Method for attaching fragrance to fragrance-attached polymer article

Abstract

To provide a novel fragrance attaching method, which is a method for attaching fragrance to polymer articles by an immersion process, enabling uniform fragrance attachment among the polymer articles.SOLUTION: A fragrance attaching method for a polymer article comprises immersing a polymer article in an aqueous dispersion of fragrance, and drying the polymer article extracted from the aqueous dispersion of fragrance.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a method for flavoring polymer products.

Background Art

[0002] Weak points of polymer products include unpleasant odors such as rubber odor, petroleum odor, and vinyl odor. In order to reduce these unpleasant odors, it has been done to reduce the unpleasant odor by imparting a fragrance to the polymer product.

[0003] For example, Patent Document 1 discloses a composition for eliminating rubber odor containing at least pine oil and limonene.

[0004] Patent Document 2 discloses a composition for eliminating rubber odor containing a hydrazide compound and a plant essential oil, wherein the plant essential oil contains at least one of pine oil and limonene.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0006] Fragrances include natural fragrances such as essential oils and resins extracted from plants and synthetic fragrances mainly obtained from petroleum, and many of them are lipophilic and lighter in specific gravity than water. As methods for flavoring polymer products, for example, there are a method of immersing the polymer product in a fragrance solution (immersion method) and a method of spraying the fragrance solution onto the polymer product (spraying method).

[0007] When flavoring polymer articles by the dipping method, if the fragrance is not sufficiently diluted and dispersed in water, due to the lipophilicity and low specific gravity of the fragrance, the fragrance tends to accumulate near the liquid surface of the fragrance solution. As a result, the state of fragrance adhesion varies among the polymer articles immersed in the fragrance solution. Therefore, although the unpleasant odor of the polymer articles with sufficient fragrance adhesion is reduced, there is a quality problem that the unpleasant odor of the polymer articles with a small amount of fragrance adhesion is not reduced.

[0008] The present invention has been made in view of the above circumstances, and an object thereof is to provide a novel flavoring method for uniformly adhering a fragrance to polymer articles in a method for flavoring polymer articles by the dipping method.

Means for Solving the Problems

[0009] The method for flavoring polymer articles of the present invention that solves the above problems is characterized by immersing the polymer articles in an aqueous dispersion of a fragrance and drying the polymer articles taken out from the aqueous dispersion of the fragrance.

Effects of the Invention

[0010] According to the flavoring method of the present invention, in a method for flavoring polymer articles by the dipping method, the fragrance can be uniformly adhered to the polymer articles.

Embodiments for Carrying Out the Invention

[0011] The method for flavoring polymer articles of the present invention is characterized by immersing the polymer articles in an aqueous dispersion of a fragrance and drying the polymer articles taken out from the aqueous dispersion of the fragrance.

[0012] The polymer material for forming the polymer article is not particularly limited. Examples of the polymer material include polyesters such as polybutylene terephthalate (PBT) and polyethylene terephthalate (PET); polyolefins such as polyethylene (PE) and polypropylene (PP); (meth)acrylic resins; acrylonitrile-butadiene-styrene copolymer (ABS resin); acrylonitrile-styrene copolymer (AS resin); epoxy resins; polyamides (PA); polyurethanes (PU); polyimides (PI); polyphenylene ether (PPE); polysulfone (PSF); polyethersulfone (PES); polyphenylene sulfide (PPS); polyarylate (PAR); polyamideimide (PAI); polyetherimide (PEI); polyetheretherketone (PEEK); polytetrafluoroethylene (PTFE); polyaminobismaleimide (PABM); polybisamidotriazole; polyphenylene oxide (PPO); polyacetal; polycarbonate (PC), and the like. These may be used alone or in combination of two or more.

[0013] Also, it is preferable that the polymer article is formed from rubber. Examples of the rubber include butyl rubber, isoprene rubber, polybutadiene rubber, styrene-butadiene rubber, natural rubber, chloroprene rubber, nitrile rubbers such as acrylonitrile-butadiene rubber, hydrogenated nitrile rubbers, norbornene rubber, ethylene-propylene rubber, ethylene-propylene-diene rubber, acrylic rubber, ethylene·acrylate rubber, fluororubber, chlorosulfonated polyethylene rubber, epichlorohydrin rubber, silicone rubber, urethane rubber, polysulfide rubber, phosphazen rubber or 1,2-polybutadiene, and the like. These may be used alone or in combination of two or more.

[0014] Specific examples of the polymer article include, for example, rubber gloves, resin gloves, umbrellas, rain shoes, raincoats, hats, bags, carpets, toys, sundries, stationery, and the like.

