CN104995350B - Fluorescent whitening highly cross-linked polyacrylate fiber, method for producing same, and fiber structure containing same - Google Patents

Abstract

The fluorescent whitening highly crosslinked polyacrylate fiber of the present invention allows an anionic fluorescent whitening agent to adhere to a highly crosslinked polyacrylate fiber that generates heat by adsorbing moisture in a gas phase. The fluorescent whitening highly crosslinked polyacrylate fiber is obtained by contacting a highly crosslinked polyacrylate fiber which generates heat by adsorbing moisture in a gas phase with an aqueous dispersion containing an anionic fluorescent whitening agent, and then treating the fiber at 10 to 200 ℃ for 20 seconds to 120 minutes. The fiber structure of the invention contains the fluorescent whitening highly-crosslinked polyacrylate fiber. Thus, a highly crosslinked polyacrylate fiber having a reduced red color, an improved whiteness, and a further improved calorific value and moisture adsorption amount when adsorbing moisture in a gas phase, and a fibrous structure containing the same are provided.

Description

Fluorescent whitening highly cross-linked polyacrylate fiber and its manufacturing method and fiber structures containing the fibers

technical field

The present invention relates to a highly crosslinked acrylic fiber to which a specific fluorescent whitening agent is adhered, a method for producing the fiber, and a fiber structure containing the fiber.

Background technique

Heat-generating fibers that utilize the heat generated when moisture is absorbed (heat of adsorption) have high heat retention properties, and are often used mainly for winter clothing and sports clothing such as mountaineering. A representative fiber that generates heat using this heat of adsorption is a highly crosslinked polyacrylate fiber (Patent Document 1). This fiber is a fiber obtained by modifying acrylic fiber as a raw material to hydrophilize the molecule and at the same time highly cross-linked. It has a fiber form with high hygroscopicity and suppressed swelling. Usual highly crosslinked polyacrylate fibers are obtained by crosslinking acrylic fibers with hydrazine or the like to suppress swelling when wet and introduce hydrophilic groups. The hydrophilic group can be introduced by hydrolyzing a part of the functional group of the fiber to convert it into a carboxyl group (-COOH) and/or an alkali metal salt type carboxyl group (eg -COONa).

The above-mentioned conventional highly cross-linked polyacrylate fibers are reddish, and there is a problem that the degree of redness increases as the wearing time becomes longer. In order to solve this problem, it has been proposed to convert some carboxyl groups into metal salts in the raw cotton production process (Patent Documents 2 and 3).

prior art literature

patent documents

Patent Document 1: Japanese Patent Publication No. 7-59762

Patent Document 2: Japanese Patent Laid-Open No. 2000-2303353

Patent Document 3: Japanese Patent Laid-Open No. 2002-294556

Contents of the invention

The technical problem to be solved by the invention

However, conventional highly cross-linked polyacrylate fibers still have a reddish color, and there is a problem that the degree of redness increases as the wearing time becomes longer, and there is still a demand for solving this problem in the market. Furthermore, there is a need to further increase the calorific value and the moisture adsorption amount when moisture in the gas phase is adsorbed.

In order to solve the above conventional problems, the present invention provides a highly cross-linked polyacrylate fiber with reduced redness, increased whiteness, and further increased calorific value and water adsorption capacity when adsorbing moisture in the gaseous phase, a method for producing the same, and a fiber containing the same. fiber structures.

Methods used to solve technical problems

The fluorescent whitening highly cross-linked polyacrylate fiber of the present invention is characterized in that an anionic fluorescent whitening agent is attached to the highly cross-linked polyacrylate fiber that absorbs moisture in the gas phase and generates heat, thereby making the highly cross-linked polyacrylate fiber The original reddish color of the acrylic fiber is reduced and whitened.

The method for producing fluorescent whitening highly cross-linked polyacrylate fibers of the present invention is characterized in that the highly cross-linked polyacrylate fibers that absorb moisture in the gas phase and generate heat are brought into contact with an aqueous dispersion containing an anionic fluorescent whitening agent. , and then treated at 10-200° C. for 20 seconds to 120 minutes to obtain fluorescent whitening highly cross-linked polyacrylate fibers.

The fiber structure of the present invention is characterized by containing the above-mentioned fluorescent whitening highly cross-linked polyacrylate fiber.

