JPWO2014188908A1 - Functional fine particles and resin products containing the same - Google Patents

Abstract

[PROBLEMS] A conventional deodorant is excellent in deodorizing properties for a specific type of odor, but many other types of odors do not exhibit sufficient deodorizing properties, such as sweat odor and A satisfactory deodorizing effect cannot be obtained for the deodorization of complex odors such as aging odors. Moreover, when it adds to resin etc., there exists a problem of reducing performance, such as abrasion resistance of resin. The present invention provides high deodorization performance and moisture absorption performance for basic odors and acidic odors without greatly reducing the wear resistance of the resin when blended in the resin in order to eliminate such problems of the prior art. Provided is a moisture-absorbing deodorant fine particle that can be used. [MEANS FOR SOLVING PROBLEMS] A functional fine particle in which 0.05% by weight or more of a basic polymer is adhered to a hygroscopic fine particle having a crosslinked structure and a salt-type carboxyl group of 1.8 mmol / g or more, and an average particle Functional fine particles having a diameter in the range of 0.01 to 200 μm. [Selection figure] None

Description

The present invention relates to moisture-absorbing and deodorizing fine particles having both moisture-absorbing performance and deodorizing performance and exhibiting high adhesion to a resin when mixed with the resin.

In recent years, along with changes in the living environment, awareness of odors and stuffiness has increased, and it has been desired that odors and stuffiness caused by body fluids generated from the body be quickly and continuously deodorized and moisture absorbed. For example, regarding odor, there is a high awareness of aging odor and sweat odor. The aging odor is composed of aldehydes such as nonenal, and the sweat odor is composed of ammonia, acetic acid, isovaleric acid, and acetaldehyde. These deodorization methods are roughly classified into physical deodorization, chemical deodorization, and sensory deodorization (masking). As a physical deodorant, activated carbon is extremely excellent. However, the activated carbon has problems such as difficulty in atomization, fixation on the fiber, and deterioration of the color of the fiber. In addition, with physical deodorization, the performance is significantly reduced by operations such as washing. Moreover, the deodorant using a catalytic action has a low immediate effect. In deodorization with a fragrance or the like, the fragrance itself can become a bad odor depending on the preference of a person, or it causes olfactory fatigue, so its use is limited. Among them, there is a method using a chemical neutralization reaction that can overcome the above-mentioned problems while being excellent in immediate effect and sustained performance.

As functional fine particles used for this purpose, for example, Patent Document 1 discloses moisture-absorbing / releasing fine particles obtained by introducing salt-type carboxyl groups into acrylonitrile-based polymer fine particles having a hydrazine bridge. The hydrazine cross-linked amino group and salt-type carboxyl group exhibit deodorizing performance against acidic odor and basic odor, but lack deodorizing performance against aldehydes. Further, when the fine particles are used in a urethane resin, the resin is likely to be worn and it is difficult to maintain practical physical properties.

Patent Document 2 discloses a polymer having an acid / aldehyde deodorizing property utilizing an amino group. Regarding the method of introducing an amino group, it is preferable to treat a high nitrile polymer with hydrazine and introduce a crosslinked structure and an amine structure simultaneously. However, in such a method, the deodorizing performance with respect to the basic odor is insufficient, so that the deodorizing performance with respect to sweat / aging odor cannot be exhibited.

JP-A-8-225610 JP-A-10-156179

The object of the present invention is to overcome the above-mentioned problems of the prior art, and when blended in a resin, it is highly resistant to basic substances and acidic substances without greatly reducing the abrasion resistance of the resin. An object of the present invention is to provide moisture absorbing and deodorizing fine particles capable of imparting deodorizing performance and moisture absorbing performance.

The object of the present invention is achieved by the following means [1] to [11].
[1] Functional fine particles in which 0.05% by weight or more of a basic polymer is attached to a hygroscopic fine particle having a crosslinked structure and a salt-type carboxyl group of 1.8 mmol / g or more, and having an average particle size Is in the range of 0.01 to 200 μm.
[2] The functional fine particles according to [1], wherein a saturated moisture absorption rate in a 20 ° C. × 65% RH environment is 15% or more.
[3] Ammonia odor removal rate: 70% or more, acetic acid odor removal rate: 80% or more, isovaleric acid odor removal rate: 85% or more, nonenal odor removal rate: 75% or more The functional fine particles according to [1] or [2].
[4] The functional fine particle according to any one of [1] to [3], wherein the peel strength retention when blended with urethane-based artificial leather is 36% or more.
[5] The ratio of the salt-type carboxyl group amount to the total carboxyl group amount in the hygroscopic fine particles is in the range of 40 to 99%, according to any one of [1] to [4] Functional fine particles.
[6] A resin product comprising the functional fine particles according to any one of [1] to [5].
[7] The resin product according to [6], wherein the resin product is artificial leather.
[8] The resin product according to [6], wherein the resin product is a film.
[9] The resin product according to [6], wherein the resin product is a fiber.
[10] The resin product according to any one of [7] to [9], wherein the resin constituting the resin product contains a urethane-based resin.
[11] The resin product according to [9], wherein the resin constituting the resin product contains a cellulose polymer and / or an acrylonitrile polymer.

