JP4041933B2 - Method for processing cellulosic fiber-containing woven or knitted fabric - Google Patents

Description

注：
１）リケンレジンＬＮＢ−２０（三木理研工業社製）
２）カタリストＭ（大日本インキ化学工業社製）
３）シャリーヌＥＦＥ２３０（日信化学社製）
４）ソフボンＰ３０００（竹本油脂社製）
５）ファインテックスＮＲＷ（大日本インキ化学工業社製）
【００４０】
【表２】

注：
６）ＪＩＳ Ｌ１０９６ Ａ法
７）ＪＩＳ Ｌ１０４１ Ｂ法 アセチルアセトン法
８）ＪＩＳ Ｌ１０９６ Ａ法 ガーレ法
９）ＪＩＳ Ｌ１０９６ Ｄ法 ペンジュラム法
１０）ＪＩＳ Ｌ１０９６ Ａ法 ラベルドストリップ法
１１）ＪＩＳ Ｌ１０５９
【００４１】
上記の結果より、実施例の方法が、洗濯後においても通気度が殆んど上がることがなく、初期の通気度にほぼ維持されること、また防皺度が高いにも拘らずホルマリン残留量が殆んどないこと、更に洗濯しても諸物性、防皺度、収縮率に大きな変動が生じることがないことが認められた。
【００４２】
〔参考例１〕
４０番双糸鹿の子（３０インチ、１８ゲージ）綿１００％編物を常法でアルカリ処理及び漂白を施し、２０秒間液体アンモニアで処理した後に、表３に示す樹脂処方・熱処理条件にて樹脂加工を行い、高圧液流加工機を用いて１３０℃×１時間熱水処理を行った後、脱水・乾燥し、テンターで柔軟剤加工を行い、所定の巾に仕上げた。
【００４３】
〔参考例２〕
参考例１において、熱水処理の際に、熱水中に柔軟剤（ＡＶＩＶＡＮ ＳＦＣ：脂肪酸アミド縮合化合物、チバガイギー社製）を５．０ｇ／ｌ添加したものを用いた以外は参考例１と同様に操作した。
【００４４】
〔比較例２〕
表３に示す樹脂処方・熱処理条件にて樹脂加工を行った。この場合、この処方はホルマリン濃度を低く抑えたため、樹脂量を減じた処方となっている。
【００４５】
以上の方法で得られた織物の性能を評価し、表３に示す結果を得た。
【００４６】
【表３】

注：
１２）リケンレジンＬＮＢ−２０：繊維素反応型Ｎ−メチロール樹脂（三木理研工業社製）
１３）Ｃａｔ．Ｍ：塩化マグネシウム系触媒（大日本インキ化学工業社製）
１４）メイカテックスＨＰ−７８０：可縫性向上剤（明成化学工業社製）
１５）ソフミンＳＮ−１５：脂肪酸エステル系柔軟剤（ミヨシ油脂社製）
１６）ＭＳＷ−２：シリコン系柔軟剤（松本油脂製薬社製）
１７）スミテックスバッファーＦＷ：ホルマリンキャッチャー（住友化学社製）
１８）ＰＥＧ−２００：ポリエチレングリコール（三洋化成工業社製）
１９）ＡＶＩＶＡＮ ＳＦＣ：脂肪酸アミド縮合化合物（チバガイギー社製）
【００４７】
上記の結果の通り、参考例１、２は、比較例２に比べ、防縮性が良好であり、残留ホルムアルデヒドも少なく、更に実用強度も維持している。また、熱水処理時に浴中柔軟剤を添加した参考例２は、防縮性等の性能を損なわずに風合いがソフトになるものであった。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for processing a cellulosic fiber-containing woven or knitted fabric. More specifically, the present invention improves the form stability of the cellulosic fiber-containing woven or knitted fabric, such as shrink-proofing and anti-molding, and uses a formaldehyde-based resin processing agent. Even in this case, the present invention relates to a method for processing a cellulosic fiber-containing woven or knitted fabric with little residual formaldehyde.
[0002]
[Prior art and problems to be solved by the invention]
Conventionally, various resin processing agents and resin processing methods have been studied in order to impart shape-stabilizing performance such as flaw prevention or shrinkage resistance to cellulosic fiber woven or knitted fabrics.
