活性剤およびノニオン性界面活性剤の併
用により分散、溶解しポリエチレンイミン水溶液の前処
理を行なう。The polyethyleneimine aqueous solution is pretreated by dispersing and dissolving it in an aqueous solution of polyethyleneimine having the above molecular weight and composition using a combination of an anionic surfactant and a nonionic surfactant.
ポリエチレンイミンをビスコースに添加するに際シてあ
らかじめポリエチレンイミンの水溶液をアニオン性およ
びノニオン性の界面活性剤を併用し、前処理することに
より、紡糸浴での凝固再生でビスカス発生が著しく減少
する効果が得られる理由については明かくではないが、
ポリエチレンイミンはカチオン性の高分子電解質であり
、ア二オン性界面活性剤を添加することでポリエチレン
イミンとアニオン性界面活性剤がある種の結合体を形成
し、ノニオン性界面活性剤は、この結合体のビスコース
中での安定化に寄与しているものと想像される。前処理
に使用出来るアニオン性の界面活性剤の種類については
高級アルコールの硫酸エステル塩および燐酸エステル塩
、アルキルベンゼンスルフォン酸塩、高級脂肪酸塩、ナ
フタリンスルフオン酸ソーダホルマリン縮合物等が有効
であり、ノニオン性の界面活性剤としては水溶液である
ポリオキシエチレン系、ジェタノールアミン系、多価ア
ルコールの脂肪酸エステル系等の界面活性剤が有効であ
る。When adding polyethyleneimine to viscose, by pre-treating the polyethyleneimine aqueous solution with anionic and nonionic surfactants, the generation of viscose can be significantly reduced during coagulation and regeneration in the spinning bath. Although it is not clear why it is effective,
Polyethyleneimine is a cationic polymer electrolyte, and by adding an anionic surfactant, polyethyleneimine and the anionic surfactant form a kind of bond, and the nonionic surfactant It is thought that this contributes to the stabilization of the conjugate in viscose. Regarding the types of anionic surfactants that can be used for pretreatment, sulfuric acid ester salts and phosphoric acid ester salts of higher alcohols, alkylbenzene sulfonates, higher fatty acid salts, naphthalene sulfonic acid soda formalin condensates, etc. are effective. As aqueous surfactants, polyoxyethylene-based surfactants, jetanolamine-based surfactants, polyhydric alcohol fatty acid ester-based surfactants, and the like are effective.
前処理に使用するアニオン性界面活性剤およびノニオン
性界面活性剤の量はポリエチレンイミン水溶液中のポリ
エチレンイミンの重量に対して種種の濃度で検討した結
果、それぞれ５〜５０ｗｔ％の間で凝固再生に明らかな
効果がある。しかしながら、界面活性剤の添加量の増加
によシポリエチレンイミン水溶液の粘度は著しく増大す
る傾向にあり、よシ高濃度の界面活性剤での処理は不適
となる。望ましくはそれぞれ１０〜３０ｗｔ％の間が工
業的な効果の面でより好適である。The amount of anionic surfactant and nonionic surfactant used for pretreatment was investigated at various concentrations based on the weight of polyethyleneimine in the polyethyleneimine aqueous solution, and it was found that the amount of each was between 5 and 50 wt% for coagulation and regeneration. It has a clear effect. However, as the amount of surfactant added increases, the viscosity of the polyethyleneimine aqueous solution tends to increase significantly, making treatment with a very high concentration of surfactant unsuitable. Desirably, a content of 10 to 30 wt% is more suitable for industrial effects.
染色性改良剤としてのポリエチレンイミンのビスコース
に対する添加量は、ビスコース中のセルローズ量に対し
０．５〜３． Ｏｗｔ％で良いがこれ以上の添加量を用
いることも何らさしつかえない、特に染色性改良への効
果、経済性の面からは１．５〜２、５ ｖｔ％がよシ望
ましい。The amount of polyethyleneimine added as a dyeability improver to viscose is 0.5 to 3.0% based on the amount of cellulose in viscose. Owt% may be sufficient, but there is no problem in using a larger amount.In particular, 1.5 to 2.5 wt% is highly desirable from the viewpoint of improving dyeability and economical efficiency.
次忙本発明の実施例を挙げるが本発明はこれら実施例に
＠足されることなく本発明の特許特求範囲内の任意の変
形を含むものである。Examples of the present invention will be described below, but the present invention includes any modifications within the scope of the patent of the present invention without addition to these examples.
