CN117364478A - Anti-acarid material - Google Patents

Anti-acarid material Download PDF

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Publication number
CN117364478A
CN117364478A CN202310668733.1A CN202310668733A CN117364478A CN 117364478 A CN117364478 A CN 117364478A CN 202310668733 A CN202310668733 A CN 202310668733A CN 117364478 A CN117364478 A CN 117364478A
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CN
China
Prior art keywords
acarid
oxalate
substrate
bedding
ion
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Pending
Application number
CN202310668733.1A
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Chinese (zh)
Inventor
中村成明
川中直树
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Japan Exlan Co Ltd
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Japan Exlan Co Ltd
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Publication date
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Publication of CN117364478A publication Critical patent/CN117364478A/en
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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
    • D06M13/192—Polycarboxylic acids; Anhydrides, halides or salts thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/58—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with nitrogen or compounds thereof, e.g. with nitrides
    • D06M11/64—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with nitrogen or compounds thereof, e.g. with nitrides with nitrogen oxides; with oxyacids of nitrogen or their salts
    • D06M11/65—Salts of oxyacids of nitrogen
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/26—Polymers or copolymers of unsaturated carboxylic acids or derivatives thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/32—Polyesters

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Biochemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Microbiology (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)

Abstract

As one of the measures against mites in bedding and the like, a method is known in which a chemical having a miticidal and repellent property is held in a wadding, a fabric and the like constituting bedding, a mat and the like to directly prevent mites. However, there are problems of safety of the drug to human body, remains of the remains of mites, reduction of the anti-mite effect due to washing, limitation of the corresponding substrate, and the like. The present invention provides a method for imparting anti-acarid properties to various substrates, which is highly safe to the human body and can prevent deterioration of anti-acarid properties even by repeated washing, and an anti-acarid raw material obtained by the method. An anti-acarid material comprising a base material and an oxalate.

