JPH0379630A - Production of modified nylon - Google Patents
Production of modified nylonInfo
- Publication number
- JPH0379630A JPH0379630A JP21424989A JP21424989A JPH0379630A JP H0379630 A JPH0379630 A JP H0379630A JP 21424989 A JP21424989 A JP 21424989A JP 21424989 A JP21424989 A JP 21424989A JP H0379630 A JPH0379630 A JP H0379630A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- amino acid
- diamine
- nylon
- modified nylon
- 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.)
- Pending
Links
- 239000004677 Nylon Substances 0.000 title claims abstract description 19
- 229920001778 nylon Polymers 0.000 title claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 239000002253 acid Substances 0.000 claims abstract description 9
- 150000004985 diamines Chemical class 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 7
- 235000008206 alpha-amino acids Nutrition 0.000 claims abstract description 7
- 150000003951 lactams Chemical class 0.000 claims abstract description 6
- 150000003839 salts Chemical class 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 14
- 229920000642 polymer Polymers 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 6
- 150000001370 alpha-amino acid derivatives Chemical class 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 2
- 235000001014 amino acid Nutrition 0.000 abstract description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 10
- 150000001413 amino acids Chemical class 0.000 abstract description 10
- SLXKOJJOQWFEFD-UHFFFAOYSA-N 6-aminohexanoic acid Chemical compound NCCCCCC(O)=O SLXKOJJOQWFEFD-UHFFFAOYSA-N 0.000 abstract description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 abstract description 6
- 229960002684 aminocaproic acid Drugs 0.000 abstract description 6
- 238000007334 copolymerization reaction Methods 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 5
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 abstract description 4
- 239000004472 Lysine Substances 0.000 abstract description 4
- 235000011037 adipic acid Nutrition 0.000 abstract description 3
- 239000001361 adipic acid Substances 0.000 abstract description 3
- 150000001371 alpha-amino acids Chemical class 0.000 abstract description 3
- 238000006116 polymerization reaction Methods 0.000 abstract description 3
- 238000004043 dyeing Methods 0.000 abstract 1
- 239000000835 fiber Substances 0.000 description 11
- 239000000975 dye Substances 0.000 description 10
- 239000000980 acid dye Substances 0.000 description 8
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 6
- 230000009477 glass transition Effects 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 229920002292 Nylon 6 Polymers 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
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 4
- 238000002074 melt spinning Methods 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- WSEQLMQNPBNMSL-FJXQXJEOSA-N diethyl (2s)-2-aminopentanedioate;hydron;chloride Chemical compound Cl.CCOC(=O)CC[C@H](N)C(=O)OCC WSEQLMQNPBNMSL-FJXQXJEOSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 235000018977 lysine Nutrition 0.000 description 3
- -1 1so-propyl Chemical group 0.000 description 2
- HVBSAKJJOYLTQU-UHFFFAOYSA-N 4-aminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C=C1 HVBSAKJJOYLTQU-UHFFFAOYSA-N 0.000 description 2
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 description 2
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 2
- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 235000003704 aspartic acid Nutrition 0.000 description 2
