KR20160013051A - Functional microparticles and resin product containing same - Google Patents

Abstract

The conventional deodorant has a good deodorizing effect for a certain type of odor, but does not show sufficient deodorization for other types of odor, and has a satisfactory deodorizing effect for deodorizing a compound odor such as sweat odor and old-age odor Is not obtained. Further, when it is added to a resin or the like, there is a problem that the performance such as abrasion resistance of the resin is lowered. Disclosure of the Invention In order to solve the problems of the prior art, the present invention provides moisture-absorbing deodorant fine particles capable of imparting high deodorizing performance and hygroscopic performance to basic odor and acid odor without significantly reducing the abrasion resistance of the resin when blended with a resin do.
Functional fine particles having a cross-linking structure and 1.8 mmole / g or more of a salt-type carboxyl group and having a basic polymer adhered in an amount of 0.05% by weight or more, and having an average particle diameter of 0.01 to 200 탆.

Description

TECHNICAL FIELD [0001] The present invention relates to functional fine particles and resin products containing the functional fine particles,

The present invention relates to a hygroscopic deodorant fine particle having both a hygroscopic property and a deodorizing property and exhibiting high adhesiveness to a resin when mixed with a resin.

In recent years, due to changes in the living environment, awareness of odor and moisturization has increased, and it is desired to continuously deodorize and absorb odor and moisture caused by body fluids generated from the body. For example, in regard to odor, there is a high awareness of the smell of the elderly, the smell of sweat. Older smells are composed of aldehydes such as nonenal, and sweat odor is composed of ammonia, acetic acid, isovaleric acid, and acetaldehyde. These deodorizing methods are largely classified into physical deodorization, chemical deodorization, and sensory deodorization (massing). As a physical deodorant, activated carbon is very excellent. However, there is a problem that the activated carbon is difficult to be atomized, is hardly fixed to the fiber, and the color of the fiber is deteriorated. In the physical deodorization, the performance is remarkably lowered by an operation such as washing. In addition, the deodorizing agent using the catalytic action has a low effect immediately. In the deodorization with a perfume or the like, the perfume itself may become an odor depending on the palatability of the person, or the use thereof is limited in that it causes the olfactory fatigue. Among them, there is a method using a chemical neutralization reaction, which is superior in immediate effect and continuous performance and can overcome the above problems.

As the functional fine particles used for this purpose, for example, Patent Document 1 discloses a moisture absorptive and desorptive fine particle obtained by introducing a salt-type carboxyl group into acrylonitrile-based polymer fine particles having a hydrazine bridge. The amino group and the salt-type carboxyl group derived from the hydrazine bridge exhibit deodorizing performance for acidic or basic odor, but lack deodorizing properties for aldehydes. In addition, when these fine particles are used in combination with a urethane resin, the resin tends to be worn and it is difficult to maintain practical properties.

Patent Document 2 discloses a polymer having an acid / aldehyde deodorizing property using an amino group. As to the introduction method of the amino group, it is preferable that the hydrazine polymer is treated with hydrazine to simultaneously introduce a crosslinked structure and an amine structure. However, in this method, since the deodorizing property against basic odor is insufficient, the deodorizing performance against sweat and old odor can not be exhibited.

Japanese Patent Application Laid-Open No. 8-225610 Japanese Patent Publication No. 10-156179

An object of the present invention is to overcome the problems of the prior art described above, and it is an object of the present invention to provide a resin composition which can impart a high deodorizing performance and a hygroscopic performance to a basic substance and an acidic substance without greatly reducing the abrasion resistance of the resin when blended with the resin And to provide a hygroscopic deodorant fine particle.

The above object of the present invention can be achieved by the following means [1] to [11].

[1] A functional fine particle having a crosslinked structure and at least 1.8 mmol / g of a salt-type carboxyl group and having at least 0.05% by weight of a basic polymer adhered to the moisture absorptive and desorptive fine particle and having an average particle diameter of 0.01 to 200 μm .

[2] The functional fine particle according to [1], wherein the saturated moisture absorption rate at 20 ° C × 65% RH is 15% or more.

[3] A process for producing a polymer having an odor removal rate of ammonia of 70% or more, an acetic acid odor removal rate of 80% or more, an isovaleric acid odor removal rate of 85% or more, and a nonenal odor removal rate of 75% 2].

[4] The functional fine particle according to any one of [1] to [3], wherein the peel strength retention when blended with the artificial leather based on yutein is 36% or more.

[5] The functional fine particles according to any one of [1] to [4], wherein the ratio of the amount of the salt-type carboxyl group to the total amount of the carboxyl groups in the moisture absorptive and desorptive fine particles is in the range of 40 to 99%.

[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 resin.

