JP2003292407A - Alicyclic diesters developing mite-proofing effect and fiber and fiber structure containing the alicyclic diesters - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for stably developing mite-proofing effect at a low concentration for a long period of time in fibers by kneading a resin with a mite-proofing compound which is water-insoluble, and has properties of excellent compatibility with a thermoplastic resin to be melt-molded and excellent weather resistance. <P>SOLUTION: The fiber has repellency by using at least one kind of alicyclic diesters represented by general formula (1) [R<SP>1</SP>is hydrogen, a 1-6C straight-chain or branched alkyl group, a chlorine atom, a 1-5C straight-chain or branched alkoxy group or a phenyl group; R<SP>2</SP>and R<SP>3</SP>are each the same or different and is a 1-12C straight-chain or branched alkyl group or a 6-10C cycloalkyl group] and represented by general formula (2) [R<SP>1</SP>, R<SP>2</SP>and R<SP>3</SP>are each as shown for general formula (1)] of the mite-proofing compounds. The fiber structure is obtained by adding 0.01-5.0 mass % of the mite-proofing compound to 100 mass parts wt. of a fiber. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to alicyclic diesters exhibiting an excellent acaricidal effect, and fibers and fiber structures containing the alicyclic diesters.

[0002]

2. Description of the Related Art In recent years, various health damages caused by mites have been attracting attention. It is known that mites act as allergens causing allergies such as asthma, atopic dermatitis, and allergic rhinitis. For example, 60 to 70% of bronchial asthma (more than 90% in children) are mites. It is said to be due. Generally, mites are vulnerable to heat, for example 50
It can be completely killed at 30 ° C for 30 minutes. However, the dead carcasses and dung of mites also act as allergens, so keeping the mites themselves is the best way to prevent their health damage.

For example, as a method of preventing mites from adhering to clothes, lumps, etc., a method having a mite repellent property (hereinafter referred to as an anti-mite agent) is directly sprayed, or fibers such as clothes and lumps are carried. There is a method of making it soak, or a method of making it soak into paper and making it contact with clothes.

As an anti-mitic agent used at this time, organic compounds such as organic phosphoric acid compounds and dialkyl phthalates,
Inorganic compounds such as orthoboric acid, sodium borate, and sodium octaborate tetrahydrate are known.

[0005]

However, it is often the case that conventional tick-proofing agents do not exhibit a suitable tick-proofing effect unless they are used in a large amount. There was a problem that a bad odor and an irritating odor were generated due to the anti-mite agent. In addition, there is a problem that organic compound anti-mitic agents are often highly harmful to the human body, and there is a concern that they may adversely affect the human body.

On the other hand, the use of a relatively less harmful anti-mitic agent, for example, an inorganic boron compound, solves the problem of adverse effects on the human body, but these are generally water-soluble. Therefore, when the clothes treated with the anti-mite agent are washed or wet with rain, the anti-mite agent is eluted and the effect of repelling mites is lost.

Therefore, a method of processing (carrying) the anti-mite agent on the surface of the fiber together with a binder such as a resin is generally used. However, in this case, although the disappearance of the mite repellant effect due to washing or the like is avoided, the mite repellant effect is attenuated over time due to poor weather resistance, such as the characteristics of the anti-mite agent such as oxidation by air or deterioration by ultraviolet rays. was there. For these reasons, there has been a demand for a tick-proofing agent that exhibits a suitable tick-proofing effect at a low concentration and is excellent in water resistance and weather resistance.

[0008] That is, an object of the present invention is to provide a tick-proofing agent which exhibits a suitable tick-proofing effect at a low concentration and is excellent in washing resistance and weather resistance. Furthermore, it aims at providing the fiber and the fiber structure containing the said anti-mitic agent.

[0009]

Means for Solving the Problems As a result of intensive investigations, the present inventors have found that cycloaliphatic diesters of cyclohexane-
1,2-diesters and 4-cyclohexene-1,2
-The inventors have found that the diesters have anti-mite properties, and have completed the present invention based on these findings.

That is, the present invention provides the following inventions. Item 1 General formula (1)

[Chemical 3] [Wherein, R ¹ represents hydrogen, straight-chain or branched alkyl group having 1 to 6 carbon atoms, a chlorine atom, a linear or branched alkoxy group having 1 to 5 carbon atoms, or a phenyl group, R ²
And R ³ are the same or different and each have 1 to 1 carbon atoms.
2 straight-chain or branched alkyl groups, having 6 to 10 carbon atoms
Represents a cycloalkyl group. ] Or general formula (2)

[Chemical 4] [In formula, R < ¹ >, R < ² > and R < ³ > are synonymous with General formula (1). ] The compound which has the mite-proof property which consists of saturated or unsaturated alicyclic diester represented by these.