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 235000013922 glutamic acid Nutrition 0.000 description 2
- 239000004220 glutamic acid Substances 0.000 description 2
- 150000003840 hydrochlorides Chemical class 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- MTCFGRXMJLQNBG-REOHCLBHSA-N (2S)-2-Amino-3-hydroxypropansäure Chemical compound OC[C@H](N)C(O)=O MTCFGRXMJLQNBG-REOHCLBHSA-N 0.000 description 1
- AKVBCGQVQXPRLD-SSDOTTSWSA-N (2r)-2-azaniumyloctanoate Chemical compound CCCCCC[C@@H]([NH3+])C([O-])=O AKVBCGQVQXPRLD-SSDOTTSWSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- ONIBWKKTOPOVIA-BYPYZUCNSA-N L-Proline Chemical compound OC(=O)[C@@H]1CCCN1 ONIBWKKTOPOVIA-BYPYZUCNSA-N 0.000 description 1
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 description 1
- ROHFNLRQFUQHCH-YFKPBYRVSA-N L-leucine Chemical compound CC(C)C[C@H](N)C(O)=O ROHFNLRQFUQHCH-YFKPBYRVSA-N 0.000 description 1
- BVHLGVCQOALMSV-JEDNCBNOSA-N L-lysine hydrochloride Chemical compound Cl.NCCCC[C@H](N)C(O)=O BVHLGVCQOALMSV-JEDNCBNOSA-N 0.000 description 1
- COLNVLDHVKWLRT-QMMMGPOBSA-N L-phenylalanine Chemical compound OC(=O)[C@@H](N)CC1=CC=CC=C1 COLNVLDHVKWLRT-QMMMGPOBSA-N 0.000 description 1
- ROHFNLRQFUQHCH-UHFFFAOYSA-N Leucine Natural products CC(C)CC(N)C(O)=O ROHFNLRQFUQHCH-UHFFFAOYSA-N 0.000 description 1
- 229920000305 Nylon 6,10 Polymers 0.000 description 1
- ONIBWKKTOPOVIA-UHFFFAOYSA-N Proline Natural products OC(=O)C1CCCN1 ONIBWKKTOPOVIA-UHFFFAOYSA-N 0.000 description 1
- MTCFGRXMJLQNBG-UHFFFAOYSA-N Serine Natural products OCC(N)C(O)=O MTCFGRXMJLQNBG-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 235000004279 alanine Nutrition 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 239000000981 basic dye Substances 0.000 description 1
- XJCBRUQMXIDJJG-UHFFFAOYSA-L calcium;5-sulfobenzene-1,3-dicarboxylate Chemical compound [Ca+2].OS(=O)(=O)C1=CC(C([O-])=O)=CC(C([O-])=O)=C1 XJCBRUQMXIDJJG-UHFFFAOYSA-L 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- FBSFTJQYCLLGKH-UHFFFAOYSA-N cyclohexylphosphonic acid Chemical compound OP(O)(=O)C1CCCCC1 FBSFTJQYCLLGKH-UHFFFAOYSA-N 0.000 description 1
- HBYXSLLRTLMMNK-UHFFFAOYSA-N cyclopentylphosphonic acid Chemical compound OP(O)(=O)C1CCCC1 HBYXSLLRTLMMNK-UHFFFAOYSA-N 0.000 description 1
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- COLNVLDHVKWLRT-UHFFFAOYSA-N phenylalanine Natural products OC(=O)C(N)CC1=CC=CC=C1 COLNVLDHVKWLRT-UHFFFAOYSA-N 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229950000244 sulfanilic acid Drugs 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は、染色性等の特性に優れた変成ナイロンの製造
法に関する。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a method for producing modified nylon having excellent properties such as dyeability.
従来の技術 ナイロンは多くの用途を有する高分子化合物である。Conventional technology Nylon is a polymeric compound that has many uses.
しかしながらナイロンは染色性に欠点があり、従来種々
の染色性の改良方法が提案されている。However, nylon has a drawback in dyeability, and various methods for improving dyeability have been proposed.
染色性の改良技術は２つに大別できる。１つは種々の添
加物をポリマー溶融時に添加し染色性を向上させる方法
、他の１つは共重合によって改良する方法である。Techniques for improving dyeability can be roughly divided into two types. One method is to add various additives when the polymer is melted to improve dyeability, and the other method is to improve the dyeability by copolymerization.
添加物による改良は、比較的容易に行えるが、添加物の
浸出や逃散による効果の低減や、ナイロンの物性の低下
等の問題がある。Improvements using additives can be made relatively easily, but there are problems such as a reduction in effectiveness due to leaching or escaping of the additives, and a decrease in the physical properties of nylon.