[11] The resin product according to [9], wherein the resin constituting the resin product contains a cellulose-based polymer and / or an acrylonitrile-based polymer.

Since the functional fine particles of the present invention have a high hygroscopic property, it is possible to realize a comfortable humidity environment by reducing the wetness caused by body fluids originating from the body, and also to provide a deodorizing performance with immediate effect and persistence against a compound odor such as an elderly smell and sweat odor . ≪ / RTI > The functional fine particles of the present invention can be added to various resins to impart the above-described hygroscopic performance and deodorization performance to these resins. In addition, since the functional fine particles of the present invention exhibit higher adhesion to resins having high cohesive strength, the abrasion resistance of the resin is not significantly reduced even when blended. Therefore, when the functional fine particles of the present invention are added to fibers, artificial leather, and foams made of these resins, the moisture absorptive and desorptive performance and the deodorizing performance can be imparted without greatly impairing abrasion resistance.

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

The amount of the salt-type carboxyl group of the moisture absorptive and desorptive fine particles employed in the present invention is preferably 1.8 mmol / g or more from the viewpoint of efficiently attaching the basic polymer and from the viewpoint of exhibiting sufficient moisture absorptive and desorptive performance and deodorization performance in the finally obtained functional fine particles of the present invention Preferably not less than 3 mmol / g, and more preferably not less than 4 mmol / g. If it is less than 1.8 mmol / g, the moisture absorptive and desorptive properties of the resulting fine particles are low, and it is also difficult to adhere a sufficient amount of the basic polymer. The upper limit of the amount of the salt-type carboxyl groups is preferably 11 mmol / g or less. If it exceeds 11 mmol / g, the cross-linking structure can hardly be introduced, so that the degree of swelling of the fine particles with respect to water can not be suppressed, and the degree of swelling of the fine particles with respect to water becomes excessively high.

When the degree of swelling of the functional fine particles of the present invention with respect to water is higher than 5 times, the fine particles swell largely due to the contact of the liquid with water when used in an aqueous resin or the like, and then shrink 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 the liquid water, an expansion difference is generated at the interface between the particles and the water-based resin, and the interface is liable to cause interface delamination. If the degree of swelling with respect to water is 5 times or less, it is difficult to cause interface detachment due to contact of the liquid with water even when mixed with an aqueous resin or the like. The lower limit of the swelling degree with respect to water is preferably 0.15 times or more, since the saturated moisture absorption rate of the functional fine particles of the present invention at 20 캜 65% RH is preferably 15% or more.

The ratio of the amount of the salt-type carboxyl group to the total amount of the carboxyl groups in the moisture absorptive and desorptive 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 the acidic substance deodorizing performance, the ionic bonding with the basic polymer and the hygroscopic performance. On the other hand, a non-salt type carboxyl group is a carboxylic acid type carboxyl group (hereinafter also referred to as an H type carboxyl group) and is a factor for manifesting ammonia deodorization performance and moisture absorption performance. The hygroscopicity is generally higher in the salt type carboxyl group than in the carboxylic acid type carboxyl group. Ammonia deodorization performance is expressed as a composite effect of hygroscopicity and carboxylic acid type carboxyl groups because they are sometimes expressed in a form dissolving in water absorbed by moisture absorption. When the ratio of the amount of the salt-type carboxyl group to the total amount of the carboxyl groups is less than 40%, it is difficult to immobilize the basic polymer by ionic bonding, and the acidic substance deodorization performance is also insufficient.

The moisture absorptive and desorptive fine particles (hereinafter also referred to as salt type carboxyl group-containing fine particles) employed in the present invention can be produced by using crosslinked acrylonitrile polymer fine particles or crosslinked (meth) acrylic acid ester polymer fine particles as a raw material.

The crosslinked acrylonitrile-based polymer fine particles are fine particles formed by an acrylonitrile-based polymer containing acrylonitrile in an amount of 40 wt% or more, preferably 50 wt% or more. As a method for introducing a crosslinked structure, a method of copolymerizing a crosslinkable monomer at the time of polymerization, or a method of introducing a hydrazine crosslinked structure after preparing acrylonitrile polymer fine particles can be employed. The method of introducing the hydrazine crosslinked structure is not particularly limited as long as the means for increasing the nitrogen content is 1.0 to 15.0% by weight. Means for treating at 0.2 to 10 hours at a hydrazine concentration of 1% to 80% It is industrially preferable. Here, the increase in the nitrogen content means that the nitrogen content (wt.% Vs. particulate) of the acrylonitrile polymer microparticles before the treatment and the nitrogen content (wt.%) Of the acrylonitrile polymer microparticles after the introduction of the hydrazine crosslinked structure ). When the increase in the nitrogen content is not satisfied by the lower limit described above, the fine particles are dissolved in water by the hydrolysis for introducing the carboxyl group in the next step, and the present invention is not achieved. When the upper limit is exceeded, it is difficult to introduce 1.8 mmol / g or more of a carboxyl group in the next step, so that the present invention is not achieved. Examples of the hydrazine used herein include hydrazine hydrate, hydrazine sulfate, hydrazine hydrochloride, hydrazine nitrate, and the like.