Since the functional fine particles of the present invention have high moisture absorption performance, it can reduce the feeling of stuffiness derived from bodily fluids generated from the body, can realize a comfortable humidity environment, and further to a complex odor such as aging odor and sweat odor. On the other hand, it is possible to develop a deodorizing performance that is immediate and lasting. Moreover, the functional fine particles of the present invention can be imparted to these resins with the above-described hygroscopic performance and deodorizing performance by being added to various resins. Moreover, since the functional fine particles of the present invention exhibit higher adhesion to a resin having a bond having a high cohesive force, the abrasion resistance of the resin is not greatly reduced even when blended. For this reason, when the functional fine particles of the present invention are added to fibers, artificial leather, foams, etc. made of these resins, it is possible to impart moisture absorption / deodorization performance and deodorization performance without significantly degrading the wear resistance. Become.

The functional fine particles of the present invention are those in which a basic polymer is attached to the surface of a hygroscopic fine particle containing a crosslinked structure and a salt-type carboxyl group of 1.8 mmol / g or more.

The amount of the salt-type carboxyl group of the moisture-absorbing / releasing fine particles employed in the present invention is such that the basic polymer is efficiently attached, and sufficient moisture-absorbing / releasing performance is obtained in the functional fine particles of the present invention finally obtained. From the viewpoint of expressing the deodorizing performance, it is necessary to be 1.8 mmol / g or more, preferably 3 mmol / g or more, and more preferably 4 mmol / g or more. If it is less than 1.8 mmol / g, the moisture absorption / release property of the resulting fine particles is low, and it is difficult to attach a sufficient amount of basic polymer, so that the deodorizing performance is insufficient. The upper limit of the salt-type carboxyl group amount is desirably 11 mmol / g or less. When it exceeds 11 mmol / g, since the introduction of a crosslinked structure is hardly possible, the degree of swelling of fine particles in water cannot be suppressed, and the degree of swelling of fine particles in water becomes too high.

In addition, when the degree of swelling of the functional fine particles of the present invention with respect to water is higher than 5 times, when mixed with an aqueous resin or the like, the fine particles are greatly swollen by contact with liquid water, and then By contracting when dried, the fine particles cause a volume change. On the other hand, since the water-based resin does not cause a large volume change with respect to liquid water, a difference in expansion occurs at the interface between the particles and the water-based resin, and physical interface peeling tends to occur. If the degree of swelling with respect to water is 5 times or less, even when mixed with an aqueous resin or the like, interfacial peeling due to contact with liquid water is unlikely to occur. In addition, the lower limit of the degree of swelling with respect to water is preferably 0.15 times or more because the saturated moisture absorption rate at 20 ° C. × 65% RH of the functional fine particles of the present invention is preferably 15% or more. preferable.

The ratio of the salt-type carboxyl group amount to the total carboxyl group amount in the hygroscopic fine particles is preferably in the range of 40 to 99%, more preferably 50 to 95%, and still more preferably 50 to 80%. . The salt-type carboxyl group is necessary for expressing the deodorizing performance of acidic substances, ionic bonds with basic polymers, and hygroscopic performance. On the other hand, the non-salt-type carboxyl group is a carboxylic acid-type carboxyl group (hereinafter also referred to as an H-type carboxyl group), which is a factor for developing ammonia deodorizing performance and moisture absorption performance. The hygroscopic performance is generally higher for salt-type carboxyl groups than for carboxylic acid-type carboxyl groups. Ammonia deodorization performance may be expressed in a form that is absorbed in moisture absorbed by moisture absorption, and thus is substantially expressed as a combined effect of moisture absorption performance and a carboxylic acid type carboxyl group. When the ratio of the salt-type carboxyl group amount to the total carboxyl group amount is less than 40%, it becomes difficult to fix the basic polymer by ionic bond, and the acid substance deodorizing performance is also insufficient.

The hygroscopic fine particles (hereinafter also referred to as salt-type carboxyl group-containing fine particles) employed in the present invention can be produced using crosslinked acrylonitrile polymer fine particles or crosslinked (meth) acrylate polymer fine particles as raw materials. it can.

The crosslinked acrylonitrile polymer fine particles are fine particles formed of an acrylonitrile polymer containing acrylonitrile in an amount of 40% by weight or more, preferably 50% by weight or more. As a method for introducing a crosslinked structure, a method of copolymerizing a crosslinking monomer at the time of polymerization, or a method of introducing a hydrazine crosslinked structure after producing acrylonitrile-based polymer fine particles can be employed. The method for introducing a hydrazine crosslinked structure is not particularly limited as long as the increase in the nitrogen content is 1.0 to 15.0% by weight, but the hydrazine concentration is 1% to 80% and the temperature is 50 to 120 ° C. Means for treating for 0.2 to 10 hours are industrially preferred. Here, the increase in the nitrogen content refers to the nitrogen content (% by weight) of the acrylonitrile polymer fine particles before the treatment and the nitrogen content of the acrylonitrile polymer fine particles after the introduction of the hydrazine crosslinking structure. This is the difference between the amount (weight% vs. fine particles). In addition, when the increase in nitrogen content is less than the said minimum, microparticles | fine-particles will melt | dissolve in water by the hydrolysis for carboxyl group introduction | transduction of the following process, and this invention is not achieved. Moreover, when exceeding an upper limit, it becomes difficult to introduce | transduce a 1.8 mmol / g or more carboxyl group at the next process, and this invention is not achieved. Examples of the hydrazine used here include hydrazine hydrate, hydrazine sulfate, hydrazine hydrochloride, and hydrazine nitrate.

