JP7544472B2 - Anti-mite products - Google Patents

Description

The present invention relates to an anti-mite product housed in a plastic case.

An insect repellent is known that is characterized by containing an insect repellent mat or sheet containing a room temperature volatile pyrethroid as an insect repellent ingredient in a breathable plastic case made of various resins, and it is known that certain plastics suppress the adsorption of the insect repellent ingredient to plastic (Patent Document 1). On the other hand, compounds known as mite repellent ingredients are highly volatile and have various functional groups, so they are more susceptible to adsorption to plastics than room temperature volatile pyrethroids, and tend to be less effective due to a decrease in the effective active ingredient. It is also known that the adhesion of volatile agents to plastics can cause embrittlement such as crazes (white discoloration) and cracks, and this phenomenon may lead to a decrease in the performance and aesthetics of the plastic. Until now, studies have been conducted on the embrittlement of plastics when solvents adhere to plastics in containerized volatile liquids, and it has been described that certain solvents can suppress the embrittlement of plastics (Patent Document 2).

Japanese Unexamined Patent Publication No. 2-275805 JP 2018-175153 A

Although the adsorption of room temperature volatile pyrethroids to plastics has been studied to date, the effect of mite repellent ingredients, which are more volatile than room temperature volatile pyrethroids, on plastics is unclear. Furthermore, Patent Document 2 describes solvents that can suppress the embrittlement of plastics, but sufficient consideration has not been given to the relationship between pest repellent ingredients other than solvents, mite repellent ingredients, fragrance ingredients, etc., and the embrittlement of plastics. Therefore, it is an important issue to find an optimal combination of mite repellent ingredients and plastics that can suppress the adsorption of mite repellent ingredients to plastics and further suppress the embrittlement of plastics.

The object of the present invention is to provide a useful anti-mite product in which a solid carrier containing a mite repellent ingredient is stored in a plastic case, which exhibits high anti-mite efficacy over a long period of time without causing a decrease in efficacy due to the mite repellent ingredient being adsorbed onto the plastic during storage and use, or a decrease in aesthetics due to the mite repellent ingredient embrittlement of the plastic.

The present invention has discovered that the following configurations are highly effective in solving the above problems.
[1] A mite-proof product, characterized in that a solid carrier containing a mite-repellent component having a boiling point of 200°C to 280°C is housed in a breathable plastic case made of one or more resins selected from copolymers having an acrylonitrile composition of 60% or more, polyesters, and polyamides.
[2] The anti-mite product according to [1], wherein the mite repellent component has a p-menthane skeleton.
[3] The anti-mite product according to [1] or [2], wherein the solid carrier is one selected from the group consisting of anti-mite mats, anti-mite sheets and anti-mite beads.

The mite repellent component having a boiling point of 200°C to 280°C used in the present invention is not particularly limited as long as it is a compound having a boiling point of 200°C to 280°C and has a mite repellent effect, but may be p-menthane-3,8-diol, menthol, menthyl acetate, isopulegol, menthone, carvone, pinocarvone, pinocarveol, d-carvone, l-carvone, terpineol, α-terpineol, piperitone, piperitenone, pulegone, dihydrocarvone, myrtenal, verbenone, methyl salicylate, ethyl salicylate, propyl salicylate, butyl ... Examples of the essential oils include ethyl, benzyl alcohol, 4-methylbenzyl alcohol, methyl benzoate, ethyl benzoate, cinnamyl acetate, benzyl propionate, eugenol, citronellol, o-anisaldehyde, citronellal, cuminaldehyde, perillaldehyde, pinocarveol, parachlorometaxylenol, isoeugenol, benzyl acetate, ethyl isovalerate, geranyl acetate, citral, 2-phenylethyl acetate, etc., and when optical isomers or geometric isomers exist, all of the isomers and possible isomer mixtures are included in the present invention. In addition, natural essential oils such as peppermint oil, lemon eucalyptus oil, eucalyptus oil, and lavender oil, which contain compounds having a mite repellent effect and have a boiling point of 200° C. to 280° C., may also be used. Among these mite repellent components, compounds having a p-menthane skeleton, such as p-menthane-3,8-diol, menthol, menthyl acetate, menthone, carvone, pinocarvone, pinocarveol, d-carvone, l-carvone, terpineol, α-terpineol, piperitone, piperitenone, pulegone, dihydrocarvone, and the like, as well as peppermint oil and lemon eucalyptus oil that contain these, are preferred from the viewpoint of low adsorption to plastics and less likely to cause embrittlement of plastics. Among these, p-menthane-3,8-diol and menthyl acetate, which are free from concerns about odor transfer, are more preferred.