The crosslinked (meth) acrylic acid ester polymer fine particles are fine particles formed from a (meth) acrylic acid ester polymer containing not less than 40% by weight, preferably not less than 50% by weight of a (meth) acrylic acid ester monomer. As a method of introducing the crosslinked structure, a method of copolymerizing a crosslinkable monomer at the time of polymerization can be employed.

The method of obtaining the crosslinked acrylonitrile polymer fine particles or the crosslinked (meth) acrylic acid ester polymer fine particles is not particularly limited and can be appropriately selected on the basis of the particle diameter required for the purpose of use. For example, in the case of obtaining a fine particle having a particle diameter equal to or less than a micron order, emulsion polymerization, dispersion polymerization, microemulsion polymerization, or the like can be used. In the case of obtaining particles having a particle diameter of several μm or more, the fine particles can be obtained by suspension polymerization, suspension precipitation polymerization or the like. From the viewpoint of increasing the moisture absorptive and desorptive rate and the deodorization rate of the ultimately obtained functional fine particles of the present invention and not affecting the appearance and physical properties of the resin product when used as an additive in a resin product or the like, The average particle diameter is preferably 0.01 to 200 占 퐉 or less and the average particle diameter is preferably 0.01 to 50 占 퐉 in consideration of the case of adding to the resin product of a thin layer When it is added to fine resin products such as fibers, the average particle diameter is preferably 0.01 to 10 μm. The form of the fine particles may be dispersed in a medium such as water.

Next, in the case of crosslinked acrylonitrile polymer fine particles, the nitrile group is hydrolyzed, and in the case of crosslinked (meth) acrylic acid ester polymer fine particles, the ester bond is hydrolyzed to introduce 1.8 mmol / g or more of a salt type carboxyl group. Examples of the hydrolysis method include basic aqueous solutions such as alkali metal hydroxides and ammonia, and means for adding a mineral acid such as nitric acid, sulfuric acid, hydrochloric acid, or an organic acid such as formic acid or acetic acid to the solution. Adjustment of the amount of the salt-type carboxyl group to be introduced can be carried out by examining the hydrolysis conditions and the amount of the salt-forming carboxyl group by an experiment. Further, hydrolysis reaction may be performed simultaneously with introduction of the hydrazine crosslinking.

In the case of hydrolysis with an acid, since an H-type carboxyl group is produced, it is necessary to convert this H-type carboxyl group into a salt type carboxyl group. As a method for this, a method of treating hydrolyzed particles with various salt type hydroxides or salts exemplified below is suitable. Examples of the salt type of the carboxyl group include alkali metals such as Li, Na and K, alkaline earth metals such as Be, Mg, Ca and Ba, and other metal ions such as Cu, Zn, Al, Mn, Ag, Fe, . In addition, when the content of the salt-type carboxyl group does not satisfy the above lower limit, high moisture absorptive and desorptive property and high deodorant property are not obtained. The salt type may be a mixture of two or more species. It is also possible to convert the salt-type carboxyl group into an H-type carboxyl group by treatment with an organic acid such as acetic acid, nitric acid, sulfuric acid or carbonic acid, if necessary.

In the present invention, a basic polymer is immobilized on the surface of a salt-type carboxyl group-containing fine particle by ionic bonding for the purpose of improving the acidic substance deodorization performance, aldehyde-based deodorization performance and resin adhesion. As a method of immobilizing by ionic bonding, a method in which salt-type carboxyl group-containing fine particles and water-soluble polymer are mixed in water and ion-bonded is suitable. For this reason, the basic polymer is preferably water-soluble. The basic polymer is not particularly limited as long as it is a basic polymer having water solubility. However, it is preferably a water-soluble polymer containing a primary or secondary amino group from the viewpoint of further improving the acidic substance, the deodorizing ability to aldehydes or the adhesion to resin. Examples of the basic polymer include polyethyleneimine and polyvinyl pyrrolidone. Particularly, polyethyleneimine is suitable because it has high density of amino groups in the molecule and is highly effective in improving the deodorizing performance of an acidic substance, the deodorizing performance of nongenel and the resin adhesion. Examples of the treatment conditions include conditions in which salt type carboxyl group-containing fine particles are immersed in an aqueous solution having a concentration of basic polymer of 1 to 10% by weight, preferably 1 to 5% by weight, and treatment is carried out at 50 to 120 캜 for 1 to 10 hours. The amount of the basic polymer to be adhered needs to be 0.05% by weight or more of the basic polymer to the salt-containing carboxyl group-containing particles, preferably 0.2% by weight or more. When the amount is less than 0.05% by weight, the desired acidic substance deodorizing ability, aldehyde-based deodorizing ability and resin adhesion performance can not be exhibited. On the other hand, since the basic polymer is immobilized by ionic bonding with the salt-type carboxyl group on the surface of the salt-type carboxyl group-containing fine particles, the upper limit of the amount of adhesion is somewhat dependent on the particle surface area and the amount of the salt-type carboxyl group present on the surface. Actually, do. By treating the basic polymer in such a range, the basic polymer having inherent tackiness is immobilized on the surface of the particle by ionic bonding, and the tackiness is greatly reduced, so that the fluidity of the particles is not impaired. When the functional fine particles of the present invention are used as an additive to a resin, the adhesion amount is preferably 1.5% by weight or less, more preferably 1.0% by weight or less in consideration of the possibility of occurrence of odor due to high- Is more preferable.

