Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
  • B01D53/26—Drying gases or vapours
  • B01D53/28—Selection of materials for use as drying agents
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
  • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
  • B01D53/26—Drying gases or vapours
  • B01D53/261—Drying gases or vapours by adsorption
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
  • B01J20/26—Synthetic macromolecular compounds
  • B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
  • B01J20/267—Cross-linked polymers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
  • B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
  • B01J20/28004—Sorbent size or size distribution, e.g. particle size
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
  • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
  • D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
  • D06N3/0068—Polymeric granules, particles or powder, e.g. core-shell particles, microcapsules
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
  • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
  • D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
  • D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
  • B01D2253/20—Organic adsorbents
  • B01D2253/202—Polymeric adsorbents
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
  • B01D2253/30—Physical properties of adsorbents
  • B01D2253/302—Dimensions
  • B01D2253/304—Linear dimensions, e.g. particle shape, diameter
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2257/00—Components to be removed
  • B01D2257/40—Nitrogen compounds
  • B01D2257/406—Ammonia
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2257/00—Components to be removed
  • B01D2257/80—Water
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2257/00—Components to be removed
  • B01D2257/90—Odorous compounds not provided for in groups B01D2257/00 - B01D2257/708
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2259/00—Type of treatment
  • B01D2259/45—Gas separation or purification devices adapted for specific applications
  • B01D2259/4541—Gas separation or purification devices adapted for specific applications for portable use, e.g. gas masks
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
  • D06N2209/00—Properties of the materials
  • D06N2209/16—Properties of the materials having other properties
  • D06N2209/165—Odour absorbing, deodorizing ability
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
  • D06N2211/00—Specially adapted uses
  • D06N2211/12—Decorative or sun protection articles
  • D06N2211/28—Artificial leather

Definitions

• 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.
• odors and stuffiness caused by body fluids generated from the body be quickly and continuously deodorized and moisture absorbed.
• odor there is a high awareness of aging odor and sweat odor.
• the aging odor is composed of aldehydes such as nonenal
• the sweat odor is composed of ammonia, acetic acid, isovaleric acid, and acetaldehyde.
• deodorization methods are roughly classified into physical deodorization, chemical deodorization, and sensory deodorization (masking).
• a physical deodorant activated carbon is extremely excellent.
• the activated carbon has problems such as difficulty in atomization, fixation on the fiber, and deterioration of the color of the fiber.
• the performance is significantly reduced by operations such as washing.
• the deodorant using a catalytic action has a low immediate effect.
• 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.
• 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.
• 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.
• 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.
• 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.
• 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.
• a resin product comprising the functional fine particles according to any one of [1] to [5].
• the resin product according to [9], wherein the resin constituting the resin product contains a cellulose polymer and / or an acrylonitrile polymer.
• 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.
• 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.
• 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.
• 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.
• 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.
• 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%, 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.
• 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.
• 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.
• 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 at a hydrazine concentration of 1% to 80% and a temperature of 50 to 120 ° C.
• 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).
• the increase in nitrogen content is less than the said minimum, microparticles
• 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. .
• 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 ⁇ m or more, the fine particles can be obtained by suspension polymerization, suspension precipitation polymerization or the like.
• 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.
• the cross-linked acrylonitrile polymer fine particles or cross-linked (meth) acrylate polymer fine particles preferably have an average particle diameter of 0.01 to 200 ⁇ m or less, and are added to a thin resin product.
• the average particle size is more preferably 0.01 to 50 ⁇ m, and when added to fine resin products such as fibers, the average particle size is preferably 0.01 to 10 ⁇ m. preferable.
• the fine particles may be dispersed in a medium such as water.
• 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.
• 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.
• 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.
• 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.
• 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.
• 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.
• 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.
• 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.
• 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.
• 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.
• 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.
• 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.
• 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.
• 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.
• 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.
• 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.
• 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.
• 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.
• 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.
• 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.
• the resin whose adhesion is improved include resins having bonds with high cohesion, such as urea resins, urethane resins, nylon resins, and ester resins.
• the urethane bond of the urethane resin exhibits a very high cohesive force of 8.74 kcal / mol.
• 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.
• 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.
• 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.
• 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 from 0.01 to 200 ⁇ m, more preferably from 0.01 to 50 ⁇ m as an average particle diameter, considering the case of mixing with other resin materials. is there. If the average particle diameter is less than 0.01 ⁇ m, it is difficult to produce, and if the average particle diameter is larger than 200 ⁇ m, 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 ⁇ m, 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 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.
• the resin product examples include artificial leather such as synthetic leather and artificial leather, film, and fiber.
• artificial leather such as synthetic leather and artificial leather, film, and fiber.
• 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.
• 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.
• 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.
• the content is preferably 0.1 to 60% by weight based on the total weight of the 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.
• 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.
• 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.
• 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
• Average particle diameter ( ⁇ m) Using a laser diffraction particle size distribution analyzer “SALD-200V” manufactured by Shimadzu Corporation, water is measured as a dispersion medium, and the average particle size ( ⁇ m) is obtained from the particle size distribution expressed on a volume basis.
• Odor removal rate (%) Place 0.5 g of sample in a Tedlar bag, seal and inject 1.5 l of air.
• 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
• the odor concentration (W4) in the Tedlar bag is measured using a Kitagawa type detector tube.
• 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 ⁇ m.
• ammonium persulfate polymerization initiator
• 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 volume reaction vessel 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 ⁇ m.
• PVA217 Kuraray Co., Ltd. polyvinyl alcohol
• 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.
• the said coating liquid was apply
• the evaluation results of the artificial leather are shown in Table 2.
• 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.
• 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.
• 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.
• 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.
• Example 9 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.
• 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.
• Example 10 A reaction vessel was charged with 210 parts of ion exchange 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.
• Eleminol MON-2 manufactured by Sanyo Chemical Industries
• 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 ⁇ m, and the basic polymer adhesion amount was 0.4% by weight.
• acrylonitrile-based polymer 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, and then the above-described aqueous dispersion-like functional fine particles of the present invention are added and mixed.
• 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.
• 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.

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