これに対し、共重合法については例えば、フランス特許
第１．８０１．３６６号明細書に塩基性染料に対する染
色性を与えるために、５−スルホイソフタル酸カルシウ
ムやスルファニル酸を共重合することが、また、酸性染
料に対する染色性を向上させるために、シクロへキシル
ホスホン酸やシクロペンチルホスホン酸を共重合させる
ことが提案されている。さらに、米国特許第３．３１３
．５９１号明細書にはビニルピリジンをグテフト共重合
する方法が提案されている。On the other hand, regarding the copolymerization method, for example, in French Patent No. 1.801.366, calcium 5-sulfoisophthalate and sulfanilic acid are copolymerized in order to impart dyeability to basic dyes. Furthermore, in order to improve the dyeability with acid dyes, it has been proposed to copolymerize cyclohexylphosphonic acid or cyclopentylphosphonic acid. Additionally, U.S. Patent No. 3.313
．． No. 591 proposes a method of copolymerizing vinylpyridine with gutteft.
これらの方法は改良の効果は認められるものの、その度
合いは小さく、十分な染色性を得るためにはこれらの共
重合成分を多量に用いる必要があり、多量に用いるとナ
イロンの優れた性質が保持し得ないという問題がある。Although these methods have an improvement effect, the degree of improvement is small, and in order to obtain sufficient dyeability, it is necessary to use a large amount of these copolymerized components, and if a large amount is used, the excellent properties of nylon will be retained. The problem is that it cannot be done.
ナイロンに対しアミノ酸を共重合させる試みとして、特
開昭６３−２８６４２９号公報および特開昭６３２８６
４３０号公報にリジンの環化体であるα−アミノ−ε−
カプロラクタムを、ラクタム等の原ａｔ分と共重合する
方法が開示されている。As an attempt to copolymerize amino acids with nylon, JP-A-63-286429 and JP-A-63286
No. 430 discloses α-amino-ε- which is a cyclized product of lysine.
A method of copolymerizing caprolactam with a raw atomic component such as lactam is disclosed.
しかしながらこの方法は、合成しにくいα−アミノ−ε
−カプロラクタムを出発物質に使用しているし、また得
られる変成ナイロンは分岐状のものが得られること、さ
らに、染料吸着における効果は認められないことが記載
されている。However, this method is difficult to synthesize α-amino-ε
- It is described that caprolactam is used as a starting material, that the resulting modified nylon is branched, and that no effect on dye adsorption is observed.
発明が解決しようとする課題
本発明の目的は物性が改良された、特に従来の共重合法
よりも酸性染料に対する染色性が飛躍的に改良されたナ
イロンの製造法を提供することにある。Problems to be Solved by the Invention An object of the present invention is to provide a method for producing nylon with improved physical properties, particularly with dramatically improved dyeability with acid dyes compared to conventional copolymerization methods.
アミノ酸を共重合させる方法について検討の結果、α−
アミノ酸の塩酸塩を用いることによって、アミノ酸自身
が分子内縮合しラクタムになることを抑制でき、あるい
は分岐を生じることを抑制できることが判明した。また
α−アミノ酸のカルボキシル基をアルキルエステルに誘
導することによって、遊離のカルボキシル基よりも飛躍
的に反応性を高めうろことが判明した。As a result of studying methods for copolymerizing amino acids, α-
It has been found that by using the hydrochloride of an amino acid, it is possible to suppress the intramolecular condensation of the amino acid itself to form a lactam, or to suppress the occurrence of branching. It has also been found that by deriving the carboxyl group of an α-amino acid into an alkyl ester, the reactivity can be dramatically increased compared to that of a free carboxyl group.
この結果共重合反応を容易に行うことが可能になり、低
温において選択的に反応を進行させることができること
がわかった。As a result, it has become possible to carry out the copolymerization reaction easily, and it has been found that the reaction can proceed selectively at low temperatures.
