JP3309505B2 - Method for producing nylon 6 for carpet fiber with excellent heat resistance during processing - Google Patents
Method for producing nylon 6 for carpet fiber with excellent heat resistance during processingInfo
- Publication number
- JP3309505B2 JP3309505B2 JP18402093A JP18402093A JP3309505B2 JP 3309505 B2 JP3309505 B2 JP 3309505B2 JP 18402093 A JP18402093 A JP 18402093A JP 18402093 A JP18402093 A JP 18402093A JP 3309505 B2 JP3309505 B2 JP 3309505B2
- Authority
- JP
- Japan
- Prior art keywords
- nylon
- amount
- heat resistance
- yarn
- acid
- 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 - Fee Related
Links
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- Polyamides (AREA)
- Artificial Filaments (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明はカーペット、カーマット
など（以下カ−ペット類と略称）に用いられる酸性染料
易染性繊維用のナイロン６の製造方法に関するものであ
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing nylon 6 for acid dye easily dyeable fibers used for carpets, car mats and the like (hereinafter abbreviated as carpets).
【０００２】[0002]
【従来の技術】ナイロン６は強度、耐摩耗性などが優れ
ているため、繊維、樹脂などの用途に幅広く使用されて
いる。繊維としては、衣料用途以外にその優れた耐摩耗
性と染色性のため、カーペット類に使用されている。カ
ーペット繊維用原糸としては、通常巻縮をかけたフィラ
メントであるBCF （Bulked Continuous Filament）糸が
用いられる。このBCF 糸を2 〜3 本撚り合せた撚糸をつ
くり、それを固定するために120 〜130 ℃で約1 分間蒸
気セットをする。染色処理などの後、バッキング工程で
この撚糸を塩ビなどの基布にうめこみ、約180 ℃で5 〜
10分加熱しヒートセットする。2. Description of the Related Art Nylon 6 is widely used for applications such as fibers and resins because of its excellent strength and abrasion resistance. As a fiber, it is used in carpets because of its excellent abrasion resistance and dyeability in addition to clothing. As the raw yarn for carpet fiber, BCF (Bulked Continuous Filament) yarn, which is usually a crimped filament, is used. Two to three strands of this BCF yarn are twisted to make a twisted yarn and steam set at 120 to 130 ° C for about 1 minute to fix it. After dyeing, etc., the twisted yarn is buried in a backing process such as PVC, and the
Heat for 10 minutes and heat set.
【０００３】このようにカーペット類の製造に際して
は、その工程で種々の熱処理を受けるため、ナイロン糸
には耐熱性（熱処理による強伸度の低下のないこと）が
要求される。またカーペット繊維用原糸としては、酸性
染料や塩基性染料に対する染色性が異なる原糸を2 〜3
種類同時に一浴で染色して多色染めとする方法がとられ
る。酸性染料に容易に染色可能にするためには、ナイロ
ン６の塩基性成分量を酸性成分量よりも多くする必要が
ある。このようなナイロン６は通常ナイロン６のモノマ
にヘキサメチレンジアミンを添加して重合することによ
り得られる。[0003] As described above, in the production of carpets, various heat treatments are performed in the process, so that the nylon yarn is required to have heat resistance (there is no decrease in the high elongation due to the heat treatment). Also, as the yarn for carpet fiber, a yarn having a different dyeing property for an acid dye or a basic dye may be a few yarns.
A method is adopted in which the dyes are simultaneously dyed in a single bath to obtain a multicolor dye. In order to be able to easily dye the acid dye, it is necessary to make the amount of the basic component of nylon 6 larger than the amount of the acid component. Such nylon 6 is usually obtained by adding hexamethylene diamine to a monomer of nylon 6 and polymerizing.