Item 2 R ¹ is hydrogen or a methyl group, and R ^1
The compound having an anti-mitotic property according to the above item 1, wherein ² and R ³ are the same or different and are a linear or branched alkyl group having 1 to 12 carbon atoms or a cycloalkyl group having 6 to 10 carbon atoms.

Item 3 R ¹ is hydrogen or a methyl group, and R ^1
The compound having an anti-mitotic property according to the above item 2, wherein ² and R ³ are the same or different and are linear or branched alkyl groups having 4 to 10 carbon atoms.

Item 4 Any one of the above items 1 to 3
At least one of the compounds having the anti-miticidal property according to the item 1.
0.01 to 5.0 mass% of seeds as a main component is contained, and a tick control agent.

Item 5 Any one of the above items 1 to 3
A fiber structure having a tick-proof property, which is obtained by adding the compound having a tick-proof property according to the item in 0.01 to 5.0 mass% to 100 parts by mass of the fiber of the fiber structure.

Item 6 The mite-proof fiber structure according to Item 3, wherein the fiber is a synthetic fiber, and the compound having the mite-proof property is kneaded into the synthetic fiber.

Item 7 The acaricide according to Item 5, wherein the fiber is selected from the following group a), and the fiber structure is constituted by a single or a mixed spinning of the selected fibers. Fiber structure with characteristics.

Item 8 The fiber structure having mite-proof properties according to Item 6, wherein the synthetic fiber is polyester.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described below. TECHNICAL FIELD The present invention relates to a compound having an anti-mite property, an anti-mite agent containing at least one compound having the anti-mite property as a main component, and a fiber and a fiber structure containing the compound having the anti-mite property. Is.

Here, the mites refer to the indigenous species that are spent indoors in the house and the stray species that have entered from the outside of the building. Examples of such mites include leopard mites and mites.

The compound having acaricidal property according to the present invention is an alicyclic diester having a structure represented by the following general formula (1) or general formula (2), and exhibits a suitable antibacterial effect. It is a thing.

[Chemical 5] [Wherein, R ¹ represents hydrogen, straight-chain or branched alkyl group having 1 to 6 carbon atoms, a chlorine atom, a linear or branched alkoxy group having 1 to 5 carbon atoms, or a phenyl group, R ²
And R ³ are the same or different and each have 1 to 1 carbon atoms.
2 straight-chain or branched alkyl groups, having 6 to 10 carbon atoms
Represents a cycloalkyl group. ]

[Chemical 6] [In formula, R < ¹ >, R < ² > and R < ³ > are synonymous with General formula (1). ]

Specific examples of R ¹ represented by the general formula (1) or the general formula (2) according to the present invention are hydrogen, methyl group, ethyl group, n-propyl group, i-propyl group and n.
A linear or branched alkyl group having 1 to 6 carbon atoms such as a -butyl group, i-butyl, sec-butyl group, t-butyl group, n-pentyl group, and n-hexyl group, a methoxy group,
Ethoxy group, n-propoxy group, i-propoxy group, n
1 to 5 carbon atoms such as -butoxy group and n-pentyloxy group
Examples of the linear or branched alkoxy group, a chlorine atom, a phenyl group and the like are preferable, and among them, hydrogen and a methyl group are preferable.

The substitution position of R ¹ is not particularly limited and may be any position of the cyclohexane ring or the cyclohexene ring.

R ² and R ³ may be the same or different and specifically, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl,
sec-butyl group, t-butyl group, n-pentyl group, n
-Hexyl group, n-heptyl group, 2-ethylhexyl group, n-octyl group, n-nonyl group, i-nonyl group, n
A linear or branched alkyl group having 1 to 12 carbon atoms such as a decyl group, an n-undecyl group, and an n-dodecyl group, a cyclohexyl group, a 2-methylcyclohexyl group, a 3-methylcyclohexyl group, a 4-methylcyclohexyl group, Examples include cycloalkyl groups having 6 to 10 carbon atoms such as cycloheptyl group and cyclooctyl group, and among them, n-butyl group, i-butyl group, n-pentyl group, n-hexyl group,
2-ethylhexyl group, n-heptyl group, n-octyl group, n-nonyl group, i-nonyl group, n-decyl group, n-
A linear or branched alkyl group having 1 to 12 carbon atoms, preferably 4 to 10 carbon atoms, such as an undecyl group or an n-dodecyl group is preferable.

