JP2005226188A - Fiber material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a nonconventional fiber material having stable negative ion-generating properties. <P>SOLUTION: The fiber material is obtained by fixing inorganic porous fine particles having ≥300 Å average pore radius, ≥0.2 ml/g pore volume, ≥20 m<SP>2</SP>/g specific surface area and 0.1-5 μm average particle diameter, and further having the negative ion-generating properties, and a binder resin free from a halogen element as a constituent component, regulated so that the weight ratio of the binder resin to the inorganic porous fine particles may be (0.1-10): 1, on the surface of a fiber. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a fiber material having a stable negative ion generation property that has not existed before. Furthermore, dress shirts, blouses, pants, skirts, polo shirts, T-shirts, training wear, jackets, coats, sweaters, pajamas, school uniforms, work clothes, white robes, yukata, underwear, lining, interlining, hats, mufflers, shoes , Slippers, socks, tights, pantyhose clothing and sheets, duvets, pillows, duvet side, duvet covers, pillow covers, bed covers, blankets, towels, cushions, cushion covers, padded cotton, toilet seat covers, tablecloths The present invention relates to a textile material that can be widely applied to bedding / interior goods such as wallpaper, curtains, goodwill, carpets, seats, interior materials, chairs, air filters and mats.

  The trend of “healing” and “relaxing” is increasing in today's stressful society, but in recent years, the balance of positive ions and negative ions in the environment and in the air has been attracting attention in recent years. And the effect they have on the mind and body of a person. Many examples of research on ions in the air have already been introduced, but in general, there are many positive ions in urban air polluted by exhaust gases from factories and automobiles, etc. On the other hand, there are a lot of negative ions in watersides such as mountain villages and forests, waterfalls, riversides, and coastal areas where air pollution is not progressing, and it has a healing effect to ease people's hearts It is said. It is also said that in an environment with a lot of positive ions, the body's decay and aging progress due to its oxidizing action, and there are attempts to neutralize and reduce the environment with artificially created negative ions. . For example, home appliances such as air conditioners, air purifiers, electric fans, and hair dryers equipped with negative ion generators that apply principles such as corona discharge are one such attempt. However, since such home appliances basically require electric power, there is a problem that they can only receive the benefits in an environment with a power supply source, and electromagnetic waves generated from the home appliance itself are generated. There is also a contradiction that will adversely affect the body.

In that respect, it can be said that it is reasonable and effective for the fiber material itself, which can be widely applied to clothing, bedding and interior goods, to generate negative ions, and many proposals have been made for such fiber material. Yes. For example, Japanese Patent Publication No. 6-104926 proposes an electret fiber in which finely divided tourmaline is fixed or contained in an organic fiber. This tourmaline, also known as tourmaline, is a substance with permanent spontaneous electric polarization that generates negative ions due to external stress, but originally the negative ions generated by tourmaline itself are weak and adhere to fibers. Since the amount is as small as 3 to 4%, there is a problem that the effect cannot be expected so much. Japanese Patent Application Laid-Open No. 11-228935 proposes a fiber product containing monazite as a negative ion generator. However, monazite originally contains a small amount of radioactive material, so it is added simultaneously with negative ions. Ion is also generated and has the disadvantage that the performance obtained is unstable, and it contains natural radioactive substances such as uranium and thorium even if it is a trace amount below the standard value, especially in large quantities. There were still concerns about the safety when stored and used. In JP-A-2001-279574, JP-A-2001-288679, JP-A-2002-309482, etc., an inorganic porous substance is fixed to a fiber using a binder resin, and a physical stimulus such as vibration or friction is used. Attempts have been made to generate negative ions, but the inorganic porous material and binder resin and their compounding ratio have not been sufficiently specified, and the magnitude relationship between the amount of negative ions and the amount of positive ions generated at that time As a result, the negative ion generation property of the resulting fiber structure is unstable.
Japanese Patent Publication No. 6-104926 JP 11-228935 A JP 2001-279574 A JP 2001-288679 A JP 2002-309482 A

  In view of the background of such prior art, the present invention is intended to provide a fiber material having a stable negative ion generating property that has not existed before. Furthermore, dress shirts, blouses, pants, skirts, polo shirts, T-shirts, training wear, jackets, coats, sweaters, pajamas, school uniforms, work clothes, white robes, yukata, underwear, lining, interlining, hats, mufflers, shoes , Slippers, socks, tights, pantyhose clothing and sheets, duvets, pillows, duvet side, duvet covers, pillow covers, bed covers, blankets, towels, cushions, cushion covers, padded cotton, toilet seat covers, tablecloths It is intended to provide textile materials that can be widely applied to bedding and interior goods such as wallpaper, curtains, goodwill, carpets, seats, interior decorations for chairs, chairs, air filters and mats.

