JPH0578983A - Shrink proofing method of wool - Google Patents

Abstract

PURPOSE:To carry out shrink proofing reduced in damage of wool and change of handle by previously subjecting a wool fiber to reducing treatment with tetrakishydroxymethylphosphonium sulfate and subjecting the treated wool fiber to resin finishing. CONSTITUTION:Wool fiber is subjected to reducing treatment in an aqueous solution of tetrakishydroxymethylphosphonium sulfate previously controlled to alkaline side and then subjected to dipping treatment, preferably in a water soluble polyether based urethane resin solution to make the resin absorbed in the wool fiber and then dried and heat-treated. According to the method, damage of wool is reduced and excellent shrink proofing is promoted and the process can be also remarkably simplified and is advantageous. Furthermore, when magnesium chloride is added to the solution in the shrink proofing, absorption of the resin can be promoted.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for shrink-proofing wool, and more particularly, to a method for covering the scale on the surface of a wool fiber with a polymer to reduce the catching of fibers with each other by scale edges.

[0002]

2. Description of the Related Art The shrink-proofing method of wool which has been industrialized at present is that the surface of a wool fiber is chemically treated, generally by various oxidization treatments, and then the resin is processed. Or, it is the mainstream to use a polyurethane-based resin to bond the wool fibers to each other to suppress the movement of the fibers to obtain a shrink-proof effect.

For the first oxidation treatment of wool fibers, strong oxidizing agents such as chlorine gas, sodium hypochlorite, dichloroisocyanuric acid and potassium permanganate are used, so that the processing conditions are strictly controlled. If not done, there is a constant risk of fatal damage to the wool. In order to avoid this risk, continuous devices have been developed for each material form to be processed (loose hair, top, woven fabric, etc.), but the investment amount is enormous.

In the second mere resin processing method, since the treatment is performed only with the resin, there is no attack on the wool fiber itself, and thus the wool is prevented from being damaged, but at least 2-3%.
If the resin solid content does not adhere to a certain degree, a satisfactory shrink-proof effect cannot be obtained. Therefore, the use of high-concentration resin liquid is indispensable, and the texture is hardened accordingly, and the variation in hardness (texture) is caused by the migration of the resin component (migration) on the processed material after padding. There is a risk that the resin may adhere to the surface of the resin or unnecessarily, and that a resin film may be formed on the surface of the padding roll (mangle roll). In addition, the urethane resin film is formed by the progress of the self-crosslinking reaction between the urethane resins to achieve the purpose. However, since the appropriate water retention is required for the progress of this reaction, preliminary drying and high temperature curing (resin However, there is a problem that it is necessary to connect these equipment and the padding equipment continuously, and a huge capital investment is required. Become.

Further, in the case of padding a circular knit, it is necessary to perform padding after opening (circular knitting is cut into a cloth shape), and a curling prevention device and a tension adjusting device are used as processing equipment. You will also need to wear.

In order to avoid the above problems of various shrink-proof processing methods, the development of an efficient absorption method by utilizing existing dyeing equipment (jet dyeing machine, wins, etc.) and the efficient absorption of resin Therefore, it is important to develop a pretreatment method that contributes to fixing in the wool fiber and minimizes damage to the wool fiber.

As a shrink-proofing method by the absorption method, which mainly uses silicone resin for wool knit products (mainly sweaters), wool pretreated with a mild oxidizer such as potassium monopersulfate is used for silicone resin. The Crosil processing method for adsorbing is known, but the processing process is complicated.

Also, several attempts in the past to try to use polyurethane resins in absorption methods have been tested in the literature, see Bayer.
The company has also proposed a method for knit products, which uses magnesium chloride and a polyurethane resin in combination, but there are problems that the process is complicated and a satisfactory effect cannot be obtained.