The crosslinked (meth) acrylate polymer fine particles are fine particles formed of a (meth) acrylate polymer containing 40% by weight or more, preferably 50% by weight or more of (meth) acrylate monomer. . As a method for introducing a crosslinked structure, a method of copolymerizing a crosslinking monomer at the time of polymerization can be employed.

The method for obtaining the crosslinked acrylonitrile-based polymer fine particles or the crosslinked (meth) acrylic ester-based polymer fine particles is not particularly limited, and may be appropriately selected based on the required particle diameter depending on the intended use. Can do. For example, in order to obtain ultrafine particles having a particle size of the order of microns or less, emulsion polymerization, dispersion polymerization, microemulsion polymerization and the like can be used. When trying to obtain particles having a particle size of several μm or more, the fine particles can be obtained by suspension polymerization, suspension precipitation polymerization or the like. In the final functional fine particles of the present invention, the moisture absorption / desorption rate and deodorization rate are increased, and when used as an additive to resin products, the appearance and physical properties of resin products are affected. In view of the absence, the crosslinked acrylonitrile polymer fine particles or the crosslinked (meth) acrylic ester polymer fine particles preferably have an average particle diameter of 0.01 to 200 μm or less, and are added to a thin resin product. In consideration of the case, the average particle size is more preferably 0.01 to 50 μm, and when added to fine resin products such as fibers, the average particle size is preferably 0.01 to 10 μm. preferable. The fine particles may be dispersed in a medium such as water.

Next, in the case of crosslinked acrylonitrile-based polymer fine particles, the nitrile group is hydrolyzed, and in the case of crosslinked (meth) acrylic ester-based polymer fine particles, the ester bond is hydrolyzed to 1.8 mmol / g or more. A salt-type carboxyl group is introduced. Examples of the hydrolysis method include means for heat treatment by adding a basic aqueous solution such as alkali metal hydroxide or ammonia, or a mineral acid such as nitric acid, sulfuric acid or hydrochloric acid, or an organic acid such as formic acid or acetic acid. . The amount of the salt-type carboxyl group to be introduced can be adjusted by examining the hydrolysis conditions and the amount of the salt-type carboxyl group to be generated by experiments. The hydrolysis reaction can also be performed simultaneously with the introduction of the hydrazine bridge.

When hydrolyzed with an acid, an H-type carboxyl group is generated, and therefore it is necessary to change the H-type carboxyl group to a salt-type carboxyl group. As a method for this, a method of treating the hydrolyzed particles with various salt-type hydroxides or salts exemplified below is preferable. The carboxyl group salt type includes alkali metals such as Li, Na and K, alkaline earth metals such as Be, Mg, Ca and Ba, Cu, Zn, Al, Mn, Ag, Fe, Co and Ni. The metal ion can be mentioned. In addition, when content of a salt type carboxyl group is less than the said minimum, high moisture absorption / release property and high deodorizing property are not acquired. Two or more salt forms may be mixed. If necessary, the salt-type carboxyl group can be converted to an H-type carboxyl group by treating with an organic acid such as acetic acid, nitric acid, sulfuric acid, or carbonic acid.

In the present invention, a basic polymer is immobilized on the surface of the salt-type carboxyl group-containing fine particles by ionic bonds for the purpose of improving the deodorizing performance of acidic substances, the deodorizing performance of aldehydes and the resin adhesion. As a method for immobilization by ionic bonding, a method of mixing salt-type carboxyl group-containing fine particles and basic polymer in water and ionic bonding is suitable. For this reason, it is desirable that the basic polymer is water-soluble. The basic polymer is not particularly limited as long as it is a water-soluble basic polymer, but it is a primary or secondary amino from the viewpoint of further improving the deodorizing performance of acidic substances, aldehydes or resin. A water-soluble polymer containing a group is preferred. Examples of such basic polymer include polyethyleneimine and polyvinylpyrrolidone. In particular, polyethyleneimine is preferable because it has a high amino group density in the molecule, and has a high effect of improving acidic substance deodorization performance, nonenal deodorization performance, and resin adhesion. The treatment conditions are such that the salt-type carboxyl group-containing fine particles are immersed in an aqueous solution having a basic polymer concentration of 1 to 10% by weight, preferably 1 to 5% by weight, and treated at 50 to 120 ° C. for 1 to 10 hours. Can be mentioned. The basic polymer should be attached in an amount of 0.05% by weight or more with respect to the salt-type carboxyl group-containing particles, and 0.2% by weight or more should be attached. It is desirable. If it is less than 0.05% by weight, the intended acidic substance deodorizing performance, aldehyde deodorizing performance and resin adhesion performance cannot be exhibited. On the other hand, since the basic polymer is immobilized by ionic bonds with the salt-type carboxyl groups on the surface of the salt-type carboxyl group-containing fine particles, the upper limit of the adhesion amount is somewhat to the particle surface area and the amount of salt-type carboxyl groups present on the surface. In practice, the upper limit is 20% by weight. By handling the basic polymer in such a range, the basic polymer that is inherently sticky is immobilized on the particle surface by ionic bonding, and the stickiness is greatly reduced, so the fluidity of the particle is not impaired. . In addition, when the functional fine particles of the present invention are used as an additive to a resin, the amount of adhesion is 1.5% by weight or less in consideration of the possibility of odor generation due to high-temperature heating such as during resin molding. It is preferable that the content be 1.0% by weight or less.