Examples of the p-menthane skeleton include a compound in which at least one hydrogen atom bonded to a carbon atom of p-menthane shown in the following chemical formula (I) is replaced with a substituent, and a compound in which at least one single bond of p-menthane is replaced with a double bond. Examples of the substituent include a hydroxyl group, an ether oxygen atom (-O-), an amino group, an alkyl group, a carboxyl group, an acyl group, an ester group, and an amide group.

The mite repellent component may be mixed with other components such as fungicides, antibacterial agents, bactericides, fragrances, deodorants, perfumes, stabilizers, antioxidants, etc., which are targeted at molds and bacteria, as long as the effects of the present invention are achieved. If necessary, the components may be dissolved in a suitable solvent such as a petroleum solvent, an aliphatic hydrocarbon solvent, an aromatic hydrocarbon solvent, an alcohol solvent, or a glycol ether solvent, and then impregnated into a mat, sheet, or beads made of a fibrous carrier such as paper, wood, nonwoven fabric, pulp, linter, or rayon, a plastic, cellulose (regenerated cellulose) beads or foam, an inorganic porous carrier such as silicate, silica, or zeolite, a sublimable carrier such as trioxane or adamantane, or a solid retention agent, to obtain a solid carrier such as an anti-mite mat, anti-mite sheet, or anti-mite beads containing the active ingredient.

The term "sheet" as used here broadly includes all film, plate and block shaped products, and may be, for example, a product in which the mite repellent component is incorporated into a sublimable solid drug, a product made into a gel by mixing with a gelling agent such as an N-acylamino acid derivative, carrageenan or xanthan gum, or a simple package of these.

The amount of active ingredient impregnated is determined appropriately depending on the size and material of the various impregnated bodies such as mats, sheets, and beads, the application location of the anti-mite product, and the period of use. For example, in the case of a pulp base paper measuring 6 cm x 8 cm and approximately 1 mm thick, a useful and highly practical anti-mite effect can be achieved inside a chest of drawers by impregnating it with 200 to 800 mg of mite repellent ingredient. In addition, in the case of cellulose beads, a useful and highly practical anti-mite effect can be achieved by containing approximately 50 to 250 mg of the mite repellent ingredient per 1 g of cellulose beads.

The present invention is characterized in that one or more resins selected from copolymers with an acrylonitrile composition of 60% or more, polyesters, and polyamides are used as the base material of the plastic case that contains the anti-mite mat, anti-mite sheet, or anti-mite beads. As the copolymer with an acrylonitrile composition of 60% or more, a copolymer mainly made of acrylonitrile monomer and an unsaturated carboxylic acid monomer is preferable, and further, olefins, vinyl esters, unsaturated carboxylic acid esters, vinyl ethers, etc. can be appropriately combined. For example, acrylonitrile-methacrylic acid-butadiene copolymer (Mitsui Chemicals, product name Barex, hereinafter referred to as Barex) is preferably used. Even if it is an acrylonitrile-based copolymer, if the acrylonitrile composition is less than 60%, it is inappropriate because it has poor chemical adsorption resistance. Examples of polyesters include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and polyarylate. Polyamide is a polymer with an acid amide bond, and examples of such as 6-nylon, 6,6-nylon, and 12-nylon can be mentioned. In addition, these polymers may contain lubricants such as paraffin wax, fatty acid esters, and fatty alcohols, stabilizers such as calcium- and zinc-containing compounds, impact strength enhancers, antioxidants, weather resistance improvers, pigments, processing aids, and heat resistance improvers, as long as they do not impair the properties of the present invention.