[0009]

Based on the above-mentioned problems, the inventor applied the reducing property of tetrakishydroxymethylphosphonium sulphate (THPS) for the purpose of improving the shrinkage prevention effect and simplifying the process, and The fiber is subjected to a reduction treatment to cleave the cystine bond (-SS-bond) of wool cystine to generate a thiol group (-SH),
After washing with water, absorb the polyurethane resin using magnesium chloride (MgCl ₂ · 6H ₂ O) as a catalyst, and then adjust the texture with a softener if necessary to minimize the damage to the wool fiber and maximize the shrink resistance. It was possible to obtain a good pilling prevention effect together with the effect.

Further, according to this method, shrink-proofing treatment before dyeing and post-treatment of dyed products except leveling acid dye (leveling type acid dye) dyeing are possible.

Further, there is an advantage that a knit can be processed into a circular knit shape before and after dyeing.

THPS is an organophosphorus compound having the following chemical formula: (HOCH ₂ ) ₄ P ⁺ · ½ (SO ₄ ²⁻ ) This THPS acts as a strong reducing agent for wool fibers and produces thiol groups by reduction.

As the polyurethane resin to be absorbed after the reduction treatment, a water-soluble polyether urethane resin is preferable. Examples of such resins include synaplet BAP
(Synthaprep BAP, manufactured by Bayer),
Elastron BAP (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) and the like are commercially available. These are low-temperature dissociative isocyanates whose functional groups are blocked with sodium bisulfite (NaHSO ₃ ) as shown by the following formula.

[0014]

[Chemical 1]

In this way, Syntaprep BA
P has three carbamoyl sulfonate groups in one molecule, and reacts rapidly under alkaline conditions to promote self-crosslinking.

It is considered that the carbamoyl sulfonate group in this molecule reacts with the thiol group of wool produced by the reducing action of THPS as follows.

W-SH + NaSO ₃ CONH-Polymer → WS-CONH-Polymer In the treatment bath, the reaction with W-SH precedes, and as the reaction progresses, the exhaustion of the polymer progresses to about 50 ° C. At the bath temperature, the self-crosslinking of the polymer is considered to proceed with a delay. The self-crosslinking level increases with the passage of time and does not fall off easily in the subsequent steps, and the drying and post-treatment 12
It is considered that self-crosslinking is completed by curing at about 0 ° C.

Thus, unlike the simple resin application by the padding method and the simple absorption by the absorption method, exhaustion is possible in addition to uniform absorption, and durability is obtained even after washing with water without falling off.

The scouring / washed woven fabric / circular knit, etc. are subjected to shrink-proofing by the method of the present invention before or after dyeing by a general method. This scouring and washing is performed in various types of washing machines and dyeing machines (Wind dyeing machine, jet dyeing machine, drum dyeing machine, paddle dyeing machine, etc.). Only when washed with a washing machine, the material is sufficiently washed with water and then taken out and put into a dyeing machine. Sometimes the dried one is put into the dyeing machine.

Next, the present invention will be described in detail step by step.

THPS pretreatment After the raw material was put into a dyeing machine, iron-free room temperature water was injected, and a wetting / deaerating / foam suppressing agent was added at 1% o. w. f (% by weight based on the weight of the processed material) is added. Then THPS
0.5-3.0% o. w. f, preferably 0.6 to
1.5% o. w. f is sufficiently dissolved in cold water, diluted and added. Furthermore, sodium carbonate (Na ₂ CO ₃ ) 0.8-
1.5% o. w. f or sodium bicarbonate (NaHCO
₃ ) 5.0-10.0% o. w. The pH of the treatment bath is 8.0 to 9.8, preferably 8.8 to 9.1 by dissolving and adding f.
Adjust the final bath volume to a bath ratio (ratio of total bath volume to processing material weight) of 1:15 to 40 (1:20 to 40 for Wins dyeing machine, drum dyeing and paddle dyeing machine, liquid flow). In the case of a dyeing machine, it is adjusted to 1: 15-30). The preferred bath ratio is 1: 20-30. It is natural to adjust the bath while operating the machine.

After continuing the operation for 5 minutes after the adjustment,
30 to 50 ° C, preferably 35 to 40 at 1.5 ° C / min
The temperature is raised to ℃ and the treatment is continued for 15 to 50 minutes. When the treatment is completed, drain the liquid, wash it with hot water in a new bath at 40 ° C and drain it.

