WO2003052195A1

WO2003052195A1 - Method for producing sewn product from cellulose fiber having form stability

Info

Publication number: WO2003052195A1
Application number: PCT/JP2002/013116
Authority: WO
Inventors: Yasuo Isome; Takanobu Ono
Original assignee: Chori Co., Ltd.; Fukusen Co., Ltd.
Priority date: 2001-12-14
Filing date: 2002-12-16
Publication date: 2003-06-26
Also published as: CN1604978A; JPWO2003052195A1; AU2002366472A1

Abstract

In a method for producing a sewn product from cellulose fibers having form stability involving an immersion step of impregnating the sewn product with a treating fluid containing a form stabilizing agent, a fluid removal step of removing an excessive amount of the treating fluid from the sewn product, a drying step of removing through vaporization a solvent in the treating fluid attached to the sewn product, a press step of pressing out the wrinkles from the sewn product and a curing step of reacting the form stabilizing agent attached to the sewn product, to thereby impart form stability to the sewn product, an improvement which comprises using a form stabilizing agent which does not by-produce formaldehyde, carrying out a step of smoothing out wrinkles prior to the above immersing step, and practicing the above immersion, fluid removal and drying steps under conditions such that the sewn product does not have wrinkles.

Description

Manufacturing method of morphologically stable cellulose fiber sewn products

The present invention relates to a method for producing a form-stable cellulose fiber sewn product that does not produce formalin as a by-product, and a form-stable cellulose fiber sewn product. Background art

Textile products that do not wrinkle even when washed and can be worn without ironing have been manufactured. Such textile products are called form-stable products, and are used in a wide range of fields such as outer garments, middle garments, underwear, and bedding. Recently, the use of form stabilizers that do not produce formalin is encouraged in view of allergy issues and safety. A common method of imparting form stability to cellulosic fiber products such as cotton and hemp is to apply a form stabilization process to the fabric at the stage of forming it into a fabric or knit, and then to sew. A number of technical developments have been made for the method. On the other hand, it is considered that the method of performing the form stabilization treatment after sewing the fabric or knitted fabric has advantages such as small lots, easy turning, and easy adaptation to diversification of products. However, a method of processing cellulosic fibers into a fabric or knitted fabric, and then performing stitching processing on these fabrics has not yet been put to practical use. This is because even if the cellulose fiber sewn product is subjected to the form stabilization treatment after sewing, fine wrinkles are generated on the surface thereof, which causes a problem in appearance quality. This is because, when performing morphologically stable processing at the stage of fabric or knitted fabric, heat treatment can be performed with uniform tension applied to the fabric or the like, but heat treatment cannot be performed with sewn products with uniform tension applied. Disclosure of the invention

The present invention has been made in view of the above circumstances, and is intended to produce a form-stable cellulose fiber sewn product having excellent form stability, a high appearance quality with no wrinkles on the product surface, and free of formalin. It is an object of the present invention to provide a method and a form-stable cellulose fiber sewn product. In order to achieve the above object, a method for producing a sewn cellulose fiber product of the present invention comprises: a immersion step of impregnating the sewn cellulose fiber product with a treatment solution containing a form stabilizer; A dewatering step of removing the treatment liquid; a drying step of evaporating and removing a solvent in the treatment liquid adhering to the cellulose fiber sewn product; a press step of extending wrinkles of the cellulose fiber sewn product; and the cellulose fiber sewn product The method for producing a morphologically stable cellulose fiber sewn product having a curing step of imparting morphological stability by reacting the morphological stabilizer attached to the Furthermore, the method includes a pressing wrinkle removing step performed prior to the dipping step, and the drying step includes forming wrinkles on the cellulose fiber sewn product. The present inventors have conducted a series of studies on the causes of wrinkles that occur during morphological stabilization. As a result, wrinkles are generated in the drying process, and the wrinkles are once disappeared in the subsequent pressing process. However, this is only latent, and in the curing process, the latent wrinkles become apparent. Ascertained. Based on this knowledge, the prevention of wrinkles in the drying step was studied.The pressing wrinkle removal step was performed prior to the dipping step, and the drying step was performed under conditions in which no wrinkles were generated. The present inventors have found that wrinkles can be prevented from occurring in the present invention, and have completed the present invention. ADVANTAGE OF THE INVENTION According to this invention, it became possible to apply a form stabilization process directly to the sewn product of cellulose fiber without deteriorating the appearance quality and without producing formalin as a by-product. BRIEF DESCRIPTION OF THE FIGURES

FIG. 1A, FIG. IB, and FIG. 1C are diagrams showing the results of electron microscope observation of Example 1 of the present invention.

FIG. 2A, FIG. 2B and FIG. 2C are diagrams showing the results of the electron microscope observation of Comparative Example 1.

FIG. 3A, FIG. 3B and FIG. 3C show the results of electron microscopic observation after washing 30 times in Example 1 of the present invention.

FIGS. 4A, 4B and 4C are views showing the results of electron microscopic observation of Comparative Example 1 after washing 30 times.

FIG. 5 is a diagram illustrating a state of surface wrinkles according to the first embodiment.

FIG. 6 is a diagram showing a state of surface wrinkles in Comparative Example 1.

FIG. 7 is a diagram showing a state of surface wrinkles in Comparative Example 2.

FIG. 8 is a view showing a state of surface wrinkles in Comparative Example 4.

