JP6155045B2 - Method for producing cellulose fiber cotton - Google Patents

Description

  The present invention relates to a cellulose fiber cotton and a treatment method for suppressing texture hardening due to repeated washing or the like.

  Woven and knitted fabrics that are often in direct contact with the skin, such as underwear, are made from natural cellulose fibers such as cotton and linen that have high water absorption and hygroscopic properties, cupra, viscose rayon, and polynosic from the viewpoint of sweat treatment function and hygiene. Such as regenerated cellulose fibers such as Tencel and Lyocell are frequently used.

  Woven knitted fabrics composed of these cellulose fibers are repeatedly stretched and contracted by wetting and drying by repeated washing, etc., causing morphological changes that cause significant texture hardening and fabric damage. , Often reduce the merchantability.

  Conventionally, as a method for improving the flexibility of a cellulose fiber, there is a case where a softening treatment is performed using a treatment agent containing a softening agent component such as silk protein, collagen, or squalane. Since the softening effect due to the treatment is also significantly reduced by repeated washing, a treatment method for improving the texture that can withstand washing is demanded.

  As a method for solving these problems, for example, a method of applying a cationic softening agent typified by a dialkyldimethyl quaternary ammonium salt or a fatty acid amide can be mentioned. This method aims to impart flexibility by smoothing the fiber surface constituting the woven or knitted fabric and reducing the friction coefficient. However, the treatment agent is largely removed by washing, and texture hardening by repeated washing is unavoidable.

  Patent Document 1 below proposes a technique in which a film is formed from a water-soluble or water-dispersible polymer on the surface of cellulose fibers, and the dimensional stability against water is improved without impairing the texture. Patent Document 2 below also proposes resin processing using glyoxal resin. However, circular knitted fabrics represented by underwear are small in size and round finished, so heat treatment (set) at 150 ° C or higher necessary for these treatments is difficult on equipment, and it is difficult to suppress texture hardening due to repeated washing. It is.

  Furthermore, in Patent Document 3 below, a cellulose-based fiber-containing structure was treated with liquid ammonia in order to impart excellent and durable shrinkage resistance to the cellulose-based fiber-containing structure without any special resin processing. Thereafter, a method for preventing shrinkage of a cellulose-based fiber-containing structure, characterized by acid treatment, has also been proposed. However, this method requires special equipment for treating liquid ammonia at −33 ° C. or lower, and particularly in the case of a circular knitted fabric using regenerated cellulose fibers, the cellulose fibers are easily stuck and the texture is hardened. There is a problem that is easy to do.

  In addition, with regard to providing a durable deodorant function, for example, Patent Document 4 discloses a method of processing a fabric product itself by immersing it in a photocatalyst-containing treatment solution. Patent Document 5 discloses that by attaching a deodorant and a photocatalyst, a fiber structure excellent in washing durability and effective in deodorizing Nonenal can be obtained. However, these methods have a problem in that the texture becomes coarse and hard due to adhesion using a binder such as an acrylic resin for application to the fiber structure.

Japanese Patent Publication No.62-12347 Japanese Patent Laid-Open No. 3-51368 JP-A-11-200241 JP 2007-126664 A Japanese Patent No. 4092554

  In view of the above situation, an object of the present invention is to provide a cellulose fiber cotton in which texture hardening due to repeated washing or the like is suppressed and a treatment method for obtaining the cellulose fiber cotton.

  As a result of intensive studies and experiments to solve the above problems, the present inventor has found that the cause of the texture hardening is that the woven or knitted fabric repeatedly expands and contracts in wet and dry by repeated washing, causing a change in shape. It was found that single yarn sticking of the fibers constituting the woven or knitted fabric was caused, and that the softener used was also dropped off by washing.

  The above-mentioned causes are common problems that occur in woven and knitted fabrics using cellulose filaments and staples. Cellulose staples are produced by applying an artificial crimp in the raw cotton state to produce a spun yarn. In this case, the crimp of the regenerated cellulose fiber retains the shape of the crimp compared to the crimp of natural cellulose fiber such as cotton. Insufficient, recycled cellulose staples lack the feeling of swelling with spun yarn, lack of feeling of swelling when dyed with yarn or woven or knitted fabric, and expand and contract the woven or knitted fabric when wet and dry by repeated washing. The problem that the cellulose fibers are likely to stick together and the texture is likely to be hardened due to the lack of a feeling of swelling by repeating the above is greater than that of natural cellulose fibers.