Polyurethane resin absorption Normal temperature water was poured into the treatment machine, and the magnesium chloride (MgCl ₂ .6H ₂ O) aqueous solution was added in an amount of 4 to 10 while the machine was operating.
Add so that it becomes g / l. Then, a sodium bicarbonate aqueous solution is added so as to be 1 g / liter, and the pH of the treatment bath is adjusted to 7.0 to 8.0. The overall bath ratio is 1:15 to 40 (1:20 to 40 in the case of Wins dyeing machine / drum dyeing machine / paddle dyeing machine, 1:15 to 30 in the case of jet dyeing machine), preferably 1:20 -30.

After 5 minutes from the adjustment, at 1 to 1.5 ° C./minute,
Raise to 40-60 ° C, preferably 50 ° C,
Polyurethane resin (Syntha
prep BAP, elastron BAP and Impra
nil DLH / DLN / DLP dispersio
n, Superflex E-2000 / E-4000 at a mixing ratio of 30/70 to 50/50) 0.5 to
3.0% o. w. f independently of cold water or 40
Thoroughly dissolve and dilute with lukewarm water below ℃. In particular, Syntheprep BAP, Elastron B
Great care must be taken in the dissolution of AP. Treatment bath temperature is 4
When kept at 0 to 60 ° C, preferably 50 ° C, about 20
The state of approaching exhaustion in about 30 minutes can be observed by making the liquid transparent.

When the bath ratio is large, for example, when it is 1:25 or more, exhaustion may be insufficient. At this time, magnesium chloride is added at 2 g / liter or the bath temperature is increased by about 10 ° C. Exhaustion progresses. 40 to 90 minutes after the addition of the resin, the liquid is drained and washed with a new bath. This is a big difference from the padding method and the conventional absorption method.

If necessary, a new bath is prepared or a softening process is performed using a silicone type softening agent in the final washing bath.

Drying and curing Unlike the padding method, in the absorption method, the resin reacts with the wool, so there is no risk of resin transfer, so there is no need for continuous processes.

In the case of a circular knit, 8 through the opening process
After drying at a temperature of 5 to 100 ° C., curing can be performed at 120 ° C. for about 5 minutes, and the surface can be processed without stickiness.

It is also possible to carry out the drying and curing simultaneously at 120 ° C. for about 10 minutes.

Thus, in the case of post-dyeing, the dyeing machine is used again,
When dyed, it is sent to the finishing process.

As described above, the main point of the method of the present invention is to perform pretreatment by THPS. T
In the HPS treatment, the pH of the bath is important, and as the pH value increases, the reduction of wool increases, that is, the cleavage of cystine bonds increases. Therefore, the damage to the wool becomes large. On the contrary, if the pH is low, less thiol groups are produced,
This will affect the subsequent absorption of the polyurethane resin, making it difficult to obtain the desired shrink-proof effect. From the above, the pH value is 8.
The 8th to 9.1th positions are preferred. PH at the end of processing is 7.7-
It will be 8.0.

Also, the amount of THPS used has a great influence. Used in excess, eg 2.5% o. w. If you use more than f,
Pink coloring may be seen on wool. Therefore,
The amount used is 0.6-1.5% o. w. The f position is preferred.

The processing temperature and processing time also have an influence.

As described above, the THPS treatment causes less damage to wool than the oxidizer-using method, but if the conditions are incorrect, the damage will increase, so careful condition control is necessary. In the case of treatment with an oxidant, depending on the season of processing (especially summer), it is necessary to treat at a temperature lower than the ambient temperature.
With the S treatment, management of the treatment temperature is significantly advantageous.

[0035]

Example 1 1/40 wool 100% smooth circular knitted knit fabric was used as a processing material, and THPS (manufactured by Nippon Kagaku Kogyo Co., Ltd.)
0% o. w. f, Na ₂ CO ₃ 1.1% o. w. f,
L14 (neutral phosphate ester-based wetting / deaerating / foaming agent,
Made by Osaka Chemical Industry Co., Ltd.) 1.0% o. w. THPS treatment was carried out at 40 ° C. for 30 minutes in a treatment bath consisting of f (pH 8.8, bath ratio 1:20). This was washed with hot water and washed with water, and then dehydrated.