実施例１
攪拌機付のステンレスタンクにて、分子量約７０．００
０のポリエチレンイミンの３０％水浴液２５１１、軟水
７２部、ドデシルベンゼンスルフオン酸ソーダ０．８部
、ポリエチレングリコールオクチルフェニルエーテル２
．２部を攪拌しなから混合。Example 1 In a stainless steel tank with a stirrer, the molecular weight was approximately 70.00.
2,511 parts of 30% polyethyleneimine bath solution, 72 parts of soft water, 0.8 parts of sodium dodecylbenzenesulfonate, 2 parts of polyethylene glycol octylphenyl ether
．． Mix the 2 parts without stirring.
溶解し、ついで攪拌を停止し、静置脱泡を行なった。こ
のポリエチレンイミン水溶液をセルローズ濃度９．０５
％、アルカリ濃度５．５％、粘度５０秒（落球法１９℃
）および熟成度９．２のビスコースに対し、インジェク
タ１ンを用いポリエチレンイミン純分がセルローズ量九
対し２． Ｏｖｔ％になる如く計算された一定量を注入
しつつミキサーにて連続混合し、孔数１０，０００．孔
径０．０６ｍφのノズルを用い、硫酸１１２１／１．硫
酸ナトリウム３３０１／ｌ、硫は亜鉛１３．５１／ｌお
よび温度４５℃の第−浴に４０ｍ／分で紡糸し、ついで
硫酸６０１／ｌ、温度９０℃の第二浴をドラフト率５０
％で通すことで湿式紡糸を行ない紡糸状態を観察した。After dissolving, stirring was stopped and defoaming was carried out. This polyethyleneimine aqueous solution has a cellulose concentration of 9.05.
%, alkaline concentration 5.5%, viscosity 50 seconds (falling ball method 19℃
) and viscose with a maturity of 9.2, using an injector of 1 injector, the pure content of polyethyleneimine was 9.2% of the amount of cellulose. While injecting a certain amount calculated to give Ovt%, continuous mixing was performed using a mixer, and the number of holes was 10,000. Using a nozzle with a hole diameter of 0.06 mφ, sulfuric acid 1121/1. Spinning at 40 m/min into a first bath containing 3301/l of sodium sulfate, 13.51/l of sulfur and zinc and a temperature of 45°C, and then a second bath containing 601/l of sulfuric acid and a temperature of 90°C with a draft rate of 50
%, wet spinning was performed and the spinning state was observed.
紡糸状態の評価は紡糸されたトウを内訳で観察するとと
もに、紡糸開始後１０分毎にトウを１０１７分サンプリ
ングし、水を張った５ ０ｃｍＸ ５０α×１０αのバ
ットにトウを泳がせ、トウ中のビスカス１ｔ（（固数）
をカウントした。The spinning condition was evaluated by observing the spun tow in detail, sampling the tow for 1017 minutes every 10 minutes after the start of spinning, and swimming the tow in a vat of 50cm x 50α x 10α filled with water. 1t ((solid number)
was counted.
以上の紡糸条件で行なった本実施例の紡糸状態は非常に
良好であシ、一定の評価基準時間である６０分経過後の
ビスカス発生はゼロであつ念。The spinning condition of this example, which was carried out under the above-mentioned spinning conditions, was very good, and we are grateful that no viscus was generated after 60 minutes, which is a certain evaluation standard time, had elapsed.
尚、ポリエチレンイミンを全く添加しない通常のビスコ
ースのみでの紡糸状態は当然ビスカスが全く発生せず良
好であった。Incidentally, when spinning only ordinary viscose without adding any polyethyleneimine, no viscose was naturally generated and the spinning condition was good.
比較例１
攪拌機付のステンレスタンクにて、実施例１と同じポリ
エチレンイミンの３０％水溶液２５部と軟水７５部を混
合、溶解した後、静置脱泡を行なった。このポリエチレ
ンイミン水溶液を用い実施例１と同じ条件、方法忙従い
紡糸を行なった。Comparative Example 1 In a stainless steel tank equipped with a stirrer, 25 parts of the same 30% aqueous solution of polyethyleneimine as in Example 1 and 75 parts of soft water were mixed and dissolved, and then left to stand for defoaming. Using this polyethyleneimine aqueous solution, spinning was carried out under the same conditions and method as in Example 1.