[0003]
By the way, the cause of wrinkles on the dough or shrinkage of the dough is caused by the fact that hydrogen bonds in the amorphous region of cellulose are broken and deformed by the action of external force or water, and in that state, hydrogen bonds are generated again. is there.
[0004]
The imparting of antifungal or shrinkage resistance by the resin processing of the dough is based on the fact that crosslinks are generated by the resin between cellulose molecules, and the hydrogen bonds are less likely to be broken by the action of external force or water due to the introduction of the crosslinks. In this case, as the resin processing agent, a method using a so-called fibrin-reactive resin such as glyoxal resin is generally used.
[0005]
However, in the conventional resin processing method, when the resin application amount is increased for the purpose of improving the anti-mold or shrinkage, the residual formaldehyde increases, and conversely, when the resin application amount is decreased, the anti-mold or There is a conflicting problem that the shrinkage resistance is lowered, and the present situation is that the resin processing is performed in a range that can be compromised with respect to the contradictory properties of the flaw prevention or shrinkage resistance and the increase in residual formaldehyde.
[0006]
For example, as a means for preventing the feather from passing through the duvet, a method of reducing the air permeability of the cotton fabric by applying a high-pressure calender treatment to the cotton fabric for the duvet. However, cotton fabrics are prone to wrinkling and cause laundry shrinkage. In this case, if the cotton fabric is treated with liquid ammonia, wrinkles are reduced and shrinkage can be prevented. However, if the cotton fabric is washed, the air permeability increases and the possibility of passing through the feathers arises. On the other hand, when the resin is used in combination, the air permeability can be kept to some extent after washing, but it is still not sufficient and the touch is hard, and the resin processing usually uses a formaldehyde-based resin as described above. There is a problem of formaldehyde, and there is a problem that it is difficult to carry out resin processing itself in applications where the regulation of residual formaldehyde is severe, such as duvets.
[0007]
The present invention has been made in order to improve the above-described circumstances, and gives the cellulosic fiber-containing woven or knitted fabric with form stability such as shrink-proofing or anti-molding while maintaining practical strength, and there is no problem of residual formaldehyde and the touch is also good. An object of the present invention is to provide a method for processing a cellulosic fiber-containing woven or knitted fabric that is good and has little property change due to washing.
[0008]
Means for Solving the Problem and Embodiment of the Invention
The present inventor has conducted extensive investigations to achieve the above objects, after the cellulosic fiber-containing textile fabric with liquid ammonia treatment, and imparting resin finishing agent and then heat calendering or the heat calender under a predetermined condition processing and subjected to Netsusho management at a predetermined temperature, by treatment with hot water and finally with a predetermined temperature, the form stability of the woven or knitted fabric are improved, simply compared with the case of applying the resin processing, the shape stability is Remarkably improved, the initial form stability is sufficiently maintained even after repeated washing, and there is no problem of residual formaldehyde even when formaldehyde resin is used as a resin processing agent, and the touch is also good. The headline and the present invention were made.
[0009]
Accordingly, in the present invention, after the cellulose fiber-containing woven or knitted fabric is treated with liquid ammonia, a resin processing agent is applied, and then a thermal calendar treatment is performed at 120 to 200 ° C., a nip pressure of 200 to 300 kgf / cm, and a speed of 5 to 15 m / min. or subjected to Netsusho management in the heat calendering treatment and 120 to 170 ° C., provides a method of processing cellulosic fiber-containing textile fabric which comprises treating by immersion in hot water is less than the last 98 ° C. or higher 0.99 ° C. To do. In this case, depending on the application, it is effective to apply a heat calendering treatment after applying a resin processing agent, and then heat-treat.
[0010]
In addition, according to the present invention, the reason why the form stability performance represented by antifouling or shrinkage is high and the residual formaldehyde is extremely low is considered to be as follows. That is, the fiber is swollen by the liquid ammonia treatment, and at the same time, the crystal structure is transferred from cellulose I or II to cellulose III. In the present invention, the resin is processed while maintaining the state where the fibers are swollen, and then further subjected to hot water treatment. By this treatment, a more stable crystal structure from cellulose III while maintaining the form formed by the resin processing It is considered that the cellulose I or cellulose II crystal structure can be returned to, and the structure becomes more stable than the case where the fiber is only subjected to the liquid ammonia treatment, and the residual formaldehyde is removed.