The solid carrier of the anti-mite mat, anti-mite sheet or anti-mite beads may be stored in a breathable nonwoven bag, brocade bag or net case. In this way, when replacing the solid carrier after a certain period of time, the work can be done without directly touching the solid carrier, so that replacement is possible without the need to wear gloves, etc., which is convenient. Of these, nonwoven bags are easy to use. The material of the nonwoven fabric is not particularly limited, but examples include polyester, polyethylene, polypropylene, polyamide, polylactic acid, rayon, etc., and polyethylene and polypropylene are preferred.

The shape and size of the breathable plastic case of the present invention are not particularly limited, but examples include a plastic case that can be stacked or folded in half in accordance with the plastic case described in Japanese Utility Model Laid-Open Publication No. 60-111675, has a space inside for storing anti-mite mats, anti-mite sheets or anti-mite beads, and has a mesh-like structure with numerous volatilization holes, and a plywood case that can be closed by overlapping a cover plate on top of the plywood, has numerous ridges arranged to allow ventilation, and has a space in the center for storing anti-mite mats, anti-mite sheets or anti-mite beads. Such plastic cases are manufactured using the polymers described above by, for example, pressing, extrusion, calendaring, inflation, blow molding, injection molding, etc., and anti-mite mats, anti-mite sheets or anti-mite beads are stored in the plastic case to obtain the anti-mite product of the present invention.

The anti-mite product of the present invention can be used in chests of drawers, drawers, storage boxes, bookcases, etc. Also, by providing a hanging part, it can be hung from a closet, hanger rack, curtain rail, etc. It can also be placed next to a pillow in a bedroom. Various designs can be incorporated into the breathable plastic, which can give the user a glamorous impression in addition to the anti-mite effect.

The anti-mite product of the present invention is usually stored sealed in a plastic film (e.g., polyethylene terephthalate, etc.) or an aluminum bag, but there is little or no migration of the active ingredient into the plastic case, and even during use there is no loss of the active ingredient due to adsorption to the plastic, and the active ingredient is released efficiently and gradually, and there is no loss of aesthetics due to embrittlement of the plastic case. Even when only the solid carrier is sealed in a plastic film or an aluminum bag during storage and stored separately from the plastic case, and when the solid carrier is placed inside the plastic case at the start of use, there is no loss of efficacy due to adsorption to the plastic case during use, and there is no loss of aesthetics due to embrittlement of the plastic case, and a high anti-mite effect can be achieved against various types of mites.

The mites to be controlled in the present invention are house dust mites such as flour mites, house dust mites, dust mites, chiggers, and house dust mites, and the product has a practical repellent effect for six months. It also has a repellent effect on various pests such as weevils, dermestid beetles, booklice, beetles, cockroaches, bedbugs, ants, mosquitoes, moths, midges, flies, moths, and burrs.

The present invention will now be described in detail with reference to Test Examples and Examples, but it is needless to say that the present invention is not limited to these.
(Test Example 1)

A pulp base paper measuring 6 cm x 8 cm and 1 mm thick was uniformly impregnated with 400 mg of mite repellent, sandwiched between two plastic plates (7 cm x 9 cm, 3 mm thick) of various substrates, placed in an aluminum bag and stored at 40°C for two weeks, after which the mite repellent remaining in the pulp base paper was extracted with acetone and analyzed by gas chromatography to determine the amount of mite repellent transferred to the plastic plate. The degree of embrittlement of the plastic plate was also evaluated.
<Evaluation criteria for plastic embrittlement>
⊚: No crazes (white discoloration) or cracks (breaks) occurred, and the shape was stable.
◯: A small number of crazes have occurred, but no cracks have occurred.
Δ: Cracks were observed.
×: Both crazes and cracks were observed.