FIG. 9 is a view showing the results of electron microscopic observation showing the results of the dissolution test of the cellulose fibers of Example 1 of the present invention. DETAILED DESCRIPTION said drying step for carrying out the invention is carried out by rotary dryer, it is preferred that the filling condition of the cellulose fibers sewn products Hama charged into the rotary dryer is 5~ 30 k gZm ³ . If the drying step is performed under these conditions, the generation of wrinkles can be more effectively prevented. In the method of the present invention, it is preferable that the immersion step is also performed under the condition that wrinkles do not occur in the sewn cellulose fiber product. In the immersion step, the treatment liquid does not flow or flows in one direction relatively to the sewn cellulose fiber product, and the flow rate is preferably in the range of 0 to 5 OmZ. The drying step is carried out by rotary dryer, filling conditions of the cellulose fibers sewn product to be filled into the tumble dryer is preferably 5~3 0 kg Z m ^3. If the immersion step is performed under these conditions, the generation of wrinkles can be more effectively prevented. In the production method of the present invention, it is preferable that the drying step and the curing step are performed in a state where the sewn cellulose fiber product is in a free shrink state. In this way, in the obtained sewn product, wrinkles are more effectively prevented, and the washing resistance and flexibility are improved. In the production method of the present invention, the form stabilizer is preferably 4,5-dihydroxy-1,3-dimethyl-2-imidazolidinone or a dimer thereof. This form stabilizer does not by-produce formalin. In the manufacturing method of the present invention, the temperature condition of the drying step is preferably in a range of 40 to 70, and the temperature condition of the pressing step is preferably in a range of 160 to 18 Ot :, and the curing step is The temperature condition is preferably in the range of 150 to 170. In the immersion liquid of the present invention, the content of the form stabilizer is in the range of 4.5 to 6.5% by mass of the entire immersion liquid, and further contains a catalyst. The content of the medium is preferably in the range of 15 to 30% by mass of the form stabilizer, and the pH is preferably in the range of 4 to 4.9. This makes it possible to impart an excellent touch to the sewn morphologically stable cellulose fiber product of the present invention. In such a sewable morphologically stable cellulose fiber product having excellent touch characteristics, the fixation ratio of the morphological stabilizer resin of the cellulose fiber is in the range of 1.0 to 3.0% by mass based on the cellulose fiber. The content of the form stabilizer is preferably in the range of 20 to 40%. The catalyst is preferably a mixture of magnesium sulfate and magnesium nitrate, and the ratio is 20 to 25% by mass of magnesium nitrate and 80 to 75% by mass of magnesium sulfate in terms of magnesium. Is preferred. Further, the content of the treatment liquid contained in the sewn cellulose fiber product after the liquid removal step is preferably 70 to 90% by mass of the sewn cellulose fiber product. According to these preferred embodiments, the touch characteristics are further improved. Next, the form-stable cellulose fiber sewn product of the present invention is manufactured by the manufacturing method of the present invention. This sewn product has no fine wrinkles on its surface, excellent appearance characteristics, and no residual formalin. Further, the sewn product of the form-stable cellulose fiber of the present invention is a product in which the fixation ratio of the form-stabilizing resin fixed to the cellulose fiber is in the range of 1.5 to 3.0% by mass based on the cellulose fiber. This product has excellent touch properties. In the sewn cellulose fiber product of the present invention, at least one fiber selected from the group consisting of cotton fiber, hemp fiber, regenerated cellulose fiber, and silk-processed fiber of each fiber may be included. In addition, the product form is, for example, a fabric or a knitted fabric, and the product type is, for example, Outer garments, middle garments, underwear, bedding or decorations.

Hereinafter, an example of the method for producing the form-stable cellulose fiber sewn product of the present invention will be described. This manufacturing method directly imparts form stability to a sewn product of cellulose fiber, and comprises a dipping step, a dewatering step, a drying step, a pressing step, and a curing step, as shown below. In the present invention, other steps may be performed in addition to these steps.

(Immersion process)

This step is a step of impregnating a sewn cellulose fiber product with a treatment liquid containing a morphological stabilizer. Cellulose fiber sewing products are not particularly limited, and can be applied to textile products for outer garments, middle garments, underwear, bedding products, and decorative articles. The treatment solution contains a form stabilizer and a catalyst that do not produce formalin. In addition, the processing liquid may further contain a fiber processing aid such as an agent for preventing a decrease in strength of a cellulose fiber product, a softening agent, and a fluorescent agent. Unnecessary wrinkles should be eliminated beforehand for the cellulose fiber sewn products to be used in the dipping process. When a wrinkled cellulose fiber sewn product is put into the dipping process, even if the subsequent pressing process gives smoothness, wrinkles become apparent in the curing process and a smooth cellulose fiber sewn product is obtained. Absent. The relative flow of the treatment liquid to the cellulose sewn product during the immersion process is constantly unidirectional with respect to the cellulose sewn product, and the relative flow rate is, for example, in the range of 0 to 30 mZ, preferably It is preferable that the thickness be in the range of 0 to 2 O mZ, more preferably in the range of 0 to 1 O mZ. Note that the relative flow does not include flowing the immersion liquid, but includes immersing the sewing product to be processed in the immersion liquid in a still water state and moving the sewn product in one direction. Also, The reason that the relative flow velocity includes 0 is to include immersion as it is in an immersion liquid in a still water state.

(Liquid removal process)

Next, in order to remove excess processing liquid from the sewn cellulose fiber product immersed in the processing liquid, it is preferable to remove liquid by a centrifuge. In this case, the centrifugal force loading on the cellulosic fibers sewn products in draining can For example, 2 0 0 ~ 1 0 0 O mZsec. 2 , preferably in the range from 2 0 0 ~ 8 0 0 m / se 2 , more preferably from 2 0 0 ~ 6 0 O mZsec . 2.

