EP1164219A1

EP1164219A1 - A method for manufacturing washable wool fabric

Info

Publication number: EP1164219A1
Application number: EP00112717A
Authority: EP
Inventors: Keiichiro Kanehisa
Original assignee: Sumitomo Corp
Current assignee: Sumitomo Corp
Priority date: 2000-06-15
Filing date: 2000-06-15
Publication date: 2001-12-19

Abstract

A method for manufacturing washable wool fabric having excellent shrink resistance and form stability wherein wool in a state of fiber, a bundle of fibers, yarn or fabric is took off scales by chemically decomposing chains of protein composing scales, and then it is soaked in a treatment tank containing cyanuric chloride or its induction with neutral or weak alkali water in room temperature, amino group of wool and cyanuric chloride or its induction compose skeletal triazine according to the reaction in Formula I and chain is restructured, and wool fabric manufactured by such method.

Description

FIELD OF THE INVENTION

The present invention relates to a method for manufacturing washable wool fabric having excellent shrink resistance and form stability and a wool fabric manufactured by the same method.

RELATED ART

Wool fabrics made of wool, which is natural material, has been inherited traditionally from the ancient Greek age to the present, and they have characteristics of heat trapping, moisture absorbing, flame proof and elasticity.
Scales on a surface of a wool fiber are lined always in a direction from the root to the top regularly as like barks of a bamboo shoot. Therefore, it feels smooth if stroked in the direction to the top, but caught if stroked otherwise. That is to say, it has so-called "friction effect in different directions". This characteristic of wool is emphasized when it is soaked during, for example, washing because water and force act against the wool and the fiber containing water swells so as to open the scales. Difference of fiber movement becomes bigger, so fibers shrink as they get entangled in each other. This is shrinking peculiar to sheep wool fibers and called "felting phenomenon". But the felting phenomenon does not occur in a dry state or in a dry cleaning solution.
Thick woven fabrics such as winter over coat for protection against the cold are made using the felting phenomenon, but the felting phenomenon becomes a shortcoming of wool in the washing point of view. That is to say, if wool clothes such as sweaters are washed at home they shrink or are felted to form piles on the surface. In order to prevent wool from shrinking and because of the other reasons. wool is subjected to many kinds of form stability processes or treatments.
First, one of the form stability treatments is ZAPRO flame proof processing. This processing was studied in IWS Development Center in the U.K. and published as "ZAPRO Processing" in 1971. It was developed based on the fact that wool is hardly flammable if dyed black or navy blue using metallic chromium compound when flameproof regulation was imposed. It is a chemical bonding method of the wool fiber wherein metallic ion is bonded to amino group by using metal complex salt such as titanium and zirconium. This processing is practiced widely because it is easy and is similar to wool dying process and does not damage qualities peculiar to wool. However, the practice has been regulated for necessity to treat drainage as an industrial waste and the other reasons.
The second one of the form stability processes is aqua-dust process. In this process resin-treated wool is disposed inside and an off-scale wool is disposed outside of a wool product. It is a new art of the wool product for sports use that absorbs sweat well and does not stick to skin when playing a sport, and makes it possible to be washable. The wool product is resin-treated for a washable function but treatment is unstable so it is feared for affecting human bodies in skin or the other disorders. Further, off-scale of wool may be effective for prevention of shrinking, but the off-scale alone cannot prevent felting caused by washing.
The third one is a processing method which can remove scales without damaging wool fiber core by a special chlorination processing technique which causes wool to also have a feeling of silk at a feeling processing. Chlorination using hypochlorite, which gives shrink resistance by rounding off the comers of scales, is a classic method. Recently a processing method by dichloro-isocyanuric acid salt or by dissolving sulfuryl chloride into organic solvent is also used. But it is impossible to get shrink resistance only from these methods, wool is processed by polyurethane resin adhered with fine ceramics or polyamide epichlorohydrin resin. However, these processes damage comfortable quality of wool by hardening for giving a washable function with a resin process.
As the prior arts described above, it is possible to give wool the washable function by the use of specific agent or resin process. But changing quality of material causes environmental, health, or other problems so it is impossible to use these processes practically even though they correspond to the needs of consumers.
Moreover, the form stability of wool according to these processes does not practice cross linking reaction described below in amino group of the wool, so if the wool is processed by these processes, wool gets injured or becomes inferior in stretch. These also cause hardening of material itself.
By the way, wool is a fiber of animals' fur, and raw silk is also an animal fiber of cocoons. Raw silk is comprised of fibroin, a main body of silk, with sericin having a glue quality gluing around the fibroin. Usually silk products are used as in forms of only fibroin (silk) while the sericin has been removed by scouring. However, raw silk is also used without removing sericin for special uses such as decorative fabric, organdy, etc. Therefore, as a process that makes sericin not to dissolve in warm water or alkali, sericin fixing method is known.
The sericin fixing method for raw silk has many kinds of processing methods and many solvents etc. have been developed. The sericin fixing methods use the following:
1. Kind of Aldehyde:
Formalin, Glutaric Aldehyde, Dialdehyde Starch, Acrylic Aldehyde
2. Kind of Heavy Metal Salt:
Chrome Alum, Dichromate+Reducing Reagent, Aluminium Alum, Acrylic Aldehyde
3. Tannin
4. Synthetic Resin
Melanine, DMEU, Epoxide
5. Cyanuric Chloride and Reacting Dyes of Dichlorotriazine Type
Among these sericin fixing methods, the methods using formalin, glutaric aldehyde, chromium salt, and cyanuric chloride and reacting dyes of dichlorotriazine type are proved to be highly useful up to now in the sericin fixing level.
However, the method using a kind of formalin affects human bodies strongly and it is very dangerous. So it is not preferable. The method using chromium salt is not the best method because of conditions such as industrial waste, and the method using synthetic resin is also not the best because the processing is unstable, the feeling is hardened, and the effect to human bodies such as skin disorders are feared.
The present invention for the first time applies one of the described sericin fixing method of raw silk which does not have these problems to wool after chemically taking off scales which may cause shrink and felt. Namely, the method composes skeletal triazine by amino group of wool and cyanuric chloride or its induction (which contains cyanuric acid salt) so that it improves innovatively the characteristics of wool, such as shrink resistance, form stability and washability.

