JP4958093B2 - Fiber structure - Google Patents

Description

  The present invention relates to a fiber structure to which a sugar alcohol having a cool feeling is attached with good durability.

  The refreshing effect of sugar alcohol (the action of removing heat from the surroundings by the endothermic reaction during hydration) is widely known. For example, it is used for gums in food applications, and a cool sensation is obtained by the intervention of saliva during chewing (for example, patent documents) 1).

  However, when processing a sugar alcohol that is water-soluble into fibers, there is a problem that the water used for washing flows out, and there is a problem of imparting washing durability that maintains the effect even after washing. .

  Regarding processing of sugar alcohol into fibers, there is known a technique of processing a resin obtained by crosslinking and polymerizing sugar alcohol via a crosslinking group into fibers (Patent Documents 2 and 3). If it is left, the OH group in the sugar alcohol is reduced, the hydration action is reduced, and a sufficient cool feeling cannot be obtained.

Also known is a method of coating the fiber surface with a polymer of a vinyl compound having a polyalkylene glycol in the main chain (Patent Documents 4 and 5), and retains the inorganic particles and the polymer with good washing durability. Although it is known, there is no disclosure about retention of organic substances such as sugar alcohols.
JP-T-2004-508809 JP 2003-20568 A Japanese Patent Laid-Open No. 2004-91949 Japanese Patent Publication No.51-2559 Japanese Patent Publication No. 63-29037

  In view of the prior art, the present invention is intended to provide a fiber structure to which a sugar alcohol having a cool feeling is attached with good durability.

  The present invention is based on the above-mentioned problem, that is, as a result of intensive investigations on improving the washing durability of water-soluble sugar alcohols, and the sugar alcohol is retained by a film formed by polymerizing a polymerizable monomer together with inorganic particles. It was clarified to solve the problem at once.

  In order to solve the above problems, the present invention has the following configuration.

  That is, the fiber structure of the present invention contains at least both ends or one end of the main chain mainly composed of polyalkylene oxide segments or side chains of the main chain containing inorganic particles and sugar alcohol on the fiber surface. A film formed by polymerizing a polymerizable monomer having two acrylic groups and / or methacryl groups is formed, and the thickness of the film is 5 to 40 nm, and the polymerizable monomer / inorganic particles The weight mixing ratio of the polymerizable monomer / the sugar alcohol is 1 / 0.01 to 0.1, and the inorganic particles are particles. It has a particle diameter of 5 to 400 nm in diameter.

  ADVANTAGE OF THE INVENTION According to this invention, the sugar alcohol which has a cool feeling effect | action can be adhered with sufficient durability, and the textile fabric which continues a cool feeling after washing can be provided.

  In the fiber structure of the present invention, first, at least two ends of the main chain mainly composed of polyalkylene oxide segments or one end or side chains of the main chain are formed on the surface of each fiber constituting the fiber structure. A film is formed by polymerizing a monomer having an acrylic and / or methacrylic group, and the film has a thickness of 5 to 40 nm, particularly preferably 10 to 30 nm. It has been made.

  If the film thickness is smaller than 5 nm, the coating itself is easily peeled off by washing or the like, and if it is larger than 40 nm, the texture is cured and the feeling of creaking increases, so that all of the effects of the present invention are exhibited well. It is difficult to obtain a fiber structure that also has a good texture.

  Furthermore, in the present invention, it is important that the coating contains sugar alcohol and inorganic particles having a specific particle size of 5 to 400 nm, and in particular, sugar alcohol and inorganic particles are added to the specific monomer described above. By mixing and polymerizing on the fiber surface to form a film, it is possible to impart an excellent cool feeling and washing durability to the fiber structure.

  In the present invention, inorganic particles having a particle diameter of 5 to 400 nm are used. The particle diameter here means an average particle diameter measured by a viscosity distribution meter. As a viscometer, Shimadzu laser diffraction type viscosity distribution analyzer SALD-2000J was used.

  In the present invention, examples of the monomer having at least two acrylic groups and / or methacrylic groups as both ends or one end of the main chain mainly composed of a polyalkylene oxide segment or a side chain of the main chain include: Polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, polyethylene glycol-polypropylene glycol dimethacrylate, polyethylene glycol-polypropylene glycol diacrylate, ethylene oxide adduct dimethacrylate of bisphenol A, ethylene oxide adduct diacrylate of bisphenol A, propylene of bisphenol A Oxide adduct dimethacrylate, propylene oxide adduct diacrylate of bisphenol A, etc. alone or 2 It can be used as a mixture or more.