The saturated or unsaturated alicyclic diesters of the general formula (1) or (2) include cyclohexane-
Examples include 1,2-diester, 4-cyclohexene-1,2-diester, 4-methylcyclohexane-1,2-diester, 4-methyl-4-cyclohexene-1,2-diester and the like.

Specific examples of these compounds include 1, 2
Dimethyl cyclohexanedicarboxylate, diethyl 1,2-cyclohexanedicarboxylate, di-n-propyl 1,2-cyclohexanedicarboxylate, di (n-butyl) 1,2-cyclohexanedicarboxylate, di (1,2-cyclohexanedicarboxylic acid di ( sec-butyl), 1,2-cyclohexanedicarboxylic acid di (i-butyl), 1,2-
Cyclohexanedicarboxylic acid di (n-pentyl), 1,
2-cyclohexanedicarboxylic acid di (n-hexyl),
1,2-Cyclohexanedicarboxylic acid di (n-heptyl), 1,2-cyclohexanedicarboxylic acid di (n-octyl), 1,2-cyclohexanedicarboxylic acid di (2
-Ethylhexyl), 1,2-cyclohexanedicarboxylic acid di (n-nonyl), 1,2-cyclohexanedicarboxylic acid di (i-nonyl), 1,2-cyclohexanedicarboxylic acid di (n-decyl), 1,2- Cyclohexanedicarboxylic acid di (n-undecyl), 1,2-cyclohexanedicarboxylic acid di (n-dodecyl), 1,2-cyclohexanedicarboxylic acid dicyclohexyl, 4-cyclohexene-1,2-dicarboxylic acid dimethyl, 4-cyclohexene-1 , 2-dicarboxylic acid dimethyl, 4-cyclohexene-1,2-dicarboxylic acid diethyl, 4-cyclohexene-1,2-dicarboxylic acid di (n-propyl), 4
-Cyclohexene-1,2-dicarboxylic acid di (n-butyl), 4-cyclohexene-1,2-dicarboxylic acid di (sec-butyl), 4-cyclohexene-1,2-dicarboxylic acid di (i-butyl), 4-cyclohexene-
1,2-dicarboxylic acid di (n-pentyl), 4-cyclohexene-1,2-dicarboxylic acid di (n-hexyl),
4-Cyclohexene-1,2-dicarboxylic acid di (n-heptyl), 4-Cyclohexene-1,2-dicarboxylic acid di (n-octyl), 4-Cyclohexene-1,2-dicarboxylic acid di (2-ethylhexyl) , 4-cyclohexene-1,2-dicarboxylic acid di (n-nonyl), 4-cyclohexene-1,2-dicarboxylic acid di (i-nonyl), 4-cyclohexene-1,2-dicarboxylic acid di (n-decyl) ), 4-cyclohexene-1,2-dicarboxylic acid di (n-undecyl), 4-cyclohexene-
1,2-dicarboxylic acid di (n-dodecyl), 4-cyclohexene-1,2-dicarboxylic acid dicyclohexyl, 4
Dimethyl-methyl-1,2-cyclohexanedicarboxylate, Diethyl 4-methyl-1,2-cyclohexanedicarboxylate, Di (n-propyl) 4-methyl-1,2-cyclohexanedicarboxylate, 4-Methyl-1,2 -Cyclohexanedicarboxylic acid di (n-butyl), 4-methyl-1,2-cyclohexanedicarboxylic acid di (i-butyl), 4-methyl-1,2-cyclohexanedicarboxylic acid di (sec-butyl), 4-methyl -1,2-Cyclohexanedicarboxylic acid di (n-pentyl), 4-methyl-1,2-cyclohexanedicarboxylic acid di (n-hexyl), 4-methyl-1,2-cyclohexanedicarboxylic acid di (n-heptyl) , 4-methyl-1,2-cyclohexanedicarboxylic acid di (n-octyl), 4-methyl-
1,2-cyclohexanedicarboxylic acid di (2-ethylhexyl), 4-methyl-1,2-cyclohexanedicarboxylic acid di (n-nonyl), 4-methyl-1,2-cyclohexanedicarboxylic acid di (i-nonyl), 4-methyl-
1,2-cyclohexanedicarboxylic acid di (n-decyl), 4-methyl-1,2-cyclohexanedicarboxylic acid di (n-undecyl), 4-methyl-1,2-cyclohexanedicarboxylic acid di (n-dodecyl), 4-Methyl-1,2-cyclohexanedicarboxylic acid dicyclohexyl, 4-methyl-4-cyclohexene-1,2-dicarboxylic acid dimethyl, 4-methyl-4-cyclohexene-
1,2-dicarboxylic acid diethyl, 4-methyl-4-cyclohexene-1,2-dicarboxylic acid di (n-propyl), 4-methyl-4-cyclohexene-1,2-dicarboxylic acid di (n-butyl), 4-Methyl-4-cyclohexene-1,2-dicarboxylic acid di (i-butyl), 4-
Methyl-4-cyclohexene-1,2-dicarboxylic acid di (sec-butyl), 4-methyl-4-cyclohexene-1,2-dicarboxylic acid di (n-pentyl), 4-methyl-4-cyclohexene-1, 2-dicarboxylic acid di (n
-Hexyl), 4-methyl-4-cyclohexene-1,
2-dicarboxylic acid di (n-heptyl), 4-methyl-4
-Cyclohexene-1,2-dicarboxylic acid di (n-octyl), 4-methyl-4-cyclohexene-1,2-dicarboxylic acid di2-ethylhexyl), 4-methyl-4-
Cyclohexene-1,2-dicarboxylic acid di (n-nonyl), 4-methyl-4-cyclohexene-1,2-dicarboxylic acid di (i-nonyl), 4-methyl-4-cyclohexene-1,2-dicarboxylic acid Di (n-decyl), 4-
Methyl-4-cyclohexene-1,2-dicarboxylic acid di (n-undecyl), 4-methyl-4-cyclohexene-1,2-dicarboxylic acid di (n-dodecyl), 4-methyl-4-cyclohexene-1, 2-dicarboxylic acid dicyclohexyl etc. are illustrated.