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 of the acidic substance and the aldehyde and the adhesion to the resin. When a low molecular weight basic compound is used, the salt-type carboxyl group and the basic compound having a low molecular weight are subjected to an ion exchange reaction to form a salt, and the adsorption and deodorization performance against acidic substances and aldehydes can not be improved, So that the adsorption and deodorizing performance of the basic substance is lowered. In the method of introducing an amino group into the fine particles of the above-mentioned crosslinked acrylonitrile-based polymer fine particles or crosslinked acrylic acid ester polymer and then performing a hydrolysis reaction to produce a carboxyl group inside the fine particles, the amino group and the carboxyl group These functional groups cause a neutralization reaction between the functional groups and form a salt in the particles, and in many cases, sufficient deodorization performance is not achieved. The hydrazine crosslinked structure of the above-mentioned crosslinked acrylonitrile-based polymer particles has a high adsorptive deodorizing ability against the acidic substance and the aldehyde originally, but the reaction is neutralized with the carboxyl group formed by the hydrolysis reaction, .

In the present invention, for the purpose of preventing this phenomenon, a basic polymer having a molecular size that can not permeate into the inside of the salt-type carboxyl group-containing fine particles is selected and the basic polymer is adsorbed to the salt carboxyl group present on the surface of the particle. That is, the functional fine particles of the present invention are in a state in which a large number of amino groups are present on the surface of the particle, and a salt type carboxyl group and an H type carboxyl group which are not neutralized with an amino group are present in the particle, and an acidic substance and an aldehyde Adsorption deodorization sites for the adsorbed deodorant sites, acidic substances and basic substances in the particles are independently present. In addition, since the basic polymer is attached by the polyion bond, it is hard to fall off and the washing durability is high. Therefore, as the basic polymer to be selected here, those having a high molecular weight are preferable, and those having a molecular weight of 300 or more are suitable. On the other hand, from the viewpoint of having water solubility, it is preferable that the molecular weight is 70000 or less.

By having the structure as described above, the functional fine particles of the present invention not only realize a pleasant humidity environment by reducing the dampness caused by body fluids originating from the body, but also have an immediate effect and persistence against a compound odor such as an elderly smell and a sweat odor It is possible to exhibit the deodorizing performance. Specifically, as a deodorizing performance, the deodorization standard of the fiber evaluation technical meeting is ammonia odor removal rate of 70% or more, acetic acid odor removal rate of 80% or more, isovaleric acid odor removal rate of 85% or more, and nonenal odor removal rate of 75% It is also possible to do.

As an advantage of allowing the basic polymer to act on the salt-containing carboxyl group-containing fine particles, an improvement in adhesion to the resin can be mentioned. Resins to be improved in adhesiveness include resins having high cohesive strength, such as urea resin, urethane resin, nylon resin and ester resin. In particular, the urethane bond of the urethane resin exhibits a very high cohesive strength of 8.74 kcal / mol. In order to improve the adhesion of the particles to a resin having a high cohesive force, it is effective to cause a large number of functional groups having active hydrogens on the surface of the particles to adhere the particles by hydrogen bonding. The salt-type carboxyl group-containing fine particles are in a state in which active hydrogens are small because many of the carboxyl groups are in a salt form. Thus, in the present invention, a basic polymer having active hydrogens is immobilized on the surface of the particles. As the functional group having active hydrogen suitable for this purpose, a primary or secondary amino group is most effective. As the basic polymer, there is no particular limitation as long as it is a basic polymer containing a primary or secondary amino group. However, as a basic polymer soluble in water, Polyethyleneimine can be suitably used.