Invention effect

The present invention can provide a highly cross-linked polyacrylate fiber with reduced redness and high whiteness by attaching an anionic fluorescent whitening agent to the highly cross-linked polyacrylate fiber that absorbs moisture in the gaseous phase and generates heat. Fiber clothing. Moreover, compared with the fiber (unprocessed product) to which an anionic fluorescent whitening agent was not adhered, the calorific value at the time of adsorption|suction of the water|moisture content of a gaseous phase was higher, and the amount of moisture adsorption also became high. In the above, the effect of reducing the redness of the fiber and increasing the whiteness is the direct effect produced by the attachment of the anionic fluorescent whitening agent, but the increase in the amount of moisture adsorption and the heat generation of moisture absorption is considered to be due to the following reasons: In addition to high In addition to the hydrophilic groups such as carboxyl groups and/or salt-type carboxyl groups possessed by cross-linked polyacrylate fibers, hydrophilic groups such as sulfonates possessed by anionic fluorescent whitening agents also work synergistically, Thus, the affinity for moisture in the gas phase is improved.

Description of drawings

Fig. 1 is an absorbance-wavelength curve of an extract from a fluorescent whitening agent highly cross-linked polyacrylate fiber according to an embodiment of the present invention.

detailed description

The inventors of the present invention obtained the following idea and conducted research on whether it is possible to provide fibers with high whiteness without redness by applying an anionic fluorescent whitening agent, which is not generally used in acrylic fibers, to highly crosslinked polyacrylic fibers . As a result, it was clear that it was surprising that not only the redness of the highly cross-linked polyacrylate fiber disappeared and the fiber with high whiteness was obtained, but also the fiber with no anionic fluorescent whitening agent attached (unprocessed product) was obtained. ) compared to the adsorption of moisture in the gaseous phase, the calorific value is higher and the moisture adsorption amount is also high. The increase in the calorific value and the amount of moisture adsorption when moisture in the gaseous phase is adsorbed is a great advantage in making more comfortable clothes. In addition, the higher the whiteness, the higher the value of the finished product.

The highly crosslinked polyacrylate fiber used in the present invention is a fiber in which the fiber is hydrophilized and highly crosslinked by modification of the acrylic fiber. That is, a hydrazine compound is cross-linked into the acrylic fiber, followed by hydrolysis and reduction treatment. As a result, fibers having hydrophilic groups such as carboxyl groups and/or salt-type carboxyl groups are obtained. As another example of the hydrophilic group, a sulfonic acid group and/or a sulfonate group may also be used.

Examples of such highly cross-linked polyacrylate fibers include "Breath Thermo" sold by the present applicant, "MOIS CARE" manufactured by Toyobo Co., Ltd., and "SUNBURNER" manufactured by Toho Textile Corporation.

Fluorescent whitening agent is a compound that absorbs ultraviolet light (wavelength 330-380nm) and emits short-wavelength (wavelength 400-450nm) fluorescence in the visible region, and is a dye that has affinity for fibers. Generally, cationic dyes are used for acrylic fibers (for example, "繊维の百科书书", Maruzen, published on March 25, 2014, pages 405 and 499). Anionic optical brighteners are known in fields other than the technical field of the present invention. For example, it has been proposed to add it to paper or resin such as inkjet recording paper, thermal paper, and radiographic paper (Japanese Patent Laid-Open No. 2005-238613, Japanese Patent Laid-Open No. 8-192577, Japanese Patent Laid-Open No. 8-211519, etc.) .

The anionic optical brightener is preferably a compound derived from diaminostilbene disulfonic acid. As this compound, the following formula (chemical formula 1) - (chemical formula 3) etc. are mentioned, for example.