In the present invention, the saturated or unsaturated alicyclic diesters represented by the general formula (1) or (2) may be used alone or in combination of two or more.

Of these, compounds in which R ¹ is hydrogen or a methyl group and R ² and R ³ are linear or branched alkyl groups having 4 to 10 carbon atoms are particularly preferable.

Preferred saturated or unsaturated alicyclic diesters are 1,2-cyclohexanedicarboxylic acid di (n-butyl), 1,2-cyclohexanedicarboxylic acid di (n-pentyl) and 1,2-cyclohexanedicarboxylic acid. Acid di (n-heptyl), 1,2-cyclohexanedicarboxylic acid di (n-octyl), 1,2-cyclohexanedicarboxylic acid di (2-ethylhexyl), 1,2-cyclohexanedicarboxylic acid di (n-nonyl), 1,2-Cyclohexanedicarboxylic acid di (i-nonyl), 1,2-
Cyclohexanedicarboxylic acid di (n-decyl), 4-methylcyclohexane-1,2-dicarboxylic acid di (n-butyl), 4-methylcyclohexane-1,2-dicarboxylic acid di (n-pentyl), 4-methylcyclohexane −
1,2-dicarboxylic acid di (n-heptyl), 4-methylcyclohexane-1,2-dicarboxylic acid di (n-octyl), 4-methylcyclohexane-1,2-dicarboxylic acid di (2-ethylhexyl), 4 -Methylcyclohexane-1,2-dicarboxylic acid di (n-nonyl), 4-methylcyclohexane-1,2-dicarboxylic acid di (n-decyl), 4-methylcyclohexane-1,2-dicarboxylic acid di (n-) Nonyl), 4-methylcyclohexane-1,
2-dicarboxylic acid di (n-decyl), 4-cyclohexene-1,2-dicarboxylic acid di (n-butyl), 4-cyclohexene-1,2-dicarboxylic acid di (n-pentyl), 4-cyclohexene-1 , 2-dicarboxylic acid di (n-hexyl), 4-cyclohexene-1,2-dicarboxylic acid di (n-heptyl), 4-cyclohexene-
1,2-dicarboxylic acid di (n-octyl), 4-cyclohexene-1,2-dicarboxylic acid di (2-ethylhexyl), 4-cyclohexene-1,2-dicarboxylic acid di (n-nonyl), 4-cyclohexene -1,2-dicarboxylic acid di (n-decyl), 4-methyl-4-cyclohexene-1,2-dicarboxylic acid di (n-butyl), 4-methyl-4-cyclohexene-1,2-dicarboxylic acid di (N-butyl), 4-methyl-4-cyclohexene-
1,2-dicarboxylic acid di (n-pentyl), 4-methyl-4-cyclohexene-1,2-dicarboxylic acid di (n-)
Hexyl), 4-methyl-4-cyclohexene-1,2
-Dicarboxylic acid di (n-octyl), 4-methyl-4-
Cyclohexene-1,2-dicarboxylic acid di (2-ethylhexyl), 4-methyl-4-cyclohexene-1,2
-Dicarboxylic acid di (n-nonyl), 4-methyl-4-cyclohexene-1,2-dicarboxylic acid di (n-decyl)
Etc. are illustrated.

