JPH07122219B2 - Washable silk fabric - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a silk woven fabric that can sufficiently withstand washing durability, particularly machine washing.

(Prior Art) Silk has long been loved as a queen of fibers for its unique texture, luster, and drape, but on the other hand, it is difficult to handle because it easily rubs. In order to overcome this drawback, a method of using an epoxide has been known as a method for modifying silk which is more durable than before. For example, a method of pad dry curing an epoxy compound with a catalyst selected from amines, acids and acid salts (Japanese Patent Publication No. 33-10654), a pad of epoxide using an alkali metal hydroxide or an alkaline salt of an alkali metal as a catalyst. dry·
There are a method of steaming or curing (Japanese Patent Publication No. 38-25198), a method of treating with an epoxide-treated cellulose-reactive crosslinking agent (Japanese Patent Laid-Open No. 62-231079), and the like.

Further, JP-A-60-65172 discloses a method for providing washable crepe noodles by using silk yarn and synthetic fiber as a cover yarn to impart washing durability to silk and facilitate handling. There is.

(Problems to be Solved by the Invention) However, the original texture of silk is impaired by the method using epoxide as described above. This is slightly improved by using a silicone finishing agent together, but the durability is low and it cannot be used for machine washing. Further, epoxy treatment alone does not provide dimensional stability after washing. In addition, JP-A-60-
Even with the method disclosed in Japanese Patent No. 65172, it is difficult to obtain sufficient dimensional stability after washing, so it is difficult to use it for applications that require repeated washing. To overcome this, increasing the proportion of synthetic fibers increases the natural wind of silk. Will be compromised. That is, none of these conventional techniques pursues anti-rub performance, performance that does not change the feeling after washing, and dimensional stability after washing to the extent that they can withstand machine washing. If so, there is a problem that the original texture of silk is lost.

The present invention is to solve the above problems, the occurrence of threads without changing the unique texture of silk, less change in the texture after washing, and excellent dimensional stability, that is, An object of the present invention is to provide a washable silk fabric that can endure machine washing.

(Means for Solving the Problems) The present inventor has obtained that anti-threading can be obtained by treating a silk fabric with an epoxy compound, and washing by treating with a silicone resin and an aminoplast resin and / or glyoxal resin. It has been found that a woven fabric excellent in dimensional stability can be obtained by treating the fabric with little change in texture afterwards and by treating the fabric with a low tension in the finishing process.

That is, the present invention provides a silk fabric treated with an epoxy compound (A), a silicone resin (B), and an aminoplast resin and / or a glyoxal resin (C),
Solubility is 30% by weight or less when immersed in 5% by weight sodium hydroxide aqueous solution at 65 ° C for 60 minutes, and change rate of bending resistance before washing and after 10 times of washing is 4% or less. A washable silk fabric having a shrinkage ratio of 3% or less.

Hereinafter, the present invention will be described in detail.

In the present invention, the solubility means the weight reduction of the silk fabric after the silk fabric is immersed in a 5 wt% sodium hydroxide aqueous solution at 65 ° C. for 60 minutes. Solubility is less than 30% by weight, preferably 20% by weight
Must be: Solubility is related to threads during washing of silk fabrics. If the solubility is 30% by weight or less, the thread grade is 3 or more, and if it is 20% by weight or less, the thread grade is 5 or less.
It is grade 4 or grade 4. The thread grade is JIS L 0217 105
A cloth (1,000 times) was taken with a scanning electron microscope, and the cloth washed 10 times by the method according to the method (however, with a bath ratio of 1: 300) was observed, and the pictures were ranked according to the degree of fibrillation of the fibers. In the unprocessed fiber which is not epoxy-processed, a large number of fibrillated ultrafine fibers are entangled on the entire surface, and this is classified as the first grade. On the other hand, almost no fibrillation was observed in the fiber before washing, and this is classified as grade 5. Class 4 with a small amount of fibrillated ultrafine fibers, class 3 with a little entangled fibrillated ultrafine fibers, and class 2 with a tangled fibrillated ultrafine fiber. .

In the present invention, the flexibility is represented by the distance L (mm) between the vertex of the horizontal bar and the lowest point of the loop in JIS L 1096 D method (heart loop method), and the flexibility of the obtained product is According to JIS L 0217 105 method (however, bath ratio 1:
300) The change rate was calculated from the bending resistance after washing 10 times by the following formula.

This difference should be 4% or less, preferably 3% or less. If the difference exceeds 4%, the change in texture is so large that it is not suitable for machine washing.

