JP2000355880A - Supply of knitted and woven fabric with antimicrobial property - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for supplying a knitted and a woven fabrics with antimicrobial properties, capable of standing repeated washing with occurrence of formalin below the lower limit of detection by a JIS method. SOLUTION: A knitted and a woven fabrics comprising a cellulosic yarn impregnated with at least a methylol-based resin, a cross-linking catalyst and a spinning oil agent is heat-treated. The methylol-based resin is a condensate of an alkyleneurea, hydroxyethyleneurea, triazone, melamine or an alkyl carbide and formalin. The heat treatment is carried out at 110-170 deg.C for 0.5-10 minutes.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for imparting antibacterial properties to a knitted fabric containing cellulosic fibers.

[0002]

2. Description of the Related Art In recent years, incidents caused by various bacteria such as food poisoning incidents caused by O-157 bacteria and the problem of Legionella spp. In a 24-hour bath have occurred frequently. In addition, bacteria caused by increased humidity due to high airtightness of houses, insufficient ventilation,
The occurrence of mold and ticks has also been reported.

[0003] Under such circumstances, interest in bacteria has been remarkably increased among consumers in recent years. In response to this trend, various antibacterial products are on the market.Specifically, a wide variety of products such as textiles, kitchen products, bath and toilet products, home appliances, and household equipment are subject to antibacterial processing. Has become.

[0004] For antibacterial processing of textile products, surfactant systems,
Alcohol, phenol, biguanide, anilide, imidazole / thiazole, isothiazolone, nitrile, fluorine, organometallic, inorganic metal,
Natural chemicals are used as antibacterial agents. Usually, a fiber mixture is impregnated with a mixed solution containing these antibacterial agents and a urethane resin and dried to impart antibacterial properties to the fiber product.

However, in the case of such conventional antibacterial-treated textiles, the antibacterial agent is released from the textiles with a relatively small number of washings, and as a result, the antibacterial effect is reduced in a relatively short time. There is a problem. Therefore, there is a need for an antibacterial processing method for textile products that exerts an antibacterial action over a long period of time.

On the other hand, in recent years, it has been actively studied to prevent cellulosic fiber products such as clothing and bedding products from wrinkling and shrink-proofing to prevent wrinkles and changes in shape of the fiber products after washing. .

The mainstream of wrinkle-proof and shrink-proof processing of cellulosic fiber products is a formalin treatment method. This method is performed in the final step of fabric production. That is, by treating a knitted or woven product, a fabric, or a garment sewn with the same using formaldehyde gas or formalin, the fibers are chemically bonded to each other to impart wrinkle resistance and shrink resistance. However, in the case of this method, since the obtained textile is exposed to a high concentration of formaldehyde which is harmful to the human body, it is necessary to remove formaldehyde remaining in the textile, which complicates the manufacturing process. ing. Furthermore, this processing method needs to be performed for each individual end product, which causes a problem that productivity is low and processing cost is high. For example, formalin can be removed by washing, but in this case the appearance is impaired,
Not made except for some products for infants.

[0008] As a wrinkle-proof and shrink-proof processing for cellulose fiber products, there is a resin processing method (JP-A-8-28406).
8, JP-A-8-325936, JP-A-9-8797
0). Also in these processing methods, the attachment of the resin and the heat treatment are performed in the final step of the fiber product. Therefore, there is a problem that productivity is low and processing cost is high.

Further, a knit shrink-prevention method has been proposed in which a spun yarn is impregnated with a working fluid containing a thermosetting resin and a catalyst, dried, and then subjected to a heat treatment (Japanese Patent No. 2571721).
issue). However, in this method, the resin adheres to the surface side of the fiber bundle composed of a set of single fibers in a biased manner, and therefore, there is a tendency that a uniform shrink-proof effect cannot be obtained.

[0010]

DISCLOSURE OF THE INVENTION The present inventors have studied various methods for solving the above problems at once. As a result, a cellulose-based raw cotton fiber such as cotton, hemp and rayon was impregnated with a working fluid containing a methylol-based resin, a cross-linking catalyst, and a spinning oil, then dried and then manufactured using the spun cellulose fiber. When the knitted fabric was subjected to heat treatment, it was found that the resulting knitted fabric product exhibited excellent antibacterial properties and also had good shrinkage and wrinkle resistance. And
It has been found that the antibacterial property is superior to the conventional antibacterial treatment in its durability and that no formalin or the like harmful to the human body is detected without any treatment other than the heat treatment.

The present invention has been completed based on the above findings, and an object of the present invention is to provide a method for imparting antibacterial properties to a knitted woven fabric which has solved the above-mentioned problems.