The adhesion of the fine particles to the resin can be evaluated by a peel strength test described later. In this peel strength test, if the peel strength of the urethane resin to which the fine particles are added is maintained at 36% or more with respect to the peel strength of the urethane resin alone, it is possible to develop abrasion resistance that is not problematic in practical use. In the functional fine particles of the present invention, a peel strength retention ratio of 36% or more can be obtained and a peel strength retention ratio of 50% or more can be achieved.

The average particle diameter of the functional fine particles of the present invention is preferably 0.01 to 200 占 퐉, more preferably 0.01 to 50 占 퐉, in view of the case where they are mixed with other resin materials. When the average particle diameter is less than 0.01 占 퐉, it is difficult to produce. When the average particle diameter is larger than 200 占 퐉, the constraint of the thickness and fiber diameter of the resin molded article becomes large. When the average particle diameter is smaller than several micrometers, it is generally easier to handle the particles dispersed in a medium such as water.

The saturated moisture absorption rate of the functional fine particles of the present invention under the condition of 20 캜 x 65% RH is preferably not less than 15%, more preferably not less than 20%, still more preferably not less than 20% Is more than 30%. The saturated moisture absorption rate at the upper limit value of the amount of the salt type carboxyl group introduced into the functional fine particles of the present invention at 11 mmol / g is 85%.

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

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, the functional fine particles of the present invention are mixed with a liquid obtained by dissolving a urethane resin in dimethylformamide, and then coated on a nonwoven fabric composed of polyester fibers. Thereafter, By drying, an artificial leather having moisture absorptive and desorptive properties and deodorizing performance can be produced.

In the case of fibers, functional fine particles of the present invention are mixed in a liquid obtained by dissolving a urethane resin in dimethylacetamide, and then processed into a fiber form by a dry spinning method. Thus, Can be produced. For example, in the case of an acrylonitrile-based fiber, it is possible to use sodium thiocyanate, nitric acid, dimethylformamide, dimethylacetamide, dimethylsulfoxide, zinc chloride And an acrylonitrile-based polymer is dissolved in a solvent such as water or the like. In the case of cellulose-based fibers, a viscous liquid prepared by adding the functional fine particles of the present invention to a viscose stock solution containing a cellulosic polymer may be prepared by spinning the viscose liquid according to a conventional method.

The addition amount of the functional fine particles of the present invention in these resin products can be suitably set in consideration of the intended deodorizing performance and the strength of the resin product, By weight to 60% by weight. When the content is less than 0.1% by weight, the properties of the functional fine particles of the present invention may not be retained. When the content exceeds 60% by weight, problems such as lowering of physical properties such as strength of the product and dropping of functional fine particles due to friction occur .

Example

Hereinafter, the present invention will be described in detail by way of examples. Parts and percentages in the examples are by weight unless otherwise specified. The amount of the salt type carboxyl group, the proportion of the salt type carboxyl group, the amount of the basic polymer, the average particle diameter, the swelling degree, the moisture absorption rate, the moisture absorption amount, the odor removal rate, the peeling strength,

(1) Amount of salt type carboxyl group (mmol / g)

About 1 g of the sufficiently dried fine particulate was precisely weighed (X [g]), 200 g of water was added thereto, and the solution was adjusted to pH 2 by adding 1 mol / l hydrochloric acid aqueous solution while being heated to 50 캜, Determine the titration curve according to the conventional method with an aqueous solution of sodium hydroxide. From this titration curve, the amount (Y [ml]) of aqueous sodium hydroxide solution consumed by the carboxyl group is determined, and the total amount of carboxyl groups is calculated according to the following formula.

Amount of total carboxyl groups [mmol / g] = 0.1 x Y / X

Separately, the titration curve is obtained in the same manner as above except that the adjustment to pH 2 by the addition of the 1 mol / l hydrochloric acid aqueous solution during the measurement of the total carboxyl groups is not carried out, and the amount of the H-type carboxyl group is calculated. From these results, the amount of salt-type carboxyl groups is calculated according to the following equation.

(Amount of salt type carboxyl group) = (amount of total carboxyl group) - (amount of H type carboxyl group)

(2) Ratio of salt type carboxyl group (%)

The proportion of the salt-type carboxyl group is calculated from the amount of the salt-type carboxyl group and the total amount of the carboxyl group calculated in (1) according to the following equation.

(Ratio of salt type carboxyl group) = (amount of salt type carboxyl group) / (total amount of carboxyl group) x 100

(3) Adhesion amount of basic polymer (% by weight)

The weight of the salt-containing carboxyl group-containing particles before the basic polymer treatment is measured (B [g]), and the weight of the particles 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.