[0011]
Hereinafter, the present invention will be described in more detail.
The processing method of the cellulosic fiber-containing woven or knitted fabric of the present invention is a treatment of the cellulosic fiber-containing woven or knitted fabric in the following process sequence.
(1) Liquid ammonia treatment step (2) resin finish applying process (3) the heat calendering step (4) the heat treatment step (5) the hot-water treatment step in this case, may be omitted if necessary to about (4) Heat treatment Engineering.
[0012]
Here, the fibers constituting the cellulose-based fiber-containing woven or knitted fabric include natural fibers such as cotton, hemp, rayon, polynosic, cupra, high-strength regenerated cellulose fibers (for example, trade name Tencel) or regenerated cellulose fibers, In addition, composite fibers obtained by mixing these natural or regenerated cellulose fibers with synthetic fibers such as polyester, acrylic, and nylon can also be used. In this case, the proportion of the cellulosic fibers in the composite fiber is generally 20% by weight or more, and particularly preferably 40% by weight or more. These cellulosic fiber-containing woven or knitted fabrics can be subjected to known treatments such as hair firing, desizing, scouring, bleaching, mercerizing, etc., as pretreatment, as necessary. The woven or knitted fabric may be dyed or printed.
[0013]
The step (1) of the present invention is a liquid ammonia treatment step, which is a step of impregnating liquid ammonia maintained at a temperature of −33 ° C. or lower at normal pressure. As the impregnation method, a method of dipping a woven or knitted fabric in a liquid ammonia bath, a method of spraying or coating liquid ammonia on a woven or knitted fabric, or the like can be used. The impregnation time is appropriately selected and is usually about 5 to 40 seconds. After the liquid ammonia treatment, the ammonia adhering to the woven or knitted fabric is removed by heating.
[0014]
After the liquid ammonia treatment, the resin processing agent (2) is applied.
In this case, the resin processing agent may be any resin as long as it reacts with the hydroxyl group of cellulose to form a crosslink. Examples of such compounds include aldehydes such as formaldehyde, glyoxal, and glutaraldehyde, and diglycidyl. Examples include epoxy compounds such as ethers, polycarboxylic acids such as tetrabutanecarboxylic acid, fibrin-reactive N-methylol compounds such as dimethylol urea, trimethylol melamine, dimethylol ethylene urea, and dimethylol dihydroxy ethylene urea. Among these, In particular, a fibrin-reactive N-methylol compound is preferred from the viewpoint of good balance between improvement in anti-mold or anti-shrinkage performance associated with resin processing and reduction in fabric strength.
[0015]
The addition amount of the resin processing agent is preferably 0.5 to 10% by weight, more preferably 1 to 8% by weight, based on the weight of the cellulosic fiber-containing woven or knitted fabric subjected to resin processing. If the addition amount is less than 0.5% by weight, the effect as the resin processing may not be sufficiently exhibited, and if it exceeds 8% by weight, the strength reduction accompanying the resin processing may be remarkably increased.
[0016]
A catalyst can be added to the resin processing agent of the present invention in order to increase the reaction activity of the resin processing agent and cellulose and to perform resin processing quickly. The catalyst is not particularly limited as long as it is a catalyst usually used for resin processing, and examples thereof include borofluoride compounds such as ammonium borofluoride, sodium borofluoride, potassium borofluoride, zinc borofluoride, and magnesium chloride. And neutral metal salt catalysts such as magnesium sulfate and magnesium nitrate, and inorganic acids such as phosphoric acid, hydrochloric acid, sulfuric acid, sulfurous acid, hyposulfite and boric acid. These catalysts can be used together with an organic acid such as citric acid, tartaric acid, apple acid, maleic acid, etc. as a co-catalyst, if necessary.
[0017]
Moreover, the auxiliary | assistant for advancing reaction of a cellulose and resin smoothly can be added to a resin processing agent as needed. That is, the auxiliary agent has an action as a reaction solvent that promotes the reaction between the resin processing agent and cellulose, or promotes the reaction even in the cross-linking reaction, and further has an action of swelling the cellulose.
