JP2017179651A - Fiber structure and manufacturing method therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fiber structure having excellent repellency to sanitary insect pests such as mosquitoes and repellency durability capable of maintaining the repellency even with washing.SOLUTION: The fiber structure has microcapsules which contain an insect-repellent component and is carried on a fiber by a binder containing a carbodiimide resin and a melamine resin or a urethane resin.SELECTED DRAWING: None

Description

  The present invention relates to a fiber structure having excellent repellency against sanitary pests such as mosquitoes and having repellent durability that can maintain repellency even after washing, and a method for producing the same.

  Conventionally, fabrics finished by impregnation with insect repellents are known. However, the active ingredient has the disadvantage of being washed out very quickly. Therefore, it is known to fix a microcapsule containing an insect repellent component on a fiber using a melamine resin or a urethane resin as a binder (Patent Document 1).

JP 2007-277800 A

  However, the methylol group contained in the melamine resin or the isocyanate group contained in the urethane resin had to be heated to 150 to 170 ° C. in order to cause a condensation reaction. Therefore, heat is transmitted to the insect repellent component contained in the microcapsule and volatilizes, thereby causing a decrease in repellency.

  An object of the present invention is to provide a fiber structure having excellent repellency against sanitary pests such as mosquitoes and having repellent durability that can maintain repellency even after washing.

  In order to solve the above problems, the present invention employs the following means. That is, the fiber structure of the present invention has a microcapsule containing an insect repellent component supported on the fiber by a carbodiimide resin exhibiting high reactivity at a low temperature and a binder containing a melamine resin or a urethane resin. It is a fiber structure characterized in that the volatilization of water is suppressed, the amount of the insect repellent component remaining in the microcapsule is increased, and the repellency is increased.

  The fiber structure of the present invention has excellent repellency against sanitary pests such as mosquitoes, and has repellency durability that can maintain repellency even after washing.

  Hereinafter, the fiber structure of the present invention will be described in detail.

  In the fiber structure of the present invention, a microcapsule containing an insect repellent component is supported on a fiber by a binder containing a carbodiimide resin and a melamine resin or a urethane resin.

  The wall material of the microcapsule used in the present invention is preferably an inorganic or organic material, and examples thereof include polystyrene, ethyl cellulose, polyamide, polyacrylic acid, melamine resin, urethane resin, silicone resin, and carboxymethyl cellulose. Among them, melamine resin is a preferable wall material because it is excellent in film strength, chemical resistance, adhesion, and transparency.

  The particle size of the microcapsules is preferably 0.1 to 20 μm. And from a viewpoint of film strength, aggregation, and product quality, specific microcapsules include microporous inorganic particles having a particle size of 0.1 to 20 μm, or hollow microporous particles having a particle size of 0.1 to 20 μm. And melamine resin-based or acrylic resin-based particles.

  The binder of the present invention includes a carbodiimide resin and a melamine resin or a urethane resin. The carbodiimide resin of the present invention has a large number of highly reactive carbodiimide groups or imide groups in the resin structure, not only the methylol group contained in the melamine resin or the isocyanate group contained in the urethane resin, but also a carboxy group, Reacts easily with hydroxyl and amino groups. The reaction temperature is 90 to 190 ° C.

  The raw material for the melamine resin of the present invention can be selected from various melamines from trimethylol melamine to hexamethylol melamine.

  When a large amount of melamine resin is used, the crosslinking effect is improved, but the texture tends to be cured. From the viewpoint of obtaining a sufficient crosslinking effect, while maintaining a soft texture, it is preferable to add 0.01 to 1 wt% as a solid content with respect to the total mass of the fiber structure, and further 0.02 to 0.5 wt%. More preferably.

  Melamine curing catalysts include inorganic phosphates such as ammonium phosphate, ammonium sulfate, ammonium nitrate, aluminum phosphate, aluminum sulfate, aluminum nitrate, zinc phosphate, zinc sulfate, zinc nitrate, ammonium formate, ammonium acetate, ammonium acrylate, Ammonium succinate, aluminum formate, aluminum acetate, aluminum acrylate, aluminum succinate, zinc formate, zinc acetate, zinc acrylate, zinc succinate and the like are preferable.

  The urethane resin of the present invention is synthesized by a reaction of polyisocyanate and polyol. The polyisocyanate used for the synthesis of the polyurethane resin refers to a compound having two or more isocyanate groups. Specific examples thereof include aliphatic polyisocyanates, aromatic polyisocyanates, copolymers thereof, and hexamethylene polyisocyanates. , Polymethylene polyphenyl polyisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 2,6-tolylene diisocyanate, 2,4-tolylene diisocyanate, naphthalene-1,4-diisocyanate Diphenylmethane-4,4'-diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, xylylene-1,4-diisocyanate, and polyisocyanates containing these as substrates. Can be mentioned. In addition, the polyol used for the polyurethane resin refers to a compound having two or more hydroxyl groups, and specific examples include ethylene glycol, propylene glycol, butylene glycol, hexanediol, polyethylene glycol, glycerin and the like and water.