(Drying process)

Next, the dewatered cellulose fiber sewn product is dried. As the dryer, a rotary dryer generally called a tumbler complete dryer is used. There is also a proposal to use a hanging dryer, which hangs on a hanger in the drying process of the cellulose fiber sewn product, but in this case, the treatment liquid drops by gravity in the initial stage of drying, and localization occurs within the same cellulose fiber sewn product. Uneven distribution of the processing liquid occurs, and the uneven distribution of the processing liquid causes the color of the product to yellow, and a uniform form-stable cellulose fiber sewn product cannot be obtained. Inside the tumble dryer, adjacent textile products come into contact with each other and rotate, and the distribution of the treatment liquid becomes uniform while having fluidity in the initial stage of drying, and a uniform form-stable cellulose fiber sewn product can be obtained. . The cellulose fibers shrink during drying, but it is preferable to promote free shrinkage without restraining the shrinkage in order to obtain a wrinkled cellulose fiber sewn product. The filling amount of the cellulose fiber sewing product to be filled in the dryer is, for example, 5 to 3 O kg / m ³ , preferably 5 to 25 _kg / m ³ , more preferably 5 to 2 O kgZm ³ . Range. If the amount of cellulose fiber sewn product to be filled into this dryer is within the above range, drying In the latter stage, each cellulose fiber sewn product is not restrained by the adjacent cellulose fiber sewn product, and shrinks freely to obtain a highly flexible, form-stable cellulose fiber sewn product, which is preferable. The drying conditions are, for example, 50 to 70, preferably 50 to 60, and more preferably 50 to 55. At such a drying temperature, wrinkles can be more effectively prevented from appearing in the curing process, even if the cellulose fiber sewn product is smoothed by a subsequent press. The drying in the drying step can be based on, for example, a water content of 8% or less, and the drying time can be selected according to the drying temperature conditions and the filling amount of the cellulose fiber sewing product in the dryer.

(Pressing process)

Then, the dried cellulose fiber sewn product is pressed to smooth wrinkles. The pressing conditions are, for example, 150 to 180 t :, preferably 160 to: 180 t :, and more preferably, 160 to 175. This pressing can be performed using a commercial iron or a clothing press. If the pressing condition is 150 or more, the cellulose fiber sewn product can be pressed more effectively and smoothly.If the pressing condition is 180 or less, the discoloration of the cellulose fiber sewn product can be prevented, and higher appearance quality can be prevented. Is obtained.

(Curing)

Next, the pressed cellulose fiber sewn product is subjected to a curing treatment to cause the morphological stabilizer to react with the cellulose fibers to impart morphological stability. The curing conditions are, for example, 150 to 170 at 1 to 6 minutes, preferably 150 to 170 at 1 to 4 minutes, more preferably 150 at 3 to 4 minutes, and 160 ^. In 2-3 minutes, 1 70 t: in! ~ 2 minutes. This If the curing process is performed under such conditions, morphologically stable cellulose fiber sewn products can be more effectively prevented from wrinkling during wearing and washing, and discoloration can be prevented, resulting in higher appearance quality. . Next, an example of the production method of the present invention, in which, in addition to the appearance quality characteristics, the touch characteristics / washing resistance characteristics are further improved, will be described below.

(Immersion process)

In the immersion process, the treatment liquid is impregnated into the sewn product of the cellulose fiber, but the treatment liquid contains a form stabilizer and a catalyst. The morphological stabilizer is a mixture of 4,5-dihydroxy-1,3dimethyl-2-imidazolidinone and a dimer thereof, and the mixture ratio of the dimer is 20 to 40% by mass. Contains 4.5 to 6.5% by mass in the treatment liquid. Further, the catalyst is a metal salt of magnesium, and a mixture of magnesium sulfate and magnesium nitrate is preferable. Among them, 20 to 25% by mass of the magnesium amount is magnesium nitrate amount, and 80 to 7% of magnesium amount. Consists of 5% by weight of magnesium sulfate. The processing liquid contains a catalyst of 15 to 30% of the form stabilizer. The pH of the processing solution is in the range of 4 to 4.9. When the content of the form stabilizer in the treatment liquid is 4.5% by mass or more, the form stability of the obtained sewn cellulose fiber product is further improved, and the content of the form stabilizer is 6.5% by mass or less. Then, yellowing of the sewn product of the cellulose fiber can be prevented. When the content of the catalyst in the treatment liquid is 8% by mass or more of the morphological stabilizer, the morphological stability of the sewn cellulose cellulose product is higher, and the content of the catalyst is 12%. When the amount is less than the mass%, the cellulose fiber sewn product can prevent yellowing. Further, when the pH of the treatment liquid is 4.9 or less, the obtained cellulose sewn product has higher form stability, and the pH is 4 If it is above, yellowing of a cellulose fiber sewing product can be prevented. (Liquid removal process)

In the liquid removing step, the treatment liquid of 70 to 90% by mass of the cellulose fiber sewn product is drained so as to adhere to the cellulose fiber sewn product. If the treatment liquid adheres to the cell-stitched fabric sewn product at 70% by mass or more, it is more effective that the wrinkles generated in the dewatering process become apparent in the obtained cellulose sewn product. When the amount of the treatment liquid adhered is 90% by mass or less, the adhesion of the treatment liquid becomes uniform, and the sewn product of the cellulose fiber can be partially prevented from yellowing.