In order to solve the above problems, the present invention employs the following means. That is, the fiber material of the present invention is an inorganic material having an anion generation property having an average particle diameter of 0.1 to 5 μm having an average pore radius of 30 nm or more, a pore volume of 0.2 ml / g or more and a specific surface area of 20 m ² / g or more. The porous fine particles and a binder resin not containing a halogen element as a constituent component are fixed on the fiber surface at a weight ratio of 0.1 to 10 binder resins with respect to the weight 1 of the inorganic porous fine particles. To do.

  ADVANTAGE OF THE INVENTION According to this invention, the fiber material which has the stable negative ion generating property which was not before can be provided. Furthermore, dress shirts, blouses, pants, skirts, polo shirts, T-shirts, training wear, jackets, coats, sweaters, pajamas, school uniforms, work clothes, white robes, yukata, underwear, lining, interlining, hats, mufflers, shoes , Slippers, socks, tights, pantyhose clothing and sheets, duvets, pillows, duvet side, duvet covers, pillow covers, bed covers, blankets, towels, cushions, cushion covers, padded cotton, toilet seat covers, tablecloths It is possible to provide textile materials that can be widely applied to bedding and interior goods such as wallpaper, curtains, goodwill, carpets, seats, interior materials, chair stickers, air filters, and mats.

  Hereinafter, the present invention will be described in detail.

The fiber material of the present invention is characterized in that a specific inorganic porous fine particle and a specific binder resin are fixed on a fiber surface at a specific ratio, and the inorganic porous fine particle itself is stable. As a result of intensive studies on this point, specifically, the average pore radius is 30 nm or more, the pore volume is 0.2 ml / g or more, and the specific surface area is The inventors have found out that those satisfying the three conditions of 20 m ² / g or more at the same time have a very good negative ion generation property. This pore radius, specific surface area, and pore volume are correlated with each other, and all represent the shape of the porous pores numerically, but in the case of diatomaceous earth generally used for wall materials, etc. When the pore radius is about 5 nm, the pore volume is about 0.05 ml / g, the specific surface area is about 20 m ² / g, and in the case of commercially available activated carbon used as a deodorant, the average pore radius is about 3 nm, the pore volume Whereas the value is about 0.7 ml / g and the specific surface area is about 25 m ² / g, the inorganic porous fine particles of the present invention have an average pore radius of 30 nm or more, which is large for the specific surface area and the pore volume. There is a great feature in that it has an average pore radius, and the mechanism is not clear, but this point is considered to be a factor that the inorganic porous fine particles have a stable negative ion generation property. The average pore radius, pore volume and specific surface area can be measured by a pore distribution measurement by a mercury intrusion method and a BET method by nitrogen gas adsorption. The negative ion generating property means that it has a property of generating negative ions, and the measurement can be performed by an air ion counter as described later.

  Furthermore, the inorganic porous fine particles having such a shape must have an average particle diameter (median diameter) in the range of 0.1 to 5 μm. When the average particle diameter is smaller than 0.1 μm, most of the inorganic porous fine particles are buried in the binder resin, so that stable negative ion generation cannot be sufficiently exhibited when a fiber material is obtained. On the other hand, when the average particle diameter exceeds 5 μm, the texture of the obtained fiber material becomes very rough and the surface quality when the fiber material is used as a product becomes very bad. Furthermore, the dispersion state of the inorganic porous fine particles on the fiber surface is deteriorated, the generation of negative ions is reduced, and the binder resin is not sufficiently exerted, and the particles fall off when worn as a product. When the product is washed and the product is washed, there are many problems that the negative ion generation property is lost due to the dropping of particles. For these reasons, it is more preferable that the inorganic porous fine particles have an average particle diameter in the range of 0.1 to 5 μm and a relative particle amount of 0.1 to 1 μm is 90% or more. These numerical values can be measured using a commonly used laser diffraction type size analyzer.