【０００４】[0004]
【発明が解決しようとする課題】ヘキサメチレンジアミ
ンの添加により製造した塩基性成分量が酸性成分量より
も多いナイロン６は、通常のナイロン６（塩基性成分量
が酸性成分量と同等又はそれ以下）に比較して耐熱性が
劣る。したがって前述した撚糸のヒートセットやバッキ
ング工程を経ることにより、糸の強伸度が著しく低下
し、カーペット類本来の機能を失うことになる。本発明
の目的はナイロン６モノマにヘキサメチレンジアミンを
添加して重合し、塩基性成分量が酸性成分量よりも多い
カーペット類用酸性染料易染性ナイロンの製造におい
て、ナイロン６の耐熱性を向上し、撚糸の熱セット時や
基布とのバッキング工程での熱による糸の強伸度低下が
おこりにくいナイロン６を得ることにある。The nylon 6 produced by adding hexamethylenediamine and having a basic component amount larger than the acidic component amount is usually nylon 6 (the basic component amount is equal to or less than the acidic component amount). ) Is inferior to heat resistance. Therefore, through the above-described heat setting or backing process of the twisted yarn, the strength and elongation of the yarn are significantly reduced, and the original function of carpets is lost. An object of the present invention is to improve the heat resistance of nylon 6 by adding hexamethylenediamine to a nylon 6 monomer and polymerizing it to produce an easily dyeable acid dyeable nylon for carpets in which the basic component amount is larger than the acidic component amount. Another object of the present invention is to obtain a nylon 6 in which the strong elongation of the yarn hardly decreases due to heat during the heat setting of the twisted yarn or the backing step with the base fabric.
【０００５】[0005]
【課題を解決するための手段】すなわち、本発明は、こ
のような耐熱性に優れ、撚糸の熱セット時や基布とのバ
ッキング工程を経ても糸の強伸度の低下しにくいナイロ
ン６を得るために、ナイロン６モノマにヘキサメチレン
ジアミンを添加して重合する、塩基性成分量が酸性成分
量よりも多い酸性染料易染性のカーペット繊維用ナイロ
ン６の製造に際し、安息香酸をナイロン６モノマに添加
して重合することを特徴とする加工時耐熱性に優れたカ
ーペット繊維用ナイロン６の製造方法に関する。カーペ
ット類とはタイルカーペット、ロールカーペット、自動
車用のラインマット、カーマットなど巻縮糸を撚り、塩
ビなどの基布にバッキングしたものである。That is, the present invention provides a nylon 6 which is excellent in such heat resistance and hardly reduces the strength and elongation of the yarn even after the heat setting of the twisted yarn or the backing process with the base fabric. In order to obtain nylon 6 for carpet fiber, which is obtained by adding hexamethylenediamine to nylon 6 monomer and polymerizing the same to obtain an acid dye, which has a basic component amount larger than the acid component amount, the benzoic acid is converted to the nylon 6 monomer. The present invention relates to a method for producing nylon 6 for carpet fibers, which is excellent in heat resistance during processing, characterized in that it is added and polymerized. The carpets are tile carpets, roll carpets, line mats for automobiles, car mats, and the like, which are twisted and backed on a base fabric such as PVC.
【０００６】ここでいう塩基性成分量、酸性成分量は次
の方法で測定する。The amount of the basic component and the amount of the acidic component are measured by the following method.
【０００７】塩基性成分量 粉末化したナイロン６を１ｇフェノール／エタノール
（８０ｇ／２０ｍｌ）混合溶媒４０ｍｌに常温で振とう
溶解し、０．０２Ｎの塩酸で中和滴定して求める。Amount of basic component 1 g of powdered nylon 6 is dissolved in 40 ml of a mixed solvent of phenol / ethanol (80 g / 20 ml) with shaking at room temperature and neutralized and titrated with 0.02N hydrochloric acid.
【０００８】酸性成分量 粉末化したナイロン６を０．５ｇベンジルアルコール２
０ｍｌに１９５℃で溶解し、０．０２Ｎの水酸化カリウ
ムのエタノ−ル溶液で中和滴定して求める。Amount of acidic component 0.5 g of powdered nylon 6 benzyl alcohol 2
The solution is dissolved in 0 ml at 195 ° C. and neutralized and titrated with a 0.02 N potassium hydroxide ethanol solution.
【０００９】塩基性成分量と酸性成分量の差が大きい
程、酸性染料に染まりやすく（濃染）なる。したがって
その差は要求される染色度から決めればよい。The greater the difference between the amount of the basic component and the amount of the acidic component, the more easily the dye is dyed with the acid dye (dense dyeing). Therefore, the difference may be determined from the required dyeing degree.