DISCLOSURE OF THE INVENTION

According to the present invention solves the problems of the prior art and improves qualities of wool, and aims to provide the method for manufacturing wool fabric which has shrink resistance, form stability and washability and wool fabric manufactured by such method.
The first aspect of the present invention provides a method for manufacturing washable wool fabric having excellent shrink resistance and form stability wherein wool in a state of fiber, a bundle of fibers, yarn or fabric is took off scales by chemically decomposing chains of protein composing scales, and then it is soaked in a treatment tank containing cyanuric chloride or its induction with neutral or weak alkali water in room temperature, amino group of wool and cyanuric chloride or its induction compose skeletal triazine according to the reaction in Formula 1 and chain is restructured.
The invention described in Claim 2 relates to the method for manufacturing wool fabric according to Claim 1 being characterized in that said taking off scales takes place when wool in a state of fiber, a bundle of fibers, yarn or fabric is dyed by dye.
The invention described in Claim 3 relates to the method for manufacturing wool fabric according to Claim 2 being characterized in that said dye comprises acid dye decomposing chained-polypeptide bondings of wool scales hydrolysisly so that the scales are took off.
The invention described in Claim 4 relates to the method for manufacturing wool fabric according to any one of Claim 1-3 being characterized in that Ph in said treatment tank is adjusted in the range of 8.0-9.0 by adding sodium hydrogencarbonate diluted to a certain rate.
The invention described in Claim 5 relates to the method for manufacturing wool fabric according to any one of Claim 1-4 being characterized in that said cyanuric chloride or its induction is processed in 3-4 owf% to water in room temperature.
The invention described in Claim 6 relates to the method for manufacturing wool fabric according to Claim 5 being characterized in that equal amount of water in room temperature and cyanuric chloride or its induction are put into the treatment tank at first, mixed by a mixer to micronize said cyanuric chloride or its induction which is not soluble in water, and, then, water as about ten times as much is added to dilute into a certain density.
The invention described in Claim 7 relates to the method for manufacturing wool fabric according to Claim 6 being characterized in that fabric ratio to liquid weight is 1:20-1:30.
The invention described in Claim 9 relates to the method for manufacturing wool fabric according to Claim 8 being characterized in that processing time is between 20 and 40 minutes.
The second aspect of the present invention provides a washable wool fabric having excellent shrink resistance and form stability wherein wool is took off scales by chemically decomposing chains of protein composing scales, and then amino group of wool and cyanuric chloride or its induction compose skeletal triazine according to the reaction in Formula 1 and chain is restructured, and said wool fabric being manufactured by the method for manufacturing wool fabric described in any one of Claims 1-9.