Based on this finding, as a result of intensive studies to maintain the crimp form of cellulose raw cotton (hereinafter referred to as cotton), we focused on treatment methods that can be heat-set at a relatively low temperature, and optimized treatment agents and treatment methods. The present inventors have found that the above object can be achieved by using a cellulose fiber wadding having a specific Si strength, and have completed the present invention.
That is, the present invention is as follows.

(1) The raw material cellulose fiber cotton is immersed in an aqueous solution at 20 to 40 ° C. containing supramolecular amino-modified silicone having a number average molecular weight of 8,000 to 200,000 at a concentration of 0.1 to 5.5% by weight. After that, the Si strength (measured and converted by SiO ₃ ) before washing , including the steps of dehydrating and then heat treating at 80 to 120 ° C. is 1.5 or more, and the following formula :
Si strength retention after washing (%) = (Si strength after 30 washings / Si strength before washing) × 100
The manufacturing method of the cellulose fiber cotton whose Si intensity | strength retention after washing shown by is 60% or more.
(2) The method according to (1) above, wherein the cellulose fiber is a regenerated cellulose fiber.
(3) above (1) or a step of spinning the cellulose fiber cotton produced by the method described in (2), method for producing spun yarn.

  In the cellulose fiber cotton of the present invention, texture hardening is suppressed by preventing single yarn sticking generated by washing and falling off of a soft component. Therefore, inner products such as underwear, outer products such as blouses and skirts, linings, pillowcases, sheets, and bedding such as futons and kets made with the cellulose fiber cotton of the present invention are used for a long period of time. It has excellent product durability against repeated wearing and washing. Furthermore, the cellulose fiber cotton of the present invention has a durable and excellent deodorizing function.

Hereinafter, the present invention will be described in detail.
The cellulose fiber cotton of the present invention has a Si strength before washing (measured and converted by SiO ₃ ) of 1.5 or more, and a Si strength retention after washing represented by the following formula is 60% or more. .
Si strength retention after washing (%) = (Si strength after 30 washings / Si strength before washing) × 100
Cellulose fiber wadding having Si strength before washing and Si strength retention after washing satisfying the above-mentioned range has excellent deodorizing function with suppressed texture hardening due to repeated washing and the like.

  Examples of the cellulose fiber according to the present invention include natural cellulose fibers such as cotton and hemp, regenerated cellulose fibers such as cupra and viscose rayon, modal and polynosic, and purified cellulose fibers such as tencel and lyocell. Among these, regenerated or purified cellulose fibers are preferable, and regenerated cellulose fibers are more preferable.

  In this specification, the raw material cellulose fiber cotton refers to cellulose fiber cotton before undergoing the treatment of the present invention, and examples thereof include cellulose raw cotton and tow-like cellulose filaments cut into a certain fiber length. Of course, cellulose fiber cotton that is commercially available, that is, cellulose fiber cotton containing a raw cotton oil agent is also included.

The cellulose fiber cotton of the present invention is characterized in that the raw material cellulose fiber cotton is immersed in an aqueous solution containing a supramolecular amino-modified silicone compound, dehydrated, and then heat-treated.
The cellulose fiber cotton of the present invention is used as it is as a filling of a futon or a ket, or is spun into a yarn and a woven or knitted fabric is produced from the obtained yarn.

  In the present specification, “amino-modified silicone” refers to a silicone oil, that is, a dimethylpolysiloxane oil in which a part of the methyl group is substituted with an organic amino group. The amino group reacts with the hydroxyl group of cellulose.

  The supramolecularized amino-modified silicone used in the present invention refers to a “supermolecular product” of amino-modified silicone obtained by applying “supermolecular technology”. An example is Parasilicon BS-230 manufactured by Ohara Palladium Chemical Co., Ltd. "Supramolecular technology" here means that multiple molecules are physically assembled by non-covalent bonds (= weak bonds) and express unprecedented functions. That's it.