  The fiber structure of the present invention can be produced by the method described below. That is, for example, first, a microcapsule containing an insect repellent component, a carbodiimide resin, and a melamine resin or a urethane resin are emulsified and dispersed in water so as to obtain a target loading amount with respect to the fiber to obtain an emulsion solution (dispersion solution). The emulsion solution (dispersed solution) can be produced by applying the emulsion solution (dispersed solution) onto the fiber by a padding method, a spray method, a dipping / centrifugal dehydration method, or a coating method, and drying at 90 to 190 ° C.

  A method in which microcapsules, carbodiimide resins, and melamine resins or urethane resins containing insect repellent components are dispersed in water and the dispersions are mixed is also preferably used. The dispersion medium is not particularly limited, but water is preferably used. That is, the method for producing a fiber structure of the present invention includes a step of dispersing a microcapsule containing an insect repellent component, a carbodiimide resin, and a melamine resin or a urethane resin in water to form a dispersion solution, and immersing the dispersion solution on the fiber. And a step of drying the fiber to which the dispersion solution has been impregnated at 110 ° C. to 130 ° C.

  The carrying method is preferably a padding method in that the insect repellent component can be imparted to the fibers without unevenness. Moreover, since this insect repellent volatilizes when the heat of drying is high, it is preferable to dry at 90-130 degreeC.

  The amount of the insect repellent component supported on the fiber is not particularly limited, but is generally preferably 0.01 to 10% by mass, more preferably 0.5 to 1% by mass relative to the dry mass of the fiber. The insect repellent component is preferably a mosquito repellent.

  The insect repellent component (preferably mosquito repellent) of the present invention is preferably supported on 10 to 10,000 ppm on the fiber. Here, the carrying amount (ppm) is intended for insect repellent components excluding the wall material of microcapsules, and is expressed by the mass of the insect repellent component relative to the mass of the fiber structure. If the insect repellent component is less than 10 ppm, a sufficient repellent effect may not be obtained, and if the insect repellent component is greater than 10,000 ppm, the resulting increase in the amount of microcapsule wall material will result in a texture of the fiber. May be damaged.

Such types of insect repellent components include sesquiterpenes, diethyltoluamide (DEET), ethylbutylacetylaminopropionate (IR 3535), picaridin, or pyrethroid and mixtures thereof. Picaridine is more preferred because it is safer than DEET despite having the same repellency as DEET, which has high repellency. Therefore, even if it is applied to clothing handled by infants such as children, it can be used more safely.
In the present invention, the fiber means a fiber such as polyester, nylon, acrylic, urethane, cotton, rayon, or wool, but is not particularly limited thereto. Moreover, the form of the fiber is not particularly limited.

  In such a fiber, a cotton-containing or urethane-containing fiber is preferable because the binder effect is increased by the reaction of the hydroxyl group of cotton or the isocyanate portion of the urethane fiber with the active group of carbodiimide, and the washing durability is increased.

  Moreover, it is preferable to contain polyester fiber and cotton, polyester fiber and polyurethane fiber, comprising polyester fiber and cotton in a mass ratio of 50:50 to 90:10, and polyester fiber and polyurethane fiber in a mass ratio of 80:20 to 90. : 10 is preferably included.

  The amount of the binder of the present invention is preferably 0.1 to 10% by mass with respect to the amount of the insect repellent component supported. The heat treatment for such a reaction is preferably a dry heat treatment and a steam heat treatment at a temperature of 90 to 130 ° C. for 0.1 to 30 minutes. The steam heat treatment produces a more uniform coating on the fiber surface. It is easy to form and the texture after film formation is flexible. For this steaming treatment, saturated steam or superheated steam at 90 to 130 ° C. is preferably used, and any steam is treated for several seconds to several minutes.

  The film thickness of the binder of the present invention is preferably 10 nm to 10,000 nm. When the film thickness of the binder is small, the texture is flexible, so that the thickness is more preferably 10 nm to 1,000 nm.

  Hereinafter, the present invention will be described in more detail with reference to examples. In this example, the repelling rate, the thickness of the coating, and the loading amount were determined by the following methods.

(1) Repelling rate Put a vinyl glove on the subject's hand and wrap a cylindrical sample on it.