Adhesion amount of basic polymer (% by weight) = (C-B) / B x 100

(4) Average Particle Diameter (μm)

(SALD-200V) manufactured by Shimadzu Seisakusho Co., Ltd., using water as a dispersion medium, and obtaining an average particle diameter (m) from a particle diameter distribution expressed on a volumetric basis.

(5) swelling degree (times)

Approximately 1 g of the sample is dried in a hot-air drier at 105 ° C for 16 hours, and its weight is measured (D [g]). Subsequently, this sample is dispersed in 500 g of purified water for 1 hour to swell. Thereafter, solid-liquid separation is carried out with a suction filter provided with a membrane filter (MIXED CELLULOSE ESTER 0.65 μm), and the weight of the solid is measured (E [g]). From the above results, the swelling degree is calculated according to the following equation.

Swelling degree [times] = (E-D) / D

(6) 20 占 폚 占 65% RH of fine particles Absorption rate (saturated moisture absorption rate) (%)

Approximately 5.0 g of the sample is dried in a hot-air drier at 105 DEG C for 16 hours to measure its weight (W2 [g]). The sample is then placed in a constant-temperature and humidity-controlled room at 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 formula.

Saturated moisture absorption rate [%] = (W3-W2) / W2 100

(7) 20 ° C × 65% RH of artificial leather Moisture absorption amount (saturated moisture absorption amount) (g / m ² )

The sample is cut into a size of 10 cm x 10 cm and dried at 105 DEG C for 16 hours by a hot air drier to measure its weight (W4 [g]). The sample is then placed in a constant-temperature and humidity-controlled room at 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 formula.

Saturated moisture absorption amount [g / m ² ] = (W 5 -W 4) × 100

(8) odor removal rate (%)

0.5 g of the sample is sealed in a Tedlar bag, and 1.5 l of air is injected. Subsequently, a predetermined concentration of acetic acid (100 ppm for ammonia, 50 ppm for acetic acid, 40 ppm for isovaleric acid, 14 ppm for acetaldehyde, and 14 ppm for nonenal) was injected into a Tedlar bag, After leaving for 120 minutes, the odor concentration (W4) in the Tedlar bag is measured using a gauge type detector tube. The blanks containing no sample are also prepared in the same concentration, and after 120 minutes, the odor concentration (W5) is measured and a blank test is performed. 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 (%)

The sample is cut to a width of 2 cm and a length of 13 cm, and then a polytape (polyurethane hotmelt tape) is thermocompression bonded to the surface of the sample, and a peel strength test is conducted by a constant rate extension type tensile tester. The test is carried out under the conditions of a tensile speed of 100 mm / min, and a load at the start of peeling (hereinafter referred to as peeling strength) is measured. The peel strength of the sample not containing the particles and the sample containing the particles are measured, and the peel strength retention ratio is calculated according to the following formula.

Peel strength maintenance ratio (%) = (peel strength of particle-containing sample) / (peel strength of non-particle-containing sample) x 100

(10) The junior wear examination

In the test using the type II friction tester according to JIS L 0849, the wet test is carried out under the following conditions: load: 500 g; Evaluation is made by observing the state of the surface of the test piece after performing the friction test a predetermined number of times.

[Example 1]

700 parts by weight of water was introduced into a 2 L-volume reaction tank, 210 parts by weight of acrylonitrile and 90 parts by weight of divinylbenzene were further mixed. While stirring the reaction vessel, 3 parts by weight of ammonium persulfate (polymerization initiator) was added and dissolved. Thereafter, the reaction tank was heated to 70 DEG C and reacted for 3 hours. After completion of the reaction, the mixture was cooled to about 20 캜 while stirring was continued to obtain crosslinked acrylonitrile-based polymer particles having an average particle diameter of 40 탆. Subsequently, 800 g of water, 100 g of NaOH and 100 g of the crosslinked acrylonitrile-based polymer particles were introduced into a 2 L-volume reaction tank and subjected to a hydrolysis reaction at 90 DEG C for 60 hours to obtain salt-containing carboxyl group-containing particles. The amount of the salt-type carboxyl group at this time was 6.2 mmol / g. Further, 900 g of water and 100 g of the salt-containing carboxyl group-containing particles were introduced into a 2 L-volume reaction tank and 0.5 g of polyethyleneimine (average molecular weight of 70000) was added with stirring, followed by reaction at 50 캜 for 30 minutes, To obtain functional fine particles. It was confirmed that the adhesion amount of the basic polymer by the polyethylene imine treatment was 0.5% by weight. The results of evaluating these particles are shown in Table 1.

[Example 2]

The same procedures as in Example 1 were carried out except that the amount of polyethyleneimine added was changed to 1.8 g in Example 1 to obtain functional fine particles. The results of evaluating these particles are shown in Table 1.