The composition and composition ratio of the inorganic porous fine particles are not particularly limited as long as they exhibit negative ion generation. However, when versatility is taken into consideration, oxides of silicon, aluminum, iron, calcium and magnesium, that is, SiO ₂ Al ₂ O ₃ , Fe ₂ O ₃ , CaO and MgO are preferably contained as main constituent components. In addition, in order to develop a more stable generation of negative ions, the constituent components are substantially free of uranium and thorium, which are natural radioactive substances, that is, when the radiation dose of the inorganic porous fine particles is measured. It is preferable that the radiation dose increase beyond the fluctuation range of the ground is not observed, and the increase in the radiation dose by the fiber material obtained by fixing this is within the fluctuation range of the background radiation. Although the value of the background radiation dose varies depending on the place and region to be measured, it cannot be generally stated. For example, when the background radiation dose is 0.063 ± 0.003 μSv / h, the inorganic porous fine particles The radiation dose preferably does not exceed 0.066 μSv / h. When the inorganic porous fine particles contain a natural radioactive substance such as uranium or thorium, due to the nature, the same amount of positive ions is generated at the same time as the generation of negative ions at the time of standing. There is almost no negative ion concentration increase amount in the atmosphere calculated from the above, and as a result, a very unstable negative ion generation property is obtained. Also, in industrial products that are expected to be produced and stored in bulk, the reason why safety remains uneasy if they contain natural radioactive materials such as uranium and thorium, even if they are less than the standard value It is preferable that the substance is not substantially contained. The radiation dose here is a value calculated from the product of the absorbed dose and the radiation weighting coefficient, and is a scale representing the influence of radiation on the human body. A radiation dose equivalent of 1 Sv (sievert) is such that radiation damage (such as nausea) begins to appear, and at 4 Sv, more than half of the people die. Normally, there is no risk of acute damage below 200 mSv, and the average radiation dose (excluding medical examinations) that Japanese people receive from nature per year is 2.4 mSv / year. Such radiation dose can be measured using a scintillation survey meter. The content of uranium and thorium, which are natural radioactive elements, can be confirmed using an inductively coupled plasma mass spectrometer.

  In the present invention, the inorganic porous fine particles do not have to be collected from nature as long as they satisfy the above requirements. For example, the inorganic porous fine particles may be ceramic or zeolite obtained by firing or chemical treatment. It doesn't matter.

  Next, in the present invention, such inorganic porous fine particles are fixed to a specific binder resin at a specific ratio on the surface of the fiber constituting the fiber material. As a method for imparting inorganic porous fine particles to a fiber material, a method in which the fiber is kneaded into the fiber when wet spinning or melt spinning is known. The result is that most of the porous fine particles are buried inside the fiber and the effect of generating negative ions cannot be sufficiently exhibited. Also, in actual production, it may cause a thread breakage during spinning, which is not preferable. On the other hand, since such inorganic porous fine particles are inorganic, there is almost no adhesiveness to the fiber even when applied alone on the fiber surface, and therefore the durability when the obtained fiber material is used for washing or the like is low. I can't get it. For these reasons, in the present invention, it is an essential condition that the inorganic porous fine particles are fixed together with the binder resin on the surface of the fibers.

  The amount of the inorganic porous fine particles attached to the fiber material of the present invention is 0.01% with respect to the weight of all the fibers constituting the fiber material in terms of the negative ion generation effect, the quality of the fiber material, and the texture. It is preferably in the range of not less than 10% by weight. If the adhesion amount is less than 0.01% by weight, the negative ion generation property may become unstable depending on the type of fiber constituting the fiber material. On the other hand, if the adhesion amount exceeds 10% by weight, the negative ion generation property is very low. However, the texture of the obtained fiber material tends to become coarse and hard, and the surface quality and coloration when the fiber material is used as a product tend to be slightly inferior to the normal product.