【００１０】塩基性成分量と酸性成分量の差を大きくす
るためにはヘキサメチレンジアミンの添加量を多くする
とよいが、添加量のアップとともに重合速度は遅くな
り、得られるナイロン６の重合度が低下したり、重合時
間が長くなり、重合設備能力が低下する。酸性染料によ
る染色のしやすさと重合速度から、ヘキサメチレンジア
ミンの添加量はナイロン６モノマ１モルに対して1/1000
モルから4/1000モル程度が好ましい。To increase the difference between the amount of the basic component and the amount of the acidic component, it is advisable to increase the amount of hexamethylenediamine. However, as the amount of addition increases, the polymerization rate decreases, and the degree of polymerization of the resulting nylon 6 decreases. Or the polymerization time becomes longer, and the capacity of the polymerization equipment decreases. From the ease of dyeing with an acid dye and the polymerization rate, the amount of hexamethylenediamine added was 1/1000 based on 1 mol of nylon 6 monomer.
The mole is preferably about 4/1000 mole.
【００１１】安息香酸の添加量が少ないと本目的とする
耐熱性向上効果が十分でなく、添加量が多いと、ヘキサ
メチレンジアミン以上に重合速度を遅くする。したがっ
て安息香酸の添加量はナイロン６モノマ１モルに対して
1/1000モルから2/1000モル程度が好ましい。If the amount of benzoic acid is small, the effect of improving the heat resistance is not sufficient, and if the amount is large, the polymerization rate is slower than that of hexamethylenediamine. Therefore, the addition amount of benzoic acid is based on 1 mole of nylon 6 monomer.
About 1/1000 mol to about 2/1000 mol is preferable.
【００１２】ヘキサメチレンジアミンと安息香酸はカプ
ロラクタム、アミノカプロン酸などナイロン６モノマに
添加して通常の方法で重合する。ヘキサメチレンジアミ
ンと安息香酸はもちろんそれぞれ単体として添加しても
よいが、ヘキサメチレンジアミンは水溶液として、安息
香酸は水に溶解しにくいので、カプロラクタムの水溶液
に溶解して添加すると、取り扱いが容易である。重合方
法は回分式でも連続式でもよいし、常圧下でも加圧下で
もよい。重合終了後のポリマは、重合装置からストラン
ド状に押し出し、ペレタイザーでペレット化した後、通
常の方法で熱水により未反応のモノマやオリゴマを除去
した後、乾燥し製糸工程に供される。Hexamethylenediamine and benzoic acid are added to a nylon 6 monomer such as caprolactam or aminocaproic acid and polymerized by an ordinary method. Hexamethylenediamine and benzoic acid may of course be added as simple substances, but hexamethylenediamine is dissolved in an aqueous solution of caprolactam, because benzoic acid is hardly soluble in water as an aqueous solution, and handling is easy. . The polymerization method may be a batch type or a continuous type, and may be under normal pressure or under pressure. After the polymerization, the polymer is extruded into a strand from a polymerization apparatus, pelletized by a pelletizer, then unreacted monomers and oligomers are removed by hot water by a usual method, and then dried and subjected to a thread forming process.
【００１３】一般にナイロン６に添加される添加剤を併
用添加してもよい。紡糸機中でのナイロン６の溶融時の
重合反応の進行に伴う溶融粘度変化を抑制するため、酢
酸やアジピン酸などのモノカルボン酸やジカルボン酸が
添加される場合がある。これらの溶融粘度安定剤を併用
添加してもよいが、安息香酸に比べ、加工時耐熱性が劣
るので、本発明の目的達成の点からは、併用しない方が
好ましい。An additive generally added to nylon 6 may be added in combination. A monocarboxylic acid or a dicarboxylic acid such as acetic acid or adipic acid may be added in order to suppress a change in melt viscosity accompanying the progress of the polymerization reaction when the nylon 6 is melted in the spinning machine. These melt viscosity stabilizers may be added in combination, but they are inferior in heat resistance during processing as compared with benzoic acid. Therefore, it is preferable not to use them together from the viewpoint of achieving the object of the present invention.
【００１４】酸化チタンなどの艶消し剤、ホウ酸マンガ
ンなどのマンガン系の耐光剤、また耐熱剤としてヨウ化
銅などの銅化合物、イルガノックス１０９８などのフェ
ノ−ル化合物、トリフェニルホスファイトなどのリン化
合物などを添加してもよい。Matting agents such as titanium oxide; manganese-based light stabilizers such as manganese borate; copper compounds such as copper iodide as heat-resistant agents; phenol compounds such as Irganox 1098; A phosphorus compound or the like may be added.
【００１５】[0015]
【実施例】以下本発明を実施例によりさらに詳細に説明
する。The present invention will be described in more detail with reference to the following examples.