Description

Anti-acarid material
Technical Field
The present invention relates to an anti-acarid material which imparts an anti-acarid property to a substrate and can maintain the effect even after washing.
Background
The variation in living environment due to the high airtight and high heat insulation of houses and the popularization of air-conditioning equipment is likely to cause mites and house dust, and the number of people suffering from allergic diseases such as asthma attacks, allergic dermatitis and rhinitis caused by these are increasing.
For example, mite allergy is caused by sucking or contacting mite antigens such as feces, carcasses, dehusked and eggs of mites as allergens, and bedding and cushions are main sources of the mite antigens.
Accordingly, as one of the measures against acarid such as bedding, there is known a method for directly preventing acarid by retaining a chemical having acarid-killing and repellent properties in a material, a fabric, or the like constituting bedding, a mat, etc., and for example, patent document 1 below discloses an antibacterial cellulose regenerated fiber characterized in that the cellulose regenerated fiber contains regenerated chitosan fine particles having a particle diameter of 10 μm or less, a nitrile-based antibacterial agent, a pyridine-based antibacterial agent, a haloalkylthio-based antibacterial agent, an organoiodine-based antibacterial agent, a thiazole-based antibacterial agent, and a benzimidazole-based antibacterial agent.
Patent document 2 discloses an antibacterial and deodorant fiber, which is characterized in that phenothrin and/or ecaritol are/is attached to the fiber surface in order to impart anti-acarid properties.
Patent document 3 below discloses a method for treating an acarid antigen, which is characterized in that a filler such as a lining material is impregnated with tannic acid, whereby the acarid antigen attached to the filler is modified to a form harmless to the human body.
Patent document 4 discloses a fiber or a fiber product comprising a fiber made of cellulose, wherein tannic acid and a crosslinking agent are attached and heat-treated to be bonded in a method for imparting anti-acarid properties.
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open No. 10-37018
Patent document 2: japanese patent laid-open publication No. 2021-80597
Patent document 3: japanese patent laid-open No. 9-301804
Patent document 4: japanese patent laid-open No. 2007-107149
Disclosure of Invention
Problems to be solved by the invention
However, in the case of applying the methods disclosed in the above patent documents 1 and 2 to bedding materials such as bedding materials, pajamas, etc., which are in direct contact with a human body, there are the following problems: the safety to human body caused by agents such as anti-acarid agents is disagreeable, or even if acarids are removed, the remains become new antigens.
On the other hand, the method disclosed in patent document 3 has a disadvantage in that the method has high safety and inactivates the acarid antigen, so that the method does not have a problem in that the removed acarid remains as a new antigen, but the effect is lost by repeated washing.
The method disclosed in patent document 4 has washing durability, but the substrate is limited to fibers including fibers made of cellulose, and there is a problem in that the substrate capable of imparting anti-acarid properties is small.
Accordingly, an object of the present invention is to provide a method for imparting an anti-acarid property to a substrate other than a substrate containing a cellulose material, which is highly safe to the human body and can prevent a decrease in the anti-acarid property even if washing is repeated, and an anti-acarid material obtained by the method.
Means for solving the problems
As a result of intensive studies to achieve the above object, it has been found that by imparting cations to a substrate and thereafter treating the substrate with oxalic acid, acarid-preventing properties can be imparted to the substrate, and acarid-preventing properties can be maintained even by repeated washing, and the present invention has been completed.
That is, the present invention has the following configurations (1) to (5).
(1) An anti-acarid material is obtained by imparting oxalate to a base material.
(2) The anti-acarid material according to (1), wherein the oxalate content is 0.001mmol/g or more.
(3) The anti-acarid material according to (1), wherein the solubility of the oxalate in water at 20℃is 1g/100g-H 2 O is less than or equal to.
(4) The acarid-preventing material according to (1), wherein the base material is a material having a negatively charged functional group.
(5) A bedding, upholstery or clothing comprising the anti-acarid material according to any one of (1) to (4).
(6) A method of making an anti-acarid material comprising: a treatment of immersing the substrate in an aqueous solution containing cations, and a treatment of immersing the substrate after the treatment in an aqueous solution containing oxalic acid.
Effects of the invention
The anti-acarid material of the present invention has an anti-acarid property by containing an oxalate. Particularly, when oxalate having low solubility in water is used, the anti-acarid property can be maintained even if washing is repeated. The use of the anti-acarid material of the present invention as a material for products requiring acarid resistance, such as interior products, bedding, and clothing, can provide acarid resistance to these products, and can be suitably used for bedding and clothing to be washed.
Detailed Description
The anti-acarid material of the present invention is described in detail below.
Examples of the oxalate used in the anti-acarid material of the present invention include zinc oxalate, ammonium oxalate, potassium oxalate, gallium oxalate, calcium oxalate, gold oxalate, silver oxalate, cobalt oxalate, cesium oxalate, iron oxalate, copper oxalate, sodium oxalate, lead oxalate, nickel oxalate, barium oxalate, magnesium oxalate, manganese oxalate, lithium oxalate, and the like.