課題を解決するための手段
本発明は、下記成分Ａと成分Ｂとを加熱共重合すること
を特徴とする変成ナイロンの製造法を提供する。Means for Solving the Problems The present invention provides a method for producing modified nylon, which is characterized by copolymerizing the following components A and B under heating.
成分Ａ
（ｉ）有機二塩基酸とジアミンとからなる混合物〈１１
）有機二塩基酸とジアミンとの塩、または（ｉｉｉ ）
−数式
％式％）
で表されるアミノ酸もしくは該アミノ酸より得られるラ
クタム
成分Ｂ
（ｉ）α−アミノ酸の塩酸塩、または
（ｉｉ）α−アミノ酸のモノもしくはジアルキルエステ
ルまたはそれらの塩酸塩
以下に本発明の詳細な説明する。Component A (i) Mixture consisting of an organic dibasic acid and a diamine <11
) a salt of an organic dibasic acid and a diamine, or (iii)
- Amino acid represented by the formula % or a lactam component B obtained from the amino acid Detailed description of the invention.
成分Ａとして用いる有機二塩基酸としては、アジピン酸
、セバシン酸、スペリン酸などが、ジアミンとしては、
ヘキサメチレンジアミン、デカメチレンジアミンなどが
あげられる。これらは上記したように、混合物として用
いるか、または上記の有機二塩基酸とジアミンとの塩と
して用いる。Examples of organic dibasic acids used as component A include adipic acid, sebacic acid, and superric acid; examples of diamines include:
Examples include hexamethylene diamine and decamethylene diamine. As described above, these are used as a mixture or as a salt of the above-mentioned organic dibasic acid and diamine.
また、−数式
％式％）
で表されるアミノ酸としては、ε−アミノカプロン酸（
ｎ＝５＞、ζ−アミノエナントＲ（ｎ＝６）、η−アミ
ノカプリル酸（ｎ＝７＞、ｒ−アミノカプリン酸（ｎ＝
８）などがあげられる。さらに該アミノ酸より得られる
ラクタムも用いることができる。In addition, as an amino acid represented by -formula%formula%), ε-aminocaproic acid (
n=5>, ζ-amino enanant R (n=6), η-aminocaprylic acid (n=7>, r-aminocaprylic acid (n=
8) etc. Furthermore, lactams obtained from the amino acids can also be used.
成分Ｂとして用いるα−アミノ酸としては、たとえば、
グリシン、アラニン、ロイシン、セリン、リジン、グル
タミン酸、アスパラギン酸、フェニルアラニン、プロリ
ンなどがあげられる。反応性から考慮すると、リジン、
グルタミン酸、アスパラギン酸などが望ましい。As the α-amino acid used as component B, for example,
Examples include glycine, alanine, leucine, serine, lysine, glutamic acid, aspartic acid, phenylalanine, and proline. Considering the reactivity, lysine,
Glutamic acid, aspartic acid, etc. are preferable.
これらのα−アミノ酸は塩酸塩またはモノもしくはジア
ルキルエステルもしくはその塩酸塩の形で使用される。These α-amino acids are used in the form of hydrochlorides or mono- or dialkyl esters or their hydrochlorides.
ここでいうアルキルは、炭素数１〜５のアルキル、例え
ばメチル、エチル、ｎ−ブロピル、″１ｓｏ−プロピル
、ｎ−ブチル、１ｓｏ−ブチル、ｔ−ブチル、ｔ−ペン
チルなどである。The term "alkyl" herein refers to alkyl having 1 to 5 carbon atoms, such as methyl, ethyl, n-propyl, 1so-propyl, n-butyl, 1so-butyl, t-butyl, t-pentyl, and the like.
これらはナイロン成分へに対しモル％で０．１〜１０％
、好ましくは１〜７％添加される。These are 0.1 to 10% in mole% to the nylon component.
, preferably 1 to 7%.