【００１６】容量８０Ｌの重合缶に９０％カプロラクタ
ム水溶液を２０ｋｇ，ヘキサメチレンジアミンをカプロ
ラクタム１モルに対して2/1000モルと3/1000モル、安息
香酸無添加とカプロラクタム1 モルに対して1/1000モル
と2/1000モル、ホウ酸マンガンをマンガンとして１０ｐ
ｐｍ、酸化チタンを０．３ｗｔ％添加して重合した。重
合は上記原料を密閉状態で攪拌しながら加熱し、缶内圧
力が１０ｋｇ／ｃｍ2になると水蒸気を留出させ、その
圧力に保持した。内液温度が２５０℃になると缶内圧力
を徐々に低下させ、７０分間で大気圧とした。その時の
内液温度は260℃であった。その後内液温度を２６０℃
に保持しながら窒素を６０分間缶内気相部にフローさ
せ、重合を完結させた。 重合終了後、溶融状態のナイ
ロン６を重合缶底部からガット状に押し出し、水で冷却
後、ペレタイザーでカッティングし、チップとした。こ
のチップを熱水で未反応モノマ、オリゴマを抽出した
後、固相重合により所定重合度にしたチップを用いて、
１０００デニール（フィラメント数４０）の巻縮ＢＣＦ
糸を製糸し、その糸の耐熱性を測定した。測定方法を次
に示す。In a polymerization vessel having a capacity of 80 L, 20 kg of a 90% aqueous solution of caprolactam, 2/1000 mol and 3/1000 mol of hexamethylenediamine per 1 mol of caprolactam, 1/1000 per 1 mol of caprolactam without addition of benzoic acid. Mole and 2/1000 mole, manganese borate as manganese, 10p
pm, and 0.3 wt% of titanium oxide was added for polymerization. In the polymerization, the above-mentioned raw materials were heated while being stirred in a closed state, and when the pressure in the can reached 10 kg / cm 2 , steam was distilled off and kept at that pressure. When the temperature of the internal solution reached 250 ° C., the pressure inside the can was gradually reduced, and the pressure was increased to the atmospheric pressure in 70 minutes. The internal solution temperature at that time was 260 ° C. After that, the temperature of the inner solution was raised to 260 ° C.
, And nitrogen was allowed to flow through the gas phase in the can for 60 minutes to complete the polymerization. After the polymerization was completed, the molten nylon 6 was extruded in a gut shape from the bottom of the polymerization can, cooled with water, and cut with a pelletizer to obtain chips. After extracting unreacted monomers and oligomers with hot water from this chip, using a chip with a predetermined degree of polymerization by solid-phase polymerization,
1000 denier (40 filaments) crimped BCF
The yarn was made and the heat resistance of the yarn was measured. The measurement method is described below.
【００１７】・糸の熱処理方法 原糸または熱セット糸（撚糸を１３０℃で１分間蒸気加
熱したもの）を熱風乾燥器中で空気中１５０℃６０分間
加熱した。Heat treatment method of yarn The original yarn or heat set yarn (twisted yarn heated at 130 ° C. for 1 minute) was heated in air at 150 ° C. for 60 minutes in a hot air dryer.
【００１８】・耐熱性の評価 熱処理前後の原糸または熱セット糸の強度、伸度をテン
シロンで測定した。（２）式により、耐熱保持率を求め
た。Evaluation of heat resistance The strength and elongation of the raw yarn or the heat-set yarn before and after the heat treatment were measured with Tensilon. The heat resistance retention was determined by the equation (2).
【００１９】[0019]
【数１】 (Equation 1)
【００２０】耐熱保持率の値が大きい程、熱処理による
強度、伸度の低下が小さいことから、耐熱性が優れ、カ
ーペット類加工時の撚糸の蒸気によるヒートセット工程
や、基布に撚糸をうめこむバッキング工程での糸の耐熱
性が優れていることになる。ヘキサメチレンジアミンと
安息香酸の添加量を変えて重合したチップを製糸し、そ
の耐熱性を測定した結果を表１に示した。The larger the value of the heat-resistant retention ratio, the smaller the decrease in strength and elongation due to heat treatment. Therefore, the higher the heat resistance, the better the heat resistance, and the heat-setting step using steam of the twisted yarn during carpet processing, or embedding the twisted yarn in the base cloth. The yarn has excellent heat resistance in the backing step. Table 1 shows the results of measuring the heat resistance of a thread formed by polymerizing chips by changing the addition amounts of hexamethylenediamine and benzoic acid.