In the present invention, the washing shrinkage refers to the washing shrinkage after 10 times of washing in JIS L 0217 105 method (where the bath ratio is 1: 300). The washing shrinkage should be 3% or less, preferably 2.5% or less. When the washing shrinkage ratio exceeds 3%, the dimensional change is too large and it is not suitable for machine washing.

No conventional processed silk fabric satisfies the three requirements of a solubility of 30% by weight or less, a change rate of bending resistance of 4% or less, and a washing shrinkage rate of 3% or less.

In such a silk fabric of the present invention, an epoxy compound (A), a silicone resin (B), and an aminoplast resin and / or a glyoxal resin (C) are fixed to the silk fabric, and the silk fabric is then bonded. Of the epoxy compound (A), the silicon-based resin (B), and the aminoplast resin and / or the method for producing a washable silk fabric, which comprises: Or, the glyoxal resin (C) is applied simultaneously or separately so that (B) and / or (C) is the last, as an aqueous solution or dispersion, and finally heat-drying and heat-treating, and final heating The drying step can be carried out by a method for manufacturing a washable silk fabric, which is characterized in that the drying step is carried out under low tension.

The epoxy compound used in the present invention is The water-soluble type containing a group is most preferable in the process.
Examples of such water-soluble epoxy compounds include ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, glycerin, sorbitol, polyglycerol, pentaerythritol, tris (2-hydroxyethyl) isocyanurate, trimethylolpropane, neopentyl glycol, phenol ethylene. Oxides, lauryl alcohol ethylene oxide mono- and polyglycidyl ethers are mentioned. Ethylene glycol, polyethylene glycol,
Polyglycidyl ethers such as propylene glycol, polypropylene glycol, phenol ethylene oxide, lauryl alcohol ethylene oxide, glycerol and polyglycerol are preferred. In particular, ethylene glycol diglycidyl ether and polyethylene glycol diglycidyl ether are preferable in terms of effects.

When ethylene glycol diglycidyl ether is used as the catalyst, sodium chloride, diethylenetriaminepentaacetic acid pentasodium and the like can be preferably used.

Next, examples of the silicone-based resin used in the present invention include silicone elastomers. Among the silicone elastomers, epoxy-modified silicone, amino-modified silicone, polyether-modified silicone, and rubber silicone are preferable in terms of texture. In particular, rubber silicone is preferable because of compatibility with epoxide, and terminal diol type laper silicone is particularly preferable.

Further, examples of the aminoplast resin used in the present invention include melamine formalin resin, triazone formaldehyde resin, urea formaldehyde resin, ethylene urea formaldehyde resin, other N-methylol resin, N-methylol ether resin, and mixtures thereof. Can be mentioned,
Melamine formalin resin is preferable in terms of hand durability. Examples of the glyoxal resin include dimethylol / dihydroxy / ethyleneurea and tetramethylol / acetylenediurea.

In the present invention, the epoxy compound (A), the silicon-based resin (B), and the aminoplast resin and / or glyoxal resin (C) are simultaneously or individually applied to the silk fabric in the form of an aqueous solution or dispersion. However, since the epoxy compound (A) impairs the feel of the silicone resin-modified silk fabric, it is not preferable to add it last.

Epoxy compound (A), silicone resin (B), and aminoplast resin and / or glyoxal resin (C)
When simultaneously applying to the silk fabric, the pad dry bake or the pad dry steam method or the like is applied.

First, when the epoxy compound (A) is applied to the silk fabric, a dipping method, a pad steam method, a pad dry steam method, a cold batch method or the like is applied, and then a silicone resin (B), and When the aminoplast resin and / or glyoxal resin (C) is applied to the silk fabric, a pad dry bake method or the like is applied.

The silicone resin (B) and the aminoplast resin and / or glyoxal resin (C) may be individually applied. In this case, it is preferable to apply the silicone resin (B) and then the aminoplato resin and / or the glyoxal resin (C).

When the epoxy compound (A) is applied to the silk fabric alone, the epoxy fabric is fixed in various forms. For example, in the cold batch method, it is left standing at 10 to 40 ° C for 20 hours or more to fix it, in the immersion heating method it is heat treated at 50 to 110 ° C to fix it, and in the pad steam method or the pad dry steam method, it is 140 to 180 ° C.
Steam for 0.5 to 2 minutes to fix.

Silicone resin (B) or aminoplast resin and /
Alternatively, after applying the glyoxal resin (C), it is dried and the resin component is cured by heat treatment.
If the dry heat method is used, heat treatment at 140 to 180 ° C. for 0.5 to 2 minutes is preferable. Then, even when the epoxy compound (A), the silicone resin (B), and the aminoplast resin and / or the glyoxal resin (C) are simultaneously applied, the drying and heat treatment are similarly performed.