[0018]
Examples of the auxiliary agent include polyhydric alcohols such as glycerin, ethylene glycol, polyethylene glycol, and polypropylene glycol, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, and diethylene glycol monobutyl ether. Nitrogen-containing solvents such as ether alcohols, dimethylformamide, morpholine, 2-pyrrolidone, dimethylacetamide, N-methylpyrrolidone, ethyl acetate, isopropyl acetate, butyl acetate, amyl acetate, ethylene glycol monomethyl ether, ethylene glycol monoethyl acetate Examples include esters such as ether and γ-butyrolactone.
[0019]
In addition, a finish agent (clogging agent) can be added to the resin processing liquid when the purpose of form stability is to reduce the air permeability of duvets, down jackets and the like. As finishing agents (clogging agents), known ones such as silicone / acrylic resins, silicone / polyurethane resins, acrylic resins, polyurethane resins, reactive silicones, and the like can be used. The solid content concentration is preferably 0.5 to 3% by weight, more preferably 1 to 2% by weight, based on the weight of the cellulosic fiber-containing woven or knitted fabric, and is appropriately selected according to the desired air permeability of the woven or knitted fabric. The
[0020]
In addition to the above-mentioned chemicals, a softening agent for adjusting the texture, a formalin catcher for reducing free formalin concentration, and the like can be added to the resin processing agent of the present invention as necessary.
[0021]
In the present invention, the resin processing agent is applied to the cellulosic fiber-containing woven or knitted fabric, but the application method is not particularly limited, and a known method such as a normal pad dry method or a gas phase reaction (VP reaction) may be employed. it can.
[0022]
In the pad dry method, a woven or knitted fabric is dipped in a preparation liquid containing a resin processing agent, then squeezed at a drawing rate of 40 to 120%, and moisture is dried at an ambient temperature of about 70 to 100 ° C. If the atmospheric temperature is less than 70 ° C., a long drying time is required, and if it exceeds 100 ° C., migration of the resin processing agent occurs, which may cause inconveniences such as uneven distribution of the processing agent.
[0023]
After the resin processing agent is applied , a thermal calendar process is performed. In particular, in a duvet or the like for which a decrease in air permeability is required, the crushing effect can be obtained more effectively, and at the same time, the resin reaction proceeds.
[0024]
This thermal calendering process can be carried out by a conventional method, usually 120 to 200 ° C., nip pressure 200 to 300 kg / cm, speed 5 to 15 m / min, and the conditions are selected according to the desired air permeability of the woven or knitted fabric. Can do.
[0025]
Next, heat treatment is performed to complete the resin reaction. Here, when the heat calendar process is performed as described above and the resin reaction can be sufficiently completed, the heat treatment can be omitted. The heat treatment is performed by heat-treating the woven or knitted fabric at a temperature of 120 to 170 ° C., preferably 130 to 160 ° C. for 1 to 15 minutes, preferably 2 to 10 minutes to form a crosslink. Depending on the type of resin to be added, the amount of resin used, the type of catalyst, the amount of catalyst added, etc., the reaction progresses slowly when the heat treatment temperature is less than 120 ° C, and the fabric becomes yellow when it exceeds 170 ° C. May occur.
[0026]
In the present invention, the hot water treatment is performed at the end, and this is represented by the anti-warming and shrink-proof properties of the woven or knitted fabric achieved in the above-mentioned treatments (2) and (3) and / or (4). The morphological stability is remarkably improved, and the woven or knitted fabric having a good form feeling and no problem of residual formaldehyde caused by the resin processing can be obtained while the morphological stability is effectively maintained even after washing. In this case, this performance is maintained for a material that requires a low air permeability such as a duvet.
[0027]
Here, the hot water treatment can be performed by treating the cellulose fiber-containing woven or knitted fabric with hot water having a temperature of 98 ° C. or higher. Specifically, any apparatus capable of performing hydrothermal treatment at high pressure may be used. For example, processing is performed using a high-pressure liquid dyeing machine, a high-pressure paddle dyeing machine, a high-pressure drum dyeing machine, a high-pressure jigger dyeing machine, a high-pressure beam dyeing machine, or the like. Depending on the fabric type and application, it can be done under no tension using a high pressure liquid dyeing machine, a high pressure paddle dyeing machine, a high pressure drum dyeing machine, etc., or a high pressure jigger dyeing machine, a high pressure beam dyeing machine, etc. Can be used while keeping the fabric smooth under slight tension.