(Fixing resin based on reaction between morphological stabilizer and cellulose fiber)

If the sewn cellulose fiber product is treated under the above conditions, 1.8 to 3.2% by mass of the fixing resin (form stabilizer resin) adheres to the cell opening fibers. When the fixing resin of the cellulose fiber sewn product is 1.8 to 3.2% by mass, the cellulose fiber sewn product according to the present invention has more effective form stability and even after repeated washing, even after repeated washing. The occurrence of wrinkles does not change, and the dimensional change rate of the sewn cellulose fiber product of the present invention does not change even after repeated washing. Furthermore, the cellulose fiber product according to the present invention has better touch, breakage resistance in washing, retention of appearance and comfort than natural products, and does not produce formalin as a by-product. Furthermore, the form-stable cellulose fiber sewn product of the present invention, which is a fixing resin in an amount of 1.8 to 3.2% by mass based on the cellulose fiber, has a softer touch when worn than a raw natural cellulose fiber product. Good quality, less deterioration in appearance quality due to repeated washing, and less damage, as a textile product High durability of cellulose In general, cellulosic fiber products are positioned as rigid and hard products, and it is widely known that repeated washing increases this hardness further. INDUSTRIAL APPLICABILITY The form-stable cellulose fiber sewn product of the present invention is flexible and has a property of maintaining initial flexibility even after repeated washing. This hardness is particularly remarkable for hemp fiber products. When wearing hemp textiles, the bends and projections of the tiny fibers hit the skin when worn, and this problem is particularly acute for those who dislike this feel or have sensitive skin. If the present invention is applied to hemp products, the hemp products will have a soft touch, not only a better texture than unprocessed natural products, but also retain this flexibility even after repeated washing. When laundered repeatedly, there is a large difference in flexibility from raw hemp-based products. According to the method of the present invention, the sewn cellulose fiber product obtained has a soft touch as compared with an unprocessed natural cellulose fiber product. Thus, the excellent quality of the product of the present invention is probably due to the fact that the cellulose fibers are subjected to the surface modification of the monofilament with the fixing resin, and the entanglement between the cellulose fiber woven fabric and the knitted fabric. This is probably because the fibers are not fixed and the fibers can move freely. In addition, with natural cellulose fibers, fine destruction occurs from the fiber surface during washing, and as a result, natural cellulose monofilaments are divided into many beard-like fibrils, and the fibrils peel off from the single fiber surface, This destruction process progresses repeatedly, and eventually breaks the single fiber. With the fibrillation of monofilaments, the surface of the natural cell mouth-fiber product is called a thread, resulting in a blurred appearance, deterioration of appearance performance, and deterioration of comfort due to reduced air permeability. In addition, the breakage of a single fiber easily occurs with a hard fiber such as hemp, giving a tingling discomfort when wearing a textile product. In the case of natural cellulose fibers, if the breakage of single fibers progresses, the fiber product will be seriously damaged visually as a starting point, and will not withstand wearing. The cellulose fiber sewn product obtained by the method of the present invention When washed repeatedly, monofilaments are much less fibrillated than unprocessed natural cellulosic products, so there is less change in comfort, deterioration in appearance quality and less damage, and durability as a textile product Is high. The reason is presumed to be the same as above. In the sewn cellulose fiber product obtained by the reaction of the method of the present invention, the fixing resin strongly reacts with all the cellulose including the fine part from the surface to the inside of the cellulose fiber. If unprocessed cellulose fibers are immersed in an aqueous solution of copper hydroxyethylene diamine, which is known as a dissolving agent for cellulose, the entire amount of the cellulose fibers will be dissolved, and the fiber form will be completely lost to form a solution. The cellulose fiber obtained under the reaction conditions of the present invention retains its fiber form even when immersed in an aqueous solution of copper hydroxyethylenediamine. It is thought to contribute to high durability, high flexibility, and high touch characteristics in sewing laundry. In this way, the morphologically stable cellulose fiber product of the present invention is obtained, but the present product may be manufactured by another manufacturing method. Cellulose fiber products obtained according to the present invention have excellent form stability, wrinkles after washing, which is a measure of form stability, are at least 3.0 grades, and this value does not change even after repeated washing. Although there is a slight shrinkage during washing, washing shrinkage does not increase when washing is repeated thereafter. Furthermore, as a result of repeating washing and drying of the cotton fiber product and the natural cotton fiber product according to the production method of the present invention, the cotton surface produced by the production method of the present invention has only a minute destruction of the surface. On the other hand, natural cotton fibers are largely fibrillated, and the sewn cellulose fiber product by the production method of the present invention exhibits high washing durability. In addition, The sewn cellulose fiber products manufactured by Ming are more flexible and provide a more comfortable fit than natural unprocessed cell mouth products.

Hereinafter, examples of the present invention will be described. Incidentally, the measurement method exemplified in the embodiment is measured by the following method.

(1) Wrinkles after washing; JIS L 1 096,

Washing method JIS L 0217 103 method Tumble drying, repeated as necessary ₍

(2) Dimensional change rate: JISL 1.096, how to wash JISL 02 1 2 7 1 03 method Tumble dry, repeated 5 times

(3) Wrinkles after washing: Washing method is tumble drying according to JIS L 0217 103 method, repeated 5 times, and visually determine the linear length generated in the back body of the sewn product of cellulose fiber. If there were wrinkles, it was determined that wrinkles had occurred.

(4) Crepe after washing: Washing method is tumble-drying according to JIS L 0217103 method, repeated 5 times, and crepe on the back of the sewn product of cellulose fiber is visually determined, and crepe on the back A sample having wrinkles was determined to have crepe.

(5) Wrinkles after washing up to 50 times: In the method for measuring wrinkles after washing described in (1), the number of washings was repeated up to 50 times.

(6) Dimensional change rate after washing up to 50 times: In the measuring method of dimensional change rate described in (2), washing was repeated up to 50 times. For the measurement of the dimensional change rate, the dimensional change rate of the length of the sewn product having the largest change rate was measured.

(7) Photographing the surface of sewn cellulose fiber products: A 500 W side light source was used as the light source, and the camera was a Nikon F 50 mm, 1.4 F intermediate ring (PR-11) Was taken with.