  The proper adhesion amount of the binder resin to the fiber varies depending on the amount of the above-mentioned inorganic porous fine particles applied to the fiber and the particle diameter, but within the range of the average particle diameter of 0.1 to 5 μm, the inorganic porous In order to obtain stable negative ion generation, it is very important that the weight of the binder resin is fixed on the fiber surface in a weight ratio of 0.1 to 10 with respect to the weight 1 of the fine particles. If the adhesion amount of the binder resin is less than 0.1 with respect to the adhesion amount of the inorganic porous fine particles, the sticking property of the inorganic porous fine particles to the fiber will be extremely lowered, so the obtained fiber material is used as a product. In this case, the inorganic porous fine particles easily fall off when used for washing or the like, and as a result, stable negative ion generation cannot be obtained. On the other hand, when the adhesion amount of the binder resin exceeds 10 with respect to the adhesion amount of the inorganic porous fine particles, most of the inorganic porous fine particles are covered with the binder resin or buried inside the resin, and the effect of generating negative ions sufficiently. As a result, it is not suitable for obtaining the stable negative ion generation property of the present invention.

  As the binder resin for fixing the inorganic porous fine particles on the fiber surface, those having good adhesiveness with both and not inhibiting the good negative ion generation performance of the inorganic porous fine particles are selected and used. There is a need to. In this regard, as a result of diligent investigation on the binder resin, it has been found that binder resins containing a halogen element as a constituent component tend to greatly hinder the negative ion generation ability of the inorganic porous fine particles. That is, it is an essential condition that the binder resin used in the present invention does not contain a halogen element as a constituent component of the resin itself. Specifically, fluorocarbon resins that contain fluorine as a component and are generally used as water and oil repellents, and copolymer resins of these resins and acrylic resins (for example, “Asahi” manufactured by Asahi Glass Co., Ltd.) "Guard" series and Dainippon Ink & Chemicals' "Mega Fuck" and "Dick Guard" series), a vinyl chloride resin that is also commonly used as a hard finish and texture adjuster, containing chlorine as a component. Copolymer resins of vinyl, ethylene, vinyl acetate, etc. (for example, “Smitex Resins 181, 182, 183” manufactured by Sumitomo Chemical Co., Ltd.) are inappropriate for use as binder resins even in small quantities. is there. The reason for this is not clear, but it is considered that the binder resin containing a halogen element having a high electronegativity in the molecule has the ability to absorb negative ions generated from the inorganic porous fine particles.

  As the binder resin that satisfies the above-described conditions, in the present invention, one or more types can be appropriately selected from silicone resins, acrylic resins, polyester resins, polyurethane resins, melamine resins, and the like. Of these, silicone-based resins, polyester-based resins, and polyurethane-based resins are preferably used when emphasizing the texture of the fiber material obtained. On the other hand, acrylic resin, polyurethane resin, and melamine resin are preferably used when washing durability is particularly important. Isocyanate compounds and carbodiimides are used as crosslinking agents for the purpose of improving the washing durability of the binder resin. It is also preferable to add a compound, a silane coupling agent, a glyoxal resin and the like as appropriate. In addition, when the fiber material is short-filled cotton for filling, it is also preferable to select a silicone resin or polyester resin with low adhesiveness in consideration of the passability of the post-process such as a card.

  In order to fix the inorganic porous fine particles and the binder resin on the fiber surface in the present invention, for example, the inorganic porous fine particles are dispersed in water together with a dispersion stabilizer, and the binder resin and the binder resin are within the range described above. After mixing to make an aqueous processing solution, a certain amount is given to the fiber material by means of padding method, dipping method, spray method, printing method, coating method, gravure processing method, foam processing method, etc., then drying and heat treatment process For example, it is possible to apply means such as fixing on the fiber. In particular, from the viewpoint of ease of work, the padding-heat treatment method is preferably applied when the shape of the fiber material is a fabric shape such as a woven or knitted fabric, and the spray-heat treatment method is preferably applied when the fiber material is a short fiber cotton. In addition, although heat processing temperature changes with kinds of binder to be used, if it is a general silicone resin and acrylic resin, it should just process on the conditions for 20 second-5 minutes within the temperature range of 100-200 degreeC.