Epoxy compound (A), silicone resin (B), and aminoplast resin and / or glyoxal resin (C)
The concentration of the aqueous solution or dispersion of the epoxy compound (A) is preferably 70 to 400 g / in the padding method, more preferably 100 to 300 g /, and 5 to 50 g / in the dipping method. It is preferably 10 to 40 g /. Such a concentration range is preferable in order to obtain both a sufficient rubbing prevention effect / moisture wrinkle prevention effect and a soft texture. Moreover, about 3-60 g / is preferable about the silicone resin (B), and 5
~ 55g / is especially preferred. Furthermore, aminoplast resin,
Glyoxal resin (C) is preferably 1 to 20 g /, 2
Particularly preferred is -15 g /. The amount of these resins deposited on the silk fabric is preferably ³ to 12 g / m ² as a solid content, and if the amount of deposition is less than this range, sufficient washing durability cannot be obtained, but if the amount of deposition is large, the silk's original wind It is not preferable because it may damage the compatibility.

What is important in the present invention is to heat-dry in the final resin application, or to heat-dry by moistening with water or an aqueous liquid after fixing the resin, that is, at least in the final heat-drying step under low tension of the silk fabric. To hold and dry.

Drying under low tension is specifically, for example, when the amount of shrinkage or unevenness of the supply of the fabric is detected when the fabric is supplied to the dryer, the supply speed is changed, or the air flow is used in combination to reduce the It can be cited as supplying. In addition, since the drying treatment tends to have a high tension due to the drying shrinkage action of the woven fabric, special attention is required, and it is important to perform the treatment more slowly than usual. As such a drying device, a short loop drier or a net-type drier modified as described above is preferable. These treatments cause the silk fabric to be sufficiently shrunk and have dimensional stability.

After finishing the drying process, 30 ~ 60 at 140 ~ 170 ℃
It is sufficient to set the heat for about 2 seconds and use a semi-decatizer steamer and a calendering process together to obtain the final product. However, as mentioned above, these steps are also carried out while keeping the tension low, and the width is 0 to 3 It is good to keep it in a very small amount of about%.

The silk fabric obtained by all the above processing steps has a solubility of 30% by weight or less, a change rate of bending resistance of 4% or less, and a washing shrinkage rate of 3% or less.

(Example) Hereinafter, the present invention will be described in detail based on examples.

In the examples, the flexural rigidity B of the texture was measured by a KES-FB system (manufactured by Kato Tech) and shown as an average value of the weft. Washing is in accordance with JIS L 0217 105 method (Bath ratio 1:30
0) Conducted 10 times.

The softness of the texture was measured by the JIS L 1096 D method, and the average value of each length and width was shown. JIS L 0 for washing
217 According to the 105 method (however, a bath ratio of 1: 300) was performed 10 times. Then, the rate of change (%) is calculated as {(softness before washing L (mm)-
Bending flexibility L (mm)) / Bending flexibility L (mm)} × 10
It was calculated by the formula of 0.

For rubbing, electron micrographs after washing were evaluated on a scale of 5 (5th grade without fibrillation, 1st grade with very high fibrillation).

The anti-yellowing property was measured by measuring the reflectance of the cloth after irradiation for 60 hours according to JIS L 0842 ((Reflectance at 650 nm-Reflectance at 425 nm)
/ 550 nm reflectance) × 100.

Alkali solubility is 65% with 5% sodium hydroxide solution
The solubility is shown when treated at 60 ° C. for 60 minutes.

Wrinkle resistance is JIS L 1096 Wrinkle resistance B method (Monsanto method)
The wrinkle resistance was measured with.

Example 1 200 g of ethylene glycol (n = 1) diglycidyl ether as an epoxide, 25 g of wurt latex FSE (manufactured by Ciba-Geigy) and 30 g of wurt latex 7261 (manufactured by Ciba-Geigy) as a silicone resin. , Beckamine MA-S (manufactured by Dainippon Ink & Chemicals, Inc.) as aminoplast resin 10g /, salt 100g / as epoxide catalyst
, Hoboton WS (Ciba-Ge
5g / made by igy) and 5g / made by Catalyst 376 (made by Dainippon Ink & Co.) as a catalyst for aminoplast resin. Fuji silk using 140 warps twin yarn and 66 weft single yarn. Was dipped and squeezed to 75% with mangle. After drying at 120 ° C, it was baked at 180 ° C for 30 seconds using a pin tenter.