  Under the conditions of an air temperature of 25 ± 2 ° C. and a humidity of 70 to 80%, the sample was inserted into a 30 × 30 × 30 cm cage in which 30 test insects (Human striped mosquito) were released for 2 minutes up to the elbow and stopped on the sample. Count the number of test insects and use it as the cumulative number of flights. The monitoring was performed by two people (A and B).

  In the test, the repelling rate is calculated by comparing the cumulative number of flying when the untreated specimen is wound with the cumulative number of flying when the treated specimen is wound.

The following formula was used for calculation of the repelling rate.
Repelling rate (%) = {(cumulative number of untreated samples−cumulative number of treated samples) / cumulative number of untreated samples} × 100.

(2) Film thickness The maximum thickness of the resin film formed by observing a cross section of a single fiber constituting the fiber structure of the present invention at 100,000 times in a transmission electron microscope (TEM) at random. Measure. However, the resin lump generated in the gap between the single fiber bundles is not judged as a resin coating even if it is connected to the single fiber surface portion.

(3) Carrying amount As described above, the carrying amount (ppm) is intended for insect repellent components excluding the wall material of microcapsules, and is represented by the mass of the insect repellent component with respect to the mass of the fiber structure. . In the following examples, the concentration of the insecticide in the chemical solution to be immersed in the chemical solution tank in which the fabric-like fibers are immersed, and the amount of the chemical solution contained in the obtained fabric by squeezing the chemical solution by passing the fabric after immersion is passed through the mangle. (Drawing weight in the chemical solution minus the weight of the cloth before dipping in the chemical solution) / weight of the cloth before dipping in the chemical solution × 100). Since it is used in an aqueous system (water density 1 kg / L), it can be converted to an aqueous solution 1 L≈1 kg.
Amount supported (ppm = mg / kg) = (insect repellent concentration g / L) × (squeezing rate / 100%) × (conversion L / kg) × (unit conversion 1000 mg / g)
Example 1
(1) 50 g / L of microcapsules having an average particle size of 1 to 3 μm, in which the wall agent is composed of melamine resin, encapsulating picaridin, which is a mosquito repellent, in a mass ratio of 20% with respect to the total amount of microcapsules (2) The urethane resin synthesized from the polyisocyanate having an isocyanate group at the polymer terminal or branching portion and the polyol having a hydroxyl group at the terminal or branching portion is 30 g / L so that the component becomes 10 g / L) (3) Emulsified and dispersed in water so that the carbodiimide resin was 3 g / L to prepare an emulsified dispersion solution.

  A cloth made of polyurethane-mixed polyester fiber having a mass ratio of polyurethane fiber to polyester fiber of 13:87 is dipped in a chemical bath containing an emulsified dispersion solution and squeezed so that the drawing rate (pickup) becomes 80%. A dry heat treatment at 0 ° C. was performed for 2 minutes and dried.

Example 2
The polyurethane-mixed polyester fiber fabric obtained in Example 1 was washed 10 times in accordance with JIS L0217 103 method.

Example 3
The polyurethane-mixed polyester fiber fabric obtained in Example 1 was washed 30 times in accordance with JIS L0217 103 method.

  Next, the mosquito repellent rate of the polyurethane-mixed polyester fiber fabric obtained in Examples 1 to 3 was evaluated by the method described above. The polyurethane-mixed polyester fiber fabric before treatment of Example 1 was used as an untreated specimen.

  From Examples 1 to 3, the insect repellent component picaridin is carried on a polyurethane-mixed polyester fiber fabric, so that high repellent property is obtained, and it has repellent durability that can maintain repellent properties even after washing. I understand.

Claims (9)

  A fiber structure in which a microcapsule containing an insect repellent component is supported on a fiber by a binder containing a carbodiimide resin and a melamine resin or a urethane resin.   The fiber structure according to claim 1, wherein a film thickness of the binder carrying the microcapsules is 10 nm to 10,000 nm.   The fiber structure according to claim 1, wherein the fiber includes cotton or polyurethane.   The fiber structure according to any one of claims 1 to 3, wherein the insect repellent component is a mosquito repellent.   The fiber structure according to claim 4, wherein the mosquito repellent is picaridin.   The fiber structure according to claim 4 or 5, wherein the mosquito repellent is supported on a fiber at 10 to 10,000 ppm.   The fiber structure according to claim 1, wherein the fiber comprises polyester fiber and cotton in a mass ratio of 50:50 to 90:10.   The fiber structure according to claim 1, wherein the fiber comprises a polyester fiber and a polyurethane fiber in a mass ratio of 80:20 to 90:10.   Microcapsules containing insect repellent components, carbodiimide resin and melamine resin or urethane resin are dispersed in water to form a dispersion solution, the dispersion solution is dipped onto the fiber, and the fiber to which the dispersion solution is dipped is applied at 110 ° C. And a step of drying at 130 ° C. to produce a fiber structure.