[0015] In the present invention, it is preferable to use an aqueous dispersion of a fragrance, and it is more preferable to use an aqueous dispersion in which the fragrance is dispersed in water by a nonionic surfactant. Nonionic surfactants have low toxicity and skin irritation and are excellent in terms of safety.

[0016] In the present invention, an aqueous dispersion in which the fragrance component has a number average particle size of 15 nm or more is regarded as an aqueous dispersion in which the fragrance is dispersed in water, and those with a number average particle size of less than 15 nm are semi-transparent or transparent and are regarded as those in which the fragrance is solubilized in water.

[0017] The fragrance used in the present invention can be appropriately selected according to the desired scent. For example, it is preferably at least one selected from the group consisting of terpenes, ester compounds, aromatic compounds, ether compounds, aldehyde compounds, alcohol compounds, ketone compounds, lactone compounds, and nitrogen-containing compounds.

[0018] Examples of fragrances that give a refreshing or cooling sensation include limonene (terpenes: lemon scent), menthol (alcohol compound: mint scent), menthone (ketone compound: mint scent), terpineol (alcohol compound: lime scent), citral (aldehyde compound: lemon scent), camphor (ketone compound: mint scent), anethole (ether compound: fennel scent), estragole (ether compound: tarragon scent), 1,8-cineole (ether compound: eucalyptus, sage, laurel scent), eugenol (alcohol compound: clove, pimento scent), cumin aldehyde (aldehyde compound: cumin scent), cinnamyl aldehyde (aldehyde compound: cinnamon scent), and the like.

[0019] Examples of the fragrance that gives a soothing feeling include, for example, cucumber alcohol (alcohol compound: fragrance of melon and watermelon), aldehyde C-8 (aldehyde compound: fragrance of orange), cucumber aldehyde (aldehyde compound: fragrance of melon and watermelon), vanillin (aldehyde compound: fragrance of vanilla), nootkatone (ketone compound: fragrance of grapefruit), raspberry ketone (ketone compound: fragrance of raspberry), ethyl caprylate (ester compound: fragrance of rum and brandy), allyl caproate (ester compound: fragrance of pineapple), isoamyl acetate (ester compound: fragrance of banana), ethyl acetate (ester compound: fragrance of melon and grape), styralyl acetate (ester compound: fragrance of grapefruit), hexyl acetate (ester compound: fragrance of apple and pear), ethyl butyrate (ester compound: fragrance of pineapple), coconut aldehyde (lactone compound: fragrance of coconut), peach aldehyde (lactone compound: fragrance of peach), methyl anthranilate (nitrogen-containing compound: fragrance of grape), rose oxide (ether compound: fragrance of rose), geraniol (alcohol compound: fragrance of geranium), linalool (alcohol compound: fragrance of lavender), β-phenethyl alcohol (alcohol compound: fragrance of rose), cyclamen aldehyde (aldehyde compound: fragrance of cyclamen), α-ionone (ketone compound: fragrance of violet), cis-jasmone (ketone compound: fragrance of jasmine), benzyl acetate (ester compound: fragrance of jasmine), and the like.

[0020] From the viewpoint of preparing an aqueous dispersion of the fragrance, the fragrance used in the present invention is preferably hydrophobic and liquid (at 25°C).

[0021] Examples of the nonionic surfactant contained in the aqueous dispersion of the fragrance used in the present invention include polyoxyalkylene type and polyhydric alcohol type. The polyoxyalkylene type is a nonionic surfactant having a polyoxyalkylene chain as a hydrophilic moiety. Examples of the polyoxyalkylene type nonionic surfactant include polyoxyalkylene alkyl ether, polyoxyalkylene alkyl phenyl ether, polyoxyalkylene alkyl amino ether, polyoxyalkylene fatty acid ester, polyoxyalkylene polyhydric alcohol fatty acid ester, polyoxyethylene / polyoxypropylene block polymer, polyoxyalkylene derivative, polyoxyethylene hydrogenated castor oil, and the like.

[0022] Examples of the polyoxyethylene alkyl ether include polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene myristyl ether, polyoxyethylene octyldodecyl ether, and the like.

[0023] Examples of the polyoxyalkylene derivative include polyoxyethylene alkylene alkyl ether, polyoxyethylene distyrenated phenyl ether, polyoxyethylene tribenzyl phenyl ether, and the like.