BRIEF EXPLANATION OF THE DRAWINGS

Figure 1 is a flow chart of one embodiment of the method for manufacturing wool fabric in accordance with the present invention.
Figures 2A-2F are electron microscope photographs of scales peculiar to wool; Figures 2A-2C and 2D-2F show original scale conditions of example materials A-C and scale conditions after being washed by water according to JIS 103 method, respectively.
Figures 3A-3F are electron microscope photographs of felting peculiar to wool; Figures 3A-3C and 3D-3F show original yarn conditions, after being woven and finished, of example materials A-C, and felting conditions after being washed by water according to JIS 103 method, respectively.

THE BEST MODE OF THE INVENTION

The method for manufacturing wool fabric which has shrink resistance, form stability and washability using wool and wool fabric manufactured by such method of the present invention is explained in details in the following.
First, the method for manufacturing wool in accordance with the present invention is described in details with using Figure 1.
At first, wool in a state of fiber, a bundle of fibers, yarn or fabric is treated chemically and scales are substantially took off from surface of wool. Typically, the treatment is carried out by oxidization breakdown of stycin SS bondings, selective main chain cutting from oxidization of polypeptide bondings, or decomposition of amino acid from oxidization to such as a part of tyrosine group. Said taking off scales may be carried out when wool is dyed by acid dye. By described procedures, chains of protein comprising scales are decomposed chemically and took off. As a matter of course, polypeptide bondings located at surface of wool fiber without scales are also weakened. In the present invention, washable wool fabric having excellent shrink resistance and form stability is manufactured by composing skeletal triazine according to the reaction in Formula 1 by amino group of wool and cyanuric chloride or its induction, and restructuring chain.
The procedures are described as the following. At first, processing water is prepared. This processing water is absorbed in processed goods (scales-off wool fiber, a bundle of fibers, yarn or fabric) for about two minutes.
Equal amount of water in room temperature and cyanuric chloride or its induction are put in a treatment tank, mixing them by a mixer. Cyanuric chloride, not soluble in water, needs to be mechanically micronized. Further, by diluting water to about ten times as much, micronization is continued or promoted. At this point, the amount of cyanuric chloride or its induction may be 10-11 owf%. Liquid ratio is preferable in 1:20-1:30. Woven wool fabric or wool yarns that are wound into a hank, a corn or a cheese is soaked in the processing water or solution in the treatment tank. At this stage sodium hydrogencarbonate liquid (diluted liquid as 20 times as much) is poured in for some minutes, for example, about three minutes. From this point, cross linking reaction between amino group of wool and cyanuric chloride or its induction starts to compose skeletal triazine according to the reaction in Formula 1.
For conducting the cross linking reaction evenly, the processing liquid comprised of cyanuric chloride or its induction is always circulated during its process and, at the same time, articles to be processed is turned regularly. The process is continued for 20-40 minutes, preferably for about 30 minutes. Ph of the processing liquid at this stage is suitable if neutral or slight alkali, i.e. 8.0-9.0. After discharging water, it is washed in fresh water in room temperature, then washed in warm water at temperature between 50 and 60C. After dehydrating and drying, cross linking reaction shall be finished. After the cross linking reaction process, the article is sent to the next process.