[0012]

The present invention to achieve the above object is as follows. [1] at least a methylol-based resin, a crosslinking catalyst,
A method for imparting antibacterial property to a knitted fabric, comprising heating a knitted fabric containing a cellulosic fiber impregnated with a spinning oil agent. [2] The method of [1], wherein the methylol-based resin is a condensate of alkylene urea, hydroxyethylene urea, triazone, melamine, or an alkyl carbide with formalin. [3] The method for imparting antibacterial property of a knitted fabric according to [1] or [2], wherein the impregnation amount of the methylol-based resin with respect to the cellulosic fiber is 1 to 10% by weight. [4] The method of any of [1] to [3], wherein the heat treatment is performed at 110 to 170 ° C. for 0.5 to 10 minutes. [5] at least a methylol-based resin, a crosslinking catalyst,
After the cellulose fiber impregnated with the spinning oil is impregnated with a processing liquid containing the cellulose raw cotton fiber, a methylol resin, a crosslinking catalyst, and a spinning oil, and then dried,
The method for imparting antibacterial property of a knitted fabric according to [1], which is a spun cellulose fiber yarn. [6] The method for imparting antibacterial property of a knitted fabric according to [5], wherein drying is performed at 80 to 100 ° C for 10 to 30 minutes.

Hereinafter, the present invention will be described in detail.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The cellulosic fibers used in the present invention may be any of natural cellulosic fibers, regenerated cellulosic fibers, and semi-synthetic cellulosic fibers. Specifically, cotton fiber, rayon fiber, and hemp fiber can be exemplified. Further, the raw cotton before spinning or the spun yarn after spinning may be used.

The knitted fabric to be subjected to the antibacterial property imparting treatment is obtained by knitting and using the above-mentioned cellulosic fiber impregnated with a treatment agent described later. The knitted fabric may be manufactured using only cellulosic fibers, or may be a blended product using fibers other than the cellulosic fibers such as polyester and polyacrylonitrile in combination. The content of the cellulosic fiber in the knitted fabric is preferably 30% by weight or more, and more preferably 4% by weight.
0 to 100% by weight is desirable. When the content of the cellulosic fiber in the knitted fabric is less than 30% by weight, the antibacterial properties may not be sufficiently exhibited.

In the present invention, the cellulose fiber is impregnated with a methylol resin, a crosslinking catalyst, and a spinning oil.

Examples of the methylol resin include alkylene urea, hydroxyethylene urea (glyoxal urea),
A reaction condensate of formaldehyde with triazone, melamine, alkyl carbide or the like can be used. These methylol-based resins are known for shrink-proofing cellulosic fiber products.

As the reaction condensate of alkylene urea and formaldehyde, Sumite Chemical Co., Ltd.
x Resin ULW, Sumitex Resin H-90, Sumitex Syrup 250
conc and the like can be exemplified.

As a reaction condensate of hydroxyethylene urea and formaldehyde, a trade name of Sumitomo Chemical Co., Ltd.
Sumitex Resin FKS, NS-2, NS-11, NS-18, NS-3spe
, NS-16, NS-19, Z-5, NS-200 and the like.

Examples of the reaction condensate of melamine and formaldehyde include Sumitex Resin (trade name, manufactured by Sumitomo Chemical Co., Ltd.).
M-3, MK, Sumitex Resin M-6, M-5S, Sumitex Resin
MC etc. can be illustrated.

Examples of the reaction condensate of triazone and formaldehyde include Sumitex Resi, trade name of Sumitomo Chemical Co., Ltd.
n W-2 can be exemplified.

The impregnation amount of the methylol-based resin with respect to the cellulosic fiber is based on 100 parts by weight of the cellulosic fiber.
It is preferable that the amount be 1 to 10 parts by weight. When the impregnation amount is less than 1 part by weight, the effect of imparting antibacterial properties is insufficient, which is not preferable. When the impregnation amount exceeds 10 parts by weight, the fiber strength is reduced.

The crosslinking catalyst is preferably a metal salt-based, organic amine-based, or the like. Examples of the metal salt system include zinc nitrate and magnesium chloride. As organic amines, 2
Preferred are -methyl-2-amino-propanol hydrochloride, morpholine hydrochloride, 2-aminobutanol phosphate and the like.

Specifically, Sumitex Accelerator ACX, S
Organic amine catalysts such as umitex Accelerator EPX (manufactured by Sumitomo Chemical Co., Ltd.), Sumitex Accelerator MX, Sumitex
Accelerator KX, Sumitex Accelerator X-60, Sumitex
Accelerator X-80, SumitexAccelerator X-100B, Sumit
Examples thereof include metal salt catalysts (manufactured by Sumitomo Chemical Co., Ltd.) such as ex Accelerator X-110 and Sumitex Accelerator X-120.