chemical formula 1

chemical formula 2

chemical formula 3

In the formulas (Chemical Formula 1) to (Chemical Formula 3), R1 to R14 represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. R1 and R2, R3 and R4, R5 and R6, R7 and R8, R9 and R10, R11 and R12, R13 and R14 may be the same as or different from each other. In addition, they may be bonded to each other to form a ring. Therefore, all of R1 to R14 may be the same or different. M represents a hydrogen atom, an alkali metal, or an alkaline earth metal. The groups represented by R1 to R14 are preferably alkyl groups other than hydrogen atoms, and are substituted or unsubstituted alkyl groups having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms, such as methyl, ethyl, isopropyl, n-propyl, n-octyl, 2-sulfoethyl, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 2-methoxyethyl, 2-(2-hydroxyethoxy ) ethyl, 2,3-dihydroxypropyl, 3,4-dihydroxybutyl, carboxymethyl, 2-carboxyethyl. Examples of the aryl group represented by R1 to R14 include substituted or unsubstituted aryl groups having 6 to 10 carbon atoms, preferably 6 to 8, such as phenyl, 3-carboxyphenyl, 4-carboxyphenyl, 3,5-dicarboxyphenyl, 2-sulfophenyl, 3-sulfophenyl, 4-sulfophenyl, 2,5-disulfophenyl. As the heterocyclic group represented by R1 to R14, one is removed from a substituted or unsubstituted 5- or 6-membered aromatic or non-aromatic heterocyclic compound having 2 to 10 carbon atoms, preferably 3 to 8 carbon atoms. The monovalent group following the hydrogen atom is 2-furyl, 2-thienyl and the like. Examples of the group in which R1 and R2, R3 and R4, R5 and R6, R7 and R8, R9 and R10, R11 and R12, R13 and R14 are bonded to each other to form a ring include a morpholinyl group. Among the alkali metals and alkaline earth metals represented by M, Na and K are particularly preferable.

More specifically, there are, for example, the following formulas (Chemical Formula 4) to (Chemical Formula 6), etc. (Chemical Formula 4) is known as Fluorescent90, (Chemical Formula 5) is known as Fluorescent353, and (Chemical Formula 6) is known as Fluorescent104.

chemical formula 4

chemical formula 5

chemical formula 6

Examples of useful compounds include the following (Chemical Formula 7) to (Chemical Formula 10). The following (Chemical Formula 7) is known as Fluorescent49, the following (Chemical Formula 8) is known as Fluorescent223, and (Chemical Formula 9) is known as Fluorescent1. (Chemical formula 10) has no Fluorescent number, but it is known. These compounds may be used alone or in combination at any ratio. Among them, the anionic styrylbenzene-based fluorescent whitening agent (Chemical Formula 11) can be used alone, and Fluorescent351 can also be used in combination with the above-mentioned distyryl-based fluorescent whitening agent in any ratio.

chemical formula 7

chemical formula 8

chemical formula 9

chemical formula 10

Chemical formula 11

The anionic fluorescent whitening agent is attached to the highly cross-linked polyacrylate fiber. Here, adhesion may be adsorption by a dyeing method, or fixation using an adhesive in combination. Adsorption by dyeing is preferred. Thereby, the texture can be maintained well and the washing resistance can be improved. In the dyeing method, it is soaked in an aqueous dispersion containing an anionic fluorescent whitening agent, and then treated at 10 to 200° C. for 20 seconds to 120 minutes to make it adsorb. As a treatment method, there are exhaust dyeing, continuous dyeing, a method using steam, and the like.

Dyes such as green, blue, and purple for adjusting color tone can also be mixed with anionic fluorescent whitening agent. As the color tone adjusting dyes (blueness agents), there are disperse dyes, acid dyes, reactive dyes, direct dyes, basic dyes and the like.

It is preferable to attach 0.01 to 2% owf of an anionic fluorescent whitening agent to a highly crosslinked polyacrylate fiber, and it is more preferable to attach 0.02 to 1.5% owf. owf is an abbreviation for on the weight of fiber (based on fiber weight).

In the present invention, the original red color of the highly cross-linked polyacrylate fiber is reduced to white and cannot be judged by the naked eye, but it can be judged objectively by measuring the color with a spectroscopic colorimeter. This spectroscopic colorimeter measures L* value, a* value, and b* value (hereinafter, simply referred to as L value, a value, and b value). This color system was standardized by CIE (International Institute of Illumination) in 1976 and adopted by JIS Z8729 in Japan. In the fiber field, it is usually used to measure color difference. L* value indicates lightness (brightness), a* value, b* value indicates hue (color) and chroma (brightness), +a* value indicates red direction, -a* value indicates green direction, +b* value Indicates the yellow direction, and the -b* value indicates the blue direction. In the present invention, the value of a is preferably 0.5 or more, more preferably 1 or more, compared to an untreated product. The b value is preferably 0.5 or more, more preferably 1 or more. When the a value and the b value are as high as 0.5 or more, it is a level at which the difference can be judged visually.

Next, the test method of the adhesion degree of the fluorescent whitening agent used by this invention is demonstrated. The fluorescent whitening agent can be judged according to JIS L 1064 method B of fluorescent whitening agent tribal judgment method for fiber products. By this measurement, if at least 1 or more of the following characteristics exists, it can be confirmed that it is a fluorescent whitening agent used by this invention.