(The Embodiment and the Comparison)

Next, the difference of characteristics between the product of the present invention that is processed with using sericin fixing method described above and a comparison is examined.
First, as a yarn, natural wool material or its complex twisted yarn was used. These yarn and material was processed with using sericin fixing method. As a sericin fixing method, it is suitable to use cross linking reaction to organic molecules (skeletal triazine) which does not have inferior material feeling or problems of environment and health. In this method, it uses triazine bonding of cyanuric chloride or reacting dyes of dichlorotriazine type.

A. (Comparison)

Wool 2/60 was prepared. But it was not treated chemically for taking off scales. This wool was wound into a corn and dyed with reacting dye. Accordingly, scales were not took off and triazine bondings (cross reaction) was occurred by the reacting dye. (First dyeing at the state of yarn)

B. (Present Invention)

Wool 2/60 was prepared. This wool yarn was wound .into a corn and dyed with acid dye. In this embodiment, selective main chain cutting was occurred by oxidization of polypeptide bondings at the time of dyeing, amino acid as protein comprising scales was decomposed, and scales are substantially took off. Then sericin fixing method was conducted by cyanuric chloride (cyanuric acid salt) or its induction (first dyed in the state of yarn).

C. (Comparison)

A fabric woven with wool 2/60 (not off-scaled) was prepared. It also was not treated chemically for taking off scales. Then it was dyed with reacting dyes of dichlorotriazine type (after dyed in the state of fabric/piece dye).
These fabric are woven by Picanor GFS, Dobby weaving machine in which the number of rotations is 340rpm in accordance with the following specification:

Number of dents per unit length 27 dents (2 reeds)/inch

Reed space 68 centimeters

Total number of warps 3672

Perchers 52/inch
After finishing and processing these woven fabrics, numerical values of shrink resistance, form stability and washability and change of the conditions in electron microscope are shown in the tables (see Table 1). The Table 1 shows results of experiment judgments estimated by Foundational Juridical Person of Fur Product Examination Organization Naka-gun Examination Center (4-14-4,Kagoya, Bisai-shi, Aichi-ken, Japan; TEL. 0586-45-2631).
Washing method is shown in JIS0217 (based on regulation 103) and results in shrink resistance for each samples are described in columns "1^st time" and "2^nd time", and wrinkling results after washing are also shown.
In relief shrinkage percentage, results under I.W.S. TM317 and 5Ax5 are described. Further form keeping property under TM281

(smoothness of the fabric) is shown in the bottom column.

Figure 2 is electron microscope photographs of scales peculiar to wool, and Figure 3 is an electron microscope photograph of feltings peculiar to wool.
Table 1 is results of the experiments wherein each of the described fabric was experimented with respect to washing method, shrinkage percentage, wrinkles after washing, relief shrinkage percentage and form keeping property.

(Hereinafter, space)

