Pest repellent for human body

Abstract

This pest repellent for a human body, which can be used on a human body, contains a repellent active ingredient (a), a diacylglutamic acid lysine salt (b), and water.

Description

Human pest repellent

[0001] The present disclosure relates to a pest repellent for human use that can be used on the human body, and more particularly to a pest repellent for human use that has excellent stability over time despite containing a reduced amount of surfactant and does not require shaking before use.

[0002] Many conventional skin repellents for mosquitoes and other pests contain ethanol and are used in liquid form. Liquid-form products often drip during use, making them difficult to apply evenly to the skin. Furthermore, the high amount of ethanol contained in repellents can cause irritation, dryness, and tightness on the skin. Therefore, technological developments have been made to emulsify and disperse hydrophobic repellent active ingredients in water without incorporating ethanol. For example, Patent Document 1 proposes a method for emulsifying and dispersing a repellent active ingredient using at least one nonionic surfactant selected from the group consisting of polyoxyethylene hydrogenated castor oil and fatty acid polyoxyethylene hydrogenated castor oil. Patent Documents 2 and 3 also propose a method for emulsifying and dispersing a repellent active ingredient using a three-phase emulsification method.

[0003] JP 2019-026603 A JP 2017-185474 A JP 2022-072114 A

[0004] However, Patent Document 1 contains a nonionic surfactant, which may cause irritation to people. Patent Document 2 has the advantage of not requiring a conventional surfactant, making it less irritating to people, but requires the preparation of closed vesicles formed from an amphiphilic substance that spontaneously forms closed vesicles or particles of a polycondensation polymer having hydroxyl groups, and special processes are required to prepare them. Patent Document 3 separates into two layers before use due to coacervation (not oil-water separation due to emulsion destabilization, but differences in apparent liquid layers due to differences in specific gravity of individual emulsified particles), and requires shaking the container to mix before use.

[0005] The present disclosure has been made in view of the above points, and its object is to provide a pest repellent for human use that has excellent stability over time and does not require shaking when used.

[0006] To achieve the above object, one aspect of the present disclosure provides a pest repellent for human use that can be used on the human body, and the pest repellent for human use contains, for example, an active repellent ingredient (a), a diacylglutamic acid lysine salt (b), and water.

[0007] The repellent active ingredient (a) may be, for example, at least one selected from the group consisting of icaridin, DEET, IR3535, and p-menthane-3,8-diol.

[0008] The concentration of the repellent active ingredient (a) may be in the range of 3% by mass or more and 30% by mass or less.

[0009] The diacylglutamic acid lysine salt (b) may be, for example, dilauroylglutamic acid lysine salt.

[0010] The concentration of the diacylglutamic acid lysine salt (b) may be in the range of 0.0009% by mass or more and 0.5% by mass or less.

[0011] The pest repellent for human use may further contain a thickener (c) as an optional component. The concentration of the thickener (c) may be in the range of 0.01% by mass or more and 5.0% by mass or less.

[0012] The pest repellent for human use may further contain a polyhydric alcohol (d) as an optional component. The concentration of the polyhydric alcohol (d) may be 15% by mass or less.

[0013] According to the present disclosure, it is possible to provide a pest repellent for human use that has excellent stability over time and does not require shaking when used, despite the reduced amount of surfactant blended.

[0014] Hereinafter, preferred embodiments of the present invention will be described in detail. Note that the following description of preferred embodiments is merely exemplary in nature and is not intended to limit the present invention, its applications, or its uses.

[0015] The pest repellent for human use according to this embodiment is a pest repellent that can be used on the human body and contains an active repellent ingredient (a), a diacylglutamic acid lysine salt (b), and water. The pest repellent for human use may further contain a thickener (c) as an optional ingredient. The pest repellent for human use may also contain a polyhydric alcohol (d) as an optional ingredient. The pest repellent for human use may also contain other ingredients other than the thickener (c) and the polyhydric alcohol (d) as optional ingredients.