(8) Cellulose monofilament fibrillation determination: Cellulose fiber sewn product cellulose cellulose single yarn surface was photographed with a scanning electron microscope (JSM-630 F, manufactured by Nippon Denshi) at an acceleration voltage of 5 kv. The state of fiber breakage was observed and judged.

(9) Resin fixation amount to cellulose fiber: Measured according to JIS 1041 by partially changing the test method.

(a) Collect about 5 g of the test specimen, place the test specimen in a 200 ml beaker, and wash with 25 ± 2 t: water. Then, a solution of 90 containing 0.25% of soap (Marcel soap 0.25%) and 0.25% of sodium carbonate (warm evening—heated in a bath) was treated in 20 Om1 for 5 minutes, then completely dried and cooled. The test piece was weighed in a PP weighing bottle. (Ml)

(b) Further, the test piece was treated with 200 ml of 20% 0.25% hydrochloric acid (incubated in a warm bath) for 30 minutes, washed five times with 90 ° hot water, and then the test piece was removed. After drying and further cooling, the test piece was placed in a PP measuring bottle and weighed.

(m2)

(c) Amount of fat fixation M 2 was determined by the following equation.

M2 = [(m l -m2) / m 2] X 100

(10) Swelling and solubility of copper hydroxyethylene diamine: cut cellulose monofilament and immerse it in aqueous solution of copper hydroxyethylene diamine IMol (Kanto Chemical Co., Ltd.) for 30 minutes. For example, a cross section of the cellulose single fiber is photographed with a scanning electron microscope, and the swelling and dissolution state of the cellulose single fiber are determined. The pH of the treatment solution was adjusted to 4.5 with the treatment solution having the composition shown in Table 1 below. 【table 1】

The polyethylene emulsion used was Fintex PE (manufactured by Sumitomo Chemical), and the dimethylsiloxane ZPEG composition used was DIC Silicone Softener (manufactured by Dainippon Ink).

(Examples 2, 3, 4, 5, 6, 7, Comparative Example 1)

For the cellulose fiber sewn product, a cotton shirt (50 single yarn, 144 x 80 yarns / inch) was used. The shirt before immersion was ironed in the sewing process and then transported in a package that would not cause wrinkles. The shirts were sequentially passed through each process using the treatment liquids shown in Table 2 below to give the form stability of Examples 1, 2, 3, 4, 5, 6, and 7.

[Table 2]

* The relative speed of the shirt processing solution when the shirt is pulled and moved in 10 minutes in one processing solution.

In Examples 1 to 7, while the shirt was immersed in the treatment liquid in the immersion step, it was immersed for 10 minutes, and then the shirt was taken out of the treatment liquid, and a centrifuge having an inner diameter of 106 cm was used. The treatment liquid remaining on the shirt after draining was adjusted to be 80% of the shirt weight. Comparative Example 1 is an ironed cotton shirt (50 single yarn, 144 × 80 Z-inches) not subjected to shape-stabilizing processing. For Examples 1 to 7 and Comparative Example 1, the wrinkles, creases and crepe wrinkles after 5 times of washing and the dimensional change after 5 times of washing were measured, and the results are shown in Table 3 below. [Table 3]

From Table 2, all of the shirts of Examples 1 to 7 were excellent in appearance quality with no wrinkles (grade), folded wrinkles or crepe after washing 5 times. Each of the shirts of Examples 1 to 7 is significantly superior in wrinkles (grade) and dimensional change after washing as compared with Comparative Example 1, and has high form stability. As described above, in Examples 1 to 7, according to the method of the present invention, generation of wrinkles during the process is prevented, and no wrinkles or crepe wrinkles are generated, and the wrinkles (grade) and dimensional change ratio after washing are excellent. The resulting shirt is obtained. The shirts of Example 1 and Comparative Example 2 were repeatedly washed 50 times, and wrinkles (grade) and dimensional change after washing were measured. The results are shown in Table 4 below.

[Table 4]