[0028]
In this case, when hydrothermal treatment is performed without tension using a high-pressure liquid dyeing machine, a high-pressure paddle dyeing machine, a high-pressure drum dyeing machine, etc., the stress of the woven / knitted structure is relieved and the shrinkage resistance is improved. In addition, the moisture-proofing degree is improved by the setting effect by the hot water treatment, and there are advantages such as imparting a beam, a squeaky feeling, and imparting a change to the surface feeling.
[0029]
In addition, when hot water treatment is performed under slight tension using a high-pressure beam dyeing machine or high-pressure jigger dyeing machine, the flatness of the dough is maintained during the hot water treatment, so that wrinkles and irregularities may enter the dough. In addition, there is an advantage that the ear portion is not wound and that a large amount of processing can be performed at the same time.
[0030]
The hot water treatment time is appropriately selected, but specifically, the hot water treatment conditions are preferably as follows.
(A) 98 ° C. or more and less than 105 ° C .: 2 hours or more, preferably 2.5 hours or more (b) 105 ° C. or more and less than 115 ° C .: 1 hour or more, preferably 1.5 hours or more (c) 115 ° C. or more and 125 ° C. Less than: 40 minutes or more, preferably 1 hour or more (d) 125 ° C. or more and less than 135 ° C .: 30 minutes or more, preferably 1 hour or more (e) 135 ° C. or more and less than 150 ° C .: 20 minutes or more, preferably 1 hour or more The upper limit of the treatment time is preferably 5 hours.
[0031]
In the hot water treatment, a softening agent can be added to the hot water for treatment, thereby imparting flexibility to the woven or knitted fabric. As the softening agent, the composition does not change when treated at a high temperature for a long time, as long as it imparts a soft texture, for example, known ones such as fatty acid amide condensation compounds and fatty acid ester compounds can be used, The amount added to the hot water can be 0.1 to 10% by weight, particularly 0.3 to 3% by weight.
[0032]
The method of the present invention is suitably used for those in which shape stability of a woven or knitted fabric is desired. In this case, the air permeability of the final processed woven or knitted fabric is selected as desired. However, in the woven fabric used for the duvet, down jacket, etc., it is preferably 1 cc or more and less than 3 cc. Sometimes wearing feeling may be reduced.
[0033]
【The invention's effect】
According to the present invention, an excellent cellulosic fiber-containing woven or knitted fabric is obtained that retains its form-stable performance typified by anti-molding or shrink-proofing even after washing and has no problems such as residual formaldehyde.
[0034]
【Example】
EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example.
[0035]
[Example 1]
Using cotton 160/2 yarn, hair sacrificing, desizing, scouring, and bleaching according to a conventional method for warp 5 pieces of warp, 231 warp / 2.54 cm, weft 200 / 2.54 cm, −34 ° C. Was treated with liquid ammonia for 20 seconds, and then the attached ammonia was removed by heating.
[0036]
Next, the resin processing liquid shown in Table 1 was impregnated, excess liquid was squeezed out with a mangle, and it adjusted so that it might become the adhesion amount of Table 1. Subsequently, after drying, a heat calendar treatment was performed at 160 ° C. × 200 kg / cm × 5 m / min, and then a heat treatment was performed at 160 ° C. × 2 minutes. Then, the hot water process (130 degreeC * 2 hours) was performed by the winding system, and it dried.
[0037]
[Comparative Example 1]
The same fabric as in the example was subjected to hair burning, desizing, scouring, bleaching, and liquid ammonia treatment, impregnated with a finishing agent shown in Table 1, dried, and then subjected to thermal calendering treatment under the same conditions as in the example.
[0038]
The performance of the woven fabric obtained by the above method (woven fabric for duvet) was evaluated, and the results shown in Table 2 were obtained.
[0039]
[Table 1]

note:
1) Riken Resin LNB-20 (Miki Riken Kogyo Co., Ltd.)
2) Catalyst M (Dainippon Ink Chemical Co., Ltd.)