(1) Within the wavelength of 300-400 nm, the maximum absorption wavelength is within the range of 330-390 nm, preferably within the range of 340-370 nm.

(2) Within the wavelength of 200-350 nm, the maximum absorption wavelength is within the range of 240-340 nm, preferably within the range of 250-320 nm.

(3) In the case of processed fabrics, when the wavelength is plotted on the horizontal axis and the absorbance is plotted on the vertical axis, and the curve is differentiated and plotted within a wavelength range of 220 to 300 nm, there is one or more upwardly convex points.

(4) Preferably, in the absorbance analysis of the solution obtained by extracting the fluorescent whitening highly cross-linked polyacrylate fiber of the present invention by the following method, within the wavelength range of 220 to 300 nm, there is one upwardly convex point above.

According to JIS L 1064 method B method for judging the group of fluorescent whitening agents of fiber products, the sample solution was prepared and extracted using methanol: water = 1:1. At this time, no concentration and purification operations were performed, and 5 g of the treated cloth was put into a 200 ml stainless steel bottle, filled with 150 ml of the above-mentioned extraction solvent, and extracted at 90-95° C. for 1 hour. Afterwards, only the cooling solution was transferred to a beaker, diluted with ionized water, and then the absorption curve was measured with a photoelectric spectrophotometer.

The present invention can be applied to any stage of cotton, silk, and cloth of highly cross-linked polyacrylate fibers. As the cloth, woven fabric, knitted fabric, non-woven fabric, etc. can be used. For example, as textiles, there are plain weave, twill weave, satin weave, plain weave, twill weave, satin weave, fancy fabric, jacquard weave, single-layer weave, double-layer weave, multi-layer weave, warp raising Tissues, weft raised fabrics, gauze fabrics, etc. Knitted fabrics include circular knitting, weft knitting, warp knitting (including crochet, Raschel warp knitting), raised knitting, etc., and there are plainknitting, plain-stitch, rib knitting), interlock stitch (smooth knitting, interlock stitch), rib stitch, purl knitting, denbigh stitch, cord stitch, Atlas stitch, chain stitch, inlay stitch, etc. In addition to being made into cloth, batting can also be made into bedding or outerwear, for example.

The fluorescent whitening highly cross-linked polyacrylate fiber of the present invention can also be mixed with other fibers. When mixing, the fluorescent whitening highly cross-linked polyacrylate fiber may be 2 to 100% by mass, and the other fibers may be 0 to 98% by mass. Examples of other fibers include polyester, polyolefin, nylon, polypropylene, rayon (including Lenzing Co., trade name "Tencel"), cupro, acetate, ethylene/vinyl alcohol (Kuraray Co. Cotton (kapok), hemp, silk, wool (wool) represented by animal hair fibers, common acrylic fibers, highly cross-linked polyacrylate fibers, and all other fibers. Fillings such as feathers are also included.

For mixing with other fibers, the following method can be used, for example.

(1) Blending: Blending is the mixing of two or more types of fibers in the cotton stage. For example, it is mixing by blending cotton, carding, drawing, and blending. It is mainly used for uniform mixing of staple fiber yarn, non-woven fabric and cotton wool.

(2) Yarn: Yarn is a mixture in which two or more kinds of yarns are twisted together. For example, in the case of double filaments, it is a mixture in which the fiber filaments of the present invention and other fiber filaments are twisted together. It is used for twisting between short-fiber yarns, between short-fiber yarns and filaments, and between filaments.

(3) Blended weaving: blended weaving is used to mix single fibers between filaments.

(4) Interlacing: Interlacing is mixing when a textile is produced using a plurality of filaments constituting the textile. For example, the warp and the weft may be made into other types of yarns or multiple types of warp and weft may be used respectively.

(5) Interknitting: interknitting is the mixing of multiple types of yarns used in the manufacture of braided fabrics.

(6) The laminated fiber layers are mixed by needle punching and water flow interweaving in the manufacture of non-woven fabrics.

The reason why it is preferable to mix with other fibers is to keep the moisture in the liquid phase in the other fibers when sweating a lot or getting wet by rain, so that the fibers of the present invention can continue to absorb moisture and generate heat. In this way, although the fiber as a whole is in a wet state, since the fiber of the present invention continues to absorb moisture and generate heat, the fiber is warm, has high heat retention, and has a good wearing feeling.