Conventionally, when an amino-modified silicone has a high molecular weight, the amino group is reduced by reacting the amino group with a cross-linking agent to bond with other molecules, and the texture-improving effect, which is a characteristic of the amino-modified silicone, may be inferior. It was. However, the amino-modified silicone by the supramolecular technology is suitable because it does not block the amino group, the polysiloxane skeletons are bonded to each other, and has a high molecular weight, so that the properties due to amino modification are not impaired.
Specifically, it is preferably a supramolecular amino-modified silicone having a number average molecular weight of 8,000 to 200,000.

Next, the processing method of raw material cellulose fiber cotton will be described in detail.
The concentration of the compound in the immersion treatment liquid containing the supramolecularized amino-modified silicone compound is preferably 0.1 to 5.5% by weight. If it is less than 0.1% by weight, it is difficult to obtain a softening effect, and if it exceeds 5.5% by weight, it is slippery. . More preferably, it is 0.1 to 3.0% by weight.

  The treatment temperature is preferably 20 to 40 ° C., more preferably 30 to 40 ° C., in order to allow the treatment liquid to uniformly penetrate the cellulose fiber. The immersion time is preferably 5 to 30 minutes, more preferably 10 to 20 minutes. As the processing apparatus, an Overmeier dyeing machine or the like is preferable.

  The raw material cellulose fiber cotton is dipped in an aqueous solution containing the supramolecular amino-modified silicone compound and then dehydrated. Dehydration is preferably performed by pressure dehydration, centrifugal dehydration and roll dehydration. The liquid content after dehydration (pickup rate) is preferably 60 to 80%.

  A heat treatment is performed following the dehydration treatment. The heat treatment temperature is preferably 80 to 120 ° C, more preferably 90 to 110 ° C. The treatment time is preferably 30 to 120 minutes, more preferably 30 to 60 minutes. As the heat treatment apparatus, a dryer can be used, and a hot air type box type dryer or a package type dryer is preferable. The tumbler dryer is not preferable because the obtained cellulose fiber cotton is easily entangled and may cause trouble such as fiber cutting in the spinning process.

The adhesion amount of the supramolecularized amino-modified silicone compound to the cellulose fiber cotton of the present invention can be determined by Si strength before washing and Si strength retention after washing, which will be described later, and a preferable range of Si strength before washing. Is 1.5 or more, more preferably 2.0 or more. Moreover, it is preferable that the Si intensity | strength retention after washing calculated by the following Formula is 60% or more.
Si strength retention after washing (%) = (Si strength after 30 washings / Si strength before washing) × 100

The cellulose fiber cotton of the present invention can be used for clothing as a batting such as a futon or a cushion, as a yarn by spinning, and as a knitted fabric made from yarn.
In spinning, a spinning method used for general fibers can be used.

  Examples of the method for mixing the cellulose fiber cotton and other fibers of the present invention include blend spinning, a method using a composite yarn of cellulosic fibers and other fibers, and a method of knitting and weaving. Moreover, you may form the composite yarn by interlace processing, fluid disturbance processing, covering, twisted yarn, etc.

The cellulose fiber cotton obtained by the present invention and the yarn and knitted fabric obtained from this cotton are subjected to ordinary scouring, bleaching and dyeing treatments as necessary.
As a processing machine used for scouring, bleaching and dyeing a knitted fabric, generally used wine dyeing machines, liquid dyeing machines and continuous scouring machines are preferred. For dyeing, it is preferable to use a wins dyeing machine, a liquid flow dyeing machine or the like, and soaping may be performed as necessary. For drying, a commonly used dryer can be used, but a tensionless net-type dryer is preferable.
In this specification, “after washing and drying is repeated 30 times” means after washing and drying are repeated 30 times according to the JIS-L-1027-103 method.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited only to these examples. First, the evaluation method in the present invention will be described.
(1) JTETC deodorant classification deodorization test A deodorization test was conducted using two components of acetic acid and isovaleric acid, and the deodorization performance was evaluated by the following method.
<Deodorization performance evaluation>
In accordance with the certification standard for deodorized textile products determined by JTETC, the above two components were subjected to a deodorization test by instrumental analysis. In the instrumental analysis test, the odor component and the sample were placed in a container, and the residual concentration of the odor component after being left for 2 hours (sample test concentration after 2 hours) was measured. The reduction rate of the odor component was calculated by the following formula using the residual concentration of the container containing only the odor component as the blank test concentration.
Decrease rate (%) = [(Blank test concentration after 2 hours−Sample test concentration after 2 hours) / (Blank test concentration after 2 hours)] × 100
Acetic acid was measured by a detector tube method, and isovaleric acid was measured by a gas chromatography method.
Judgment: The case where all the conditions of the acetic acid reduction rate of 80% or more and the isovaleric acid reduction rate of 85% or more were satisfied was judged as pass “◯”, and the others were judged as fail “x”.