  As the fibers constituting the fiber material in the present invention, general synthetic fibers, regenerated fibers, natural fibers and the like can be appropriately selected and used. Specifically, polyester, polyamide, polyacrylonitrile, polyethylene, polypropylene, and the like can be used. Synthetic fibers, semi-synthetic fibers such as diacetate and triacetate, regenerated fibers such as rayon, cupra and tencel, and natural fibers such as cotton, hemp, pulp, wool and silk can be used. Moreover, there is no problem even if these are used in an arbitrary ratio of two or more, kneaded, blended, blended, and knitted. Moreover, as a form of the fiber material, any form may be used as long as it is composed of fibers such as a woven fabric, a knitted fabric, and a non-woven fabric, as well as a string-like material and a thread-like material.

  The fiber material of the present invention thus obtained can stably generate negative ions with energy applied by external physical stimulation such as stagnation, vibration and friction. In the present invention, negative ions and positive ions are fine particles in the air (air ions) charged negatively or positively that can be detected by an air ion counter. The air ion counter is a device that measures the concentration of negatively or positively charged particles by flowing air containing air ions into the ion concentration detector, and the principle of measurement is to use a detection plate charged to an arbitrary potential. The total charge amount of the collected air ions is measured, and the ion concentration is obtained by dividing this by the elementary charge amount. The unit is represented by the number of ions per unit volume (pieces / cc). In the present invention, an air ion counter “ITC-201A” manufactured by Andes Electric Co., Ltd. is used, and physical stimulation of 500 Pa or more is applied to the fiber material in an environment of a temperature of 20 ° C. and a relative humidity of 65% RH. Measurements were taken as given. Here, the temperature includes an allowable fluctuation range of ± 1 ° C. and relative humidity of ± 5%. In addition, the physical stimulus includes an allowable variation range of ± 100 Pa.

  The amount of negative ions generated in the fiber material obtained by the present invention when such a measuring device is used is such that the distance from the fiber material surface is 10 cm when the fiber materials are rubbed together at a pressure of 500 Pa, for example. The difference [A−B] between the negative ion concentration [A] and the positive ion concentration [B] detected by the air ion counter at 100 points / cc or more (that is, the atmosphere is 100 ions / cc or more and negative ions are rich). State) level.

  As described above, the fiber material of the present invention has stable negative ion generation that has not been heretofore, and dress shirts, blouses, pants, skirts, etc. that are craving for effects such as `` healing '' and `` relaxing '', Polo shirts, T-shirts, training wear, jackets, coats, sweaters, pajamas, school uniforms, work clothes, white robes, yukata, underwear, lining, hats, scarves, shoes, slippers, socks, tights, pantyhose, etc. Product use and sheets, futon, pillow, futon side, duvet cover, pillow cover, bed cover, blanket, towel, cushion, cushion cover, padded cotton, toilet seat cover, tablecloth, wallpaper, curtain, goodwill, carpet, sheet, Car interior materials, chairs, air filters, mats, etc. It is optimal for use in goods applications.

  EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example, this invention is not limited to these Examples. In addition, the measurement and evaluation in an Example were performed in accordance with the following method.

<Laundry test>
According to JIS L0217 103 method, 20 home washing tests were carried out.

<Pore volume, average pore radius>
Measurement method: Mercury intrusion method pore distribution measurement (PD)
Equipment: Carlo Elba Model 2200 <specific surface area>
Measurement method: BET-1 point method, distribution method, TDC detection apparatus: QUANTA CHROME QUANTA SORB OS-8
Pretreatment: N ₂ under 250 ° C. × 15 minutes <Negative ion generation>
Apparatus: Air ion counter ITC-201A manufactured by Andes Electric Co., Ltd.
Conditions: Temperature 20 ± 1 ° C, relative humidity 65 ± 5%, suction amount 30L / min.
(1) Prepare two 10 cm × 10 cm samples (2) Hold the sample obtained in (1) in both hands and move to the 10 cm point from the detection unit of the measuring device (3) 2 samples 1 reciprocation per second (4) Measure the negative ion concentration change and the positive ion concentration change for 1 minute while maintaining the state of (3). (5) Repeat the above measurement 5 times. Price:
An average value [A] for 1 minute of negative ion concentration and an average value [B] for 1 minute of positive ion concentration are calculated (unit: pieces / cc), and the difference [AB] between the two values is 100 pieces / cc. The above was regarded as passing.