As described above, in the present invention, a basic polymer is attached to the salt-type carboxyl group-containing fine particles in order to improve the adsorption and deodorization performance for acidic substances and aldehydes and the adhesion to the resin. When a low molecular weight basic compound is used, the salt-type carboxyl group and the low molecular weight basic compound undergo an ion exchange reaction to form a salt, which not only improves the adsorption and deodorization performance for acidic substances and aldehydes. Moreover, the adsorption | suction deodorizing performance with respect to the basic substance which the salt type carboxyl group containing fine particle had also will fall. In addition, it is also possible to introduce a carboxyl group in the fine particles by introducing an amino group into the fine particles of the above-mentioned crosslinked acrylonitrile polymer fine particles or fine particles of the crosslinked acrylate polymer in advance and then performing a hydrolysis reaction. In this case, since an amino group and a carboxyl group are mixed in each other, a neutralization reaction is caused between these functional groups to form a salt inside the particle, so that sufficient deodorizing performance cannot be exhibited in many cases. The hydrazine cross-linked structure of the above-mentioned cross-linked acrylonitrile polymer particles also has a high adsorption / deodorization performance for acidic substances and aldehydes, but the neutralization reaction with the carboxyl group produced by the hydrolysis reaction As a result, sufficient performance cannot be achieved.

In the present invention, for the purpose of preventing these phenomena, a basic polymer having a molecular size that cannot penetrate into the salt-type carboxyl group-containing fine particles is selected, and the basic polymer is selected with respect to the salt-type carboxyl group present on the particle surface. Are ion-adsorbed. That is, the functional fine particle of the present invention has a large number of amino groups on the particle surface, and is in a state in which salt-type carboxyl groups and H-type carboxyl groups that are not neutralized by amino groups are present inside the particles, Adsorption and deodorization sites for acidic substances and aldehydes are present on the particle surface, and adsorption and deodorization sites for acidic substances and basic substances are present independently inside the particles. Further, since the basic polymer is attached by polyion bonds, it is difficult to drop off and has high washing durability. Accordingly, the basic polymer selected here is preferably one having a high molecular weight, and one having a molecular weight of 300 or more is preferred. On the other hand, from the viewpoint of water solubility, those having a molecular weight of 70000 or less are preferred.

By having the structure as described above, the functional fine particles of the present invention not only realize a comfortable humidity environment by reducing the stuffy feeling derived from the body fluid generated from the body, but also aging odor, sweat odor, etc. It is possible to develop a deodorizing performance that is immediate and lasting for complex odors. Specifically, as the deodorization performance, the ammonia odor removal rate which is the deodorization standard of the Fiber Evaluation Technical Council: 70% or more, the acetic acid odor removal rate: 80% or more, the isovaleric acid odor removal rate: 85% or more and Nonenal odor removal rate: 75% or more can be expressed.

Moreover, the improvement of the adhesiveness with respect to resin is mentioned as an advantage of making a basic polymer act on salt-type carboxyl group-containing fine particles. Examples of the resin whose adhesion is improved include resins having bonds with high cohesion, such as urea resins, urethane resins, nylon resins, and ester resins. In particular, the urethane bond of the urethane resin exhibits a very high cohesive force of 8.74 kcal / mol. In order to improve the adhesion of the particles to such a resin having a high cohesive force, it is effective to make a large number of functional groups having active hydrogen present on the particle surface and to adhere the particles by hydrogen bonding. The salt-type carboxyl group-containing fine particles are in a state where there are few active hydrogens because most of the carboxyl groups are salt-type. Therefore, in the present invention, a basic polymer having active hydrogen is immobilized on the particle surface. A primary or secondary amino group is most effective as a functional group having an active hydrogen suitable for such purposes, and a basic polymer containing a primary or secondary amino group is a basic polymer. Although there is no particular limitation as long as it is a water-soluble basic polymer, polyethyleneimine having the highest amine value can be suitably used.