When preparing a fiber structure by mixing with the above-mentioned other fibers, the cationic fluorescent whitening agent can also be made to adhere to other fibers. That is, the fluorescent whitening highly cross-linked polyacrylate fiber to which the anionic fluorescent whitening agent of the present invention is attached may be mixed with fibers other than the highly cross-linked polyacrylate fiber to which the cationic fluorescent whitening agent is attached. Mix to prepare a fiber construct.

For example, when using fibers that have undergone water absorption and quick-drying processing as other fibers in polyester fibers, for a large amount of perspiration or being wet by rain, since the polyester fibers absorb water in the liquid phase and dry quickly, the moisture absorption and heat generation of the fibers of the present invention The effect is easy to last, and as a result, it is difficult to vaporize and cool, and it becomes warmer. Furthermore, as a synergistic effect, since the heat generation persistence of the fiber of the present invention also contributes to the (water absorption) drying property of the polyester fiber itself, the drying becomes quicker, and it becomes a cloth with a better wearing feeling.

As the fiber structure of the present invention, silk, woven fabric, braided fabric, nonwoven fabric, filler, etc. are preferable. As a filler, it can be mixed with feathers and used. In addition, examples of the fiber structure include clothes, hats, earmuffs, scarves, gloves, socks, sleeping bags, quilts, pillows, cushions, blankets, lap rugs, carpets, materials, and floors related to housing. Materials, wall materials, tatami mats, etc. In particular, it is suitable for clothing used in cold seasons or sportswear for mountaineering and skiing. Clothing includes underwear, underwear, shirts, jackets, sweaters, pants, parkas, windbreakers, training clothes, raincoats, stockings, girdles, scarves, hats, gloves, socks, earmuffs, and the like.

The fluorescent whitening highly cross-linked polyacrylate fiber and the fiber structure containing the fiber of the present invention have the following advantages.

(1) When it is made into clothes, the degree of warmth is improved due to the improvement of heat generation.

(2) White clothing suitable for sports or men can be provided due to whitening.

(3) Even in colors other than white, the color-developing property becomes favorable.

(4) Since the hygroscopicity is improved, the feeling of stuffiness inside the clothes is further reduced.

(5) During production, since the fiber strength is reduced, the quality problems caused by blurred colors can be improved without reducing the spinnability or dyeability.

Example

Hereinafter, it demonstrates more concretely using an Example. However, the present invention is not limitedly interpreted by the following examples.

(Examples 1-2, Comparative Examples 1-2)

(1) Processing of raw cotton made of highly cross-linked polyacrylate fiber (trade name "Breath Thermo")

0.1 kg of the raw cotton was weighed, and the anionic fluorescent whitening agent produced by Showa Chemical Industry Co., Ltd., the trade name "hakkol BS (made from diaminostilbene disulfonic acid) Derivative compound)", weigh pure water in such a way that the bath ratio reaches 1:20. Put the Breath Thermo raw cotton into the dyeing machine together with the above-mentioned chemicals, slowly raise the temperature from room temperature (18°C), and process it at 80°C for 30 minutes. After that, it is dehydrated and put into a blow dryer to dry. Let this be Example 1.

(2) Processing of fabrics containing highly cross-linked polyacrylate fibers (trade name "Breath Thermo")

For the woven fabric fabric with a weight per unit area of 150 ^g /m2 obtained by blending 10% by mass of "Breath Thermo" fiber and 90% by mass of polyester (PET) staple fiber, the basis is calculated relative to the value of the woven fabric. The fluorescent whitening agent was weighed in the manner of 0.5%owf%, and the pure water was weighed in such a manner that the liquor ratio relative to the cloth reached 1:20. Together with the above chemicals, the cloth was put into a dyeing machine, and the temperature was gradually raised from room temperature (18° C.), and treated at 130° C. for 30 minutes. After that, it is dehydrated and put into a blow dryer to dry. Let this be Example 2.

(3) The unprocessed "Breath Thermo fiber" raw cotton of Example 1 was used as Comparative Example 1.

(4) The unprocessed fabric of Example 2 was used as Comparative Example 2.

<Color evaluation>

Color (L value, a value, b value) was measured using a spectroscopic colorimeter (manufactured by Nippon Denshoku Industries Co., Ltd., model SE-2000).