The amount of the cross-linking catalyst impregnated in the cellulosic fiber is 0.5 to 100 parts by weight of the cellulosic fiber.
It is preferably 5 parts by weight. If the impregnation amount is less than 0.5 part by weight, the crosslinking reaction becomes insufficient, which is not preferable. When the impregnation amount exceeds 5 parts by weight, there are drawbacks such as that the dyed fabric tends to yellow.

As the spinning oil, a nonionic or cationic spinning oil is preferable since the crosslinking catalyst is cationic. Also, an anionic spinning oil agent can be used by adding a precipitation inhibitor. The spinning oil itself is known to those skilled in the art.

The amount of the spinning oil impregnated into the cellulosic fibers is 0.7 to 100 parts by weight of the cellulosic fibers.
Preferably it is 1 part by weight. If the impregnated amount is less than 0.7 parts by weight, the yarn after spinning may be uneven in count, which is not preferable. If the impregnation amount exceeds 1 part by weight, troubles such as winding around rollers during the spinning process are apt to occur, which is not preferable.

The above-mentioned methylol resin, crosslinking catalyst and spinning oil may be individually impregnated into cellulosic fibers. However, a working fluid prepared by previously dissolving a methylol-based resin, a crosslinking catalyst, and a spinning oil in a solvent is prepared.
This may be impregnated into cellulosic fibers, and then the solvent of the working fluid may be distilled off. Water is particularly preferred as the solvent. When using water as the solvent for the processing fluid,
The water distillation temperature (drying temperature) is set to 80 to 100 ° C, and 10
It is preferred to dry for ~ 30 minutes. By drying under the above-mentioned drying conditions, water in the working fluid can be efficiently distilled off, and the curing of the methylol-based resin can be effectively prevented.

Examples of the method of impregnating the processing liquid with the cellulosic fibers include an immersion method, a spray method, a kiss roll method and the like.

In addition to the above-mentioned methylol-based resin, crosslinking catalyst and spinning oil, various components can be impregnated into the cellulose-based fiber. Specifically, a softener, a raising agent, an antistatic agent, a leveling agent and the like can be exemplified. Further, an antibacterial agent, a shrinkproofing agent, and the like can be appropriately impregnated as a supplement.

If the cellulosic fibers impregnated with at least the methylol resin, the crosslinking catalyst, and the spinning oil as described above are raw cotton, then the fiber is spun according to the usual method of spinning cellulosic fibers. .

As described above, the impregnation of the working fluid is not limited to the raw cotton, but may be performed in a spun yarn state. Also in this case, the impregnation method and the solvent distillation conditions are the same as described above.

Next, a knitted fabric is manufactured using the thus obtained spun yarn of a cellulose fiber impregnated with at least a methylol-based resin, a crosslinking catalyst, and a spinning oil. The production of the knitted fabric conforms to the conventional method of producing a knitted fabric.

In the present invention, an antibacterial property is imparted to the knitted fabric by heating the knitted fabric.

The heating temperature in the heat treatment is 110 to 17
0 ° C is preferable, and particularly preferably 120 to 150 ° C. When the heating temperature is lower than 110 ° C., the effect reaction rate of the resin is low, and the heating time is undesirably long. On the other hand, if the heating temperature exceeds 170 ° C., the fiber strength is undesirably reduced.

The heating time depends on the heating temperature, but is usually preferably 0.3 to 20 minutes, particularly preferably 0.5 to 10 minutes.

In the present invention, as described above, a knitted fabric containing a cellulose fiber impregnated with at least a methylol-based resin, a cross-linking catalyst, and a spinning oil agent is subjected to a heat treatment to thereby impart antibacterial properties to the knitted fabric. Is to be granted.
The exact reason for exerting antimicrobial properties is currently unknown.

The present inventor has reported that a methylol-based resin chemically bonded to cellulose continuously releases a trace amount of formalin that cannot be detected by the formaldehyde analysis method specified in JIS L1041. It is presumed that the bactericidal action of formalin imparts antibacterial properties to the knitted fabric.

Hereinafter, the present invention will be described more specifically with reference to examples.

[0040]

EXAMPLES (Example 1, Comparative Example 1) A scoured cotton wool fiber (San Hawkin cotton) was spread to a thickness of 2 to 3 cm, and a processing solution was sprayed on the cotton wool fiber from above using a shower.