[0016] The human pest repellent can be distributed on the market as a pest repellent product, for example, in a state where it is contained in a container or the like. The form of the human pest repellent when distributed may be, for example, any of liquid, emulsion, cream, gel, spray, aerosol, metered-dose aerosol, sheet, tissue, etc. Examples of containers that contain the human pest repellent include trigger spray containers, mist spray containers, pump spray containers, and aerosol containers. When the human pest repellent is contained in a metered-dose aerosol, the amount sprayed per time can be set to any amount. In the case of an aerosol container, a propellant for spraying the human pest repellent is also contained in the container. In the case of sheets or tissue, the human pest repellent can be impregnated or attached to the sheet or tissue, and then contained in a bag or the like and distributed on the market.

[0017] The human pest repellent can be used by adhering it to human skin. In the case of an aerosol product or spray product containing the human pest repellent, the human pest repellent can be adhered to the skin by spraying it toward the skin. In addition, when the human pest repellent is in the form of a liquid, emulsion, cream, or gel, it can be used by applying it to the skin. In addition, when the human pest repellent is impregnated in or attached to a sheet or tissue, the sheet or tissue can be used to adhere it to the skin. In addition, the human pest repellent may be attached to clothing, for example.

[0018] <Repellent active ingredient (a)> The repellent active ingredient (a) is an ingredient that has a repellent effect against pests. Pests include, but are not limited to, mosquitoes, and agents that have a repellent effect against various pests can be used as the repellent active ingredient (a).

[0019] Examples of the repellent active ingredient (a) include icaridin, DEET (diethyltoluamide), 3-(N-n-butyl-N-acetyl)aminopropionic acid ethyl ester (IR3535), p-menthane-3,8-diol, 2-ethyl-1,3-hexadiol, butyl 3,4-dihydro-2,2-dimethyl-4-oxo-2H-pyran-6-carboxylate, n-hexyltriethylene glycol monoether, methyl 6-n- Examples of suitable insect repellents include pentyl-cyclohexene-1-carboxylate, dimethyl phthalate, eucalyptol, α-pinene, geraniol, citronellal, camphor, linalool, terpenol, carvone, dioctyl phthalate, dibutyl phthalate, naphthalene, cinnamon, camphor, lemongrass, clover, thyme, geranium, bergamot, bay laurel, pine, red peach, benny royal, eucalyptus, and Indian sedan; and pyrethroid insecticides such as natural pyrethrins, pyrethrins, allethrin, phthalthrin, resmethrin, furamethrin, phenothrin, permethrin, cyphenothrin, prallethrin, etofenprox, empenthrin, and transfluthrin. The pest repellent for human use may contain only one arbitrarily selected from these as the repellent active ingredient (a), or may contain a mixture of two or more arbitrarily selected from these as the repellent active ingredient (a).

[0020] <Diacylglutamic acid lysine salt (b)> By including diacylglutamic acid lysine salt (b) in the pest repellent for human use, it is possible to make it a stable emulsion-based repellent. Furthermore, as will be described later, even if the pest repellent contains diacylglutamic acid lysine salt (b), the repellent effect of the repellent active ingredient (a) is sufficiently exhibited, and the duration of the repellent effect can be ensured for a long period of time.

[0021] Examples of the diacylglutamic acid lysine salt (b) contained in the human pest repellent include the following components. Examples of fatty acid residues constituting the acyl group of the diacylglutamic acid lysine salt contained in the human pest repellent include fatty acid residues having from 8 to 22 carbon atoms, specifically caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, oleic acid, linoleic acid, behenic acid, etc., which may be derived from animals or plants, such as coconut oil fatty acid, palm oil fatty acid, and hydrogenated beef tallow fatty acid. Examples of these salts include alkali metal salts such as sodium and potassium, organic amine salts such as triethanolamine salts, and basic amino acid salts such as arginine.

[0022] The diacyl glutamic acid lysine salt (b) may contain one or more selected from the group consisting of sodium dilauroyl glutamic acid lysine, sodium dimyristoyl glutamic acid lysine, sodium distearoyl glutamic acid lysine, and sodium dilinoleoyl glutamic acid lysine, and preferably contains sodium dilauroyl glutamic acid lysine.

[0023] The diacylglutamic acid lysine salt (b) can be synthesized, for example, by reacting L-lysine hydrochloride with N-fatty acyl-L-glutamic acid anhydride. Commercially available diacylglutamic acid lysine salt (b) includes, for example, Pellicer L-30 (trade name) (dilauramigoyl glutamic acid lysine sodium, active content 29%, water 71%) and Pellicer LB-10 (trade name) (dilauramigoyl glutamic acid lysine sodium, active content 10%, 1,3-butylene glycol 10%, water 71%), manufactured by Asahi Kasei Finechem Corporation.