In the saturated or unsaturated alicyclic diesters represented by the general formula (1) or (2), two ester groups have the same side (cis) with respect to the cyclohexane ring or cyclohexene ring plane. It may be on the opposite side (trans form) or on the opposite side (trans form), and any stereoisomers can be used for acaricide use.

The compound having the anti-mite property exhibits excellent anti-mite property when used alone or in combination with the compound having the anti-mite property according to the present invention having a different structure. It is also possible to use it as an anti-mitic agent containing 0.01 to 5.0% by mass as a main component of at least one compound having this anti-mitic property. In this case, too, the compound having the anti-mite property is used alone or in combination with the compound having the mite-proof property according to the present invention having a different structure.

The compound having the anti-mite property and the anti-mite agent containing the compound having the anti-mite property express excellent anti-mite property at a low concentration. In addition, this compound is water-insoluble, that is, has water resistance, and does not elute in water even if the clothes are washed after being processed into clothes, for example, so that it is prevented from mites by washing or getting wet with water. The effect is less likely to be attenuated.

In addition to the compound having the anti-mite property, various additives such as a plasticizer, an antioxidant and an emulsifier can be added to the anti-mite agent. Further, in order to facilitate the treatment of the processed material such as the fiber structure and paper, it is preferable to dissolve or disperse the compound having the anti-mite property and various additives in a suitable solvent (hereinafter,
Collectively called dispersion). By doing this,
When treating a compound having a tick-proof property to a work piece,
It is possible to use the coating method of coating the dispersion on the work piece, the dipping method of immersing the work piece in the dispersion, etc., which is easier than the case of using a solid compound having an anti-mite property as it is. In addition, it is possible to process a compound having a tick-proof property into a processed material.

The fiber structure referred to here is composed of various natural fibers and synthetic fibers. As the natural fibers, cotton, wool, silk, hemp, etc. are used, and as the synthetic fibers, nylon, polyester are used. , Polypropylene, acrylic, vinylidene, polyurethane, vinylon and the like can be preferably used. Note that the fiber structure is not limited to a form composed of only a single fiber, and may be a mixture of a plurality of types of fibers.

Since the fiber structure has a high frequency of contact with the human body, it is preferable to prepare it by using water as the main solvent. Since the compound having an anti-mitotic property according to the present invention is water-insoluble, it is made into a dispersion, for example, an emulsified state by using a suitable emulsifier and a necessary minimum amount of alcohols such as polyhydric alcohol.

Further, various binders may be added in order to more surely support the compound having the mite-preventing property on the fiber structure. For example, in the case of processing the compound having the mite-proof property on paper, the use of a nitrified cotton resin makes it possible to more effectively carry the compound having the mite-proof property on the paper. Further, in the case of supporting it on a film or the like, it is preferable to add a resin constituting the film. Of course, the binder may be composed of only a single type of resin, or a structure in which a plurality of types of resins are mixed and used can be selected. With this configuration, it is possible to prevent the mite prevention property from being attenuated due to washing or the like.

When the workpiece is a fiber structure,
The compound having the anti-mite property is 0.01 to 5.0% by mass, and more preferably 100% by mass of the fiber.
It is preferable to add 0.5 to 3.0% by mass. This is because if the addition amount is 0.01% by mass or less, a sufficient acaricide-preventing effect is not exhibited. On the other hand, when the added amount is 5.0% by mass or more, there is no difference in the persistence of the mite prevention effect, and the compound having the mite prevention property is relatively expensive. .

When the fibers of the fiber structure are synthetic fibers, the compound having the mite-proof property may be kneaded into the synthetic fibers. By doing so, as in the case where the compound having the mite-proofing property is simply carried on the fiber, the compound having the mite-proofing property does not fall off from the fiber, so that the mite-proofing effect lasts for a long time. become.