本発明の変成ナイロンは、それ自体公知のナイロンの製
造方法を適用して製造できる。例えば、成分Ａと成分Ｂ
を窒素気流下に、２７０℃以下好ましくは１５０〜２５
０℃の反応温度で、必要ならば減圧下において、加熱共
重合することにより容易に得ることができる。The modified nylon of the present invention can be manufactured by applying a known nylon manufacturing method. For example, component A and component B
under a nitrogen stream at 270°C or lower, preferably 150-25°C.
It can be easily obtained by heating copolymerization at a reaction temperature of 0°C, if necessary under reduced pressure.
このようにして得られた変成ナイロンは、溶融紡糸法な
どのそれ自体公知の方法で繊維にすることができる。あ
るいは溶融成形や溶媒に溶解しキャストすることによっ
て、フィルムを製造できる。The modified nylon thus obtained can be made into fibers by a method known per se, such as a melt spinning method. Alternatively, a film can be produced by melt molding or dissolving in a solvent and casting.
以下実施例によって、本発明をさらに詳細に説明する。The present invention will be explained in more detail below with reference to Examples.
実施例１
ε−アミノカプロン酸３．８６ｇとりジンモノ塩酸塩０
．１１ｇ （ε−アミノカプロン酸に対し２モル％〉
との混合物を、窒素気流下において１７０℃から２４０
℃に毎分４℃の速度で昇温した。さらに２４０℃で２時
間放置し、同温度で２ｍａｉ）１ｇ以下に減圧し、３０
分間加熱を続は反応を完結させた。得られた共重合体は
白色の固体であった。このものを９７重量％の濃硫酸に
溶解して１％溶液とし、３０℃でのインヘレント粘度を
測定した結果０．７５であった。また、ガラス転移温度
は３９℃、融解温度は２１０℃であった。Example 1 3.86 g of ε-aminocaproic acid and 0 gin monohydrochloride
．． 11g (2 mol% based on ε-aminocaproic acid)
The mixture was heated from 170°C to 240°C under a nitrogen stream.
℃ at a rate of 4° C. per minute. Further, leave it at 240℃ for 2 hours, reduce the pressure to 1g or less at the same temperature, and
Continue heating for a minute to complete the reaction. The obtained copolymer was a white solid. This product was dissolved in 97% by weight concentrated sulfuric acid to make a 1% solution, and the inherent viscosity at 30°C was measured and found to be 0.75. Further, the glass transition temperature was 39°C, and the melting temperature was 210°C.
この共重合体を細かく破砕し、８０℃で２４時間減圧乾
燥して絶乾状態とした。次に、小型の背圧押出式溶融紡
糸機（単ホール、ノズル孔径０．５ｅｍφ）を用いて、
窒素気流中、２３０〜２４０℃で溶融した共重合体を、
背圧４〜６ｋｇ／ｍ−で紡出した。この紡出糸を約４倍
に延伸した。This copolymer was finely crushed and dried under reduced pressure at 80° C. for 24 hours to bring it to an absolutely dry state. Next, using a small back pressure extrusion type melt spinning machine (single hole, nozzle hole diameter 0.5emφ),
The copolymer melted at 230 to 240°C in a nitrogen stream,
It was spun at a back pressure of 4-6 kg/m. This spun yarn was drawn approximately 4 times.
このようにして得られた繊維は全く着色しておらず、引
張強度４ｇ／デニール及び伸度４１％を有した。この繊
維を酸性染料オレンジ■を用いて９０℃で２時間処理し
た（染料濃度１４■／ｌ、浴比１／ ２０００）。繊維
は良好な洗濯堅牢性を有する濃い色相の赤橙色に染色さ
れた。染料吸尽量は２０．２■／ｇであった。−吉兆変
成試料のナイロン６繊維は濃い色相には染色されず、染
料吸尽量も７■／ｇと少量であった。The fibers thus obtained were completely uncolored and had a tensile strength of 4 g/denier and an elongation of 41%. This fiber was treated with the acid dye Orange ■ at 90° C. for 2 hours (dye concentration 14 ■/l, bath ratio 1/2000). The fibers were dyed a deep red-orange color with good washfastness. The amount of dye exhausted was 20.2 .mu./g. - The nylon 6 fibers of the Kitcho modified sample were not dyed to a deep hue, and the amount of dye exhausted was as small as 7 μ/g.