The adhesion of the fine particles to the resin can be evaluated by a peel strength test described later. In such a peel strength test, if the peel strength of the urethane resin to which fine particles are added is maintained at 36% or more with respect to the peel strength of the urethane resin alone, wear resistance that does not cause a problem in practice can be exhibited. In the functional fine particles of the present invention, a peel strength retention of 36% or more can be obtained, and a peel strength retention of 50% or more can also be achieved.

The size of the functional fine particles of the present invention is preferably 0.01 to 200 μm, more preferably 0.01 to 50 μm, as an average particle size, considering the case of mixing with other resin materials. is there. If the average particle diameter is less than 0.01 μm, it is difficult to produce, and if the average particle diameter is larger than 200 μm, restrictions such as the thickness of the resin molded product and the fiber diameter are not preferable. Further, when the average particle diameter is smaller than several μm, it is generally easier to handle it when dispersed in a medium such as water.

The saturated moisture absorption rate at 20 ° C. × 65% RH of the functional fine particles of the present invention is preferably 15% or more, more preferably 20% or more, from the viewpoint of providing a comfortable environment due to moisture absorption / release performance. More preferably, it is 30% or more. The saturated moisture absorption at 11 mmol / g, which is the upper limit of the amount of salt-type carboxyl groups introduced in the functional fine particles of the present invention, is 85%.

The resin constituting the resin product of the present invention is not particularly limited, and examples thereof include urea resins, urethane resins, nylon resins, ester resins, silicone resins, acrylic resins, acrylonitrile resins, and cellulose resins.

Examples of the resin product include artificial leather such as synthetic leather and artificial leather, film, and fiber. For example, in the case of artificial leather, after mixing the functional fine particles of the present invention with a liquid in which a urethane resin is dissolved in dimethylformamide, the nonwoven fabric composed of polyester fibers is coated, and then desolvated and dried in an aqueous solution. By doing so, an artificial leather having moisture absorption / release properties and deodorizing performance can be produced.

In the case of fibers, moisture absorption and deodorization performance is achieved by mixing the functional fine particles of the present invention in a liquid in which a urethane resin is dissolved in dimethylacetamide and then processing into a fiber form by a dry spinning method. The urethane fiber which has can be manufactured. It can also be applied to fibers using materials other than urethane resin. The spinning solution thus prepared can be produced by spinning according to a conventional method. In the case of cellulosic fibers, a viscose solution for spinning prepared by adding the functional fine particles of the present invention to a viscose stock solution containing a cellulosic polymer can be produced by spinning according to a conventional method. it can.

The addition amount of the functional fine particles of the present invention in these resin products can be appropriately set in consideration of characteristics such as the intended deodorizing performance and the strength of the resin product. It is preferable to set it as 0.1 to 60 weight% with respect to the weight of the whole product. If it is less than 0.1% by weight, the characteristics of the functional fine particles of the present invention may not be utilized. If it exceeds 60% by weight, the functional fine particles are deteriorated due to a decrease in physical properties such as product strength or friction. Problems such as dropping off may occur.

Hereinafter, the present invention will be described specifically by way of examples. Parts and percentages in the examples are on a weight basis unless otherwise indicated. The salt-type carboxyl group amount, salt-type carboxyl group ratio, basic polymer adhesion amount, average particle diameter, swelling degree, moisture absorption rate, moisture absorption rate, odor removal rate, peel strength, and Gakushin abrasion test are as follows. Depending on the method.

(1) Salt-type carboxyl group content (mmol / g)
About 1 g of sufficiently dried test fine particles are precisely weighed (X [g]), 200 g of water is added thereto, and then 1 mol / l hydrochloric acid aqueous solution is added to the solution while being heated to 50 ° C. to adjust to pH 2. Then, a titration curve is obtained according to a conventional method using a 0.1 mol / l sodium hydroxide aqueous solution. From the titration curve, the amount of sodium hydroxide aqueous solution consumed by the carboxyl groups (Y [ml]) is determined, and the total amount of carboxyl groups is calculated according to the following formula.
Total carboxyl group amount [mmol / g] = 0.1 × Y / X
Separately, a titration curve is obtained in the same manner as described above except that the pH is not adjusted to 2 by addition of a 1 mol / l hydrochloric acid aqueous solution during the measurement operation of the total carboxyl group amount, and the H-type carboxyl group amount is calculated. From these results, the salt-type carboxyl group amount is calculated according to the following formula.
(Salt-type carboxyl group amount) = (Total carboxyl group amount)-(H-type carboxyl group amount)

(2) Ratio of salt-type carboxyl groups (%)
The ratio of the salt-type carboxyl group is calculated according to the following formula from the salt-type carboxyl group amount and the total carboxyl group amount calculated in (1).
(Salt-type carboxyl group amount ratio) = (Salt-type carboxyl group amount) / (Total carboxyl group amount) × 100

(3) Amount of basic polymer attached (% by weight)
The weight of the salt-type carboxyl group-containing particles before the basic polymer treatment is measured (B [g]), and the particle weight after the basic polymer treatment is measured (C [g]). From the above measurement results, the basic polymer adhesion amount is calculated according to the following formula.
Basic polymer adhesion amount (% by weight) = (C−B) / B × 100

(4) Average particle diameter (μm)
Using a laser diffraction particle size distribution analyzer “SALD-200V” manufactured by Shimadzu Corporation, water is measured as a dispersion medium, and an average particle size (μm) is obtained from the particle size distribution expressed on a volume basis.