<Real monitor monitor test>
About the fiber material obtained by the following Example and Comparative Examples 1-9, a black formal style women's jacket was sewed, and 10 women in their 20s to 40s (20s: 2 people, 30s: 6 people, One-week wearing evaluation was carried out on subjects composed of two people in their 40s. The evaluation after wearing was evaluated in the form of selecting and answering from the following five items.

I: More comfortable than usual
II ： Somehow more comfortable than usual
III: No change
IV: Somewhat unpleasant than usual V: Unpleasant than usual I indicates that evaluation is the best, and V indicates the worst evaluation.

Example 1
First, a fabric for women's outerwear was prepared as a base fabric for evaluation by the following procedure.

  Ordinary polyethylene terephthalate was melt spun by a conventional method and then drawn to obtain a drawn yarn of 90 dtex 36 filaments. The drawn yarn was subjected to S twisting 1,800 times / m by a double twister to obtain a twisted yarn. Next, the twisted yarn was used as a warp yarn and a weft yarn to be woven into a satin woven fabric having a warp density of 115 pieces / inch × 58 pieces / inch. The raw machine thus obtained was subjected to a relaxation scouring process by a conventional method, followed by an intermediate set (180 ° C. × 30 seconds), immersed in a 3% caustic soda aqueous solution and subjected to a 13% alkali weight reduction process, and then commercially available black After dyeing with a dye (“Dianics Black BG-FS”), the substrate was subjected to reduction washing and water washing treatment and dried to obtain an evaluation base fabric of the present invention.

  On the other hand, the inorganic porous fine particles of the present invention were prepared by the following method.

As the raw material, rocks collected from the bedrock mining site in Tanakakurayama, Fukushima Prefecture, about 5-10m below the topsoil were used. The rock is passed through an impact pulverizer to form a pulverized granule, then sieved to a particle having an average particle size of about 3 μm, and further subjected to a wet pulverizer to have an average particle size of 0.47 μm Fine particles) were obtained. As a result of measuring the pore volume, the average pore radius, and the specific surface area of the fine particles, the pore volume was 0.32 ml / g, the average pore radius was 50 nm, and the specific surface area was 37.8 m ² / g. As a result of analyzing the main constituent components of the inorganic porous fine particles, the main components are 55.0% by weight of silicon dioxide, 13.0% by weight of aluminum oxide, 4.1% by weight of iron oxide, and 3.6% by weight of calcium oxide. Magnesium oxide 1.6% by weight, sulfur 1.1% by weight, potassium 0.47% by weight, titanium oxide 0.16% by weight, and the like. Furthermore, as a result of confirming the inclusion of uranium and thorium using an inductively coupled plasma mass spectrometer, no significant amount was confirmed.

The inorganic porous fine particles were dispersed in an aqueous solvent to obtain a processing agent Z having a solid concentration of 20% by weight. During dispersion, sodium hexametaphosphate was added at a concentration of 5% by weight as a dispersant in order to improve the liquid stability. The processing agent Z was mixed with an acrylic binder resin (“Light Epoch T-23M” manufactured by Kyoeisha Chemical Co., Ltd., solid content concentration 20% by weight) and diluted with water to prepare a treatment liquid having the following composition. The base fabric for evaluation (woven fabric for women's outerwear) is dipped in this, padded at a drawing rate of 80%, pre-dried at 110 ° C. for 2 minutes, and then heat-treated at 160 ° C. for 2 minutes to obtain inorganic porous fine particles and a binder A fiber material in which the resin was fixed on the fiber surface was obtained.
Processing agent Z: 20 g / l
Acrylic binder resin: 20 g / l
The weight ratio of the inorganic porous fine particles to the total fiber weight of the obtained fiber material was 0.32% by weight, and the weight ratio of the inorganic porous fine particles to the binder resin was 1: 1. With respect to such a fiber material, the radiation dose was measured using a scintillation survey meter, but no radiation dose above the background was confirmed.