[0024] The polyoxyalkylene polyhydric alcohol fatty acid ester is a fatty acid ester in which a polyoxyalkylene chain is added to a polyhydric alcohol such as glycerin, polyglycerin, sorbitol, or sucrose, and examples thereof include polyoxyethylene glycerin fatty acid ester, polyoxyethylene polyglycerin fatty acid ester, polyoxyethylene sucrose fatty acid ester, polyoxyethylene sorbitan fatty acid ester, and the like.

[0025] Examples of polyoxyethylene sorbitan fatty acid esters include polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan triisostearate, and the like.

[0026] Examples of the polyhydric alcohol type nonionic surfactant include polyhydric alcohol fatty acid esters, polyhydric alcohol alkyl ester ethers, fatty acid dialkylolamides, and the like.

[0027] The polyhydric alcohol fatty acid ester is a fatty acid ester of a polyhydric alcohol such as glycerin, polyglycerin, sorbitol, or sucrose, and examples thereof include glycerin fatty acid ester, sorbitan fatty acid ester, and sucrose fatty acid ester.

[0028] Examples of sorbitan fatty acid esters include sorbitan monolaurate, sorbitan monopalmitate, sorbitan monooleate, and the like.

[0029] Examples of glycerin fatty acid esters include glycerol monostearate, glycerol monooleate, and the like.

[0030] The HLB (Hydrophile Lypophile Balance) value of the nonionic surfactant is preferably 9.5 or more, more preferably 10 or more, still more preferably 10.5 or more, and preferably 15 or less, more preferably 13 or less, still more preferably 12 or less. If the HLB value is 9.5 or more, the emulsifying dispersibility of the fragrance is good, and if it is 15 or less, the foaming of the aqueous dispersion of the fragrance by the surfactant is suppressed. In the present invention, the HLB value is calculated by the following Griffin formula. HLB value = 20 × {(molecular weight of hydrophilic part) / (total molecular weight)}

[0031] The aqueous dispersion of the fragrance used in the present invention preferably contains 7 to 80 parts by mass of a nonionic surfactant with respect to 100 parts by mass of the fragrance component. The content of the nonionic surfactant is more preferably 10 parts by mass or more, still more preferably 21 parts by mass or more, preferably 70 parts by mass or less, and still more preferably 63 parts by mass or less with respect to 100 parts by mass of the fragrance component. If the content of the nonionic surfactant is 7 parts by mass or more, the fragrance can be uniformly dispersed in water. Further, by setting it to 80 parts by mass or less, foaming of the aqueous dispersion of the fragrance by the surfactant is suppressed.

[0032] The concentration of the fragrance component in the aqueous dispersion of the fragrance used in the present invention is preferably 0.005% by mass or more, more preferably 0.01% by mass or more, still more preferably 0.03% by mass or more, preferably 5% by mass or less, more preferably 3% by mass or less, and still more preferably 1% by mass or less.

[0033] By setting the concentration of the fragrance water to 0.005% by mass or more, a sufficient amount of the fragrance that can reduce the unpleasant odor of the article can be imparted. Further, by setting the concentration of the fragrance water to 5% by mass or less, the production cost can be reduced and the environmental load during drainage can be suppressed.

[0034] The fragrance-imparting method of the present invention includes a step of immersing a polymer article in the aqueous dispersion of the fragrance. The time for immersing the polymer article in the aqueous dispersion of the fragrance is not particularly limited, but is preferably 5 minutes or more, more preferably 8 minutes or more, still more preferably 10 minutes or more, preferably 60 minutes or less, and more preferably 30 minutes or less.

[0035] When immersing the polymer article in the aqueous dispersion of the fragrance, the temperature of the aqueous dispersion is not particularly limited, but is preferably 5°C or higher, more preferably 8°C or higher, still more preferably 10°C or higher, preferably 80°C or lower, more preferably 60°C or lower, and still more preferably 50°C or lower.

[0036] When immersing the polymer article in the aqueous dispersion of the fragrance, the amount of the fragrance used per 100 g of the polymer article is preferably 0.001 g or more, more preferably 0.01 g or more, still more preferably 0.1 g or more, preferably 20 g or less, more preferably 10 g or less, and still more preferably 2 g or less. This is because if the amount of the fragrance used is within the above range, the unpleasant odor of the polymer molded article can be sufficiently reduced.

[0037] The method for flavoring the polymer article of the present invention is obtained by taking out the polymer article immersed in the aqueous dispersion of the fragrance from the aqueous dispersion of the fragrance and drying it.

[0038] The drying of the polymer article to which the aqueous dispersion of the fragrance adheres is preferably carried out at a temperature of 30°C to 90°C for 50 minutes or more and 240 minutes or less. By drying under the above conditions, drying can be carried out while suppressing the volatilization of the fragrance.