観察された紡糸状態は、紡糸開始後数分よシ著しく大き
なビスカスが発生し、紡糸を継続することが不能となっ
た。ノズルを交換し、再紡糸を行なったが同様の結果で
あった。The observed spinning state was such that a significantly large amount of viscous was generated several minutes after the start of spinning, making it impossible to continue spinning. The nozzle was replaced and re-spinning was performed, but the results were the same.
比較例２
攪拌機付のステンレスタンクにて実施例１と同シ／リエ
チレンイミンの３０％水溶液２５部、軟水７３．５１（
Ｓ、ドデシルベンゼンスルフオン酸ソーダ１．５部を混
合、溶解した後、静置脱泡を行なった。このポリエチレ
ンイミン水溶液を周込実施例１と同じ条件、方法に従い
紡糸の評価を実施した。Comparative Example 2 In a stainless steel tank equipped with a stirrer, 25 parts of the same 30% aqueous solution of polyethyleneimine as in Example 1 and 73.51 parts of soft water (
After mixing and dissolving 1.5 parts of S and sodium dodecylbenzenesulfonate, the mixture was left to stand for degassing. This polyethyleneimine aqueous solution was incorporated and the spinning was evaluated according to the same conditions and method as in Example 1.
紡糸状態は、紡糸開始後の最初の１０分目において著し
く大きなビスカスを多発Ｌ／ ％紡糸の継続は不能とな
った。ノズルを交換し、再紡糸を行なったが、結果は同
様であった。Regarding the spinning condition, in the first 10 minutes after the start of spinning, a significantly large amount of viscous was generated at a high rate of L/%, making it impossible to continue spinning. The nozzle was replaced and respinning was performed, but the results were the same.
比較例３
攪拌機付のステンレスタンクにて、実施例１と同じポリ
エチレンイミンの３０％水溶液２５部、軟水７３．５部
、プリエチレングリコールオクチルフェニルエーテル１
．５部を混合、溶解した後、静置脱泡を行なった。この
プリエチレンイミン水溶液を用い実施例１と同じ条件、
方法に従い紡糸を行なった、
紡糸開始後、２０分目のトウよりビスカスの発生を認め
、３０分目には著しく大きなビスカスが発生し、紡糸を
停止した。Comparative Example 3 In a stainless steel tank equipped with a stirrer, 25 parts of the same 30% aqueous solution of polyethyleneimine as in Example 1, 73.5 parts of soft water, and 1 part of polyethylene glycol octylphenyl ether
．． After mixing and dissolving 5 parts, the mixture was left to stand and defoamed. The same conditions as in Example 1 using this preethyleneimine aqueous solution,
Spinning was carried out according to the method. After 20 minutes after the start of spinning, generation of viscous was observed from the tow, and at 30 minutes, a significantly large amount of viscous was generated, and spinning was stopped.
以上の結果を次表に示す。The above results are shown in the table below.
第−表
実施例２
攪拌機付のステンレスタンクにて、分子量約３０．００
０のポリエチレンイミン１５部と軟水８５部に対して、
第二衣に示す種々の割合でナフタリンスルフオン酸ソー
ダホルマリン縮合物（アニオン性界面活性剤）とポリエ
チレングリコールノニルフェニルエーテル（ノニオン性
界面活性剤）を混合、溶解後、静置脱泡し、ビスコース
添加用の徨々のポリエチレンイミン水溶ｗ１．を調整し
念。Table - Example 2 In a stainless steel tank with a stirrer, the molecular weight was approximately 30.00.
For 15 parts of polyethyleneimine and 85 parts of soft water,
After mixing and dissolving naphthalene sulfonic acid soda formalin condensate (anionic surfactant) and polyethylene glycol nonylphenyl ether (nonionic surfactant) in various proportions shown in the second coating, the mixture is left to stand for defoaming, and Aqueous polyethyleneimine w1 for course addition. Please make sure to adjust it.