3) Charine EFE230 (manufactured by Nissin Chemical)
4) Softbon P3000 (Takemoto Yushi Co., Ltd.)
5) Finetex NRW (Dainippon Ink Chemical Co., Ltd.)
[0040]
[Table 2]

note:
6) JIS L1096 Method A 7) JIS L1041 Method B Acetylacetone Method 8) JIS L1096 Method A Gurley Method 9) JIS L1096 Method D Pendulum Method 10) JIS L1096 Method A Labeled Strip Method 11) JIS L1059
[0041]
From the above results, the method of the example shows that, even after washing, the air permeability is hardly increased, the initial air permeability is substantially maintained, and the formalin residual amount is high despite the high degree of fouling. It was confirmed that there was almost no change in the physical properties, the degree of weathering, and the shrinkage rate even after washing.
[0042]
[ Reference Example 1 ]
No. 40 twin yarn Kanoko (30 inch, 18 gauge) 100% cotton knitted fabric is subjected to alkali treatment and bleaching in the usual way, treated with liquid ammonia for 20 seconds, and then processed with resin formulation and heat treatment conditions shown in Table 3 After performing a hydrothermal treatment at 130 ° C. for 1 hour using a high-pressure liquid flow processing machine, it was dehydrated and dried, processed with a softener using a tenter, and finished to a predetermined width.
[0043]
[ Reference Example 2 ]
In Reference Example 1 , similar to Reference Example 1 except that a softener (AVIVAN SFC: fatty acid amide condensation compound, manufactured by Ciba Geigy) was added to hot water during the hot water treatment. Operated.
[0044]
[Comparative Example 2]
Resin processing was performed under the resin prescription and heat treatment conditions shown in Table 3. In this case, this formulation is a formulation with a reduced amount of resin because the formalin concentration is kept low.
[0045]
The performance of the fabric obtained by the above method was evaluated, and the results shown in Table 3 were obtained.
[0046]
[Table 3]

note:
12) Riken Resin LNB-20: Fibrin-reactive N-methylol resin (Miki Riken Kogyo Co., Ltd.)
13) Cat. M: Magnesium chloride catalyst (Dainippon Ink Chemical Co., Ltd.)
14) Maycatex HP-780: Sewing improver (manufactured by Meisei Chemical Co., Ltd.)
15) Sofmin SN-15: fatty acid ester softener (manufactured by Miyoshi Yushi Co., Ltd.)
16) MSW-2: Silicone softener (Matsumoto Yushi Seiyaku Co., Ltd.)
17) Sumitex buffer FW: formalin catcher (manufactured by Sumitomo Chemical Co., Ltd.)
18) PEG-200: Polyethylene glycol (manufactured by Sanyo Chemical Industries)
19) AVIVAN SFC: fatty acid amide condensation compound (Ciba Geigy)
[0047]
As shown in the above results, Reference Examples 1 and 2 have better shrinkage resistance than Comparative Example 2, have less residual formaldehyde, and maintain practical strength. Further, in Reference Example 2 in which the softening agent in the bath was added during the hot water treatment, the texture became soft without impairing the performance such as shrinkage resistance.

Claims (5)

After processing the cellulosic fiber-containing textile fabric with the liquid ammonia, to grant resin finish, followed by 120 to 200 [° C., nip pressure 200~300kgf / cm, rate of 5 to 15 m / min by heat calendering or the heat calendering and 120 to 170 subjected to Netsusho management at ° C., the processing method of the cellulosic fiber-containing textile fabric characterized by immersing the treated hot water in less than last 98 ° C. or higher 0.99 ° C.. The method according to claim 1, wherein the processing liquid containing the resin processing agent further contains a crosslinking catalyst and a crosslinking reaction aid . The method according to claim 1 or 2, wherein the processing fluid containing the resin processing agent further contains a plugging agent . The method according to claim 1, 2 or 3, wherein the hot water treatment is performed by a high pressure liquid dyeing machine, a high pressure paddle dyeing machine, a high pressure drum dyeing machine, a high pressure jigger dyeing machine or a high pressure beam dyeing machine . The method according to any one of claims 1 to 4 , wherein a softening agent is added to the liquid during the hot water treatment.