The working fluid is an aqueous solution, and its composition is a methylol-based resin (Sumitex Resin NS-200 manufactured by Sumitomo Chemical Co., Ltd.).
Glyoxal resin) concentration: 222 cc / L, cross-linking catalyst (Sumitex Accelerator MX, metal salt catalyst manufactured by Sumitomo Chemical Co., Ltd.) concentration: 100 cc / L, spinning oil (Marbor 510C, Matsumoto Yushi Pharmaceutical Co., Ltd., nonionic)
The concentration was 10 cc / L.

Using a roller squeezing machine and a centrifugal dewatering machine, the amount of the working fluid adhering to the cotton wool fibers sprayed with the working fluid was adjusted to 60% by weight based on the raw cotton fibers. Next, the raw cotton fibers to which the processing liquid was attached were heated at 80 ° C. for 10 minutes using a dryer. The impregnated amount of the methylol resin in the dried raw cotton fiber was 2% by weight.

Next, the dried raw cotton fiber was spun. A knitted fabric was manufactured using the spun yarn. 150 knitted fabric
C. for 2 minutes to obtain a knitted fabric with antibacterial properties according to the present invention.

An evaluation test of antibacterial properties was performed using the above knitted fabric. That is, the washing of the knitted fabric was repeated, and the relationship between the number of washing times and the antibacterial property of the knitted fabric was determined. For comparison,
The same evaluation test was performed using a commercially available antibacterial cotton product in which an antibacterial agent (quaternary ammonium salt) was fixed to a fiber with a resin. The test method of the antibacterial evaluation was in accordance with the “Quantitative Antibacterial Test Method for Textile Products” (Textile Product New Function Evaluation Council). The test bacterium was Staphylococcus aureus.

The test results are shown in FIG. The commercial cotton product of Comparative Example 1 has a quaternary ammonium salt fixed to the cotton product with a crosslinkable urethane resin, but has a bacteriostatic activity value of 2.2 or more until washing is performed 10 times. Was. But,
Subsequent washing reduced the bacteriostatic activity value to 2.2 or less, and the antibacterial effect rapidly declined. On the other hand, the knitted fabric of Example 1 showed a bacteriostatic activity value of 3 or more even when the number of washings exceeded 200, indicating that the antibacterial property was maintained.

Example 2 A spun yarn of cotton raw cotton fiber (San Hawkin cotton) was immersed in a processing liquid.

The working fluid is an aqueous solution, and its composition is a methylol resin (Sumitex Resin NS-200 manufactured by Sumitomo Chemical Co., Ltd.)
Glyoxal resin) concentration: 222 cc / L, cross-linking catalyst (Sumitex Accelerator MX, metal salt catalyst manufactured by Sumitomo Chemical Co., Ltd.) concentration: 100 cc / L, spinning oil (Marbor 510C, Matsumoto Yushi Pharmaceutical Co., Ltd., nonionic)
The concentration was 10 cc / L.

Using a centrifugal dehydrator, the amount of the working liquid was adjusted to 60% by weight based on the spun yarn. Next, the spun yarn to which the processing liquid was attached was heated at 80 ° C. for 10 minutes using a dryer. The impregnated amount of the methylol-based resin in the dried spun yarn was 2% by weight.

Next, a knitted fabric was manufactured using the spun yarn. This knitted fabric was heated at 150 ° C. for 2 minutes to obtain a knitted fabric having antibacterial properties according to the present invention.

(Test Example 1, Comparative Test Example 1) The knitted fabric to which the antibacterial property imparting method of the present invention has been applied simultaneously has a good shrinkproof effect. 2. Description of the Related Art Conventionally, there has been known a problem that the size of a cotton product shrinks due to washing. For the purpose of solving this problem, shrinkproofing with a resin or gas treatment with formaldehyde is generally performed at the final stage of the production of cotton products to impart shrinkage resistance to the cotton products.

However, since the shrink-prevention processing with the resin is performed for each individual product at the stage of the final product, the processing is extremely complicated.

Further, since the shrink-prevention treatment using formaldehyde is performed at the stage of the final product, there is a problem that a large amount of formaldehyde remains in the final product.

Table 1 shows that the knitted fabric provided with the antibacterial property in Example 1 and a commercially available cotton product subjected to shrink-prevention treatment with formaldehyde in the final stage were washed, and the formalin residual amount with respect to the number of washings was washed. Are shown as Test Example 1 and Comparative Test Example 1.

Commercial cotton products have extremely high formaldehyde residue when the number of washings is small. In contrast, the knitted fabric of Example 1 had a small amount of formaldehyde residue from the beginning, and the absorbance difference was 0.05 or less according to the detection method specified in JIS L1041.
It was expressed below the standard value of No. 4.