これらのポリエチレンイミン水溶液７をセルローズ濃度
９．２０％、アルカリ濃度５．６０％、粘度５３秒（落
球法１９℃）および熟成度９．０のビスコースに対し、
インジェクシ璽ンを用いポリエチレンイミン純分がセル
ローズ量に対し２．５ ｗｔ％になる如く計算された一
定の量を連続的に注入し、ミキサーにて混合しつつ、孔
数ｓ、ｏｏｏ、孔径０．０６５ｍφのノズルにより実施
例１と同様の紡糸第−浴へ４０ｍ／分で紡糸し、ついで
やはり同様の第二浴をドラフト率４０％で通すことで紡
糸を行ない紡糸状態を評価した。評価の方法は実施例１
と同様に行なっ六つ結果は第二衣に示した。These polyethyleneimine aqueous solutions 7 were added to viscose having a cellulose concentration of 9.20%, an alkali concentration of 5.60%, a viscosity of 53 seconds (falling ball method at 19°C), and a maturity level of 9.0.
Using an injector, continuously inject a fixed amount calculated so that the pure polyethyleneimine content is 2.5 wt% based on the amount of cellulose, and while mixing with a mixer, the number of holes is s, ooo, and the pore diameter is 0. Using a nozzle of .065 mφ, the material was spun at 40 m/min into the same spinning bath as in Example 1, and then passed through a similar second bath at a draft rate of 40%, and the spinning state was evaluated. The evaluation method is Example 1
The same procedure was carried out and the results are shown in the second figure.
第二衣
＊紡糸状態の評価（紡糸開始６０分間での判定）不良
；ビスカスの発生多く、６０分以内に紡糸停止やや不良
；ビスカス発生Ｘ０３以上
やや良好；ビスカス発生５〜１０コ
良好 ；ビスカス発生２〜４コ
非常圧良好：ビスカス発生はとんどなし実施例３
分子量１００，０００のポリエチレンイミンを用いる以
外は実施例１と全く同一条件でポリエチレンイミン水溶
液を調整し、かつ、ポリエチレンイミンの純分をセルロ
ーズ量に対し０．５〜３．０％の範囲で０．５％ピッチ
となるように６水準の量で添加して紡糸を行ない、その
後、これらポリエチレンイミンの各添加量で紡糸された
トウを５ｃＩＩＬの長さに各々カッティングし、熱湯浴
（９５°Ｃ）で処理し、続いて常法に従い精練°および
乾燥を行なった。Second garment *Evaluation of spinning condition (judgment 60 minutes after starting spinning) is poor
; Lots of viscous generated, spinning stopped within 60 minutes, somewhat poor; Viscous generated X03 or higher, slightly good; 5 to 10 viscous generated, good; 2 to 4 viscous generated, very good pressure: Almost no viscous generated Example 3 A polyethyleneimine aqueous solution was prepared under exactly the same conditions as in Example 1 except that polyethyleneimine with a molecular weight of 100,000 was used, and the pure content of polyethyleneimine was adjusted to 0.0% in the range of 0.5 to 3.0% based on the amount of cellulose. Polyethyleneimine was added in 6 levels to give a pitch of .5% pitch and spun.The tows spun with each added amount of polyethyleneimine were then cut to a length of 5 cIIL and heated in a hot water bath (95°C). ), followed by scouring and drying according to conventional methods.
この様にして得たポリエチレンイミンの各添加量の繊維
をＫａｙｉｎｏｌ Ｍｉｌｌ ｉｎｇ Ｒｅｄ ＢＷ
（日本化薬社裂の酸性染料）１％ｏｗｆ ｅ浴比１：５
０．助剤として酢酸アンモン５％ｏｗｆと氷酢酸２％ｏ
ｗｆ ｆ：用い、１００℃３０分間染色した。The fibers with each added amount of polyethyleneimine obtained in this way were processed into Kayinol Milling Red BW.
(Nippon Kayakusha's acid dye) 1% owf e-bath ratio 1:5
0. Ammonium acetate 5%Of and glacial acetic acid 2%OF as auxiliaries
wf f: was used and stained at 100°C for 30 minutes.
その結果は第三表に示したようにポリエチレンイミンの
添加率によシ染着量が変化し、特に１． Ｏｖｔ％以下
では大きく低下した。また２、５ ｖｔ％では染着量は
フラットになった。堅牢度の面からは１．５〜２．５
ｙｔ％がよ）好ましかった。As shown in Table 3, the results show that the amount of dyeing changes depending on the addition rate of polyethyleneimine, especially in 1. It decreased significantly below Ovt%. Further, at 2.5 vt%, the dyeing amount became flat. In terms of fastness, it is 1.5 to 2.5.
yt%) was preferable.