[0024] <Water> The water contained in the pest repellent for human use may be, for example, tap water, ion-exchanged water, purified water, or the like.

[0025] <Thickener (c)> Examples of the thickener (c) contained in the human pest repellent include the following components. The thickener (c) may be any of a natural thickener, a semi-synthetic thickener, a synthetic thickener, and an inorganic thickener. Furthermore, the thickener (c) may be obtained by mixing two or more arbitrarily selected from the natural thickener, the semi-synthetic thickener, the synthetic thickener, and the inorganic thickener, or by mixing all of the natural thickener, the semi-synthetic thickener, the synthetic thickener, and the inorganic thickener.

[0026] Examples of natural thickeners include plant-based polymers such as gum arabic, tamarind gum, tragacanth gum, galactan, guar gum, xanthan gum, carob gum, locust bean gum, karaya gum, carrageenan, pectin, agar, quince seed, algae colloid, and starch, microbial polymers such as dextran, dextrin, succinoglucan, and pullulan, and animal polymers such as collagen, casein, albumin, and gelatin. Only one of these may be arbitrarily selected as the thickener (c), or a mixture of two or more arbitrarily selected types may be used as the thickener (c).

[0027] Examples of semi-synthetic thickeners include starch-based polymers such as carboxymethyl starch and methylhydroxypropyl starch, cellulose-based polymers such as methylcellulose, nitrocellulose, ethylcellulose, methylhydroxypropyl cellulose, hydroxyethyl cellulose, sodium cellulose sulfate, hydroxypropyl cellulose, carboxymethyl cellulose, sodium carboxymethyl cellulose, crystalline cellulose, and cellulose powder, and alginic acid-based polymers such as sodium alginate and propylene glycol alginate. Of these, only one arbitrarily selected type may be contained as the thickener (c), or a mixture of two or more arbitrarily selected types may be contained as the thickener (c).

[0028] Examples of synthetic thickeners include vinyl polymers such as polyvinyl alcohol, polyvinyl methyl ether, polyvinylpyrrolidone, carboxyvinyl polymer (carbomer), etc., polyoxyethylene polymers such as polyethylene glycol (molecular weight 1500, 4000, 6000, etc.), polyoxyethylene-polyoxypropylene copolymer polymers, acrylic polymers such as sodium polyacrylate, polyethyl acrylate, acrylic acid-alkyl methacrylate copolymer, polyethyleneimine, cationic polymers, etc. Among these, only one arbitrarily selected type may be contained as the thickener (c), or a mixture of two or more arbitrarily selected types may be contained as the thickener (c).

[0029] Examples of inorganic thickeners include bentonite, AlMg silicate, laponite, hectorite, silicic anhydride, etc. Among these, only one arbitrarily selected type may be contained as the thickener (c), or a mixture of two or more arbitrarily selected types may be contained as the thickener (c).

[0030] <Polyhydric Alcohol (d)> Examples of the polyhydric alcohol (d) contained in the human pest repellent include glycerin, diglycerin, triglycerin, polyglycerin, 3-methyl-1,3-butanediol, 1,3-butylene glycol (1,3-BG), isoprene glycol, polyethylene glycol, 1,2-pentanediol, 1,2-hexanediol, propylene glycol, dipropylene glycol, polypropylene glycol, ethylene glycol, diethylene glycol, neopentyl glycol, maltitol, reduced starch syrup, sucrose, lactitol, palatinit, erythritol, sorbitol, mannitol, xylitol, xylose, glucose, lactose, mannose, maltose, galactose, fructose, inositol, pentaerythritol, maltotriose, sorbitan, trehalose, starch hydrolysis sugars, and starch hydrolysis sugar reduced alcohols. Among these, only one arbitrarily selected type may be contained as the polyhydric alcohol (d), or a mixture of two or more arbitrarily selected types may be contained as the polyhydric alcohol (d). Among these, from the viewpoint of the stability over time of the human pest repellent, the polyhydric alcohol is preferably a polyhydric alcohol having a total carbon number of 5 or less, and more preferably a polyhydric alcohol having a total carbon number of 3 or less.