From Table 4, it can be seen from the table that the shirt of Example 1 had little change in the initial level of wrinkles (grade) after washing up to 30 times of repeated washing, and the dimensional change after washing was small even after repeated washing. However, the shirt was durable for long-term use. In Comparative Example 1, the wrinkles (grade) after the initial washing were low, and the wrinkles (grade) after the washing decreased with repeated washing. In Comparative Example 1, the dimensional change rate after washing was large from the beginning, and the dimensional change rate increased as washing was repeated. Next, the shirts of Example 1 and Comparative Example 1 were repeatedly washed, and the five A determination of rilation was made. FIG. 1 is a photograph taken by a scanning electron microscope (SEM, the same applies hereinafter) of the cellulose fiber single yarn surface of the shirt of Example 1, and FIG. 2 is an electron micrograph of the cellulose fiber single yarn surface of the shirt of Comparative Example 1. The images were taken with a microscope and all of them were before washing, and it was determined that there was no fibrillation. FIG. 3 is a photograph of the cellulose fiber single yarn surface of the shirt of Example 1 taken with an electron microscope after washing 30 times, and it can be determined that fibrillation has hardly progressed. Fig. 4 is a photograph of the cellulose fiber single yarn surface of the shirt of Comparative Example 1 after washing 30 times, taken with an electron microscope. Fibrillation has progressed greatly. More specifically, in FIG. 1 of Example 1, the photograph of FIG. 1 (a) was photographed at a magnification of 2,000, and the side surfaces of a plurality of single yarns were photographed. The photographs in FIGS. 1 (b) and 1 (c) were taken at 100,000 magnifications, and each photographed the surface of a single yarn. As shown in the figure, the surface of the single yarn has a mountain-like morphology that seems to have reacted with the treating agent, and the reaction state differs between the single yarns. In FIG. 2 of Comparative Example 1, the photograph of FIG. 2 (a) was photographed at 2,000 times, and the side surfaces of a plurality of single yarns were photographed. The photographs in Figs. 2 (b) and 2 (c) were taken at a magnification of 100,000 and each photographed the surface of a single yarn. As shown in the figure, the mountain-like shape on the surface of the single yarn is smoother than in FIG. 1, and there is no difference in the mountain-like shape between the single yarns. Fig. 3 is a side photograph of the cellulose monofilament after washing the shirt of Example 1 30 times. The photograph of Fig. 3 (a) was photographed at 2,000 times, and the side surfaces of a plurality of single yarns were observed. Have been taken. Damage to the single yarn after 30 washes is a slight bead on the surface of the second yarn from the right, which is the only sign of damage. The photographs in Figs. 3 (b) and 3 (c) were taken at 100,000 magnifications, and each photographed the surface of a single yarn. As shown in the figure, the cross section of the cotton fiber is flat, and the width of the single fiber varies from middle to bottom depending on the shooting direction. No damage to the cellulose fibers due to washing can be found from the photographs in Figs. 3 (b) and (c). No. FIG. 4 is a photograph of cellulose single fibers after washing the shirt of Comparative Example 1 30 times. The photograph in Fig. 4 (a) is a side photograph of a plurality of single fibers taken at a magnification of 2,000, and a large number of mustaches are observed on the surface of the single yarn. This is a fibrillated cellulosic fiber that has been worn and worn by washing. The photographs in Figs. 4 (b) and (c) each photograph the surface of one single fiber at a magnification of 1,000. As shown, a large number of fibrillated products are observed. From these facts, it can be seen that the cellulose monofilament of the shirt according to the method of the present invention does not fibrillate even after washing 30 times, and the washing durability is high. On the other hand, in the case of natural unprocessed cellulose fiber, the surface of the single fiber became fibrillated after 30 washes, and surface peeling began to occur, indicating that the washing durability was low. As described above, the cotton sewn product according to the method of the present invention has no wrinkles (grade) after washing, no dimensional change after washing, and no surface damage of the fiber even after repeated washing, and can be used for a long time. It can be seen that there is high form stability and no damage due to washing.

(Comparative examples 2, 3, 4, 5, 6, 7)

As the cellulose fiber sewn product, a cotton shirt (50 single yarn, 144 x 80 lines, Z inch) was used. The shirt before immersion was ironed in the sewing process and then transported in a package that would not cause wrinkles. This shirt was sequentially passed through each step under the conditions shown in Fifth, to give the morphological stability of Comparative Examples 2, 4, 5, 6, and 7. After the dewatering, the processing liquid was drained by adjusting the time of the dewatering step so that the treatment liquid was 80% of the weight of the shirt. [Table 5]

In Comparative Examples 2 to 7, while the shirt was immersed in the treatment liquid in the immersion step, the specimen was immersed for 10 minutes, then the shirt was taken out of the treatment liquid, and a centrifugal separator having an inner diameter of 106 cm was used. The treatment liquid remaining on the shirt after draining was adjusted to be 80% of the shirt weight. For Comparative Examples 2 to 8, the wrinkles (grade) after 5 times of washing and the dimensional change rate after 5 times of washing were measured, and the presence or absence of folded wrinkles and creases were determined. Table 6 shows the results. [Table 6]

According to Table 6, in Comparative Example 2, since the treatment liquid was reversed, creases occurred on the wrinkles after washing, and the appearance quality of the obtained shirt was low. The reversal of the treatment liquid during the immersion process has the effect of squeezing the shirt fabric in the forward and reverse directions, and this history of the immersion process seems to have become apparent after curing. In Comparative Example 3, the obtained shirt had wrinkles, and the appearance quality was low. It is considered that the wrinkles against which the shutter was pressed by the high centrifugal force became apparent. Comparative Example 4 Wrinkles occurred after washing, the amount of shirt filling in the dryer was high, the movement of the shirt in the dryer was suppressed, and wrinkles when put in the dryer became apparent after washing. It seems to have done. Then, the obtained product has a wrinkled shirt Appearance quality is low. In Comparative Example 5, creases and crepe wrinkles were present, and the appearance quality of the obtained shirt was low. Probably, the reaction of the morphological stabilizer progressed in the dryer, and the shirt was once pressed in the pressing process to increase wrinkles, but the wrinkles in the dryer were apparently caused by washing. In Comparative Example 6, wrinkles were frequently generated after washing, which is probably due to the fact that the wrinkles generated before that were not suppressed in the pressing step. In Comparative Example 7, the obtained product had many wrinkles and creases. Probably, the reaction of the morphological stabilizer did not progress during the curing process. Next, photographs of the surface of the cellulose fiber sewn product of Example 1, Comparative Example 1, Comparative Example 2, and Comparative Example 4 were taken. FIG. 5 shows the results of Example 1, FIG. 6 shows the results of Comparative Example 1, FIG. 8 shows the results of Comparative Example 2, and FIG. 7 shows the results of Comparative Example 4. In Example 1, there was no major defect, and there was no problem in appearance quality. In Comparative Example 1, deep wrinkles were generated at an acute angle, and the appearance quality was low in terms of form stability of the sewn product of cellulose fiber, so that the product was not practical. In Comparative Example 2, a large number of crepe wrinkles occurred, which was unsuitable as a form-stable cellulose fiber sewing product. In Comparative Example 2, the treatment liquid flows during the immersion step when applying the form stability.In Comparative Example 4, a large pressure is applied when applying the form stability, and under these conditions, a cellulose fiber sewn product having excellent appearance performance Cannot be obtained. In Comparative Example 2, a large number of small wrinkles were observed, and these were regarded as reduced surface wrinkles. Also, in Comparative Example 4, there was a long streak-like wrinkle on the right side of the photograph (FIG. 7), which was regarded as a folded wrinkle.