  A women's jacket is sewed using the fiber material thus obtained, and the negative ion generation before and after home washing is evaluated, and the wearing monitor test evaluation for subjects composed of 10 women in their 20s to 40s (Questionnaire survey, wearing period 1 week) was conducted. The results are shown in Table 1. As is clear from Table 1, the obtained fiber material had negative ion generation excellent in washing durability, and the result of the questionnaire survey was also good.

Comparative Example 1
A sample was prepared in the same manner as in Example 1 except that no treatment was performed on the evaluation base fabric in Example 1, and the sample was used for evaluation (unprocessed product of Example 1). The results are shown in Table 1. As is clear from Table 1, the raw fiber material to which the inorganic porous fine particles are not fixed did not generate negative ions, and no significant difference was found in the questionnaire survey.

Comparative Example 2
In Example 1, when polyethylene terephthalate was melt-spun by a conventional method, evaluation was performed in the same manner as in Example 1 except that 0.5% by weight of the inorganic porous fine particles of Example 1 were kneaded inside the fiber. A base fabric was created. The women's jacket was sewed without any treatment on the evaluation base fabric thus obtained, and then the negative ion generation evaluation and the monitor test evaluation were performed in the same manner as in Example 1. The results are shown in Table 1. As is clear from Table 1, when the inorganic porous fine particles were kneaded inside the fiber, the generation level of negative ions was not sufficient, and no significant effect was found in the questionnaire survey.

Comparative Example 3
In Example 1, a sample was prepared in the same manner as in Example 1 except that the binder resin was not added to the treatment liquid containing the processing agent Z, and the sample was used for evaluation. The weight ratio of the inorganic porous fine particles to the total fiber weight of the obtained fiber material was 0.31% by weight. The results are shown in Table 1. As apparent from Table 1, when no binder resin was used, no negative ions were generated from the sample after 20 washings.

Comparative Example 4
In Example 1, a sample was prepared in the same manner as in Example 1 except that the composition of the treatment liquid containing the processing agent Z was changed as follows, and used for evaluation.
Processing agent Z: 20 g / l
Acrylic binder resin: 400 g / l
The weight ratio of the inorganic porous fine particles to the total fiber weight of the obtained fiber material was 0.32% by weight, and the weight ratio of the inorganic porous fine particles to the binder resin was 1:20. The results are shown in Table 1. As is apparent from Table 1, when the binder resin was excessive, almost no negative ions were generated from the sample. In the questionnaire survey, no significant effect was observed.

Comparative Example 5
The binder resin used in the treatment liquid in Example 1 is an acrylic binder resin (“Light Epoch T-23M” manufactured by Kyoeisha Chemical Co., Ltd., solid content concentration 20% by weight) to a fluoroacrylate binder resin (Kyo Silk Co., Ltd.). A sample was prepared in the same manner as in Example 1 except that it was changed to “Max Guard EC-400” manufactured by Kasei Co., Ltd. (solid content concentration: 20% by weight), and used for evaluation. The weight ratio of the inorganic porous fine particles to the total fiber weight of the obtained fiber material was 0.32% by weight, and the weight ratio of the inorganic porous fine particles to the binder resin was 1: 1. The results are shown in Table 1. As is apparent from Table 1, when the binder resin contains fluorine in the constituent components, no negative ions were generated from the sample. In the questionnaire survey, no significant effect was observed.

Comparative Example 6
The binder resin used in the treatment liquid in Example 1 was changed from an acrylic binder resin (“Kyoeisha Chemical Co., Ltd.“ Light Epoch T-23M ”, solid concentration 20% by weight) to a vinyl chloride / ethylene / vinyl acetate copolymer resin ( A sample was prepared in the same manner as in Example 1 except that it was changed to “Sumitex Resin 181” manufactured by Sumitomo Chemical Co., Ltd., with a solid content concentration of 50% by weight. The weight ratio of the inorganic porous fine particles to the total fiber weight of the obtained fiber material was 0.32% by weight, and the weight ratio of the inorganic porous fine particles to the binder resin was 1: 2.5. The results are shown in Table 1. As is clear from Table 1, when the binder resin contains chlorine in the constituent components, no negative ions were generated from the sample. In the questionnaire survey, no significant effect was observed.