<Fever Evaluation>

The samples of Examples 1-2 and Comparative Examples 1-2 were placed in a constant temperature dryer, and dried extremely at 120° C. for 12 hours. Put the above sample into a desiccator, place it in an environment of 20°C, and adjust the temperature so that the sample reaches 20°C. Put the temperature-adjusted sample into an environmental test room set at 20° C. and a relative humidity of 90% RH, and measure the temperature change of the sample surface at this time with a temperature recorder. Compare the temperature 3 minutes after the start of the test.

<Evaluation of Hygroscopicity>

The samples of Examples 1-2 and Comparative Examples 1-2 were placed in a constant temperature dryer, and dried extremely at 120° C. for 12 hours. Let A be the weight of the sample after extreme drying. Next, the above-mentioned sample was placed in a constant temperature and humidity chamber, and was allowed to absorb moisture (20° C., relative humidity: 60% RH, 12 hours). Let the weight of the sample after moisture absorption be B. The moisture absorption rate was calculated from the following formula.

Moisture absorption rate (%)=[(B-A)/A]×100.

The above results are shown in Table 1 together.

Table 1

<strength evaluation>

The fibers of Example 1 and Comparative Example 1 were subjected to a JIS L 1015 tensile strength test. As a result, the fibers of Example 1 and Comparative Example 1 were both 0.51 cN/dtex, showing no change in strength. In addition, the tensile strength test of JIS L 1018 8.17.1A (Muellen type) was performed on the fabrics of Example 2 and Comparative Example 2. As a result, both the fabrics of Example 2 and Comparative Example 2 were 421 kPa, and the strength did not change.

From the above results, it can be confirmed that the fiber of Example 1 and the fabric of Example 2 have lower redness (a value) and yellowness (b value) and higher whiteness than those of the comparative example, and the calorific value when absorbing moisture in the gas phase Higher and more hygroscopic. Also, there is no change in intensity.

Using methanol: water = 1:1, according to JIS L 1064 method B method for determining the family of fluorescent whitening agents of fiber products, the fiber of Example 1 was prepared and extracted as a sample solution. At this time, without concentration or purification, 5 g of the treated cloth was directly put into a 200 ml stainless steel bottle, filled with 150 ml of the above-mentioned extraction solvent, and extracted at 90-95° C. for 1 hour. Thereafter, only the coolant was transferred to a beaker, diluted with ionized water, and the absorption curve was measured with a photoelectric spectrophotometer (manufactured by Hitachi, model U-2800A). As a result, as shown in FIG. 1 , in the wavelength range of 220 to 260 nm, one or more upwardly convex points (shoulder) were found. From this, the presence of the fluorescent whitening agent can be confirmed.

(Example 3, Comparative Example 3)

In this example, the cloth dyed black was evaluated. A knitted fabric fabric having a basis weight of 150 g/m ² obtained by blending 10% by mass of "BreathThermo" fibers and 90% by mass of polyester (PET) staple fibers was used.

Optical brightener: The optical brightener used in Example 1 is 0.5% owf relative to "Breath Thermo" raw cotton

Disperse dyes: 2.0% owf relative to cloth

Auxiliary (dispersant): 1g/L relative to the fabric

Bath ratio: Use pure water in such a way that it reaches 1:20 relative to the fabric

Together with the above chemicals, the cloth was put into a dyeing machine, and the temperature was gradually raised from room temperature (18° C.), and treated at 130° C. for 30 minutes. After that, it is dehydrated and put into a blow dryer to dry.

Proportional Example 3 was dyed in the same manner as in Example 3 except that no fluorescent whitening agent was added.

Table 2 shows the results of the fabrics obtained in Example 3 and Comparative Example 3 together. Wherein, the dyed matter is black, and there is no difference in the L value, a value, and b value obtained by the spectroscopic colorimeter, so it is judged by naked eyes.

Table 2

From the above results, it can be confirmed that the fabric of Example 3 has lower red (a value) and yellow (b value) compared to Comparative Example 3, and is a vivid color, and has a higher calorific value when absorbing moisture in the gas phase, and is hygroscopic. Also taller.

(Example 4)

In this example the results of the wash test are shown. The fluorescent whitening treated cloth obtained in Example 2 was washed 10 times according to JIS L 0217 103 method. Use a color meter to measure the color of the fabric before and after washing. The results are shown in Table 3.

table 3

L a b before washing 89.5 2.7 -3.3 after washing 89.4 2.6 -3.3

As shown in Table 3, the L value and a value were lowered by 0.1 after washing, but there was no difference when viewed visually. The b value does not change, and it can be judged that the durability against washing is high.