(2) Evaluation method of texture (softness before washing, softness after washing) Knitting fabric obtained by 10 subjects according to the following five-level evaluation criteria for knitted fabric before and after washing according to the following washing method The texture of the fabric was evaluated and an average value was derived.
5: Very soft.
4: Slightly soft.
3: Neither.
2: Slightly hard.
1: Very hard.
For the evaluation, a knitted fabric conditioned in an environment of 20 ° C. × 65% RH was used.

(3) Washing method According to JIS-L-1027 103 method, washing and drying were repeated 30 times.
(4) Method for detecting Si intensity Using an X-ray fluorescence analyzer RIX3001 (manufactured by Rigaku Corporation), Si element strength (measured with SiO ₃ and converted) was measured.
Measurement conditions: 8 SCN 2θ scan, 3 OHMTL 30 mm

(5) Measuring method of K / S value of dyeing | staining thing The visual infection color density of a sample is measured using the Macbeth spectrophotometer MS-2020 type | mold. Specifically, a sample 5 cm × 5 cm is sandwiched between predetermined places of a spectrophotometer, and each K / S value in a wavelength range of 400 to 700 nm is measured. The visual infection color density is estimated using the K / S value at the maximum absorption wavelength. The greater the K / S value, the higher the staining density.

<Example 1>
A 1.4 dtex × 38 mm long Bemberg short fiber cotton (cupra: manufactured by Asahi Kasei Fibers Co., Ltd.) was placed in an overmeier dyeing machine, and a supermolecular amino-modified silicone (manufactured by Ohara Paradium Chemical Co., Ltd., Parasilicon BS-230 ( A 0.5 wt% aqueous solution having a number average molecular weight of 12,000)) was treated at 35 ° C. for 30 minutes, dehydrated under pressure, and then heat treated at 85 ° C. for 90 minutes in a package type dryer.
The obtained Bemberg short fiber cotton was spun by a ring spinning machine to obtain a spun yarn (single yarn fineness 1.4 dtex) of Bemberg 40 cotton count.
Using the spun yarn obtained, a milled knitted fabric was prototyped on a 19GG small-size round knitting machine. The obtained knitted fabric was scoured with a liquid dyeing machine under the following conditions, and dried with a net-type dryer at 130 ° C. for 1 minute. A circular knitted fabric having a basis weight of 155 g / m ² , a cellulose mixture ratio of 100% by mass, a course number of 50, and a wale number of 24 was obtained.
<Conditions> Scouring: Scoreroll FC-250 (Kitahiro Chemical Co., Ltd.) 1 g / l
20 minutes at 80 ° C
Table 1 shows the evaluation results of the circular knitted fabric obtained at 60 ° C for 20 minutes.

<Comparative Example 1>
0.4% by weight of an oil containing 37% by weight of sodium stearyl sulfate was applied to the 1.4 dtex × 38 mm long Bemberg short fiber cotton used in Example 1. Using a Bemberg short fiber cotton to which only the obtained oil agent was applied, a circular knitted fabric having a basis weight of 155 g / m ² , a cellulose mixture ratio of 100 mass%, a course number of 50, and a wale number of 24 was obtained in the same manner as in Example 1. .
The evaluation results of the obtained circular knitted fabric are shown in Table 1.