Next, MgCl ₂ .6H ₂ O 6.0 g /
Liter and a treatment bath (pH 7.8, bath ratio 1:20) consisting of 1.0 g / liter of NaHCO ₃ at 50 ° C. for 10 minutes, and then treated with Synthaplet BAP (Syntha).
prep BAP) 1.0% o. w. f and Impranil DLP Dispersion
(Dispersion, Bayer) 1.0% o.
w. f was added and treated at 50 ° C. for 60 minutes. This is washed with water and dehydrated, and then dried at 85 ° C for 15 minutes to obtain 120
It was cured at 10 ° C for 10 minutes.

The area shrinkage of the fabric thus shrink-proofed was evaluated by the following method (method A) to evaluate the shrinkage-proof effect. The area shrinkage was 8.8% after washing for 5 hours. It was

[Method A] According to IWS TM185. However, the test equipment is a household electric washing machine and NaH ₂ P
A test solution consisting of O ₄ 4.5 g / liter and Na ₂ HPO ₄ 8 g / liter was washed at a bath ratio of 1:30 at 40 ° C. for 60 minutes at a time, drained, and then replaced with room temperature water. Rinsing was carried out for 12 minutes at a bath ratio of 2 times by changing water each time. After dehydration, it was flat-dried and naturally dried, and then the area shrinkage ratio was measured. By repeating this, the area shrinkage rate is 10
The wash time until the percentage was exceeded was measured.

Example 2 As a polyurethane resin, Synthapret BA
P 1.0% o. w. f and Impranil DLN
dispersion 1.0% o. w. Shrinkproofing was performed in the same manner as in Example 1 except that f was used.

The area shrinkage was determined by Method A, and it was 4.48% after washing for 5 hours.

Comparative Example 1 The area shrinkage of a 1/40 wool 100% smooth circular knitted fabric which was not subjected to shrink-proofing was determined by method A, and was 36.41% after 1 hour of washing. ..

Comparative Example 2 Synthappr without pretreatment by THPS
et BAP 1.0% o. w. f and Impranil
DLP dispersion 1.0% o. w. f
Processed by.

When the area shrinkage was determined by the A method, it was 23.89% after 1 hour of washing.

Comparative Example 3 Synthappr without pretreatment by THPS
et BAP 1.0% o. w. f and Impranil
DLN dispersion 1.0% o. w. f
Processed by.

The area shrinkage was determined by the A method and was 16.28% after 1 hour of washing.

Example 3 Using 1/30 wool 100% strongly twisted worsted crepe fabric as a processing material, THPS 0.8% o. w. f, Na ₂
CO ₃ 1.1% o. w. f, L14 1.0% o.
w. Treatment bath consisting of f (pH 8.9, bath ratio 1:15)
Then, the THPS treatment was performed at 40 ° C. for 30 minutes. This was washed with hot water and washed with water, and then dehydrated.

Next, 6.0 g of MgCl ₂ .6H ₂ O /
Liter and NaHCO ₃ 1.0 g / liter in a treatment bath (pH 7.8, bath ratio 1:15) at 50 ° C. for 10 minutes, and then Synthappret BAP
1.0% o. w. f and Impranil DLN di
spersion 1.0% o. w. add f, 50
It was treated at 60 ° C for 60 minutes. After washing and dehydrating this,
It was dried at 85 ° C for 15 minutes and cured at 120 ° C for 10 minutes.

The area shrinkage of the woven fabric subjected to the shrink-proofing treatment in this manner was determined by the A method, and was 1.0 in a washing time of 3 hours.
%Met. Moreover, when a pilling test (ICI method) was performed, an improvement of about the second grade was observed before the shrink-proofing.