(Examples 5-11, Comparative Example 4)

In this Example and the comparative example, except having made the density|concentration of a fluorescent whitening agent into Table 4, it experimented similarly to Example 1, and performed the colorimetry and the moisture absorption measurement. The results are shown in Table 4. Among them, the highly cross-linked polyacrylate fiber (trade name "Breath Thermo") whose red color is stronger than the high cross-link polyacrylate fiber (trade name "Breath Thermo") raw cotton used in Examples 1, 2, and Comparative Examples 1 and 2 was used. "BreathThermo") raw cotton.

Table 4

From the results in Table 4, the following can be known.

(1) When the fluorescent whitening agent is more than 0.01% owf, the a value is lower than that of the comparative example, and the degree of redness is reduced.

(2) When the fluorescent whitening agent is more than 0.02% owf, both a value and b value are lower than those of the comparative product by more than 0.5, and the product becomes whiter.

(3) When the fluorescent whitening agent is below 2% owf, it becomes slightly bluish white.

(4) When the fluorescent whitening agent is less than 1.5% owf, the degree of blueness is small and the whiteness is obvious.

(5) When the fluorescent whitening agent is 0.01% owf or more, hygroscopicity will improve.

Claims (10)

1. a fluorescent brightening height Acusol772 Acusol771 series fiber, it is characterised in that make anionic property On the high Acusol772 Acusol771 series fiber that fluorescent whitening agent is attached to adsorb the moisture of gas phase and generates heat, So that the original red colour system color of high Acusol772 Acusol771 series fiber reduce and by whitening, described Anionic optical brighteners is the compound or styryl derived by diaminobenzil disulfonic acid Benzene compounds.

Fluorescent brightening height Acusol772 Acusol771 series fiber the most according to claim 1, wherein, Described anionic optical brighteners adheres to relative to high Acusol772 Acusol771 series fiber 0.01～2%owf.

Fluorescent brightening height Acusol772 Acusol771 series fiber the most according to claim 1 and 2, its In, described anionic optical brighteners as dye adsorption on high Acusol772 Acusol771 series fiber.

Fluorescent brightening height Acusol772 Acusol771 series fiber the most according to claim 1 and 2, its In, described fluorescent brightening height Acusol772 Acusol771 series fiber is poly-with the high crosslinking not carrying out fluorescent brightening Acrylate series fiber is compared, and water adsorption amount and moisture absorption heating amount are higher.

Fluorescent brightening height Acusol772 Acusol771 series fiber the most according to claim 1 and 2, its In, described fluorescent brightening height Acusol772 Acusol771 series fiber is with the water extraction 60 minutes of 90～95 DEG C And in the spectrophotometric analysis of the solution obtained, in the range of wavelength 220～300nm, raise up Point is more than 1.

6. fluorescent brightening height Acusol772 Acusol771 series fiber according to any one of Claims 1 to 5 Manufacture method, it is characterised in that make the moisture of absorption gas phase and the high Acusol772 Acusol771 system generated heat Fiber contacts with the aqueous dispersions containing anionic optical brighteners, then processes at 10～200 DEG C 20 seconds～120 minutes, thus obtain fluorescent brightening height Acusol772 Acusol771 series fiber.

The manufacturer of fluorescent brightening height Acusol772 Acusol771 series fiber the most according to claim 6 Method, wherein, described manufacture method is exhaustion dyeing method, continuous dyeing method or the process employing steam Method.

8. a fibrous structure thing, it is high that it contains the fluorescent brightening according to any one of Claims 1 to 5 Acusol772 Acusol771 series fiber.

Fibrous structure thing the most according to claim 8, wherein, described fibrous structure thing is attachment The fluorescent brightening height Acusol772 Acusol771 series fiber having anionic optical brighteners is attached with sun with removing The mixture of the fiber beyond the high Acusol772 Acusol771 series fiber of ionic fluorescent whitening agent.

The most according to claim 8 or claim 9, fibrous structure thing, wherein, constitute described fibrous structure In the spectrophotometric analysis of the solution that the fiber of thing obtains at the water extraction 60 minutes with 90～95 DEG C, In the range of wavelength 220～300nm, the point raised up is more than 1.