(5) Swelling degree (times)
About 1 g of the sample is dried with a hot air dryer at 105 ° C. for 16 hours, and the weight is measured (D [g]). Next, the sample is dispersed in 500 g of pure water for 1 hour to swell. Thereafter, solid-liquid separation is performed with a suction filter in which a membrane filter (MIXED CELLULOSE ESTER 0.65 μm) is set, and the weight of the solid is measured (E [g]). From the above results, the degree of swelling is calculated according to the following equation.
Swelling degree [times] = (ED) / D

(6) 20 ° C. × 65% RH moisture absorption rate (saturated moisture absorption rate) of fine particles (%)
About 5.0 g of the sample is dried with a hot air drier at 105 ° C. for 16 hours and weighed (W2 [g]). Next, the sample is placed in a thermo-hygrostat adjusted to a temperature of 20 ° C. and 65% RH for 24 hours. Thereafter, the weight of the sample is measured (W3 [g]). From the above measurement results, the saturated moisture absorption rate is calculated according to the following equation.
Saturated moisture absorption [%] = (W3-W2) / W2 × 100

(7) 20 ° C. × 65% RH moisture absorption (saturated moisture absorption) of artificial leather (g / m ² )
After the sample is cut into a size of 10 cm × 10 cm, it is dried with a hot air dryer at 105 ° C. for 16 hours and the weight is measured (W4 [g]). Next, the sample is placed in a thermo-hygrostat adjusted to a temperature of 20 ° C. and 65% RH for 24 hours. Thereafter, the weight of the sample is measured (W5 [g]). From the above measurement results, the saturated moisture absorption amount is calculated according to the following equation.
Saturated moisture absorption [g / m ² ] = (W5−W4) × 100

(8) Odor removal rate (%)
Place 0.5 g of sample in a Tedlar bag, seal and inject 1.5 l of air. Next, a prescribed concentration of odor (100 ppm for ammonia, 50 ppm for acetic acid, 40 ppm for isovaleric acid, 14 ppm for acetaldehyde, 14 ppm for nonenal) is injected into a Tedlar bag and 120 ° C. at room temperature. After leaving it alone, the odor concentration (W4) in the Tedlar bag is measured using a Kitagawa type detector tube. In addition, a blank without a sample is also prepared at the same concentration, and after 120 minutes, the odor concentration (W5) is measured to make a blank test. From the above results, the odor removal rate is calculated according to the following equation.
Odor removal rate [%] = (W5-W4) / W5 × 100

(9) Peel strength retention (%)
After the sample is cut into a width of 2 cm and a length of 13 cm, a polycotape (polyurethane hot melt tape) is thermocompression bonded to the surface of the sample, and a peel strength test is performed using a constant speed extension type tensile tester. Tensile speed: A test is performed under the condition of 100 mm / min, and a load at the start of peeling (hereinafter referred to as peeling strength) is measured. For each of the sample containing no particles and the sample containing particles, the peel strength is measured, and the peel strength retention is calculated according to the following equation.
Peel strength retention ratio (%) = (Peel strength of sample containing particles) / (Peel strength of sample containing no particles) × 100

(10) Gakushin Abrasion Test A test using a Gakushin friction tester type II conforming to JIS L 0849. As test conditions, load: 500 g, white cloth for friction: No. 11 canvas in a wet state and a wet test. carry out. Evaluation is made by observing the state of the surface of the test piece after a predetermined number of friction tests.

[Example 1]
A 2 L reaction vessel was charged with 700 parts by weight of water and an additional mixture of 210 parts by weight of acrylonitrile and 90 parts by weight of divinylbenzene. While stirring the reaction vessel, 3 parts by weight of ammonium persulfate (polymerization initiator) was added and dissolved. Thereafter, the reaction vessel was heated to 70 ° C. and reacted for 3 hours. After completion of the reaction, the mixture was cooled to about 20 ° C. while continuing stirring, to obtain crosslinked acrylonitrile polymer particles having an average particle size of 40 μm. Next, 800 g of water, 100 g of NaOH, and 100 g of the crosslinked acrylonitrile polymer particles were charged into a 2 L reaction tank, and a hydrolysis reaction was performed at 90 ° C. for 60 hours to obtain salt-type carboxyl group-containing particles. The amount of the salt-type carboxyl group at this time was 6.2 mmol / g. Furthermore, 900 g of water and 100 g of the salt-type carboxyl group-containing particles were charged into a 2 L reaction tank, and 0.5 g of polyethyleneimine (average molecular weight 70000) was added while stirring and reacted at 50 ° C. for 30 minutes, and then washed. -Drying treatment was performed to obtain functional fine particles. It was confirmed that the amount of basic polymer deposited by the polyethyleneimine treatment was 0.5% by weight. The results of evaluating the particles are shown in Table 1.