さらに上記のようにして得られた共重合体を、ホットプ
レスでフィルムに成形した。このフィルムは、酸性染料
を使用することによって濃い色相を有する赤橙色に染色
することができた。染料吸尽量は２２ｍｇ／ ｇで、非
変成ナイロン６フィルムの７、２ ｍｇ／ ｇよりは著
しく改良された値であった。Furthermore, the copolymer obtained as described above was molded into a film by hot pressing. This film could be dyed red-orange with a deep hue by using acid dyes. The amount of dye absorbed was 22 mg/g, which was significantly improved compared to 7.2 mg/g for the unmodified nylon 6 film.
また、得られた共重合体を蟻酸溶液とし、これよりキャ
ストフィルムに成形した。このフィルムは濃い色相を有
する赤橙色に染色することができた。染料吸尽量は２５
■／ｇであり、非変成ナイロン６フィルムの８■／ｇよ
りもはるかに多かった。Further, the obtained copolymer was made into a formic acid solution and formed into a cast film. This film could be dyed red-orange with a deep hue. The amount of dye exhausted is 25
■/g, which was much higher than the 8 ■/g of the non-denatured nylon 6 film.
実施例２
ε−アミノカプロン酸３．７８ｇとりジンモノ塩酸塩０
．２１９ｇ （ε−アミノカプロン酸に対する比率約
４モル％〉を用いた以外は、実施例１と同様にして重合
を行った。Example 2 3.78 g of ε-aminocaproic acid and 0 gin monohydrochloride
．． Polymerization was carried out in the same manner as in Example 1, except that 219 g (approximately 4 mol % relative to ε-aminocaproic acid) was used.
得られた共重合体のインヘレント粘度は０．７であり、
ガラス転移温度は３９℃、溶融温度は２００℃であった
。溶融紡糸した繊維を４倍に延伸すると、引張強度３．
４ｇ／デニール及び伸度３８％を有した。The inherent viscosity of the obtained copolymer was 0.7,
The glass transition temperature was 39°C and the melting temperature was 200°C. When melt-spun fibers are stretched 4 times, the tensile strength is 3.
It had a denier of 4 g/denier and an elongation of 38%.
この繊維をオレンジ■で染色すると、良好な洗濯堅牢性
を有し赤橙色に染色された。染料吸尽量は３５．１ｎ＋
ｇ／ ｇであり、−吉兆変成試料のナイロン６の染料吸
尽量は７■／ｇであった。When this fiber was dyed with orange ■, it was dyed reddish-orange with good washing fastness. The amount of dye exhausted is 35.1n+
g/g, and the dye exhaustion amount of nylon 6 in the -Kiccho modified sample was 7 g/g.
実施例３
セバシン酸３．８４ ｇ （０，０１９モル）、グルタ
ミン酸ジエチルエステル塩酸塩０．２４ ｇ （０，０
０１モル）およびヘキサメチレンジアミン２．３５ ｇ
（０，０２０２モル〉の混合物を、窒素気流下で１７
０℃から２２０℃まで毎分４℃の速度で昇温し、この温
度で２時間加熱した。さらに、２５０℃に昇温し２時間
加熱した。Example 3 Sebacic acid 3.84 g (0,019 mol), glutamic acid diethyl ester hydrochloride 0.24 g (0,0
01 mol) and 2.35 g hexamethylene diamine
(0,0202 mol) of a mixture of 17
The temperature was raised from 0°C to 220°C at a rate of 4°C per minute, and the mixture was heated at this temperature for 2 hours. Furthermore, the temperature was raised to 250°C and heated for 2 hours.