Then, after immersing in water and squeezing with a roll to dehydrate, the length of the cloth is measured by photoelectric tube control to form a constant loop, and the nip roll is driven by a torque motor to form a short loop and sent to the conveyor. In addition, a jet air nozzle was installed at the dryer inlet along the width of the cloth to prevent the loop from returning, and a wind pressure was applied from above against the wind pressure from the bottom of the dryer. It was dried at low temperature at 0 ° C. The width of the dry cloth was 110 cm. Next, with a finishing width of 112 cm, it was immersed in water and tentering was performed for final setting at 140 ° C. for 60 seconds, and steaming set by a semi-decatizer was performed, followed by calendering at room temperature.

The texture, the texture after washing, the yellowing prevention property, the alkali solubility, the wrinkle resistance, and the shrinkage factor of the laundry of this silk fabric were examined and shown in Table 1 (Example 1). For comparison, a bath containing 200 g / of ethylene glycol diglycidyl ether and 100 g / of sodium chloride was prepared, processed in the same manner, and examined for physical properties and the like, and shown in Table 1 (Comparative Example 1). The unprocessed materials are also shown in Table 1 (Comparative Example 2). Unprocessed materials have a large change in texture before and after washing, and often cause rubbing. The processing of only epoxide changes the texture before and after washing, and the texture is hard. Compared with the comparative example, the example had a soft texture and had very little change in texture and rubbing during washing.

Example 2 Polyethylene glycol (n = 13) diglycidyl ether was used as an epoxide at 200 g /, and Ult latex ESC (manufactured by Ciba-Geigy) was used as a silicon-based resin at 25 g /,
Beckamine MA-S (manufactured by Dainippon Ink & Chemicals, Inc.) as an aminoplast resin 10g /, salt as an epoxide catalyst 100g
/, 5g / of Uruto Latex Catalyst ZF (manufactured by Ciba-Geigy) as a catalyst for silicone resin, 5g / of Catalyst 376 (manufactured by Dainippon Ink) as a catalyst for aminoplast resin, and water in a bath Then, Fuji silk, which uses 140-twisted warp yarn and 140-twisted weft yarn, was dipped and squeezed to 72% with a mangle. After drying at 120 ° C, it was baked at 170 ° C for 60 seconds using a pin tenter. After performing the same finishing process as in Example 1, the texture, the texture after washing, the yellowing prevention property,
Alkali solubility, wrinkle resistance and washing shrinkage were investigated and shown in Table 2 (Example 2). For comparison, polyethylene glycol (n = 13) diglycidyl ether 200 g /, salt 1
A bath containing 00 g / was prepared, processed in the same manner, and examined for physical properties and the like, and shown in Table 2 (Comparative Example 3). The unprocessed materials are also shown in Table 2 (Comparative Example 4). In the examples, it is clear that the texture before washing is close to unprocessed, and the change in texture and the occurrence of rubbing during washing are small.

Example 3 200 g / w of diglycerol diglycidyl ether was used as an epoxide, 100 g / w of diethylenetriaminepentaacetic acid 5 sodium was used as a catalyst for an epoxide, and water was adjusted to 1 bath, and a warp yarn of 120 count twin yarn and a weft yarn of 120 count twin yarn were used. Fuji silk was dipped and squeezed to 74% with mangle. After drying at 120 ° C, baking was performed at 170 ° C for 60 seconds with a pin tenter.
This was used as Comparative Example 5, and 10 g / light silicone A-500 (manufactured by Kyoeisha Oil & Fat Co., Ltd.) as a silicone resin, 15 g / wurt latex 7261 (manufactured by Ciba-Geigy), and Beckamine LFK (manufactured by Dainippon Ink and Chemicals) as a glyoxal resin. ) 15g /, Hoboton WS as a catalyst for silicone resin
(Ciba-Geigy) 5g /, Ultholatex Catalyst ZF (Ciba-Geigy) 5g /, Catalyst G (Dainippon Ink) as glyoxal resin catalyst
10 g /, and water were adjusted to one bath, and the epoxy-treated cloth was dipped and squeezed to 70%. After drying at 120 ° C, 1 with a pin tenter
Baking at 70 ° C for 1 minute. This was designated as Comparative Example 6, further after once immersed in water, as in Example 1, a short loop dryer, a semi-decatizer steamer, and a calendar were sequentially passed through to finish. Taking this as Example 3, the texture, the texture after washing, the anti-yellowing property, the alkali solubility, the wrinkle resistance, and the shrinkage factor of washing were examined and shown in Table 3. The unprocessed one is shown in Table 3 as Comparative Example 7. The change in texture is improved by the effect of silicone resin. It is also clear that the washing shrinkage rate is improved by the low tension drying.