[0031] <Propellant> When a human pest repellent is contained in an aerosol container, a propellant is also contained in the aerosol container. Examples of such propellants include liquefied petroleum gas (LPG), dimethyl ether (DME), and compressed gases (carbon dioxide, nitrogen). Of these, only one arbitrarily selected propellant may be contained as the propellant, or a mixture of two or more arbitrarily selected propellants may be contained as the propellant. The ratio of human pest repellent to propellant can be set as desired, taking into consideration the efficacy of the human pest repellent, etc.

[0032] <Other Components> The human pest repellent may contain components (other components) other than the components described above. Examples of other components contained in the human pest repellent include additives such as other surfactants, other solvents (such as lower alcohols), repellent efficacy enhancers, water repellents, astringent components, antiperspirant components, moisturizers, emollients, irritation-reducing components, anti-inflammatory components, barrier function repair components, bactericides / antiseptics, warming components, cooling components, deodorants, other thickeners, pigments, pH adjusters, fragrances, UV absorbers, antioxidants, plant extracts, amino acids, and texture improvers (powder). Of these, only one arbitrarily selected component may be contained as the other component, or a mixture of two or more arbitrarily selected components may be contained as the other component.

[0033] <Concentration of each component> The lower limit of the concentration of the repellent active ingredient (a) is 3 mass% or more, preferably 5 mass% or more, based on the total mass of the pest repellent for human use. If the concentration of the repellent active ingredient (a) is equal to or more than the above lower limit, the repellent effect against pests is more easily exhibited when the pest repellent for human use is applied to the skin.

[0034] The upper limit of the concentration of the repellent active ingredient (a) is 30% by mass or less, preferably 25% by mass or less, and more preferably 20% by mass or less. If the concentration of the repellent active ingredient (a) is the upper limit or less, the stability of the pest repellent for human use is superior.

[0035] The lower limit of the concentration of diacylglutamic acid lysine salt (b) is 0.0009% by mass or more, preferably 0.009% by mass or more, based on the total mass of the pest repellent for human use. The upper limit of the concentration of diacylglutamic acid lysine salt (b) is 0.45% by mass or less, preferably 0.18% by mass or less. If the concentration of diacylglutamic acid lysine salt (b) is less than the lower limit or more than the upper limit, the stability of the pest repellent for human use may be reduced.

[0036] The lower limit of the concentration of the thickener (c) is 0.01% by mass or more, preferably 0.1% by mass or more, based on the total mass of the pest repellent for human use. The upper limit of the concentration of the thickener (c) is 5.0% by mass or less, preferably 2.0% by mass or less. If the concentration of the thickener (c) is less than the lower limit or more than the upper limit, the stability of the pest repellent for human use may be reduced.

[0037] The concentration of the polyhydric alcohol (d) is preferably 15% by mass or less, more preferably 10% by mass or less, based on the total mass of the pest repellent for human use. By setting the concentration range of the polyhydric alcohol (d) to 15% by mass or less, the pest repellent for human use becomes a uniform emulsion, and the emulsified state can be stably maintained for a long period of time.

[0038] <Target pests of human pest repellents> In addition to mosquitoes, target pests of human pest repellents include black flies, horseflies, midges, stable flies, house mites, bedbugs (cimex lectularius), ticks, fleas, chiggers, land leeches, midges, moth flies, house ants, etc. The human pest repellents also have a repellent effect against these pests.

[0039] The present invention will be explained in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples. The preparation methods in the examples are also merely examples, and other preparation methods may also be used.

[0040] <Production (Preparation) Method of Examples and Comparative Examples> (Examples 1 to 13, Comparative Examples 1 to 5) A carboxyvinyl polymer is dissolved in ion-exchanged water and neutralized to pH 7 using a 1% aqueous solution of sodium hydroxide. Then, sodium dilauroyl glutamate lysine is added and the mixture is heated to 70°C. While stirring the aqueous phase at 5000 rpm using a homomixer, the repellent active ingredient (a) heated to 70°C is added and the mixture is stirred for 30 minutes.

[0041] Examples 14 to 21 A carboxyvinyl polymer is dissolved in ion-exchanged water and neutralized to pH 7 using a 1% aqueous solution of sodium hydroxide. Then, sodium dilauroyl glutamate lysine and a polyhydric alcohol (d) are added, and the mixture is heated to 70° C. While stirring the aqueous phase at 5000 rpm using a homomixer, icaridin heated to 70° C. is added, and the mixture is stirred for 30 minutes.