[Example 2]
In Example 1, except that the addition amount of polyethyleneimine was changed to 1.8 g, the same treatment as in Example 1 was performed to obtain functional fine particles. The results of evaluating the particles are shown in Table 1.

[Example 3]
In Example 1, except that the amount of polyethyleneimine added was changed to 4.4 g, the same treatment as in Example 1 was performed to obtain functional fine particles. The results of evaluating the particles are shown in Table 1.

[Example 4]
A 2 L reaction tank is charged with 700 parts by weight of water and 30 parts by weight of polyvinyl alcohol (PVA217 Kuraray Co., Ltd.), 210 parts by weight of acrylonitrile, 90 parts by weight of divinylbenzene, and 3 parts by weight of azobisisovaleronitrile (polymerization initiator). ) Was additionally charged and stirred with a homomixer to atomize the monomer. Thereafter, the reaction vessel was heated to 70 ° C. and reacted for 3 hours. After the completion of the reaction, the mixture was cooled to about 20 ° C. while continuing stirring to obtain crosslinked acrylonitrile polymer particles having an average particle diameter of 5 μm. Next, 800 g of water, 100 g of NaOH, and 100 g of the crosslinked acrylonitrile polymer particles were charged into a 2 L reaction tank, and a hydrolysis reaction was performed at 90 ° C. for 60 hours to obtain salt-type carboxyl group-containing particles. The amount of the salt-type carboxyl group at this time was 6.2 mmol / g. Furthermore, 900 g of water and 100 g of the salt-type carboxyl group-containing particles were charged into a 2 L reaction tank, and 1.8 g of polyethyleneimine (average molecular weight 70000) was added while stirring and reacted at 50 ° C. for 30 minutes, and then washed. -Drying treatment was performed to obtain functional fine particles. It was confirmed that the amount of basic polymer adhered by the polyethyleneimine treatment was 1.8% by weight. The results of evaluating the particles are shown in Table 1.

[Example 5]
In Example 4, the same process as Example 4 was performed except having changed the preparation amount of polyvinyl alcohol into 0.4 weight part, and functional fine particles were obtained. The results of evaluating the particles are shown in Table 1.

[Example 6]
In Example 2, the same treatment as in Example 2 was performed except that the amount of acrylonitrile charged was changed to 75 parts by weight and the amount of divinylbenzene charged was changed to 225 parts by weight to obtain functional fine particles. The results of evaluating the particles are shown in Table 1.

[Example 7]
In Example 1, except that the amount of polyethyleneimine added was changed to 0.1 g, the same treatment as in Example 1 was performed to obtain functional fine particles. The results of evaluating the particles are shown in Table 1.

[Example 8]
In Example 1, after obtaining salt-type carboxyl group-containing particles, the particles were re-dispersed in water, and 1 mol / L hydrochloric acid was added dropwise so that the pH was 5. The ratio of carboxyl group amount was adjusted to 45%, and then the same polyethyleneimine treatment as in Example 1 was performed to obtain functional fine particles. The results of evaluating the particles are shown in Table 1.

[Example 9]
After dispersing 100 parts by weight of the functional fine particles prepared in Example 2 in 200 parts by weight of a DMF solvent, urethane resin paint (manufactured by DIC Corporation: Crisbon non-volatile content 30%): blended in 411 parts by weight for coating A liquid was created. Further, a nonwoven fabric having a basis weight of 100 g / m ^{2 made} of polyester fiber (fineness: 5.5 dtex, fiber length: 51 mm) / nylon fiber (fineness 3.3 dtex, fiber length: 45 mm) = 66/33 was prepared by a needle punch manufacturing method. . The said coating liquid was apply | coated to this nonwoven fabric so that it might become 186 g / m < ² >, and after removing the solvent by being immersed in a water bath, it dried and obtained artificial leather. The evaluation results of the artificial leather are shown in Table 2.

[Comparative Example 1]
In Example 1, the same treatment as in Example 1 was carried out except that the polyethyleneimine adhesion treatment was not carried out to obtain fine particles. The results of evaluating the particles are shown in Table 1.

[Comparative Example 2]
In Example 2, the same treatment as in Example 1 was performed except that the amount of acrylonitrile charged was changed to 55 parts by weight and the amount of divinylbenzene charged was changed to 245 parts by weight, to obtain fine particles. The results of evaluating the particles are shown in Table 1.

[Comparative Example 3]
In Example 1, the same process as Example 1 was performed except having changed the polyethyleneimine addition amount into 0.04g, and the microparticles were obtained. The results of evaluating the particles are shown in Table 1.

[Comparative Example 4]
In Example 1, after obtaining salt-type carboxyl group-containing particles, the particles were re-dispersed in water, and 1 mol / L hydrochloric acid was added dropwise so that the pH was 3.5. The ratio of the salt-type carboxyl group amount was adjusted to 27%, and then the same polyethyleneimine treatment as in Example 1 was performed to obtain fine particles. The results of evaluating the particles are shown in Table 1.