【００２１】[0021]
【表１】 [Table 1]
【００２２】安息香酸を添加したものは原糸、熱セット
糸ともに耐熱強度（伸度）保持率が大きい。したがって
糸の耐熱性が優れ、カーペット加工時の熱による強伸度
の低下が少ない。The benzoic acid-added yarn has a high heat-resistant strength (elongation) retention rate for both the raw yarn and the heat-set yarn. Therefore, the heat resistance of the yarn is excellent, and the decrease in the elongation due to heat during carpet processing is small.
【００２３】[0023]
【発明の効果】本発明の耐熱性に優れたカ−ペット類用
ナイロン６の製造方法は次の効果を奏する。本発明で得
られた酸性染料易染性ナイロンは撚糸の熱セット工程や
基布とのバッキング工程での熱による強度、伸度の低下
が小さく、カーペット類の性能が向上する。本発明の製
造法はBCF 用ナイロン糸を製造する場合に有用である。The method of the present invention for producing nylon 6 for carpets having excellent heat resistance has the following effects. The acid dye easily dyeable nylon obtained in the present invention has a small decrease in strength and elongation due to heat in the heat setting step of the twisted yarn and the backing step with the base fabric, and the performance of carpets is improved. The production method of the present invention is useful when producing nylon yarn for BCF.
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.7，ＤＢ名) D01F 6/60 D01F 6/80 D01F 6/90 C08G 69/16 ──────────────────────────────────────────────────の Continued on the front page (58) Field surveyed (Int.Cl. 7 , DB name) D01F 6/60 D01F 6/80 D01F 6/90 C08G 69/16
Claims (3)
ミンを添加して重合する、塩基性成分量が酸性成分量よ
りも多い酸性染料易染性のカーペット繊維用ナイロン６
の製造に際し、安息香酸をナイロン６モノマに添加して
重合することを特徴とする加工時耐熱性に優れたカーペ
ット繊維用ナイロン６の製造方法。1. Nylon 6 for carpet fiber, which is easily dyeable with an acid dye, wherein the amount of a basic component is larger than the amount of an acid component, wherein hexamethylenediamine is added to a nylon 6 monomer for polymerization.
A method for producing nylon 6 for carpet fibers having excellent heat resistance during processing, characterized by adding benzoic acid to nylon 6 monomer and polymerizing the same during the production of the polymer.
とが下記（１）式を満たすことを特徴とする請求項１記
載の加工時耐熱性に優れたカーペット繊維用ナイロン６
の製造方法。 ２モル／ポリマ１０5ｇ≦［塩基性成分量］−［酸性成分量］≦７モル／ポリマ １０5ｇ・・・・（１）2. The nylon 6 for carpet fiber according to claim 1, wherein the amount of the basic component and the amount of the acidic component of the nylon 6 satisfy the following formula (1).
Manufacturing method. 2 mol / polymer 10 5 g ≦ [basic component amount] - [the acid component amount] ≦ 7 mol / polymer 10 5 g ···· (1)
する添加量が1/1000モルから2/1000モルであることを特
徴とする請求項１記載の加工時耐熱性に優れたカーペッ
ト繊維用ナイロン６の製造方法。3. The nylon 6 for carpet fiber according to claim 1, wherein the amount of benzoic acid added per mole of the nylon 6 monomer is 1/1000 mol to 2/1000 mol. Manufacturing method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18402093A JP3309505B2 (en) | 1993-07-26 | 1993-07-26 | Method for producing nylon 6 for carpet fiber with excellent heat resistance during processing |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18402093A JP3309505B2 (en) | 1993-07-26 | 1993-07-26 | Method for producing nylon 6 for carpet fiber with excellent heat resistance during processing |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0742020A JPH0742020A (en) | 1995-02-10 |
| JP3309505B2 true JP3309505B2 (en) | 2002-07-29 |
Family
ID=16145941
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18402093A Expired - Fee Related JP3309505B2 (en) | 1993-07-26 | 1993-07-26 | Method for producing nylon 6 for carpet fiber with excellent heat resistance during processing |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3309505B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19854421B4 (en) * | 1998-11-25 | 2006-11-02 | Ems-Inventa Ag | Process for the preparation of polyamide-6 for spinning purposes |
| DE10030515A1 (en) * | 2000-06-28 | 2002-01-10 | Basf Ag | polyamides |
-
1993
- 1993-07-26 JP JP18402093A patent/JP3309505B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0742020A (en) | 1995-02-10 |
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