[0042] Examples 22 to 26: Thickener (c) is dissolved in ion-exchanged water, and sodium dilauroyl glutamate lysine is added. When the thickener is a carboxyvinyl polymer, it is dissolved in ion-exchanged water, neutralized to pH 7 with a 1% aqueous solution of sodium hydroxide, and then sodium dilauroyl glutamate lysine is added. While stirring the aqueous phase at room temperature at 5,000 rpm using a homomixer, icaridin at room temperature is added, and the mixture is stirred for 30 minutes.

[0043] Comparative Example 6 A pest repellent for human use in Comparative Example 6 was prepared by mixing 10% by mass of DEET, 40% by mass of ethanol, and 50% by mass of ion-exchanged water.

[0044] The "balance" of ion-exchanged water in Tables 1 to 5 indicates the amount of ion-exchanged water that makes the total amount of the human pest repellent 100% by mass. By using diacylglutamic acid lysine salt (b), an emulsion-based repellent can be easily prepared. The above-described preparation method can also be applied to repellent active ingredients (a) other than DEET and icaridin. The same applies to diacylglutamic acid lysine salt (b).

[0045]

[0046]

[0047]

[0048]

[0049]

[0050] <Stability Test Evaluation> The pest repellents for human use (Examples 1 to 26, Comparative Examples 1 to 5) prepared by the above-mentioned preparation methods were each stored for one month at 50° C. The condition (appearance) of each pest repellent for human use immediately after preparation and after one month of storage was visually evaluated, and the stability of the pest repellent for human use was evaluated according to the following criteria (stability at 50° C. for one month).

[0051] The viscosity of the human pest repellents was measured using a B-type viscometer TVB-10 (manufactured by Toki Sangyo Co., Ltd.). Rotors M4, THM1 to THM3 were used depending on the viscosity of each human pest repellent, and the viscosity was measured at 12 rpm after 60 seconds. pH was measured using a pH meter LAQUAF-72 (manufactured by Horiba, Ltd.).

[0052] (Evaluation criteria for stability) ◯: No separation, uniformly emulsified and dispersed.

[0053] △: Relatively large oil droplets are present but not separated.

[0054] ×: Separated into two layers.

[0055] The results of the stability tests are shown in Tables 1 to 5. In Examples 1 to 26, the human pest repellents did not separate immediately after preparation and after one month of storage at 50°C, and were uniformly emulsified and dispersed, or did not separate even if relatively large oil droplets were present, whereas in Comparative Examples 1 to 5, the human pest repellents separated into two layers.

[0056] As shown in Tables 1 and 2, the human pest repellents of Examples 1 to 8 were able to emulsify and disperse the repellent active ingredient (a) when the concentration of the repellent active ingredient (a) was in the range of 5% by mass or more and 30% by mass or less, and the stability test results after one month were also good. Other repellent active ingredients (a) could also be emulsified and dispersed in the range of 5% by mass or more and 30% by mass or less. On the other hand, as in Comparative Examples 1 to 4, when the concentration of the repellent active ingredient (a) was 40% by mass or more, the human pest repellent separated into two layers immediately after preparation or after one month of storage at 50°C. Similarly, when the other repellent active ingredient (a) was 40% by mass or more, the human pest repellent separated into two layers immediately after preparation or after one month of storage at 50°C.

[0057] As shown in Table 3, the human pest repellents of Examples 9 to 13 were able to emulsify and disperse the repellent active ingredient (a) when the diacylglutamic acid lysine salt (b) concentration was in the range of 0.0009% by mass or more and 0.45% by mass or less, and the stability test results after one month were also good. Other repellent active ingredients (a) could also be emulsified and dispersed in the range of 0.0009% by mass or more and 0.45% by mass or less. Meanwhile, when the diacylglutamic acid lysine salt (b) concentration was 0.9% by mass or more, as in the case of the human pest repellent of Comparative Example 5, the human pest repellent separated into two layers after one month of storage. Similarly, when the other repellent active ingredients (a) were 0.9% by mass or more, the human pest repellent separated into two layers after one month of storage.