Example 4 As a polyurethane resin, Synthapret BA
P 0.5% o. w. f and Impranil DLN
Dispersion 0.5% o. w. Shrinkproofing was performed in the same manner as in Example 3 except that f was used. The area shrinkage was calculated by method A, and it was 8.33 after washing for 3 hours.
%Met. Moreover, when a pilling test (ICI method) was performed, an improvement of about the second grade was observed before the shrink-proofing.

The shrinkproof crepe fabric was dyed black with a general wool dyeing method using a chrome dye (acid mordant dye). When the area shrinkage ratio of the finished product was determined by the A method, it was 8.68% after washing for 3 hours.

Comparative Example 4 The area shrinkage of a 1/30 wool 100% strongly twisted worsted crepe woven fabric which has not been subjected to shrink-proofing was determined by the A method, and was 1
The washing time was 13.05%.

Example 5 As a processing material, the warp yarn is 2/48 wool 100% worsted yarn, the density is 272 yarns / 10 cm, and the weft yarn is 1/20 wool 1.
Using a woven fabric of 00% wool yarn and density of 193/10 cm,
Synthaprep BA as a polyurethane resin
P 0.5% o. w. f and Impranil DLN
Dispersion 0.5% o. w. Shrinkproofing was performed in the same manner as in Example 3 except that f was used. The area shrinkage was calculated by the A method, and it was 4.85 after washing for 3 hours.
%Met.

This shrinkproof fabric was dyed with chrome in the same manner as in Example 4, and the area shrinkage of the finished product was determined by method A to be 11.3% after washing for 3 hours. ..

Comparative Example 5 The area shrinkage was determined by method A without shrink-proofing the processed material (woven fabric) used in Example 5, and was 18.48% after 1 hour of washing.

Example 6 Using 2/60 wool 100% Tenjiku circular knit fabric as a processing material, THPS 1.0% o. w. f, Na ₂
CO ₃ 1.1% o. w. treatment bath (pH 8.
8. The THPS treatment was carried out at 40 ° C. for 30 minutes at a bath ratio of 1:20). This was washed with hot water and washed with water, and then dehydrated.

Then, MgCl ₂ .6H ₂ O 6.0 g /
Liter and a treatment bath (pH 7.0) consisting of 1.0 g / liter of NaHCO ₃ at 50 ° C. for 10 minutes, and then Synthapret BAP 2.0% o.
w. f was added and treated at 50 ° C. for 60 minutes. This is washed with water and dehydrated, and then dried at 85 ° C for 15 minutes to obtain 120
It was cured at 10 ° C for 10 minutes.

The area shrinkage of the thus-shrinkproofed fabric was evaluated by the method (method B) shown below, and the area shrinkage was 2.99%.

[Method B] According to JIS L 0217 103 method, using a household electric washing machine, a synthetic detergent for weakly alkaline clothes 2 g / liter, bath ratio 1:30, 40 ° C. × 3
After treatment for 0 minutes, the operation was stopped and the water was drained. Next, the water was replaced with fresh water at room temperature, and rinsed for 12 minutes with the same bath ratio by changing the water every time, twice, dehydrated, flat-dried, and naturally dried. After repeating the above operation once more, the area shrinkage ratio was measured.

Example 7 As a polyurethane resin, Synthapret BA
P 1.0% o. w. f and Impranil DLN
dispersion 1.0% o. w. Shrinkproofing was performed in the same manner as in Example 6 except that f was used.

When the area shrinkage ratio was calculated by the B method, it was 1.5.
%Met.

Comparative Example 6 The area shrinkage ratio of a 2/60 wool 100% plain knit circular knit fabric which has not been subjected to shrink-proofing was determined by the B method to be 1
It was 9.41%.

Example 8 A shrink-proofing process was carried out in the same manner as in Example 1 except that a 24 gauge 1/48 wool 100% smooth circular knitted knit fabric processed product was used as a processing material.

When the area shrinkage ratio was determined by the B method, it was 1.0
%Met.

Example 9 As a processing material, a 24 gauge 1/48 wool 100% smooth circular knitted knit fabric processed product was used, and as a polyurethane resin, Synthappret BAP 1.0%
o. w. f and Impranil DLN disper
sion 1.0% o. w. Example 1 except that f was used
Shrinkproof processing was performed in the same manner as in.