Examples of the base material used in the anti-acarid material of the present invention include fiber structures such as fibers, threads, yarns (including covered yarns), filaments (fileament), woven fabrics (Japanese: articles), knitted fabrics (Japanese: articles), nonwoven fabrics, papers, sheets, laminates, cotton-like bodies (including spherical and block-like bodies), and resin molded articles such as particles, beads, films, coating films, and injection molded articles. In addition, combinations thereof are also possible.
The fibers that can be used as the base material are not particularly limited, and common natural fibers, organic fibers, semisynthetic fibers, and synthetic fibers can be used, and inorganic fibers, glass fibers, and the like can be used depending on the application. Specific examples thereof include cotton, hemp, silk, wool, nylon, rayon, polyester, acrylic fiber, and acrylic fiber. Examples of the resin constituting the resin molded body which can be used as the base material include polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyurethane, acrylic resin, ABS resin, and the like.
The substrate used in the present invention is preferably a substrate having a negatively charged functional group. The negatively charged functional group can trap cations in the method for producing an anti-acarina material of the present invention, which will be described later, and thus can efficiently produce oxalate. Examples of the negatively charged functional group include acidic groups such as carboxylic acid groups, sulfonic acid groups, and phosphoric acid groups, and polar groups such as nitrile groups, carbonyl groups, and hydroxyl groups.
The amount of the negatively charged functional group in the substrate is preferably a content capable of capturing a cation commensurate with the content of oxalate described later.
As the substrate having a negatively charged functional group, acrylic fibers, cationic dyeable polyester fibers, cationic dyeable rayon, and the like are exemplified as the substrate having a sulfonic acid group, and acrylic fibers are exemplified as the substrate having a carboxylic acid group.
Further, the oxalate content in the anti-acarid material of the present invention is preferably 0.001mmol/g or more, more preferably 0.01mmol/g or more. If the oxalate content is less than 0.001mmol/g, a sufficient anti-acarid effect may not be obtained. On the other hand, the upper limit of the content of the oxalate is not particularly limited, but when the oxalate is silver oxalate, it is preferably 1mmol/g or less from the viewpoints of easy coloring and cost.
In addition, when the anti-acarid material of the present invention is applied to applications for washing bedding, clothing, etc., it is preferable to use oxalate having a solubility of 1g/100g-H in water at 20 ℃ 2 The amount of O or less is more preferably 0.1g/100g-H 2 And O or less. By using such oxalate having low solubility in water, the oxalate is not easily dissolved in the washing liquid or the washing water, and therefore even in washingThe anti-acarid performance can be maintained after that. Examples of the oxalate having low solubility in water include silver oxalate, magnesium oxalate, and calcium oxalate. Among them, silver oxalate is particularly preferable because it also has antibacterial properties.
For the above-described anti-acarid material of the present invention, it can be obtained by: the method comprises immersing a substrate in an aqueous solution containing cations, treating the substrate at a treatment temperature of 40 to 130 ℃ for 5 to 120 minutes, immersing the substrate in an aqueous solution containing oxalic acid, and treating the substrate at a treatment temperature of 40 to 130 ℃ for 5 to 120 minutes to form salts of the cations and oxalic acid on the substrate.
Here, the amount of the cation contained in the aqueous solution containing the cation is preferably 0.001mmol or more, more preferably 0.01mmol or more, per 1g of the substrate. The amount of oxalic acid contained in the aqueous solution containing oxalic acid is preferably 0.001mmol or more, more preferably 0.01mmol or more, per 1g of the substrate.
Examples of the cations include zinc ion, ammonium ion, potassium ion, gallium ion, calcium ion, gold ion, silver ion, cobalt ion, cesium ion, iron ion, copper ion, sodium ion, lead ion, nickel ion, barium ion, magnesium ion, manganese ion, lithium ion, and the like, which are capable of generating the oxalate by reaction with oxalic acid. Among them, silver ion, magnesium ion and calcium ion are preferable, and silver ion is particularly preferable.
Examples of the aqueous solution containing these cations include aqueous solutions of nitrate, sulfate, phosphate, and the like, in which the cations are used as counter ions.
Examples of the product containing the acarid-preventing material of the present invention include bedding, clothing, and upholstery. For example, bedding materials, bedding covers, bedding liners, carpets, toweling, night gowns (such as pajamas, skirt-type pajamas), bed sheets, pillows, pillowcases, towels, handkerchiefs, clothing materials, clothing lining, clothing liners, slippers, carpets, mats, curtains, chair cloths, wallcoverings, floor coverings, and the like. These articles may be composed solely of the anti-acarid material or may be combined with other materials.
Examples
The present invention will be specifically described with reference to the following examples, but the present invention is not limited to these examples. The evaluation methods of the characteristics in the examples are as follows.
(1) Oxalate content
The atomic absorbance of the solution obtained by wet-decomposing the sample was measured by an atomic absorbance analyzer to determine the metal content. Based on the results of the content of the metal obtained, the oxalate content was calculated using the following formula.
Oxalate content (mmol/g) =metal content (g/g)/atomic weight of metal (g/mmol) ×valence of metal/2
(2) Anti-acarid test
According to JIS L1920: 2007 (method for testing acarid resistance of fiber products; repellency test-glass tube method A method). As the non-processed sample, a conventional polyester cotton was used. In addition, according to the standards of the performance evaluation agreement of the interior fabrics, the test was judged to have the anti-acarid effect when the repellency was 50% or more.