さらにこの温度で、２ｍ＋＋＋Ｈｇ以下の減圧にして３
０分間加熱を続は反応を完結した。得られた重合体は白
色の固体で、インヘレント粘度０．８１、ガラス転移温
度３１℃、融解温度２１１ｔ：であった。溶融紡糸（紡
糸温度約２３０℃）し、４倍延伸した繊維は１張強度４
．３ｇ／デニール、伸度３８％で、酸性染料オレンジ■
に対し、良好な洗濯堅牢性を有する濃い色相を有する赤
橙色に染色された。染料吸尽量は２６．５■で、非変成
ナイロン６１０繊維試料の染料吸尽量に比較すると大幅
に改良された。Furthermore, at this temperature, the pressure is reduced to 2m+++Hg or less and 3
After heating for 0 minutes, the reaction was completed. The obtained polymer was a white solid with an inherent viscosity of 0.81, a glass transition temperature of 31°C, and a melting temperature of 211t. Fibers melt-spun (spinning temperature approximately 230°C) and stretched 4 times have a tensile strength of 4.
．． 3g/denier, elongation 38%, acid dye orange■
On the other hand, it was dyed red-orange with a deep hue with good wash fastness. The dye exhaustion amount was 26.5 cm, which was significantly improved compared to the dye exhaustion amount of the unmodified nylon 610 fiber sample.
実施例４
アジピン酸２．７７ｇ （０，０１９モル）、グルタミ
ン酸ジエチルエステル塩酸塩０．２４ｇ （０，００１
モル）およびヘキサメチレンジアミン２．３５ ｇ
＜０．０２０２モル）の混合物を、窒素気流下において
１７０℃から２７０℃まで毎分５℃の速度で昇温し、こ
の温度で１時間加熱した。得られた重合体は薄い褐色の
固体であった。このものはインヘレント粘度０．６０、
ガラス転移温度４５℃、融解温度２４８℃であった。こ
の重合体の溶融紡糸によって得られた繊維は、酸性染料
オレンジ■で濃い色相を有する赤橙色に染色された。Example 4 2.77 g (0,019 mol) of adipic acid, 0.24 g (0,001 mol) of glutamic acid diethyl ester hydrochloride
mole) and 2.35 g hexamethylene diamine
<0.0202 mol) was heated from 170°C to 270°C at a rate of 5°C per minute under a nitrogen stream and heated at this temperature for 1 hour. The obtained polymer was a light brown solid. This one has an inherent viscosity of 0.60,
The glass transition temperature was 45°C and the melting temperature was 248°C. The fibers obtained by melt spinning this polymer were dyed red-orange with a deep hue with the acid dye Orange ■.
実施例５
セバシンＭ１２２．４３ｇ （０，０１２モル〉、リジ
ンモノ塩酸塩０．１１６ｇ （０，０００６４モル）お
よびヘキサメチレンジアミン１．４２ｇ （０，０１２
２モル）の混合物を、窒素気流下において１７０℃から
２２０℃まで毎分４℃の速度で昇温し、この温度で５０
分間加熱を続けた。Example 5 Sebacin M 122.43 g (0,012 mol), lysine monohydrochloride 0.116 g (0,00064 mol) and hexamethylene diamine 1.42 g (0,012 mol)
A mixture of 2 mol) of
Heating continued for minutes.
得られた重合体は白色固体で、インヘレント粘度０．７
６、ガラス転移温度２９℃、融解温度２０６℃であった
。この重合体の溶融紡糸で得られた繊維は、酸性染料オ
レンジ■で濃い色相を有する赤橙色に染色された。The resulting polymer was a white solid with an inherent viscosity of 0.7.
6. The glass transition temperature was 29°C and the melting temperature was 206°C. The fibers obtained by melt spinning this polymer were dyed red-orange with a deep hue with the acid dye Orange ■.