Various synthetic fibers can be used as the synthetic fibers in which a compound having a tick-proofing property is kneaded. As such, for example, nylon, polyester, polypropylene, acrylic, vinylidene, polyurethane,
Examples include vinylon. The amount of the compound having anti-mite property to be mixed into these synthetic fibers is 0.01 to 5.0% by mass, preferably 0.5 to 3.0% by mass, relative to 100 parts by mass of the synthetic fibers. . If the amount of the compound having the mite-preventing property to be kneaded is less than 0.01% by mass, the mite-preventing effect is not properly exhibited. Further, when the kneading amount is 5.0% by mass or more, the elasticity of the synthetic fiber itself is lowered and the fiber itself becomes brittle, and there is no difference in the effect with the increase of the addition amount.

The compound having an anti-mite property according to the present invention is excellent in compatibility with the resin component constituting the synthetic fiber and is also excellent in high temperature stability. Therefore, the resin component is melted to prepare a fiber structure. In doing so, there is no decomposition or deterioration due to high temperature treatment. Therefore, a suitable acaricide-preventing effect is exhibited even after the fiber is spun.

[Preparation of acaricide against mite] A method of preparing a drug against mites using the compound having acaricide properties according to the present invention will be described below. First, a compound having anti-mite properties is dissolved using a minimum amount of a polar solvent such as alcohol. In addition to this, surfactants (anionic type, nonionic type,
Alternatively, it can be appropriately selected depending on the compound having acaricide-preventing properties, such as a mixture thereof, and mixed. Then, this is poured into water to disperse the compound having anti-mite property in water.

The anti-mite agent according to the present invention includes not only anti-mite agents and surfactants but also antibacterial agents, antifungal agents,
Other insect repellents, deodorants, fragrances, antioxidants, ultraviolet absorbers, etc. can be used in combination. By doing so, it becomes possible to provide a tick-proofing agent suitable for a wide range of uses.

The amount of the substance of the present invention used is 0.01 to 5.0% by mass, preferably 0.5 to 5.0% by mass based on 100 parts by mass of the fiber.
3.0% by mass, 0.01 to 5.0 parts by mass of one or more kinds of resin emulsions such as polyacryl, polyester, polyurethane, etc., per 100 parts by mass of the anti-mitic agent in order to impart washing resistance. %, Preferably 0.5-3.
0% by mass is used in combination, and then dried. 100 after drying
Heat treatment at 150 ° C., preferably 110 to 130 ° C., can sufficiently withstand 10 to 25 times of washing.

[Kneading a compound having anti-mite properties into synthetic fibers] Synthetic fibers are formed by first melting a high-molecular compound constituting the fibers and then spin-molding the molten high-molecular compound. Therefore, the synthetic fiber of the compound having the anti-mite property according to the present invention is obtained by melting the polymer compound constituting the fiber, that is, nylon, polyester, polypropylene, acryl, vinylidene, polyurethane, vinylon, according to the present invention. It is obtained by adding and melting a compound having an anti-mite property and spinning it. Of course, as in the case of the above-mentioned anti-mitic agent, an antibacterial agent, an antifungal agent, another insect repellent, or a deodorant, a flavoring agent,
It is also possible to knead together an antioxidant and an ultraviolet absorber.

Further, synthetic resins include heat stabilizers, lubricants, dyes, pigments, antibacterial agents, ultraviolet absorbers, antioxidants, antistatic agents, flame retardants, deodorants, fragrances, inorganic fillers, etc. You may mix | blend the additive of suitably. The mixture of this drug and the resin is hereinafter referred to as the raw material.

With such a constitution, the mite-repellent action is suitably exhibited in the mite-proof fiber according to the present invention.

[0046]

EXAMPLES [Example 1] Hereinafter, the post-processing conditions will be described in detail by examples. After dissolving 10 g of each of the following three kinds of anti-mite agents in 65 g of the solvent Shellsol A (product of Shell Petroleum Co., Ltd.), 12 g of Solpol 2942S (product of Toho Chemical Industry Co., Ltd.) and Nonipol 100 (Sanyo Chemical Co., Ltd.) as emulsifiers. 4 g of Kogyo Co., Ltd. product and 9 g of calcium dodecylbenzene sulfonate are added respectively, and well stirred to obtain a uniform liquid. Acaricide No. 1 4-Cyclohexene-1,2-dicarboxylic acid di-n-butyl No. 2 4-Cyclohexene-1,2-dicarboxylic acid di-n-heptyl No. 3 1,2-Cyclohexanedicarboxylic acid di-n
-Octyl

0.5% of the drug shown in the above drug prescription,
It diluted with water so that it might become 1.0% and 3.0%. Cotton broad (No. 40) was immersed in this chemical solution for 1 minute, then squeezed at a squeezing ratio of 80%, and dried at 80 ° C. for 5 minutes. This cotton cloth was used for a repellent test against Dermatophagoides farinae. The test results are shown in Table 1.