(Example 8, Comparative Example 8)

A hemp blouse (60 single yarn, 52 x 56 inches) was used as the cellulose fiber sewing product. After ironing in the process, creases occur It was transported in such a package. In Example 8, form stabilization was applied to the hemp blouse from the dipping step to the curing step under the same conditions as in Example 1. The blouse after the deliquoring was subjected to a deliquoring step time adjustment so that the treatment liquid was 80% of the weight of the blouse, and liquored. Comparative Example 8 is a hemp blouse to which no form stability was imparted. In Comparative Example 8, a blouse made of natural hemp not subjected to morphological stability was used. The blouses of Example 8 and Comparative Example 8 were compared with wrinkles (grade) after 5 times of washing, creases after washing, creases after washing, dimensional change rate, and damage during washing, and blouses before washing. The touch of the blouse after washing was measured. Table 7 shows the results.

[Table 7]

* 1 Visual judgment using a loupe.

* 2 Judged by wearing test.

In Table 7, in Example 8 and Comparative Example, a large difference was observed in wrinkles (grade) after 5 times of washing, folded wrinkles after washing, crepe after washing, and dimensional change rate. Also wash No damage was observed by rinsing in Example 8, but in Comparative Example 8, fluff was observed at the sites shown in Table 7, and fiber cutting had begun. Furthermore, in terms of the blouse's feel, Example 8 was superior to Comparative Example 8 even before washing, but Example 8 did not change after washing, whereas Comparative Example 8 had a firmer hardness after washing. Was increasing. As a result, the blouse of Example 8 after the washing was a blouse with much better touch than that of Comparative Example 7. The resulting hemp blouse showed good results in terms of wrinkles (grade) after 5 washes, creases after washing, creases after washing, dimensional change, and damage during washing. From this, it was found that the method of the present invention provided high form stability and no damage due to washing using a sewn product of cellulose fiber.

(Comparative Examples 9, 10 and 11 and 12 and 13 and 14)

Adjust the composition of the treatment solution shown in Table 8, and sew a cotton white shirt (50 single yarn, 144 x 80 inches) into these treatment solutions for 10 minutes for cellulose fiber sewing products. After passing through the process, the treatment liquid of 80% by mass of the shirt is attached to the shirt, and then dried with a tumbler dryer at 50 at 30 minutes, and then the shirt is pressed with an iron at 170, In addition, curing was performed at 160 for 3 minutes.

[Table 8]

* 1 The form stabilizer is 4,5-dihydroxy-1,3-dimethyl-2-imidazolidinone and contains 30% by mass of a dimer.

* 2 The catalyst is magnesium sulfate (7 hydrate) / magnesium nitrate (6 hydrate) in a weight ratio of 7Z3.

Form Stability of Shirts Obtained in Comparative Examples 9, 10, 11, 12, 13 and 14 For Comparative Examples 2 to 8, wrinkles (grade) after 5 times of washing, dimensions after 5 times of washing The rate of change was measured, and the presence or absence of wrinkles and creases and the color of the shirt were determined. Table 9 shows the results.

[Table 9]

As shown in Table 9, in Comparative Example 9, the obtained shirt had poor wrinkle (grade) after 5 washes, a large dimensional change rate, and low form stability. This is probably because the content of the morphological stabilizer in the treatment liquid was small. The color of the shirt obtained in Comparative Example 10 was yellowed, and the processing solution contained an excessive amount of a morphological stabilizer that could be practically used as the appearance quality, which seems to be the cause of yellowing. In Comparative Example 11, the obtained shirt had poor wrinkle (grade) after 5 washes, a large dimensional change rate, and low form stability. It is considered that the amount of catalyst in the processing solution was low, and morphological stability could not be obtained. The color of the yellowish powder obtained in Comparative Example 12 is yellow, and cannot be put to practical use as the appearance quality. Excess catalyst was present in the processing solution, which may have caused yellowing. The shirt obtained in Comparative Example 13 had poor wrinkles (grade) after 5 washes, a large dimensional change rate, and low form stability. High pH in processing solution, reaction of morphological stabilizer First, it seems that morphological stability could not be obtained. The color of the shirt obtained in Comparative Example 14 was yellow, and in addition, the strength of the shirt fabric was low, so that the shirt could not be used practically. The pH of the treatment solution is acidic, which may be the cause of the quality deterioration of the shirt.

(Example 9, 1 0, 1 1, 1 2)

The composition of the treatment solution shown in Table 10 was adjusted. For a cellulose fiber sewn product, a cotton white shirt (50 single yarn, 144 x 80 inches) was immersed in these treatment solutions for 10 minutes. After the treatment liquid of 80% by mass of the shirt is adhered to the shirt, it is dried with a tumbler dryer at 50 for 30 minutes, and then the shirt is pressed with an iron of 170, and further, with 16 O: Curing was performed for 3 minutes.

[Table 10]

* 1 The form stabilizer is 4,5-dihydroxy-1,3-dimethyl-2-imidazolidino Containing 30% by weight of dimer.