[Comparative Example 5]
In Example 9, except that the functional fine particles prepared in Example 2 were not added, the same treatment as in Example 9 was performed to obtain an artificial leather. The results of evaluating the artificial leather are shown in Table 2.

[Comparative Example 6]
In Example 9, the same treatment as in Example 9 was performed except that the particles prepared in Comparative Example 1 were used in place of the functional fine particles prepared in Example 2, and an artificial leather was obtained. The results of evaluating the artificial leather are shown in Table 2.

From the comparison of Examples 1 to 3 and 7 of Table 1 and Comparative Example 1, it can be seen that the acidic substance and the aldehyde deodorizing performance are dramatically improved by attaching the basic polymer to the particle surface. Further, it can be seen that the basic substance deodorization performance and moisture absorption performance are not significantly hindered. From the comparison between Example 9 and Comparative Example 6, it can be seen that the urethane resin adhesion is improved by the presence of the basic polymer. Note that “-” in the table indicates that measurement was not performed.

[Example 10]
The reaction tank was charged with 210 parts of ion-exchanged water and 2 parts of Eleminol MON-2 (manufactured by Sanyo Chemical Industries). Next, the temperature of the reaction vessel was increased to 60 ° C., and the mixture was maintained at 60 ° C. while stirring, and a monomer mixture solution consisting of 78 parts of ethyl acrylate, 5 parts of methyl methacrylate, and 17 parts of divinylbenzene, An aqueous solution in which 0.6 part of ammonium persulfate is dissolved in 30 parts of water and an aqueous solution in which 0.5 part of sodium pyrosulfite is dissolved in 30 parts of water are dropped over 3 hours. After completion of the dropwise addition, the same conditions are maintained for 2 hours. Polymerization was performed. The resulting emulsion was 21% solids. 400 parts of a 10% aqueous sodium hydroxide solution was added to 480 parts of the emulsion, and a hydrolysis reaction was carried out at 95 ° C. for 48 hours. Next, the hydrolyzed emulsion was placed in a cellulose semipermeable membrane and immersed in ion-exchanged water for desalting, and then ion-exchanged water was added to obtain emulsion-like particles having a solid content of 5%. The total amount of carboxyl groups in the particles was 6.0 mmol / g, the amount of salt-type carboxyl groups was 5.6 mmol / g, and the moisture absorption rate was 53%.

Polyethyleneimine (average molecular weight 70000) is added to the emulsion-like particles while stirring and reacted at 50 ° C. for 30 minutes, and then washed and dried to obtain the functionality of the present invention in the form of an aqueous dispersion. Fine particles were obtained. The average particle size of the functional fine particles was 0.4 μm, and the basic polymer adhesion amount was 0.4% by weight.

Next, 90% by weight of acrylonitrile, 9% by weight of methyl acrylate, and 1% by weight of sodium methallylsulfonate were subjected to aqueous suspension polymerization to prepare an acrylonitrile-based polymer. The acrylonitrile-based polymer is dissolved in an aqueous sodium thiocyanate solution having a concentration of 45% by weight so that the polymer concentration becomes 12% by weight. A spinning dope containing 4% by weight of the functional fine particles with respect to the acrylonitrile polymer was prepared. The stock solution was extruded into a 15 wt% sodium thiocyanate aqueous solution at -2.0 ° C, then washed with water, stretched 12 times, wet-heat treated at 110 ° C for 10 minutes, and dried and densified with a hot air dryer at 120 ° C. As a result, an acrylonitrile fiber containing the functional fine particles of the present invention was prepared. The odor removal rate of the fiber was 98% ammonia, 90% acetic acid, 84% isovaleric acid, and 89% nonenal.

Claims (11)

Functional fine particles in which 0.05% by weight or more of a basic polymer is adhered to a moisture absorbing / releasing fine particle having a crosslinked structure and a salt-type carboxyl group of 1.8 mmol / g or more, and an average particle size of 0.1%. Functional fine particles characterized by being in the range of 01 to 200 μm. 2. The functional fine particle according to claim 1, which has a saturated moisture absorption rate of 15% or more in an environment of 20 ° C. × 65% RH. An ammonia odor removal rate: 70% or more, an acetic acid odor removal rate: 80% or more, an isovaleric acid odor removal rate: 85% or more, and a nonenal odor removal rate: 75% or more. 3. Functional fine particles according to 1 or 2. The functional fine particles according to any one of claims 1 to 3, wherein a peel strength retention when blended with urethane-based artificial leather is 36% or more. The functional fine particles according to any one of claims 1 to 4, wherein a ratio of a salt-type carboxyl group amount to a total carboxyl group amount in the hygroscopic fine particles is in a range of 40 to 99%. A resin product comprising the functional fine particles according to claim 1. The resin product according to claim 6, wherein the resin product is artificial leather. The resin product according to claim 6, wherein the resin product is a film. The resin product according to claim 6, wherein the resin product is a fiber. The resin which comprises a resin product contains urethane type resin, The resin product in any one of Claims 7-9 characterized by the above-mentioned. The resin product according to claim 9, wherein the resin constituting the resin product contains a cellulose polymer and / or an acrylonitrile polymer.