[0048]

[Table 1]

Washing resistance test of chemicals: 3 g of the chemical indicated in the chemical formulation and 3 g of the following resin emulsion (resin concentration: 50% by mass) were added to 94 g of water, and sufficiently stirred to obtain a uniform liquid. Cotton broad (40) and cotton 35
After immersing the mixed fabric of / Tetron 65 for 1 minute, draw ratio 8
It was dried at 0 ° C. for 5 minutes. The heat treatment was performed at 130 ° C. for 1 minute. Table 2 shows the analysis of the residual amount of the drug after washing, and Table 3 shows the result of the mites repellent effect. Resin emulsion used Polyacrylic resin Trade name Boncoat AB-409 Dick Hercules Co., Ltd. Polyester resin Trade name Pethresin A-1243G Matsumoto Yushi Co., Ltd. Polyurethane resin Trade name Elastron BAP Daiichi Kogyo Co., Ltd.

[0050]

[Table 2]

[Table 3] Washing test: The washing test was performed according to JIS L0217-103 method. Washing frequency: 0 times, 10 times, 25 times

Analytical method of alicyclic diester after washing: 30 × 30 cm of the cloth after washing was used as a cylindrical filter paper No. Using Soxhlet extractor 84 (Toyo Roshi Kaisha, Ltd.) for 2 hours with methanol as a solvent, 100 m of methanol was used.
1 and analyzed by gas chromatography.

[Example 2] The resin kneading conditions will be described in detail below with reference to examples. (A) Mite-proofing agent used in the experiment Mite-proofing agent Di-iso-butyl 1,2-cyclohexanedicarboxylate (B) Synthetic resin PP (Mitsui Noprene JHH-G) Ny (Kanebo Nylon MC112) PET (used in the experiment Teijin Polyester TR-8550) (C) Method for Producing Resin Containing Acaricide A film was produced after kneading 1% of an insect repellent into a resin used. Kneading temperature PP: 210 to 230 ° C. Ny: 230 to 250 ° C. PET: 260 to 280 ° C. (D) Method for producing a resin film containing an anti-mitic agent (1) Polypropylene [trade name: Mitsui Noprene JHH
-G] was heated at a temperature of 210 ° C to 230 ° C and kneaded by adding 1.0% of the agent of the present invention, and then used in an experiment as a film having a thickness of 30 µm by a Labo Plastomill. (2) 6 nylon [Product name: Kanebo Nylon MC11
2) was kneaded by adding 1.0% of the chemical | medical agent of this invention in heating temperature 230-250 degreeC, Then, it used for the experiment as a film with a thickness of 30 micron by Labo Plastomill. (3) Polyester [Product name: Teijin Polyester T
R-8550] at a heating temperature of 260 to 280 ° C.,
After 1.0% by mass of the insect repellent of the present invention was added and kneaded, it was used in an experiment as a film having a thickness of 30 microns by a Labo Plastomill. A repellent test against Dermatophagoides farinae was performed using this film. The test results are shown in Table 4.

[0053]

[Table 4]

[Tick repellent test method] The tick repellent test was carried out by the invasion blocking method. Here, the intrusion prevention method will be described. As shown in FIG. 1, the invasion prevention method has a diameter of 4c.
4c diameter in a plastic petri dish of m and 0.6 cm in height
The sample cut out is spread on m, and 0.05 g of powdered feed containing no mite is placed on it. This is the diameter 9c
Place it in the center of a plastic petri dish with a height of 1.5 m and a height of 1.5 cm. Between the large and small petri dishes, about 3,000 individuals of a well-propagated mite medium are added as the number of living mites and spread uniformly. Put this on the adhesive sheet, 27 × 13 × 9 cm
Put the adhesive sheet in a plastic container for food preservation, keep a saturated saline solution on the lid to keep the humidity inside the container at about 75%, store it in a thermostat at 25 ° C ± 1 ° C, and after raising it overnight,
The samples were counted after collecting mites by the water jet method. The repellent rate (%) was calculated based on the following formula. In addition, the test was conducted with N number = 3 in consideration of variations, and the mosquito deer mite was used in the test. Tick repelling rate (%) = (1-number of invading mites in test section / number of invading mites in control section) × 100 The repelling rate for having a tick-proof property is 70% or more. (Control = medium on untreated sample, test = medium on sample)

[Water Jet Method] Here, the water jet method will be described. What is the water jet method, as shown in FIG.
A method of spreading on a sieve that is a mesh, arranging a vat of the same diameter (volume of about 5 liters) under the sieve, spraying water vigorously with a shower on this sieve, and washing and collecting mites attached to the sample. Is. In this embodiment, it is washed off and falls into the lower bat. When the vat becomes full, all water in the vat is removed by suction filtration to collect mites. Repeat this operation 2-3 until mites are no longer collected
Repeat times.