Example 4 20 g / ethylene glycol diglycidyl ether as an epoxide and 100 g / sodium salt as an epoxide catalyst
, And adjust the water to one bath, soak Fuji silk using warp 120 count twin yarn, weft 120 count twin yarn, heat up to 90 ℃, and process for 60 minutes.
After washing with water and drying, light silicone A-500 (manufactured by Kyoeisha Yushi) as silicone resin is 5 g /, and Beckamine LFK (manufactured by Dainippon Ink) as glyoxal resin is 10 g /
, Catalyst G as a catalyst for glyoxal resin
(Dainippon Ink) 10g /, and adjust the water to one bath,
The epoxy treated cloth was dipped and squeezed to 70%. After drying at 120 ° C, it was baked at 160 ° C for 90 seconds with a pin tenter.
After further immersing this in water, as in Example 1, a short loop dryer, a semi-decatizer steamer, and a calendar were sequentially passed through to finish. Taking this as Example 4, the texture, anti-yellowing property, alkali solubility, wrinkle resistance, and washing shrinkage ratio were examined and shown in Table 4. The unprocessed materials are also shown in Table 4 (Comparative Example 8). The processing effect is clear.

Example 5 20 g / g of ethylene glycol (n = 1) diglycidyl ether was used as an epoxide, 100 g / g of sodium sulfate was used as a catalyst of an epoxide, and water was adjusted to a Jigger. Fuji silk was dipped and heat-treated at 90 ° C for 90 minutes. After washing with water, it was continuously dyed in blue with a reactive dye using a jigger and soaped.
Furthermore, as a silicone resin, light silicone A-700
(Kyoeisha fat and oil, 20% pure) 10g /, Beckamine LFK as glyoxal resin (Dainippon Ink, pure 45
%) 10 g /, catalyst G of glyoxal resin G (Dainippon Ink, 30% pure) 10 g /, reactive dye fixing agent Chinofix EW200 (Ciba Geigy) 5 g /, and a bath containing water is prepared. did. And
Dip a cloth dyed with epoxy and dyed in blue and squeeze it with a mangle
Narrowed down to%. Next, in the same manner as in Example 1, in order to form a constant loop, the length of the cloth is measured by controlling the photoelectric tube, the nip roll is driven by the torque motor to form a short loop, and the short loop is sent to the conveyer. A jet air nozzle is provided along the width of the cloth to prevent the loop from returning and a short loop dryer is used to apply wind pressure from above against the wind pressure from the bottom of the dryer.
It was dried at low temperature at 0 ° C. The cloth width of the dry cloth was 113 cm.
Next, tentering is done with a finishing width of 114.5 cm, final set at 160 ° C for 60 seconds while feeding the cloth with 1% overfeed to make the width even, and steam setting with a semi-decatizer is performed, then calender at room temperature. Treated. The finished width was 114 cm.

Texture of such silk fabric, texture after washing, alkali solubility,
It was made of wrinkle, and its shrinkage upon washing was examined and shown in Table 5 (Example 5). For comparison, a cloth of the same kind, which had been scoured and not subjected to epoxy treatment, was subjected to the steps after dyeing in the same manner as in Example 5 to examine the physical properties (Comparative Example 9). In addition, the raw cloth which was only scoured, dried and set is also shown in Table 5 (Comparative Example 10). Example 5
The cloth was less rubbed even after repeated washings, and therefore had little change in color and little change in texture, and was sufficiently washable and practical. It was found that when the fabric of Comparative Example 9 was repeatedly washed, rubbing occurred, the color changed to whitish, the texture became slightly hard, and the fabric could not be repeatedly washed. Also in Comparative Example 10, it was found that the texture became hard after washing and the shrinkage was large, and it could not withstand repeated washing.

(Effects of the Invention) The silk fabric according to the present invention is less likely to cause threads even after repeated washing, has little change in texture, and has dimensional stability, and is useful as a casual application. It can also be applied to applications where conventional silk fabrics could not be used.

Further, the silk fabric of the present invention can be obtained by a slight modification of the conventional device, and its usefulness is clear.

Claims (1)

[Claims] 1. A silk fabric treated with an epoxy compound (A), a silicone resin (B), and an aminoplast resin and / or a glyoxal resin (C) in a 5 wt% sodium hydroxide aqueous solution at 65 ° C. Solubility when soaked for 30 minutes or less, softness before washing and washing
A washable silk fabric characterized in that the rate of change in bending resistance after 10 times is 4% or less and the shrinkage factor in washing is 3% or less.