[0058] As shown in Table 4, the human pest repellents of Examples 14 to 21 contained polyhydric alcohol (d) as an additive, and in all cases a uniform emulsion was produced, and the stability test results after one month were also good.

[0059] As shown in Table 5, the human pest repellents of Examples 22 to 26 contained thickener (c) as an additive, but all of them produced uniform emulsions and showed good results in the stability test after one month. Even when thickener (c) was added to the other examples, the stability test results after one month were also good.

[0060] <Test for sustained blood-sucking prevention effect (pest repellent test)> A human pest repellent was administered to the forearms of four subjects at a dose of 1.67 μL / cm ２ The test substance was applied evenly to the skin in an amount equivalent to 100 ml, and a glass ring containing 10 female Aedes albopictus mosquitoes was pressed against the skin for 5 minutes after each time period (6 hours, 8 hours, 10 hours, and 12 hours), and the number of Aedes albopictus mosquitoes that had bitten blood was counted. The blood-sucking inhibition rate was then evaluated using the following formula. The human pest repellent used was Example 6. As a comparative example, an aqueous ethanol solution containing 10% DEET (Comparative Example 6) was used.

[0061]

[0062] In the following formula, "treated area" refers to a condition in which a human pest repellent (Example 6 or Comparative Example 6) was applied, and "untreated area" refers to a condition in which nothing was applied.

[0063] Blood-sucking prevention rate (%) = (1 - blood-sucking mosquito rate in treated area / blood-sucking mosquito rate in untreated area) x 100 The results are shown in Table 7. In Example 6, a blood-sucking prevention rate of 90% or more was confirmed even 10 hours after application, but in Comparative Example 6, the blood-sucking prevention rate fell below 80% 10 hours after application.

[0064]

[0065] The above-described embodiments are merely illustrative in all respects and should not be interpreted as limiting. Furthermore, all modifications and variations within the scope of the claims are within the scope of the present invention. For example, with regard to the repellent active ingredient (a), the above-described repellent active ingredient (a) provides long-term stability and exhibits pest repellent effects, as in Examples 1 to 6. With regard to the diacylglutamic acid lysine salt (b), the above-described diacylglutamic acid lysine salt (b) provides long-term stability, as in Examples 1 to 6, without substantially impairing the pest repellent effect of the repellent active ingredient (a). With regard to the thickener (c), the above-described thickener (c) provides long-term stability, as in Examples 1 to 6, without substantially impairing the pest repellent effect of the repellent active ingredient (a). With regard to the polyhydric alcohol (d), the above-described polyhydric alcohol (d) provides long-term stability, as in Examples 1 to 6, without substantially impairing the pest repellent effect of the repellent active ingredient (a).

[0066] As described above, the pest repellent for human use according to the present disclosure can be used to repel pests such as mosquitoes, black flies, horseflies, midges, stable flies, house dust mites, bedbugs (cimex lectularius), ticks, fleas, chiggers, leeches, midges, moths, house flies, and fire ants, and can be used, for example, as an insect repellent to be applied to human skin.

Claims

1. A pest repellent for human use, comprising an active repellent ingredient (a), a diacylglutamic acid lysine salt (b), and water.

2. The pest repellent for human use according to claim 1, wherein the repellent active ingredient (a) is at least one selected from the group consisting of icaridin, DEET, IR3535, and p-menthane-3,8-diol.

3. A pest repellent for human use according to claim 1, wherein the concentration range of the repellent active ingredient (a) is 3% by mass or more and 30% by mass or less.

4. A pest repellent for human use according to claim 1, wherein the diacylglutamic acid lysine salt (b) is dilauroylglutamic acid lysine salt.

5. A pest repellent for human use according to claim 1, wherein the concentration range of the diacylglutamic acid lysine salt (b) is 0.0009% by mass or more and 0.5% by mass or less.

6. The pest repellent for personal use according to claim 1, further comprising a thickening agent (c).

7. A pest repellent for human use according to claim 6, wherein the concentration range of the thickener (c) is 0.01% by mass or more and 5.0% by mass or less.

8. The pest repellent for human use according to claim 1, further comprising a polyhydric alcohol (d).

9. A pest repellent for human use according to claim 8, wherein the concentration range of the polyhydric alcohol (d) is 15% by mass or less.

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