[0055]

[Table 1] Washing was performed according to JIS L0217 103 method, and tumbler drying was performed.

[0056]

EXAMPLES 3-5, COMPARATIVE EXAMPLE 2 A knit product using a blended yarn of Vescott (Vescott brand name Toho Textile Co., Ltd.) impregnated with a working fluid under the same conditions as in Example 1 and ordinary cotton Was manufactured (Examples 3 to 5). The counts were all 40 /-. Knitting organization is: India (3
The fabric was knitted at 0 "x 22G) and dyed with a circular dyeing machine. Knitting and dyeing were all performed under the same conditions.
All the knitted products of Examples 3 to 5 exhibited good antibacterial properties.

Next, the knit products of Examples 3 to 5 and 1
Washing and drying of a knit product (Comparative Example 2) manufactured using cotton yarn made of 00% ordinary cotton were repeated. Washing was performed according to JIS L0217 103 method, and tumbler drying was performed.

Tables 2 and 3 show changes in the shrinkage ratio of the knit product with respect to the number of washings.

[0059]

[Table 2] Tumble: The vertical RFC (70) indicates that 70% by weight of Bescott raw cotton and 30% by weight of ordinary cotton are contained (the same applies hereinafter).

[0060]

[Table 3] Tumble: horizontal As is clear from Tables 2 and 3, the knit product according to the present invention was also excellent in shrink resistance.

[0061]

The knitted fabric provided with the antibacterial property by the method of the present invention has a methylol resin chemically bonded to cellulosic fibers. Therefore, it is difficult for the methylol-based resin to be detached from the knitted fabric by washing or the like, so that the antibacterial property is maintained for a long time. Moreover, the amount of formalin generated is below the lower detection limit according to the JIS method and is safe.

Furthermore, the impregnation of the methylol resin into the cellulosic fibers is carried out in the state of a fibrous yarn or a spun yarn. Is easy. Furthermore, according to the method of the present invention, the obtained knitted fabric can be imparted with antibacterial properties and also with shrinkproof properties.

[Brief description of the drawings]

FIG. 1 is a graph showing the relationship between the number of washings and the bacteriostatic activity value.

[Procedure amendment]

[Submission date] June 22, 1999 (1999.6.2
2)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0015

[Correction method] Change

[Correction contents]

The knitted fabric to be subjected to the antibacterial property imparting treatment is obtained by knitting and using the above-mentioned cellulosic fiber impregnated with a treatment agent described later. The knitted fabric may be manufactured using only cellulosic fibers, or may be a blended product using fibers other than the cellulosic fibers, such as polyester and polyacrylonitrile. The content of the cellulosic fiber in the knitted fabric is preferably 30% by weight or more, particularly 40% by weight.
-100% by weight is desirable. When the content of the cellulosic fiber in the knitted fabric is less than 30% by weight, the antibacterial property may not be sufficiently exhibited.

 ────────────────────────────────────────────────── ─── Continued on the front page F term (reference) 3B154 AA12 AB02 AB20 AB21 BA19 BA32 BB12 BB32 BD12 BD13 BD18 BD20 BF01 BF04 BF12 DA16 DA18 DA28 DA30 4L033 AA02 AB01 AB05 AB06 AC09 AC10 CA24 CA33

Claims (6)

[Claims] 1. A method for imparting antibacterial property to a knitted fabric, comprising heating a knitted fabric containing cellulose fibers impregnated with at least a methylol-based resin, a crosslinking catalyst, and a spinning oil. 2. The method according to claim 1, wherein the methylol resin is a condensate of alkylene urea, hydroxyethylene urea, triazone, melamine or an alkyl carbide with formalin.
3. The method for imparting antibacterial property of a knitted fabric according to item 1. 3. The method for imparting antibacterial property to a knitted fabric according to claim 1, wherein the impregnation amount of the methylol-based resin with respect to the cellulosic fibers is 1 to 10% by weight. 4. Heat treatment at 110-170 ° C. for 0.5-
The method for imparting antibacterial property of a knitted fabric according to any one of claims 1 to 3, which is performed for 10 minutes. 5. A cellulose fiber impregnated with at least a methylol-based resin, a cross-linking catalyst, and a spinning oil, and a cellulose-based cotton fiber impregnated with a working fluid containing a methylol-based resin, a cross-linking catalyst, and a spinning oil. The method for imparting antibacterial property to a knitted woven fabric according to claim 1, which is a cellulosic fiber yarn spun and then spun after drying. 6. The method according to claim 5, wherein the drying is carried out at 80 to 100 ° C. for 10 to 30 minutes.