JPH0686706B2 - Shrinkproof processing method for wool - Google Patents

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 by scale edges.

[0002]

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

For the first oxidation treatment of the wool fiber, a strong oxidizing agent such as chlorine gas, sodium hypochlorite, dichloroisocyanuric acid, potassium permanganate, etc. is used, so that the processing conditions are strictly controlled. Unless it is done, there is a constant risk of fatal damage to wool. In order to avoid this risk, a continuous device has 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 of hardness (texture) is caused by the migration of resin content (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 padding roll (mangle roll) surface. In addition, the progress of the self-crosslinking reaction between the urethane resins leads to the formation of a urethane resin film, which achieves its purpose. However, since the appropriate water retention is required for the progress of this reaction, preliminary drying and high temperature curing (resin Requires a huge amount of capital investment due to problems such as the need for a process such as heat treatment for curing the resin and curing the resin) and continuity of these equipment and padding equipment. 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 install.

In order to avoid the above problems of various shrink-proof processing methods, development of an efficient absorption method by utilizing existing dyeing equipment (jet dyeing machine, wins, etc.) and 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 a silicone resin for wool knit products (mainly sweaters), wool pretreated with a mild oxidizer such as potassium monopersulfate is used as a silicone resin. The Crosil processing method for adsorbing is known, but the processing process is complicated.

Also, several attempts in the past 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 polyurethane resin in combination, but there are problems such as complicated processes and inability to obtain satisfactory effects.

[0009]

[Means and Actions for Solving the Problems] Based on the above-mentioned problems, the inventor applied the reducing property of tetrakishydroxymethylphosphonium sulfate (THPS) for the purpose of improving the shrinkage-preventing effect and simplifying the process. 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 damage to the wool fiber and maximize the shrink resistance. In addition to the effect, a good pilling prevention effect could be obtained.

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.

The polyurethane resin to be absorbed after the reduction treatment is preferably a water-soluble polyether urethane resin. Examples of such resins include synaplet BAP
(Synthapret BAP, manufactured by Bayer),
Elastron BAP (manufactured by Daiichi 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 THPS reducing action as follows.

W-SH + NaSO ₃ CONH-polymer → W-S-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. It is considered that at the bath temperature, the self-crosslinking of the polymer is delayed. The self-crosslinking level increases with the passage of time and does not easily come off in the subsequent steps.
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 scoured and washed woven fabric, circular knit, etc. are shrink-proofed 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, then taken out and put into the dyeing machine. Sometimes the dried one is put into the dyeing machine.

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

THPS pretreatment After the raw material was put into the dyeing machine, iron-free room temperature water was injected, and the wetting / deaerating / foaming agent was added at 1% o. w. f (% by weight relative to 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.
The final bath volume is adjusted to a bath ratio (ratio of the total treatment bath volume to the processing material weight) of 1: 15-40 (in the case of Wins dyeing machine or drum / paddle dyeing machine, 1: 20-40, liquid flow). In the case of a dyeing machine, adjust 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,
30-50 ° C, preferably 35-40 at 1.5 ° C / min
The temperature is raised to ° C and the treatment is continued for 15 to 50 minutes. When the treatment is completed, the liquid is drained, washed with hot water and washed with a new bath at 40 ° C, and drained.

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 to the treatment machine for 4 to 10 minutes while operating the machine.
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 ℃. Especially Synthaprep 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
A situation in which exhaustion is approached 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 in 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 final washing bath is used for softening with a silicone softening agent.

Drying / Curing Unlike the padding method, since the resin reacts with wool in the absorption method, there is no risk of resin transfer, and therefore it is not necessary to continue the process.

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 so that the processed surface can be processed without stickiness.

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

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

As described above, the most important point of the method of the present invention is to perform the 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.

The influence of the amount of THPS used is also large. Overused, 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, although the THPS treatment causes less damage to wool than the method using an oxidant, if the conditions are wrong, the damage will increase, so careful control of the conditions is required. 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 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, 6.0 g of MgCl ₂ .6H ₂ O /
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. After washing and dehydrating this, it is dried at 85 ° C for 15 minutes,
Curing was carried out at 0 ° C for 10 minutes.

With respect to the fabric subjected to the shrink-proofing treatment in this manner, the area-shrinkage rate was evaluated by the method (A method) shown below, and the shrink-proof effect was evaluated. The area-shrinkage rate 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 performed for 12 minutes at a bath ratio of 2 times, changing the 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 has not been subjected to shrink-proofing was determined by method A to be 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 ratio was determined by the A method, it was 23.89% after 1 hour of washing.

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

When the area shrinkage was determined by the A method, it was 16.28% after washing for 1 hour.

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, 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. In addition, when a pilling test (ICI method) was performed, an improvement of about grade 2 was observed before the shrink-proofing process.

Example 4 Synthapret 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 method A, and it was 8.33 after washing for 3 hours.
%Met. In addition, when a pilling test (ICI method) was performed, an improvement of about grade 2 was observed before the shrink-proofing process.

The shrinkproof crepe fabric was dyed black by a general wool dyeing method using a chrome dye (acid mordant dye). When the area shrinkage rate 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,
Synaptprep 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 chromium 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 it 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 performed 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, 6.0 g of MgCl ₂ .6H ₂ O /
Liter and a treatment bath (pH 7.0) consisting of NaHCO ₃ 1.0 g / liter 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. After washing and dehydrating this, it is dried at 85 ° C for 15 minutes,
Curing was carried out at 0 ° C for 10 minutes.

The area shrinkage of the fabric thus shrink-proofed was evaluated by the method (method B) shown below, and the shrinkage-proofing effect was evaluated. As a result, 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 with the same bath ratio for 12 minutes. The water was changed twice for each time, dehydrated, dried, 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 knit knitted textured 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 the processing material, a 24 gauge 1/48 wool 100% smooth circular knit knitted fabric processed product was used, and as the 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.

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

Comparative Example 7 24 gauge 1/48 wool 10 which has not been shrink-proofed
The area shrinkage of the 0% smooth circular knit knit fabric processed product obtained by the B method was 21.15%.

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 a 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 ratio of the fabric which has been subjected to the shrink-proofing treatment in this way was determined by the A method, and was 6.5 in a washing time of 3 hours.
%Met. Further, the hue difference before and after the shrink-proofing was measured by using a colorimeter Macbeth Cara-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 44%.

Example 11 As a processing material, 22 gage 1/48 wool 100% smooth circular 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 performed 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.

Then, MgCl ₂ .6H ₂ O 6.0 g /
Liter and a treatment bath consisting of 1.0 g / liter of NaHCO ₃ at 50 ° C. for 10 minutes, and then 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. After washing and dehydrating this, it is dried at 85 ° C for 15 minutes,
Curing was carried out at 0 ° C for 10 minutes.

The area shrinkage of the fabric which has been subjected to the shrink-proofing treatment in this manner was determined by the method A to be 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-colored dyed product was subjected to the same shrink-proofing treatment, and the hue difference before and after the shrink-proofing treatment was measured.

[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 method for shrink-proofing wool, which comprises preliminarily treating the wool fiber with tetrakishydroxymethylphosphonium sulphate when applying a polymer to the wool fiber by an absorption method to perform shrink-proofing. 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.