* 2 The catalyst is magnesium sulfate (7 hydrate) / magnesium nitrate (6 hydrate) in a weight ratio of 7/3. Example 9 For the comparative example 28 of the morphological stability of the shirt obtained in 101 1 1 1 2 13, the wrinkles (grade) after 5 times of washing and the dimensional change rate after 5 times of washing were measured. The presence or absence of creases and creases and the color of the shirt were determined. Table 11 shows the results. 【table

In addition, the whiteness of the shirts obtained in Example 9 11 1 1 1 2 13 was all satisfactory. From Table 11, the shirts obtained in Example 9 1 0 1 1 1 2 13 show that the wrinkles (grade) after 5 washes show a high series, and the dimensional change rates show a low value. It was found that there was good morphological stability. Next, for the shirt obtained in Example 1 and the shirt of Comparative Example 1, cellulose single fibers were collected from each shirt. Next, each single yarn was tested for copper hydroxyethylenediamine swelling and solubility. The single yarn of Example 1 did not dissolve and swelled. This was photographed with an electron microscope. Figure 9 shows the photograph taken. According to FIG. 9, the single fiber of Example 1 was not dissolved by the aqueous solution of copper hydroxyethylene diamine. On the other hand, the single fiber of Comparative Example 1 dissolved and became a solution, and it was not possible to take an image with an electron microscope. Usually, a difference in the solubility of the sample indicates that there is a difference in the chemical structure of the sample, and the chemical structure is different between Example 1 and Comparative Example 1. In addition, according to FIG. 9, except for the hole present in the center of the cellulose single fiber, no portion seemingly missing due to dissolution by the aqueous solution of copper hydroxyethylene diamine can be found. Therefore, it seems that the chemical structure of all the sites of the cellulose single fiber was changed by the method of the present invention. With this change in chemical structure, it is presumed that the sewn cellulose fiber product according to the method of the present invention can obtain not only form stability but also durability and soft touch during washing. The hole in the center of Fig. 9 is a slit-like narrow gap that exists when the cotton single fiber is not processed, which is deformed into a circular shape by the swelling of the single fiber. It was not eluted by Next, in the products of Examples 1, 8, 9, 10, 10, 11, 12, and 13 and Comparative Examples 9, 10, 11, and 13, the amount of resin fixed on the cellulose fiber and the touch were evaluated. The relationship with the characteristics of was investigated. The results are shown in Table 12 below. As can be seen from this table, it can be said that, when the resin fixing amount is in the range of 1.8 to 3.2%, characteristics such as touch to the skin are excellent. The touch characteristics were evaluated by a touch method after 5 washings. Other characteristics are as described above. [Table 1 2]

Industrial applicability

As described above, according to the production method of the present invention, the sewn cellulose fiber product can be directly subjected to the morphological stabilization treatment, and the obtained product has excellent appearance characteristics.

Claims

The scope of the claims

1. An immersion step of impregnating the cellulose fiber sewn product with a treatment liquid containing a form stabilizer, a dewatering step of removing excess treatment liquid from the cellulose fiber sewn product, and adhering to the cellulose fiber sewn product. A drying step of evaporating and removing the solvent in the treated liquid, a pressing step of expanding wrinkles of the sewn cellulose fiber product, and a form stabilizer attached to the sewn cellulose fiber product reacting to impart morphological stability. The method for producing a morphologically stable cellulose fiber sewn product having a curing step, wherein the morphological stabilizer does not produce formalin as a by-product, and further includes a press wrinkle removing step performed prior to the dipping step. The manufacturing method, characterized in that the drying step is performed under the condition that wrinkles do not occur in the sewn cellulose fiber product.

2. The drying step is performed by a rotary dryer, and the filling condition of the cellulose fiber sewing product to be charged into the rotary dryer is 5 to 30 kg / m.

^{3. The} method according to claim 1, wherein the method is ³ .

3. The production method according to claim 1, wherein the immersion step is performed under conditions that do not cause wrinkles in the sewn cellulose fiber product.

4. The immersion step, wherein the treatment liquid does not flow or flows in one direction relative to the cellulose fiber sewn product, and the flow rate is in a range of 0 to 50 mZ. Manufacturing method.

5. The method according to claim 1, wherein the drying step is performed in a state where the sewn cellulose fiber product is in a free shrinkage state.

6. The method according to claim 1, wherein the form stabilizer is 4,5-dihydroxy-1,3-dimethyl-2-imidazolidinone or a dimer thereof.

7. The temperature condition of the drying step is in a range of 40 to 70, the temperature condition of the pressing step is in a range of 160 to 18 O :, and the temperature condition of the curing step is in a range of 150 to 170. The manufacturing method according to claim 1, wherein

8. In the immersion liquid, the content of the morphological stabilizer is in the range of 4.5 to 6.5% by mass of the entire immersion liquid, and further contains a catalyst. 2. The method according to claim 1, wherein the pH is in the range of 15 to 30% by mass of the agent and the pH is in the range of 4 to 4.9.

9. The production method according to claim 6, wherein the content of the form stabilizer is in a range of 20 to 40% by mass.

10. The catalyst is a mixture of magnesium sulfate and magnesium nitrate, and the ratio is 20 to 25% by mass of magnesium nitrate and 80 to 75% by mass of magnesium sulfate in terms of magnesium amount. The manufacturing method according to claim 8.

1 1. The method according to claim 8, wherein the content of the treatment liquid contained in the sewn cellulose fiber product after the liquid removal step is 70 to 90% by mass of the sewn cellulose fiber product.

1 2. A morphologically stable cell mouth fabric sewn product in which the fixation ratio of the form stabilizer resin fixed to the cellulose fibers is in the range of 1.5 to 3.0% by mass based on the cell mouth fibers.

1 3. A morphologically stable cell mouth fabric sewn product produced by the method of claim 1.

14. The sewing of the form-stable cellulose fiber according to claim 12, comprising at least one fiber selected from the group consisting of cotton fiber, hemp fiber, regenerated cellulose fiber, and silk-processed fiber of each fiber. Product.

1 5. The form-stable cellulose fiber sewn product according to claim 12, wherein the product form is a woven or knitted fabric.

1 6. The form-stable cellulose fiber sewing product according to claim 12, wherein the type of the product is an outer garment, a middle garment, an underwear, a bedding product, or a decorative product.