[0056]

INDUSTRIAL APPLICABILITY The mite-proof fiber of the present invention is kneaded with an effective mite-proof component in the fiber in addition to conventional post-processing in order to control indoor dust mite, which has been a problem in recent years. It is also possible that the fiber is excellent in durability and does not deteriorate in mite prevention performance by washing or the like, and exhibits excellent mite prevention property. Further, the agent having an anti-mite property used in the present invention is not only excellent in durability and does not deteriorate the anti-mite performance in washing, but is also particularly excellent in safety.

[Brief description of drawings]

FIG. 1 is a layout view of a petri dish used for an invasion prevention method in a tick repellent test according to the present invention.

FIG. 2 is a layout view of a water jet method used for mite recovery in a tick repellent test according to the present invention.

[Explanation of symbols]

1 Petri dish (9 cm diameter) 2 Petri dish (diameter 4 cm) 3 test samples 4 Tick medium 5 powdered feed 6 Adhesive sheet 7 showers 8 sieves (diameter 18 cm / 30 mesh) 9 bats (18 cm in diameter)

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) D06M 13/224 D06M 13/224 (72) Inventor Takahiro Muramatsu 4-17-28 Chuo, Edogawa-ku, Tokyo Yamato Chemical Industry Co., Ltd. (72) Inventor Sayuri Yokota 4-17-28 Chuo, Edogawa-ku, Tokyo Yamato Chemical Industry Co., Ltd. (72) Inventor Tomoki Koshiyama 13 Yasaka-cho, Fukumi-ku, Kyoto, Kyoto Shin-Nippon Rika Co., Ltd. In-house F-term (reference) 4H011 AC04 AC06 BA01 BB06 BC03 BC07 BC19 BC20 DA07 DA10 DA13 DD05 DH02 DH04 DH05 4J002 AB011 AD031 BB121 BD101 BF021 BG021 CF001 CK021 CL001 EH136 FD02 G31 KK05

Claims (8)

[Claims] 1. A compound represented by the general formula (1): [Wherein, R ¹ represents hydrogen, straight-chain or branched alkyl group having 1 to 6 carbon atoms, a chlorine atom, a linear or branched alkoxy group having 1 to 5 carbon atoms, or a phenyl group, R ²
And R ³ are the same or different and each have 1 to 1 carbon atoms.
2 straight-chain or branched alkyl groups, having 6 to 10 carbon atoms
Represents a cycloalkyl group. ] Or general formula (2) [In formula, R < ¹ >, R < ² > and R < ³ > are synonymous with General formula (1). ] The compound which has the mite-proof property which consists of saturated or unsaturated alicyclic diester represented by these. 2. R ¹ is a hydrogen atom or a methyl group, and R ²
And R ³ are the same or different substituents, and are a straight-chain or branched alkyl group having 1 to 12 carbon atoms and a cycloalkyl group having 6 to 10 carbon atoms, respectively. Having compounds. 3. R ¹ is a hydrogen atom or a methyl group, and R ²
And R ³ are the same or different substituents, and each is a straight-chain or branched alkyl group having 4 to 10 carbon atoms, and the compound having acaricidal property according to claim 1. 4. A compound containing 0.01 to 5.0% by mass as a main component of at least one compound having a tick-proof property according to any one of claims 1 to 3. Acaricide. 5. The compound 1 having a tick-proof property according to any one of claims 1 to 3 is a fiber 1 of a fiber structure.
A fiber structure having a mite-proof property, which is obtained by adding 0.01 to 5.0 mass% to 100 mass parts. 6. The fiber structure having mite-proof properties according to claim 5, wherein the fibers are synthetic fibers, and the compound having mite-proof properties is kneaded into the synthetic fibers. 7. The fiber is selected from the following group a):
The fiber structure having mite-proof properties according to claim 5, wherein the fiber structure is constituted by a single spinning or a mixed spinning of the selected fibers. a) cotton, wool, silk, linen, nylon, polyester,
Polypropylene, acrylic, vinylidene, polyurethane, vinylon. 8. The fiber structure having mite-proof properties according to claim 6, wherein the synthetic fiber is polyester.