[Example 3]

The same procedures as in Example 1 were carried out except that the amount of polyethyleneimine added was changed to 4.4 g in Example 1 to obtain functional fine particles. The results of evaluating these particles are shown in Table 1.

[Example 4]

700 parts by weight of water and 30 parts by weight of polyvinyl alcohol (manufactured by PVA217 Kuraray Co., Ltd.) were introduced into a reaction vessel of 2 L capacity, 210 parts by weight of acrylonitrile and 90 parts by weight of divinylbenzene and azobisisobalononitrile And 3 parts by weight (polymerization initiator) were further introduced and stirred with a homomixer to atomize the monomers. Thereafter, the reaction tank was heated to 70 DEG C and reacted for 3 hours. After completion of the reaction, the mixture was cooled to about 20 캜 while stirring was continued to obtain crosslinked acrylonitrile-based polymer particles having an average particle diameter of 5 탆. Subsequently, 800 g of water, 100 g of NaOH and 100 g of the crosslinked acrylonitrile-based polymer particles were introduced into a 2 L-volume reaction tank and subjected to a hydrolysis reaction at 90 DEG C for 60 hours to obtain salt-containing carboxyl group-containing particles. The amount of the salt-type carboxyl group at this time was 6.2 mmol / g. Further, 900 g of water and 100 g of the salt-containing carboxyl group-containing particles were introduced into a 2 L-volume reaction tank and 1.8 g of polyethyleneimine (average molecular weight of 70000) was added with stirring, followed by reaction at 50 캜 for 30 minutes, To obtain functional fine particles. The adhesion amount of the basic polymer by the polyethyleneimine treatment was found to be 1.8 wt%. The results of evaluating these particles are shown in Table 1.

[Example 5]

Functional microparticles were obtained in the same manner as in Example 4 except that the amount of polyvinyl alcohol introduced was changed to 0.4 parts by weight. The results of evaluating these particles are shown in Table 1.

[Example 6]

Functional fine particles were obtained in the same manner as in Example 2 except that the amount of acrylonitrile introduced was changed to 75 parts by weight and the amount of divinylbenzene introduced to 225 parts by weight. The results of evaluating these particles are shown in Table 1.

[Example 7]

The same procedures as in Example 1 were carried out except that the amount of polyethyleneimine added was changed to 0.1 g to obtain functional fine particles. The results of evaluating these particles are shown in Table 1.

[Example 8]

After obtaining the salt-containing carboxyl group-containing particles in Example 1, the particles were redispersed in water, and hydrochloric acid having a concentration of 1 mol / L was added dropwise so as to have a pH of 5, and the ratio of the amount of the salt- 45%, and then the same polyethyleneimine treatment as in Example 1 was carried out to obtain functional fine particles. The results of evaluating these particles are shown in Table 1.

[Example 9]

100 parts by weight of the functional fine particles prepared in Example 2 were dispersed in 200 parts by weight of a DMF solvent and then mixed with 411 parts by weight of a urethane resin coating material (manufactured by DIC; did. A nonwoven fabric having a weight per unit area of 100 g / m ² composed 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 punching method did. The nonwoven fabric was coated with the coating solution so that the coating solution had a density of 186 g / m ² , and then immersed in a water bath to remove the solvent, followed by drying to obtain artificial leather. The evaluation results of this 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 adhesion treatment of polyethyleneimine was not carried out to obtain fine particles. The results of evaluating these particles are shown in Table 1.

[Comparative Example 2]

Fine particles were obtained in the same manner as in Example 2 except that the introduction amount of acrylonitrile was changed to 55 parts by weight and the introduction amount of divinylbenzene was changed to 245 parts by weight. The results of evaluating these particles are shown in Table 1.

[Comparative Example 3]

The same procedure as in Example 1 was carried out except that the amount of polyethyleneimine added was changed to 0.04 g in Example 1 to obtain fine particles. The results of evaluating these particles are shown in Table 1.

[Comparative Example 4]

After obtaining the salt-containing carboxyl group-containing particles in Example 1, the particles were redispersed in water, and hydrochloric acid having a concentration of 1 mol / L was added dropwise so as to have a pH of 3.5, and the ratio of the amount of the salt- 27%. Then, the same polyethyleneimine treatment as in Example 1 was carried out to obtain fine particles. The results of evaluating these particles are shown in Table 1.

[Comparative Example 5]

Artificial leather was obtained in the same manner as in Example 9 except that the functional fine particles prepared in Example 2 were not added. The evaluation results of the artificial leather are shown in Table 2.

[Comparative Example 6]

Artificial leather was obtained in the same manner as in Example 9, except that the particles prepared in Comparative Example 1 were used instead of the functional fine particles prepared in Example 2. The evaluation results of the artificial leather are shown in Table 2.