As a result of the test, when the plastics were polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, 6-nylon, 6,6-nylon, and Barex, and a mite repellent component having a boiling point of 200°C to 280°C was used, almost no adsorption of the mite repellent component to the plastic or embrittlement of the plastic was observed (Examples 1 to 20). Among them, when the mite repellent component having a boiling point of 200°C to 280°C was a compound having a p-menthane skeleton (Examples 1 to 14), it was found to be particularly excellent in terms of preventing adsorption to plastic and preventing embrittlement of plastic when evaluated comprehensively. On the other hand, when the mite repellent component had a boiling point of less than 200°C (Comparative Example 1), adsorption to plastic and embrittlement of plastic were observed, and when the mite repellent component had a boiling point of more than 280°C (Comparative Example 2), embrittlement of plastic was observed. In the case of polycarbonate and polyphenylene ether (Comparative Examples 3 and 4), almost no transfer due to adsorption to plastics was observed for mite repellent components with boiling points of 200° C. to 280° C., but embrittlement of the plastic was observed. Also, in JP-A-2-275805, even in the case of chlorinated polypropylene and methylpentene polymer (Comparative Examples 5 and 6) in which no adsorption of room-temperature volatile pyrethroids was observed, transfer due to adsorption to plastics was observed for mite repellent components with boiling points of 200° C. to 280° C.
(Test Example 2)

The anti-mite mat was impregnated with a drug solution containing 450 mg of p-menthane-3,8-diol on a pulp base paper of 6 cm x 8 cm and 1 mm thickness, and housed in a mesh-like plastic case (thickness 3 mm) molded using polyethylene terephthalate as a base material to obtain the anti-mite product of the present invention. After storing this in a sealed state at room temperature for one year, it was hung on a chest of drawers (volume 400 L) and used. For six months, it kept house dust mites such as flour mites, house dust mites, dust mites, and cheylet mites away, and maintained a high anti-mite effect.
(Test Example 3)

The anti-mite mat is impregnated with a liquid containing 450mg of menthyl acetate and 5mg of fragrance on a pulp base paper of 6cm x 8cm and 1mm thickness, and is stored in a mesh-like plastic case (3mm thick) molded using Barex as a base material to obtain the anti-mite product of the present invention. After storing this in a sealed state at room temperature for one year, it is hung on a chest of drawers (volume 400L) and used. For six months, it keeps away house dust mites such as acarid mites, house dust mites, dust mites, and cheylet mites, and maintains a high anti-mite effect.
(Test Example 4)

The anti-mite beads, which are made by adding 1000mg of p-menthane-3,8-diol, 100mg of perfume, and 6mg of vegetable deodorant component to 6.0g of granular pulp with an average particle size of 5.5mm, are put into a bag (9cm x 12.5cm) made of a nonwoven fabric made of polyethylene/polypropylene with air permeability on both sides, and are stored in a mesh-like plastic case (thickness 8mm) molded by using polyethylene terephthalate, to obtain the anti-mite product of the present invention. When this is hung in a closet (volume 900L) and used, it is found that it keeps away house dust mites such as flour mites, house dust mites, dust mites, and cheylet mites for 6 months, and maintains a high anti-mite effect.

Claims (2)

The anti-mite product is characterized in that a solid carrier containing only a mite repellent component having a boiling point of 212°C to 265°C (excluding pyrethroids volatile at room temperature) as a mite repellent component is housed in an air-permeable plastic case made of one or more resins selected from copolymers having an acrylonitrile composition of 60% or more and polyamides . 2. The anti-mite product according to claim 1 , wherein the solid carrier is one selected from the group consisting of an anti-mite mat, an anti-mite sheet and an anti-mite bead.