(3) Washing method
Regarding the washing method, according to JEC326 (SEK marking fiber product washing method), JAFET standard compounding lotion was used as the lotion.
Example 1
1kg of an acrylic fiber (type K8, cationic dyeability, manufactured by Exlan industries, ltd.) was immersed in an aqueous solution containing 4.73g of silver nitrate, treated at 98℃for 0.5 hours, and then, an aqueous solution containing 1.25g of oxalic acid was added thereto, and treated at 98℃for 0.5 hours. The obtained fiber was washed with water and dried, whereby an anti-acarid material containing silver oxalate was obtained. The evaluation results of the obtained anti-acarid material are shown in Table 1. The solubility of silver oxalate in water at 20℃was 0.00327g/100g-H 2 O。
Example 2
An anti-acarid material was obtained in the same manner as in example 1 except that the acrylic fiber was changed to a cationic dyeable polyester fiber (Tetoron, toli Co.). The evaluation results of the obtained anti-acarid material are shown in Table 1.
Example 3
1kg of an acrylic fiber (type K8 manufactured by Exlan industries, japan) was immersed in an aqueous solution containing 4.15g of magnesium nitrate, treated at 98℃for 0.5 hours, then an aqueous solution containing 2.51g of oxalic acid was added thereto, and treated at 98℃for 0.5 hours. The obtained fiber was washed with water and dried, whereby a magnesium oxalate-containing anti-acarid material was obtained. The evaluation results of the obtained anti-acarid material are shown in Table 1. The solubility of magnesium oxalate in water at 20℃was 0.104g/100g-H 2 O。
Example 4
1kg of an acrylic fiber (type K8 manufactured by Exlan industries, japan) was immersed in an aqueous solution containing 4.57g of calcium nitrate, treated at 98℃for 0.5 hours, then an aqueous solution containing 2.51g of oxalic acid was added thereto, and treated at 98℃for 0.5 hours. The obtained fiber was washed with water and dried, whereby a magnesium oxalate-containing anti-acarid material was obtained. The evaluation results of the obtained anti-acarid material are shown in Table 1. The solubility of calcium oxalate in water at 20℃was 0.00067g/100g-H 2 O。
Example 5
The evaluation results after further washing 10 times for the anti-acarid material in example 1 are shown in table 1.
Example 6
An anti-acarid material was obtained in the same manner as in example 1 except that 4.73g of silver nitrate was changed to 3.15g of silver nitrate and 1.25g of oxalic acid was changed to 0.83g of oxalic acid. The evaluation results of the obtained anti-acarid material are shown in Table 1.
Example 7
An anti-acarid material was obtained in the same manner as in example 1 except that 4.73g of silver nitrate was changed to 0.47g of silver nitrate and 1.25g of oxalic acid was changed to 0.13g of oxalic acid. The evaluation results of the obtained anti-acarid material are shown in Table 1.
Example 8
The evaluation results after further washing 10 times for the anti-acarid material in example 7 are shown in table 1.
Comparative example 1
A material of comparative example 1 containing silver chloride was obtained in the same manner as in example 1 except that 1.25g of oxalic acid was changed to 28.4g of a 1N aqueous hydrochloric acid solution. The evaluation results of the obtained materials are shown in table 1.
Comparative example 2
The material of comparative example 2 was obtained in the same manner as in example 1 except that 1.25g of oxalic acid was changed to 1.12g of sodium dihydrogen phosphate. The evaluation results of the obtained materials are shown in table 1.
Comparative example 3
A silver sulfonate-containing material was obtained in the same manner as in example 1 except that the aqueous solution containing oxalic acid was not added. The evaluation results of the obtained materials are shown in table 1. The acrylic fiber as a base material contains a sulfonic acid group as a fixing site (Japanese: dyed seat).
Comparative example 4
Materials were obtained in the same manner as in example 1 except that the materials were not immersed in an aqueous solution containing silver nitrate, and the evaluation results of the obtained materials are shown in table 1.
[ Table 1]
As is clear from Table 1, each of the materials of examples 1 to 8 containing oxalate had excellent anti-acarid effects. As shown in example 7 in particular, the anti-acarid material of the present invention maintains an anti-acarid effect even when repeatedly washed. On the other hand, in comparative examples 1 to 3 in which oxalic acid was not used, the effect of preventing mites was insufficient. In comparative example 4, oxalic acid was used, but the effect of preventing mites was insufficient because salt formation with cations did not occur.

Claims (6)

1. An anti-acarid material is obtained by imparting oxalate to a base material.
2. The anti-acarid material according to claim 1, wherein,
the oxalate content is more than 0.001 mmol/g.
3. The anti-acarid material according to claim 1, wherein,
the solubility of oxalate in water at 20 ℃ is 1g/100g-H 2 O is less than or equal to.
4. The anti-acarid material according to claim 1, wherein,
the substrate is a material having a negatively charged functional group.
5. A bedding, upholstery or clothing comprising the anti-acarid material of any one of claims 1 to 4.
6. A method of making an anti-acarid material comprising:
treatment of immersing a substrate in an aqueous solution containing cations
The treated substrate is immersed in an aqueous solution containing oxalic acid.
CN202310668733.1A 2022-07-07 2023-06-07 Anti-acarid material Pending CN117364478A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2022109921 2022-07-07
JP2022-109921 2022-07-07

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CN117364478A true CN117364478A (en) 2024-01-09

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CN202310668733.1A Pending CN117364478A (en) 2022-07-07 2023-06-07 Anti-acarid material

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CN (1) CN117364478A (en)

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