When the area shrinkage ratio was determined by the B method, it was 0.5.
%Met.

Comparative Example 7 24 gauge 1/48 wooles 10 without shrink-proofing
The area shrinkage rate of the 0% smooth circular knit knit fabric processed product was 21.15% as determined by the B method.

Example 10 As a processing material, 1/24 wool 100% Tenjiku circular knitted fabric milling type acid dye dark red dyeing product was used.
PS 0.8% o. w. f, Na ₂ CO ₃ 1.0%
o. w. f, L14 1.0% o. w. THPS treatment was carried out at 40 ° C. for 30 minutes in the treatment bath consisting of f (pH 8.95). This was washed with hot water and washed with water, and then dehydrated.

Then, MgCl ₂ .6H ₂ O 6.0 g /
Liter and NaHCO ₃ 1.0 g / liter in a treatment bath (pH 7.0) at 50 ° C. for 10 minutes, and then Synthapret BAP 0.75% o.
w. f and Impranil DLP dispersi
on 0.75% o. w. f was added and treated at 50 ° C. for 60 minutes. After washing and dehydrating this, 85 ℃ × 1
It was dried for 5 minutes and cured at 120 ° C. for 10 minutes.

The area shrinkage of the shrinkproof fabric thus obtained was determined by method A to be 6.5 after a washing time of 3 hours.
%Met. Further, when the hue difference before and after the shrink-proofing was measured by using a colorimeter Macbescala-Eye 2020 Plus, it was found that there was no problem in practical use.

As a comparative example, the area shrinkage ratio was determined by the A method without applying the shrink-proofing treatment.
It was 44%.

Example 11 As a processing material, 22 gage 1/48 wool 100% smooth circular knit knit fabric leveling type acid dye gray dyed product was used, and THPS 0.68% o. w. f, Na ₂
CO ₃ 0.85% o. w. f, L14 1.0% o.
w. The THPS treatment was carried out at 40 ° C. for 30 minutes in the treatment bath consisting of f. This was washed with hot water and washed with water, and then dehydrated.

Next, 6.0 g of MgCl ₂ .6H ₂ O /
Liter, treated with a treatment bath consisting of 1.0 g / liter of NaHCO ₃ at 50 ° C. for 10 minutes, and then treated with Syntha
prep BAP 0.5% o. w. f and Impra
nil DLP dispersion 0.5% o.
w. f was added and treated at 50 ° C. for 60 minutes. This is washed with water and dehydrated, and then dried at 85 ° C for 15 minutes to obtain 120
It was cured at 10 ° C for 10 minutes.

When the area shrinkage ratio of the fabric subjected to the shrink-proofing treatment in this way was determined by the A method, it was 10.
It was 45%. Further, the hue difference before and after the shrink-proofing was measured using a colorimeter Macbeth Color-Eye 2020 Plus, and it was a hue difference that was not a problem in practical use.

As a comparative example, the area shrinkage ratio was determined by the A method without applying the shrink-proofing treatment.
It was 0%.

The leveling dye brown-dyed product was subjected to the same shrink-proofing treatment, and the hue difference before and after the shrink-proofing treatment was measured. As a result, it was found that there was no problem in practical use.

[0076]

As described above, according to the shrink-proofing method of the present invention, the shrink-proofing effect of wool is remarkably improved and the process can be simplified. Further, it is possible to minimize the damage of the wool and the hardening of the texture due to the adhesion of the resin, and it is possible to obtain a good pilling prevention effect.

Claims (3)

[Claims] 1. A shrink-proofing method for wool, which comprises treating the wool fiber with tetrakishydroxymethylphosphonium sulfate in advance when shrink-proofing is performed by adhering a polymer to the wool fiber by an absorption method. 2. The shrink-proofing method for wool according to claim 1, wherein the polymer attached to the wool fiber is a polyurethane resin. 3. The wool fiber is treated with an aqueous solution of tetrakishydroxymethylphosphonium sulfate whose pH is adjusted to 8.0 to 9.8.
The shrink-proof processing method for wool described.