実施例６
実施例３におけるグルタミン酸ジエチルエステル塩酸塩
の代わりにグルタミン酸塩酸塩０．１８ｇ（０，００１
モル）を用いた以外は、実施例３と同様な方法で重合し
た。褐色のインヘレント粘度０．３８を示す重合体が得
られた。Example 6 In place of glutamic acid diethyl ester hydrochloride in Example 3, 0.18 g (0,001
Polymerization was carried out in the same manner as in Example 3, except that mol) was used. A brown polymer having an inherent viscosity of 0.38 was obtained.
発明の効果
本発明で得られる変成ナイロンは、従来のナイロンが有
していた酸性染料に対する染色性が著しく改良されてい
る。Effects of the Invention The modified nylon obtained by the present invention has significantly improved dyeability with acid dyes, which conventional nylon had.
Claims (2)
徴とする変成ナイロンの製造法。成分Ａ （ｉ）有機二塩基酸とジアミンとからなる混合物 （ｉｉ）有機二塩基酸とジアミンとの塩、または （ｉｉｉ）一般式 Ｈ＿２Ｎ（ＣＨ＿２）＿ｎＣＯＯＨ（ｎは５〜１０の整
数）で表されるアミノ酸もしくは該アミノ酸より得られ
るラクタム成分Ｂ （ｉ）α−アミノ酸の塩酸塩、または （ｉｉ）α−アミノ酸のモノもしくはジアルキルエステ
ルまたはそれらの塩酸塩(1) A method for producing modified nylon, which comprises copolymerizing the following components A and B under heating. Component A (i) a mixture consisting of an organic dibasic acid and a diamine (ii) a salt of an organic dibasic acid and a diamine, or (iii) represented by the general formula H_2N(CH_2)_nCOOH (n is an integer from 5 to 10) lactam component B (i) hydrochloride of α-amino acid, or (ii) mono- or dialkyl ester of α-amino acid or hydrochloride thereof
０．１〜１０モル％である請求項１記載の製造法。(2) The method according to claim 1, wherein the amount of component B is 0.1 to 10 mol% based on component A in the polymer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21424989A JPH0379630A (en) | 1989-08-22 | 1989-08-22 | Production of modified nylon |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21424989A JPH0379630A (en) | 1989-08-22 | 1989-08-22 | Production of modified nylon |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0379630A true JPH0379630A (en) | 1991-04-04 |
Family
ID=16652640
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21424989A Pending JPH0379630A (en) | 1989-08-22 | 1989-08-22 | Production of modified nylon |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0379630A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102985464A (en) * | 2010-06-29 | 2013-03-20 | 三菱瓦斯化学株式会社 | Polyamide compound |
| RU2579138C2 (en) * | 2010-12-27 | 2016-03-27 | Мицубиси Гэс Кемикал Компани, Инк. | Polyamide composition |
-
1989
- 1989-08-22 JP JP21424989A patent/JPH0379630A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102985464A (en) * | 2010-06-29 | 2013-03-20 | 三菱瓦斯化学株式会社 | Polyamide compound |
| EP2589616A1 (en) * | 2010-06-29 | 2013-05-08 | Mitsubishi Gas Chemical Company, Inc. | Polyamide compound |
| EP2589616A4 (en) * | 2010-06-29 | 2014-05-14 | Mitsubishi Gas Chemical Co | Polyamide compound |
| CN102985464B (en) * | 2010-06-29 | 2015-04-01 | 三菱瓦斯化学株式会社 | Polyamide compound |
| JP5867391B2 (en) * | 2010-06-29 | 2016-02-24 | 三菱瓦斯化学株式会社 | Polyamide compound |
| RU2579138C2 (en) * | 2010-12-27 | 2016-03-27 | Мицубиси Гэс Кемикал Компани, Инк. | Polyamide composition |
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