Normal wool fabrics manufactured conventionally have many characteristics such as heat-trapping, moisture absorbing, flameproof and elasticity because they are natural fibers. However, needs of consumer diversifies and demands addition of other kinds of function to these materials. But natural material itself does not become form stable.
As known, wool has two layers of ortho-cortex and palla-cortex equally existed or disposed. This is called "bilateral structure" and its molecule structure and chemical composition in each part is different, so extreme cramps occur resulting in crimps. Further, the surface of wool is covered with scales that are very easily entangled to be easily felted.
Figures 3A-3F are electron microscopic photographs of the states of the crimps. As shown in Figs.3B and 3E, they proved that woven fabric off-scaled first by dying step and then processed with cyanuric chloride or its induction according to the present invention became form stable.
Figures 2A-2F are electron microscopic photographs of the states of the scales. Only the scales of wool in accordance with the present invention shown in Figure 2B had been removed substantially through dying process with acid dye. Thereafter the wool was processed with sericin fixing method. Therefore, no felting phenomenon was perceived.
As shown in Table I and Figures 3A and 3D, material using yarn dyed wool 2/60 ([A] Comparison) was not suitable in the view point of form stability and washability because it is processed with sericin fixing method without taking off scales and scales are more easily entangled than in a natural state. As shown in Table 1 and Figures 3C and 3F, Piece dyed wool 2/60 which was woven to a fabric using reacting dyes of dichlorotriazine type ([C] Comparison) did not felt so much (it is supposed that it is treated by sericin fixing method in a state of fabric so it could not fix sufficiently scales at the surface of wool fibers), but it had insufficient effect for shrink resistance.
As shown in Table 1 ([B] Present Invention) and Figures 3B and 3E, cross linking reaction between amino group of wool 2/60 in accordance with the present invention and cyanuric chloride might have brought shrink resistance, form stability and washability.
According to the present invention, the sericin fixing method of raw silk was able to prove improvement of functions such as shrink resistance, form stability and washability by the wool washability experiment without using formalin or resin treatment.
The prior arts comprise formalin, special agent or resin treatment, and these arts harden material or cause environmental and health problems. The cross linking reaction between the organic fibers and cyanuric chloride or its induction is conducted 100 percent in water in room temperature, and is not producing CO, NOx and dioxin unlike the prior processing art in high temperature. Further, when reaction is completed, water discharged becomes salt and water, so discharging water to rivers does not contaminate environment.
By an international conference for prevention of the Earth warming, dry-cleaning solvent used now is being banned or regulated globally.
The material processed by the present invention is washable, so it is possible to avoid dry-cleaning.
This invention is cooperated by Kyoto-fu, Kyoto Industrial Art and Fiber College, Osaka City College, and Kyoto-fu Woven Products Instruction Center.
This invention is acknowledged by New Industrial Department of Industrial Planning Department of Kinki Trade and Industrial Bureau, so it is extremely useful in industry.

Claims

A method for manufacturing washable wool fabric having excellent shrink resistance and form stability wherein scales are taken off from wool in a state of fiber, a bundle of fibers, yarn or fabric by chemically decomposing chains of protein composing scales, and then said wool is soaked in a treatment tank containing cyanuric chloride or its induction with neutral or weak alkaline water at room temperature, whereby amino groups of wool and cyanuric chloride or its induction compose skeletal triazine according to the reaction in Formula (1) and the chain is restructured.
The method for manufacturing wool fabric according to Claim 1 being characterized in that said taking off scales takes place when wool in a state of fiber, a bundle of fibers, yarn or fabric is dyed by a dye.
The method for manufacturing wool fabric according to Claim 2 being characterized in that said dye comprises acid dye decomposing chain-polypeptide bonds of wool scales by hydrolysis so that the scales are taken off.
The method for manufacturing wool fabric according to any one of Claim 1-3 being characterized in that the pH in said treatment tank is adjusted in the range of 8.0-9.0 by adding sodium hydrogencarbonate diluted to a certain rate.
The method for manufacturing wool fabric according to any one of Claims 1-4 being characterized in that said cyanuric chloride or its induction is processed at 3-4 % by weight in water at room temperature.
The method for manufacturing wool fabric according to Claim 5 being characterized in that an equal amount of water at room temperature and cyanuric chloride or its induction are put into the treatment tank at first, mixed by a mixer to micronize said cyanuric chloride or its induction which is not soluble in water, and, then, about ten times as much water is added to dilute to a certain percentage by weight.
The method for manufacturing wool fabric according to Claim 6 being characterized in that the ratio fabric to liquid weight is 1:20-1:30.
The method for manufacturing wool fabric according to any one of Claim 1-7 being characterized in that processing liquid comprising cyanuric chloride or its induction is always circulated during the processing and, at the same time, articles to be processed are turned regularly.
The method for manufacturing wool fabric according to Claim 8 being characterized in that processing time is between 20 and 40 minutes.
A washable wool fabric having excellent shrink resistance and form stability wherein scales have been taken off from wool said by chemically decomposing chains of protein composing scales, and then amino groups of said wool and cyanuric chloride or its induction compose skeletal triazine according to the reaction in Formula (1) and the chain is restructured, and said wool fabric being manufactured by the method for manufacturing wool fabric described in any one of Claims 1-9.