  A polymerization initiator can be used to polymerize such a monomer. Examples of the polymerization initiator include general vinyl polymerization initiators such as ammonium persulfate, potassium persulfate, azobisisobutyronitrile, and ammonium sulfate. Can be used. By using such a polymerization initiator, a continuous or non-continuous film can be formed on the fiber surface by treatment in a saturated water vapor or supersaturated water vapor atmosphere at 80 to 160 ° C. for 0.5 to 10 minutes. The thickness of the coating can be controlled by the resin adhesion amount.

  That is, the concentration of the active resin component when preparing a mixture of a polymerizable monomer and a polymerization catalyst and the squeezing rate when the fiber structure is impregnated with the resin liquid and squeezed with mangle, that is, the pressure applied to the mangle are appropriately adjusted. By doing so, the resin adhesion amount, that is, the film thickness of the coating film can be controlled. In general, the control is performed by changing the concentration of the effective resin component of the squeezed resin at a constant pressure, and the thickness of the coating tends to be reduced if the effective resin component concentration is lowered or the squeezing rate is increased.

  In the present invention, the above-described coating on the fiber surface forms a coating continuously or non-continuously on the surface of a single fiber, and is difficult to fall off even by washing. Is obtained. And if it has good water absorption, sweat absorbency will improve, and the water | moisture content in sweat will be utilized for the hydration action of sugar alcohol. Further, at the time of forming the film, it is important to add both sugar alcohol and inorganic particles in order to obtain washing durability. The sugar alcohol provides a cool sensation, and the dry touch formed on the surface of the coating with inorganic particles allows you to spend comfortably when sweating and hot.

  Examples of inorganic particles that can be used in the present invention include aluminum oxide, silicon oxide, titanium oxide, kaolinite, talc, calcium carbonate, calcium silicate, magnesium oxide, and the like. These may be used alone or in combination of two or more. Can be used. Among them, silicon oxide having a uniform particle diameter is easy to obtain, which is preferable. A core particle of silica is generated in the reaction medium by the polymerization reaction of silicon, and by controlling the particle growth, a particle having a specific particle diameter can be obtained.

  The particle diameter of the particles is 5 to 400 nm, preferably 10 to 200 nm. If it is less than 5 nm, it is difficult to form fine irregularities, and if it exceeds 400 nm, the formation of a polymer film may be insufficient. Therefore, the inorganic particles must have a particle size in the range of 5 to 400 nm. A particle having a particle size outside the particle size range does not affect the formation of the unevenness, for example, more than 0% and 10% is included. As the inorganic particles in the particle range, commercially available inorganic particles in a specific particle range can be used, but it is preferable to use them in a dispersion state.

  In the present invention, any sugar alcohol can be used as long as it has an endothermic reaction at the time of hydration, and preferably xylitol, sorbitol, glycerol, erythritol, maltitol, mannitol, dipentaerythritol, etc. Among these, xylitol is particularly preferably used.

  As the sugar alcohol used in the present invention, an aqueous solution of a sugar alcohol can be used, and other organic components such as sugars such as erythritol and oils such as squalane and glycerin can be added as necessary.

  The weight mixing ratio of the polymerizable monomer, sugar alcohol and inorganic particles of the present invention is as follows: monomer / inorganic particles = 1.0 / 0.4 to 1.0, monomer / sugar alcohol = 1 It is necessary to be 0.0 / 0.01 to 0.1. If the amount of inorganic particles is less than 0.4, the surface unevenness is small and it is easy to feel stickiness of sweat, and if it is more than 1.0, the film-forming property is deteriorated. When the sugar alcohol is less than 0.01, it is difficult to feel cool, and when it is more than 0.1, the film-forming property is deteriorated. When the film forming property is deteriorated, the washing durability is also deteriorated, which is not preferable.

  In the present invention, as a method of forming a film containing inorganic particles and sugar alcohol, a fiber fabric is immersed in an aqueous liquid in which a polymerizable monomer, a polymerization initiator and inorganic particles are mixed, and then squeezed with a mangle or the like. After adjusting to a predetermined adhesion amount, a treatment is performed in an atmosphere of saturated steam or supersaturated steam at 80 to 160 ° C. for 0.5 to 10 minutes, preferably 1 to 4 minutes, and then with a nonionic surfactant. Wash in a washing solution containing sodium carbonate, etc. at a temperature of 40 to 80 ° C. for 1 to 5 minutes, wash with water to remove unreacted monomers and polymerization initiator, dry at 100 to 130 ° C., and 140 to 180 ° C. A heat setting method or the like can be employed. Moreover, after giving an aqueous liquid and drying at 100-130 degreeC, the method of carrying out a water vapor treatment can also be employ | adopted. As long as the effect of the present invention is not impaired after such film formation processing, an antistatic agent, a water-absorbing agent, a moisture-absorbing agent, a water-repellent agent, an oil-repellent agent, an antifouling agent, a colorant, a lubricant, a sewability. It may be treated with an improver or the like.