From the comparison of Examples 1 to 3 and 7 and Comparative Example 1 in Table 1, it can be seen that the adhesion of the acidic substance and aldehyde deodorization is remarkably improved by attaching the basic polymer to the surface of the particles. Also, it can be seen that the basic substance deodorizing performance and moisture absorbing performance are not greatly deteriorated there. From the comparison between Example 9 and Comparative Example 6, it can be seen that the adhesion of the urethane resin is improved by the presence of the basic polymer. In the table, " - " indicates that the measurement was not performed.

[Example 10]

210 parts of ion-exchanged water and 2 parts of Eleminol MON-2 (manufactured by Sanyo Chemical Industries, Ltd.) were introduced into the reaction tank. Then, the temperature of the reaction vessel was raised to 60 ° C., and while stirring the mixture at 60 ° C., a mixture of monomer mixture consisting of 78 parts of ethyl acrylate, 5 parts of methyl methacrylate and 17 parts of divinylbenzene and 0.6 parts of ammonium persulfate was added to 30 parts of water , And 0.5 part of sodium pyruvate in 30 parts of water was dropped over 3 hours. After completion of the dropwise addition, polymerization was carried out by maintaining the same conditions for 2 hours. The obtained emulsion had a solid content of 21%. 400 parts of a 10% aqueous sodium hydroxide solution was added to 480 parts of the emulsion, and the hydrolysis reaction was carried out at 95 DEG C for 48 hours. Subsequently, the hydrolyzed emulsion was put into a cellulose semipermeable membrane, desalted by immersion in ion-exchanged water, and ion-exchanged water was added to obtain emulsion phase particles having a solid content of 5%. The total amount of carboxyl groups of the particles was 6.0 mmol / g, the amount of salt type carboxyl group was 5.6 mmol / g, and the moisture absorption rate was 53%.

To the emulsion phase particles, polyethyleneimine (average molecular weight: 70000) was added with stirring, and the mixture was allowed to react at 50 占 폚 for 30 minutes. Thereafter, washing and drying treatment were carried out to obtain functional fine particles of the present invention on an aqueous dispersion. The average particle diameter of the functional fine particles was 0.4 탆, and the basic polymer adhered amount was 0.4% by weight.

Subsequently, acrylonitrile polymer was prepared by aqueous suspension polymerization of 90% by weight of acrylonitrile, 9% by weight of methyl acrylate and 1% by weight of sodium methallylsulfonate. This acrylonitrile-based polymer was dissolved in an aqueous solution of sodium thiocyanate having a concentration of 45% by weight so as to have a polymer concentration of 12% by weight, and then the functional fine particles of the present invention on the aqueous dispersion described above were added and mixed to prepare an acrylonitrile- To prepare a spinning stock solution containing 4% by weight of the functional fine particles. This stock solution was extruded into a 15 wt% aqueous solution of sodium thiocyanate at -2.0 DEG C, followed by water washing and stretching to 12 times, followed by wet heat treatment at 110 DEG C for 10 minutes and drying and densification with a hot air drier at 120 DEG C, To prepare an acrylonitrile-based fiber containing fine particles. The odor removal rates of the fibers were 98% ammonia, 90% acetic acid, 84% isovaleric acid, and 89% nonrenal.

Claims (11)

Functional fine particles having a cross-linking structure and 1.8 mmol / g or more of a salt-type carboxyl group and having at least 0.05 wt% of a basic polymer adhered to the moisture absorptive and desorptive fine particles, wherein the average particle diameter is in the range of 0.01 to 200 μm. The functional fine particles according to claim 1, characterized in that the saturated moisture absorption rate under a condition of 20 ° C × 65% RH is 15% or more. The process according to any one of claims 1 to 3, characterized by having an ammonia odor removal rate of not less than 70%, an acetic acid odor removal rate of not less than 80%, an isovaleric acid odor removal rate of not less than 85%, and a nonenal odor removal rate of not less than 75% By weight. The functional fine particle according to any one of claims 1 to 3, wherein the retention strength of the peel strength when blended with the artificial leather of yretein is 36% or more. The functional fine particle according to any one of claims 1 to 4, wherein the ratio of the amount of the salt-type carboxyl group to the total amount of the carboxyl groups in the moisture absorptive and desorptive fine particles is in the range of 40 to 99%. A resin product comprising the functional fine particles according to any one of claims 1 to 5. 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. 10. The resin product according to any one of claims 7 to 9, wherein the resin constituting the resin product contains a urethane resin. The resin product according to claim 9, wherein the resin constituting the resin product contains a cellulose-based polymer and / or an acrylonitrile-based polymer.