<Example 2>
The milled knitted fabric obtained in Example 1 was scoured with a liquid dyeing machine under the following conditions, dyed with a reactive dye, soaped, and dried with a net-type dryer at 130 ° C. for 1 minute. A circular knitted fabric having a basis weight of 155 g / m ² , a cellulose mixture ratio of 100% by mass, a course number of 50, and a wale number of 24 was obtained.
<Conditions> Scouring: Scoreroll FC-250 (Kitahiro Chemical Co., Ltd.) 1 g / l
20 minutes at 80 ° C
Hot water washing: 20 minutes at 60 ° C
Staining: Sumifix HF Blue BG gran 1.0% omf
Sodium sulfate 30g / l
Sodium carbonate 15g / l
90 minutes at 60 ° C
Neutralization: Acetic acid 1cc / l
10 minutes at 40 ° C
Soaping: Grand Up NC (Sanyo Kasei Co., Ltd.) 1cc / l
20 minutes at 90 ° C
Table 1 shows the evaluation results of the circular knitted fabric obtained at 60 ° C for 20 minutes.

<Comparative example 2>
The milled knitted fabric obtained in Comparative Example 1 was scoured with a liquid dyeing machine in the same manner as in Example 2, dyed with a reactive dye, soaped, and dried with a net-type dryer at 130 ° C. for 1 minute. did. A circular knitted fabric having a basis weight of 155 g / m ² , a cellulose mixture ratio of 100% by mass, a course number of 50, and a wale number of 24 was obtained.
The evaluation results of the obtained circular knitted fabric are shown in Table 1.

<Comparative Example 3>
An aqueous solution containing 2% by weight of amino-modified silicone (Nikka Silicone AMZ-3 (manufactured by Nikka Chemical Co., Ltd.)) was applied to the milled knitted fabric obtained in Comparative Example 1, and 130 ° C. × 1 in a net-type dryer. A circular knitted fabric having a basis weight of 155 g / m ² , a cellulose mixture ratio of 100% by mass, a course number of 50, and a wale number of 24 was obtained.
The evaluation results of the obtained circular knitted fabric are shown in Table 1.

<Examples 3 to 6, Comparative Example 4>
Concentration of supramolecular amino-modified silicone (Ohara Palladium Chemical Co., Ltd., Parasilicon BS-230 (number average molecular weight 12,000)) was 0.05% by weight (Comparative Example 4), 0.2% by weight (implementation) Example 3) Performed under the same conditions as in Example 2 except that the content was changed to 1.0% by weight (Example 4), 3.0% by weight (Example 5), and 5.0% by weight (Example 6). did. The obtained circular knitted fabric was subjected to a deodorization test, and the results are shown in Table 2. In addition, the deodorization test of the circular knitted fabric obtained in Example 2 was also conducted, and the obtained results are also shown in Table 2.

From the results in Table 1, when Examples 1 and 2 are compared with Comparative Examples 1 and 2, there is a difference in softness before washing. Furthermore, the softness after washing is large, and the flexibility of Examples 1 and 2 is obvious. In Comparative Example 3, the softness before washing decreases after washing clearly indicates that the softener is not durable. From a comparison between Example 2 and Comparative Example 2, it is clear that there is no difference in dyeability.
From the results in Table 2, Examples 2, 3, 4, 5, and 6 obtained the deodorizing effect.

  Cellulose fiber cotton obtained by the present invention is prevented from sticking of single yarn and soft components generated by washing, and texture hardening is suppressed. Therefore, inner products such as underwear, outer products such as blouses and skirts, linings, pillow covers, sheets, and bedding such as futons and kets made of cellulose fiber cotton obtained by the present invention are long. Excellent product durability against repeated wear and wash over time.

Claims (3)

After immersing the raw material cellulose fiber cotton in a 20 to 40 ° C. aqueous solution containing supramolecular amino-modified silicone having a number average molecular weight of 8,000 to 200,000 at a concentration of 0.1 to 5.5% by weight, Including the step of dehydrating and then heat-treating at 80 to 120 ° C., the Si strength before washing (measured by SiO ₃ and converted) is 1.5 or more, and the following formula :
Si strength retention after washing (%) = (Si strength after 30 washings / Si strength before washing) × 100
The manufacturing method of the cellulose fiber cotton whose Si intensity | strength retention after washing shown by is 60% or more. The method according to claim 1, wherein the cellulose fiber is a regenerated cellulose fiber. Comprising the step of spinning the cellulose fiber cotton produced by the process of claim 1 or 2, the manufacturing method of the spun yarn.