  When the fiber structure of the present invention is observed with a transmission electron microscope (TEM) at a magnification of 100,000, for example, a film having a thickness of 5 to 40 nm containing the inorganic particles and sugar alcohol is formed on the single fiber. Can be confirmed.

  The fibers constituting the fiber structure of the present invention are not particularly limited, but polyester fibers, polyethylene fibers, polypropylene fibers, polyamide fibers, polyvinyl alcohol fibers, polyvinyl chloride fibers, polyacrylonitrile fibers, Synthetic fibers such as polylactic acid fibers, semi-synthetic fibers such as rayon and acetate, and natural fibers such as cotton, hemp, silk, and wool can be used, and these can be used alone or in combination of two or more. In addition, long fibers or short fibers may be used, and these may be mixed and used.

  As the structure of the fiber fabric of the present invention, woven fabrics, knitted fabrics, nonwoven fabrics and the like made of the above-mentioned fibers can be used.

  The water absorption of the fiber structure of the present invention is preferably 5 seconds or less when measured by the following measurement method. Water absorption that satisfies this value can also be imparted to a fiber structure composed of hydrophobic fibers such as polyester fibers by coating the coating of the present invention. This is because the hydrophilic film is constituted by the ether group of the polymerizable monomer and the hydroxyl group of the sugar alcohol. Water is absorbed quickly when sweating, and the hydration reaction of the sugar alcohol also proceeds promptly, thereby making it easier to obtain a cool feeling.

Measuring method of water absorption (water absorption rate):
A fiber fabric measuring 15 cm in length and 15 cm in width is fixed to an embroidery frame with a diameter of 10 cm or more and placed horizontally. A drop of distilled water is dropped from the upper 5 cm using an injection needle. Measure the time to be absorbed. The measurement is performed three times, and the average value of the three measurement times is the water absorption (water absorption rate).

  The fiber structure of the present invention can be used suitably for sportswear, training wear, blouse, dress shirt, skirt, slacks, gloves, hat, lining, underwear, or socks because a cool feeling can be obtained. is there.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these. Moreover, the quality evaluation in an Example was implemented with the following method.

(1) Coolness:
Fold the dough (5cm x 5cm) adjusted to 35 ° C so that the dough surface is on the outside, and fill the gap between the dough with the alcohol thermometer so that it is perpendicular to the long side of the folded dough Place the tip of the side in the middle, wrap the short side of the fabric around the thermometer, fix the cloth with rubber bands, and fix the thermometer vertically.
After confirming that the reading of the thermometer is 35 ° C., add 5 ml of distilled water (water temperature 32 ° C.) and read the temperature every 5 minutes.

(2) Wear test:
Create a polo shirt that is sewn using a polymerizable monomer-treated cloth on the right half and a dyed cloth that has not been treated with a polymerizable monomer on the left half, and an adult boy wears it and walks for 1 hour outdoors. The left and right wearing feelings were compared by relative evaluation with the left half as having no refreshing feeling.

(3) Water absorption:
As described above.

(4) Washing durability:
A weak alkaline synthetic detergent specified in JIS K 337 is dissolved in an automatic inversion swirl electric washing machine to a concentration of 0.2%, a bath ratio of 1:50, and a temperature of 40 ± 2 ° C. under strong conditions. The process of washing for 10 minutes and then draining and rinsing with water for 5 minutes was taken as one time, and this was repeated 10 times, followed by air drying.

(5) Measurement method of film thickness:
The film thickness on the fiber surface of the present invention refers to a value obtained by the following method.

  Osmic acid dyeing is performed in advance on the coating on the surface of the fiber structure so that the coating and the fiber body can be easily distinguished. About the dyed fiber structure, a vertical cross section is cut out, 10 fibers are selected at random, and the film thickness is measured with a transmission electron microscope (TEM) at one place for each. For the horizontal cross section, the film thickness at 10 locations is measured in the same manner. The average value of a total of 20 measured values is defined as the thickness of the coating of the present invention.

(6) Measuring method of particle diameter of inorganic particles:
The average value was measured using a Shimadzu laser diffraction viscosity distribution analyzer SALD-2000J.