比較例４
実施例１で得たポリエチレンイミンを全く添加せずに紡
糸したレーヨンを実施例３と同一の処法条件で染色した
。結果は汚染程度に染色されたのみであった。Comparative Example 4 The rayon obtained in Example 1 and spun without adding any polyethyleneimine was dyed under the same processing conditions as in Example 3. The result was that the dye was only stained to the extent of contamination.
比較例５
分子量約ｓ、ｏｏｏのポリエチレンイミンを用いること
以外はすべて実施例１と同一の条件で紡糸を行なったポ
リエチレンイミン２ｗｔ％のレーヨンを実施例３と同一
の処法条件で染色した。Comparative Example 5 Rayon containing 2 wt % of polyethyleneimine was dyed under the same processing conditions as in Example 3, which was spun under the same conditions as in Example 1 except that polyethyleneimine having a molecular weight of about s, ooo was used.
その結果、実施例３でのポリエチレンイミンの対セル２
ｗｔ％添加レーヨンに比して染着量はかなシ劣シ、染浴
に染料残が見られた。これはポリエチレンイミンの分子
量が小さいため紡糸して凝固再生時に溶出し、繊維内の
ポリエチレンの歩留シ量が少なくなったためと思われる
。As a result, the cell 2 of polyethyleneimine in Example 3
Compared to the wt% added rayon, the dyeing amount was slightly inferior, and dye residue was observed in the dye bath. This is thought to be because polyethyleneimine has a small molecular weight and is eluted during spinning and coagulation and regeneration, reducing the amount of polyethylene retained within the fiber.
第三表Table 3
Claims (1)
の水溶液にアニオン性およびノニオン性の界面活性剤を
それぞれポリエチレンイミンの重量に対して５〜５０％
分散、溶解した水溶液をビスコースに添加、混和し、紡
糸浴にて凝固再生することを特徴とする染色性の優れた
レーヨンの製造方法。Anionic and nonionic surfactants are added to an aqueous solution of polyethyleneimine having a molecular weight of about 10,000 or more in an amount of 5 to 50% based on the weight of polyethyleneimine.
A method for producing rayon with excellent dyeability, characterized by adding a dispersed and dissolved aqueous solution to viscose, mixing it, and coagulating and regenerating it in a spinning bath.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11228387A JPS63282307A (en) | 1987-05-11 | 1987-05-11 | Production of rayon having excellent dyeability |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11228387A JPS63282307A (en) | 1987-05-11 | 1987-05-11 | Production of rayon having excellent dyeability |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63282307A true JPS63282307A (en) | 1988-11-18 |
| JPH0159361B2 JPH0159361B2 (en) | 1989-12-18 |
Family
ID=14582817
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11228387A Granted JPS63282307A (en) | 1987-05-11 | 1987-05-11 | Production of rayon having excellent dyeability |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63282307A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0692558A1 (en) * | 1994-06-30 | 1996-01-17 | Hoechst Aktiengesellschaft | Process for the production of aminated fibres from regenerated cellulose |
| WO1996014451A1 (en) * | 1994-11-03 | 1996-05-17 | Ostthüringische Materialprüfgesellschaft Für Textil Und Kunststoffe Mbh Rudolstadt | Regenerated cellulose moulding and process for producing it |
| JP2010229312A (en) * | 2009-03-27 | 2010-10-14 | Fuji Xerox Co Ltd | Resin composition and resin-molded article |
| CN110359282A (en) * | 2019-07-02 | 2019-10-22 | 东莞德永佳纺织制衣有限公司 | A kind of wicking function ameliorative way of viscose glue class fabric |
-
1987
- 1987-05-11 JP JP11228387A patent/JPS63282307A/en active Granted
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0692558A1 (en) * | 1994-06-30 | 1996-01-17 | Hoechst Aktiengesellschaft | Process for the production of aminated fibres from regenerated cellulose |
| WO1996014451A1 (en) * | 1994-11-03 | 1996-05-17 | Ostthüringische Materialprüfgesellschaft Für Textil Und Kunststoffe Mbh Rudolstadt | Regenerated cellulose moulding and process for producing it |
| JP2010229312A (en) * | 2009-03-27 | 2010-10-14 | Fuji Xerox Co Ltd | Resin composition and resin-molded article |
| CN110359282A (en) * | 2019-07-02 | 2019-10-22 | 东莞德永佳纺织制衣有限公司 | A kind of wicking function ameliorative way of viscose glue class fabric |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0159361B2 (en) | 1989-12-18 |
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