Comparative Example 7
A pore volume of 0.044 ml / g, an average pore radius of 5.1 nm, a specific surface area of 16.9 m ² / g and an average particle size of 0 prepared from diatomaceous earth collected in Ishikawa Prefecture as inorganic porous fine particles in Example 1 A sample was prepared in the same manner as in Example 1 except that 24 μm inorganic porous fine particles were used, and used for evaluation. The weight ratio of the inorganic porous fine particles to the total fiber weight of the obtained fiber material was 0.32% by weight, and the weight ratio of the inorganic porous fine particles to the binder resin was 1: 1. The results are shown in Table 1. As apparent from Table 1, when the average pore radius, pore volume, and specific surface area of the inorganic porous fine particles are outside the range defined in the present invention, the level of negative ion generation from the sample is low. In the questionnaire survey, no significant effect was observed.

Comparative Example 8
# 730 sold by Fuji Silysia Chemical Co., Ltd. as inorganic porous fine particles in Example 1 (pore volume 0.44 ml / g, average pore radius 2.5 nm, specific surface area 700 m ² / g, average particle size A sample was prepared for evaluation in the same manner as in Example 1 except that 3.0 μm inorganic porous fine particles were used, and the weight ratio of the inorganic porous fine particles to the total fiber weight of the obtained fiber material was as follows. The weight ratio between the inorganic porous fine particles and the binder resin was 1: 1, and the results are shown in Table 1. As is clear from Table 1, the average pores of the inorganic porous fine particles Even when only the radius is outside the scope of the present invention, the level of negative ion generation from the sample is low, and no significant effect was found in the questionnaire survey.

Comparative Example 9
A sample was prepared in the same manner as in Example 1 except that monazite, which is a natural radioactive mineral, was used instead of the inorganic porous fine particles in Example 1, and the sample was used for evaluation. The monazite ore used was from Australia and the composition was 61.33% by weight of rare earth oxide, 26.28% phosphorus pentoxide, 6.55% thorium oxide and 0.34% uranium oxide. It was. The weight ratio of the inorganic porous fine particles to the total fiber weight of the obtained fiber material was 0.32% by weight, and the weight ratio of the inorganic porous fine particles to the binder resin was 1: 1. Further, as a result of confirming the radiation dose of the fiber material, the radiation dose clearly showed a significant radiation dose of 0.090 ± 0.003 μSv / h against the background of 0.063 ± 0.002 μSv / h. The results are shown in Table 1. As is apparent from Table 1, when the fiber material contains a natural radioactive substance, the same amount of positive ions as the negative ions are generated from the sample, and when the number of both is subtracted, the result is that the positive ions are rich. Became. In the questionnaire survey, the reason was not clear, but many negative (unpleasant) opinions were seen.

Claims (7)

Inorganic porous fine particles having an average pore radius of 30 nm or more, a pore volume of 0.2 ml / g or more and a specific surface area of 20 m ² / g or more and an average particle size of 0.1 to 5 μm and having negative ion generation property and halogen as a constituent A fiber material, wherein a binder resin not containing an element is fixed on a fiber surface at a weight ratio of 0.1 to 10 of the binder resin with respect to 1 of the weight of the inorganic porous fine particles. 2. The fiber material according to claim 1, wherein the inorganic porous fine particles are substantially free from a natural radioactive substance, and an increase in radiation dose due to the fiber material is within a fluctuation range of background radiation. The fiber material according to claim 1 or 2, wherein the inorganic porous fine particles contain oxides of silicon, aluminum, iron, calcium, and magnesium as main components. The weight ratio of the inorganic porous fine particles to the weight of all the fibers constituting the fiber material is in the range of 0.01 wt% or more and 10 wt% or less. Fiber material. When a repeated stress of 500 Pa or more accompanied by friction and / or vibration is applied to the fiber material in an environment of a temperature of 20 ° C. and a relative humidity of 65% RH, an air ion counter is used at a point where the distance from the fiber material surface is 10 cm. 5. The difference [A−B] between the detected negative ion concentration [A] and the positive ion concentration [B] is 100 / cc or more, according to claim 1. Fiber material. A clothing product comprising the fiber material according to any one of claims 1 to 5 as at least a part thereof. A bedding / interior product comprising at least a part of the fiber material according to claim 1.