Examples 1-3, Comparative Examples 1-10
After knitting a circular knitted fabric in which a false twisted yarn of 110 dtex / 48 filament and 167 dtex / 72 filament made of polyethylene terephthalate is knitted at a ratio of 60:40, the woven fabric is always used in a continuous scourer at a temperature of 95 ° C. According to the method, scouring, washing with hot water, drying at 130 ° C., and further setting a pin tenter at 180 ° C. Subsequently, it was dyed with a liquid dyeing machine, dried at 130 ° C., and further pintter set at 170 ° C. to obtain a white knitted fabric with a wale / course density of 34/38 / 2.54 cm.

  The dyed fabric was treated by the following method, and the performance was evaluated.

<Polymerizable monomer>
Polyethylene glycol dimethacrylate (active ingredient 100% by weight) having a molecular weight of 1000 as the polyalkylene oxide segment was used.

<Inorganic particles>
An aqueous dispersion of silicon oxide having the following particle size was used. In addition, an active ingredient here is a silicon oxide in an aqueous dispersion, and includes several percent of particles having a particle size other than those shown.
a. Snowtex XS (particle size approximately 4nm) (Nissan Chemical Industry Co., Ltd., active ingredient 20% by weight)
b. Snowtex 20 (particle size 10-20nm) (Nissan Chemical Industries, Ltd., active ingredient 20% by weight)
c. Snowtex OL (particle size 40-50nm) (manufactured by Nissan Chemical Industries, Ltd., 20% by weight active ingredient)
d. MP4540 (particle size 420-480 nm) (Nissan Chemical Industry Co., Ltd., active ingredient 40% by weight)

<Sugar alcohol>
TASTEX COOLEX-A (manufactured by Bayer Chemicals Japan Ltd., active ingredient 2.5% by weight) was used.

<Adjustment of treatment liquid>
A monomer is dissolved in water at concentrations of 3 g / l, 10 g / l, 20 g / l, and 40 g / l, and 2 g / l of ammonium persulfate is added as a polymerization initiator. The active ingredient of xylitol is 0.005, 0.01, 0.02 with respect to monomer 1 so that the weight ratio of 0.1, 0.4, 0.9, 1.2 to body 1 , 0.04, 0.08, and 0.16 in weight ratio. A treatment solution not containing silicon oxide and a treatment solution not containing xylitol were also prepared.
Amount of silicon oxide used (g / l) = monomer amount (g / l) × silicon oxide amount ÷ active ingredient weight%
Amount of xylitol used (g / l) = monomer amount (g / l) × xylitol amount ÷ active ingredient weight%

<Processing conditions>
The dyed cloth was immersed in the treatment liquid, squeezed with mangle, and adjusted so that the amount of the treatment liquid adhered was 100% by weight, and then treated in a saturated steam atmosphere at 106 ° C. for 3 minutes.
Subsequently, it was washed for 1 minute in a 60 ° C. aqueous solution containing 1 g / L of a nonionic surfactant and 1 g / L of sodium carbonate, washed with water, dried at 130 ° C., and pinter set at 160 ° C.

  As is clear from Table 1, in comparison with the comparative example, the examples are those in which silicon oxide and xylitol are mixed in a specific ratio to the polymerizable monomer, and have a fine unevenness of 5 to 40 nm. It is understood that the coating film is formed, and the cool feeling is excellent, the water absorption is good, and the washing resistance is also excellent.

Claims (5)

  At least two acrylic groups and / or methacrylic groups as both ends or one end of the main chain mainly composed of polyalkylene oxide segments or side chains of the main chain containing inorganic particles and sugar alcohol on the fiber surface A film is formed by polymerizing a polymerizable monomer having a thickness of 5 to 40 nm, and the polymerizable monomer / inorganic particle weight mixing ratio is 1 / 0.4. -1.0, and the weight mixing ratio of the polymerizable monomer / the sugar alcohol is 1 / 0.01 to 0.1, and the inorganic particles have a particle diameter of 5 to 400 nm. The fiber structure characterized by being.   The fiber structure according to claim 1, wherein the inorganic particles are silicon oxide.   The fiber structure according to claim 1 or 2, wherein the sugar alcohol is xylitol. The fiber structure according to claim 1, 2 or 3, wherein the water absorption (water absorption speed) measured by the following measurement method is 5 seconds or less.
Measuring method of water absorption (water absorption rate):
A fiber fabric measuring 15 cm in length and 15 cm in width is fixed to an embroidery frame with a diameter of 10 cm or more and placed horizontally. A drop of distilled water is dropped from the upper 5 cm using an injection needle. Measure the time to be absorbed. The measurement is performed three times, and the average value of the three measurement times is defined as water absorption (water absorption rate).   The fiber structure according to any one of claims 1 to 4, wherein the fiber structure is sportswear, training wear, blouse, dress shirt, skirt, slacks, gloves, hat, lining, underwear or socks.