Examples

[0039] Hereinafter, the present invention will be described in detail with reference to examples. However, the present invention is not limited by the following examples, and any modifications and embodiments within the scope not departing from the gist of the present invention are all included in the scope of the present invention.

[0040] [Preparation of perfume water] 3.5 g of a water-insoluble fragrance and the surfactant described in Table 1 were put into a 13 L bucket so as to have the blending amounts described in Tables 2 to 4, and stirred well with a medicine spoon for 2 minutes. Then, 7 kg of water was added and mixed. The dispersion state of the fragrance in the obtained mixed solution was confirmed. <State of the mixed solution> Separation: The fragrance is not dispersed, and the fragrance particles are separated on the liquid surface. Emulsification: The fragrance is dispersed and the mixture becomes cloudy. Soluble: The fragrance is solubilized and the mixture becomes transparent.

[0041]

Table 1

[0042]

Table 2

[0043]

Table 3

[0044]

Table 4

[0045] [Fragrancing of Rubber Gloves] Twelve natural rubber gloves (Good Ne by Sumitomo Rubber Industries, Ltd.) were put into the mixture obtained above and stirred for 10 minutes. Twelve natural rubber gloves were taken out from the mixture and dried at 50 °C for 100 minutes.

[0046] [Evaluation of Fragrance Odor] The odor intensity of the fragrance odor of twelve rubber gloves was evaluated based on the following criteria, and the number of sheets for each odor intensity was shown in Tables 2 to 4. 0: No odor is felt. 1: A little odor is felt. 2: Odor is felt. 3: Strong odor is felt.

[0047] Based on the difference in the odor intensity of the fragrance, the variation of the twelve sheets was evaluated according to the following criteria. The evaluation results were shown in Tables 2 to 4. <Evaluation Criteria> 〇: No variation (The odor intensities are all the same. For example, the odor intensity of all 12 sheets is 2). △: There is a slight variation (the difference in odor intensity is one level. Example: odor intensity 2 → 8, odor intensity 1 → 4). ×: There is variation (the difference in odor intensity is two levels. Example: odor intensity 3 → 2, odor intensity 2 → 7, odor intensity 1 → 3).

[0048] From the results of Comparative Example 1, when no surfactant was used, the average value of the fragrance odor intensity was 2.2, and there was variation among the polymer articles within the batch.

[0049] When comparing Examples 1 - 7 with Comparative Examples 2 and 3, when 11 parts by mass of NIKKOL PBC - 31 (HLB 9.5) was added per 100 parts by mass of the fragrance component (Example 4), 8 parts by mass of Emalgen 106 (HLB 10.5) was added (Example 2), 9 parts by mass of Emalgen 109P (HLB 13.6) was added (Example 3), 7 parts by mass of hydrogenated castor oil (HLB 14.5) was added (Example 1), and 12 parts by mass of Leodol TW - O - 120V (HLB 15) was added, the variation among the polymer articles within the batch was improved to a slightly varying degree.

[0050] On the other hand, when 15 parts by mass of Leodol SP - L10 (HLB 8.6) was added to the fragrance (Comparative Example 2) and 17 parts by mass of Leodol Super TW - L120 (HLB 16.7) was added (Comparative Example 3), the variation among the articles within the batch was not improved. From these results, when using surfactants with HLB values of 9.5 - 15, an improvement effect on the variation among the polymer articles within the batch was observed in a smaller amount.

[0051] When comparing Example 4 with Comparative Example 5, adding 11 parts by mass of NIKKOL PBC - 31 (HLB 9.5) to the fragrance (Example 4) shows an improvement in variation, but adding 3 parts by mass (Comparative Example 5) does not. Also, when comparing Example 1 with Comparative Example 4, adding 7 parts by mass of hydrogenated castor oil (HLB 14.5) to the fragrance (Example 1) shows an improvement in variation, but adding 5 parts by mass (Comparative Example 4) does not. From these results, it can be said that using 7 parts by mass or more of surfactants with HLB values of 9.5 - 15 improves the variation among the polymer articles within the batch.

[0052] In Examples 9 to 20, a surfactant having an HLB value of 9.5 to 15 was added in an amount of 21 parts by mass or more based on 100 parts by mass of the fragrance component. By doing so, the variation between the polymer articles in the batch disappeared, and the variation improvement effect was higher than that in Examples 1 to 8.

[0053] Comparing Examples 9 to 16 and Examples 17 to 20. When a surfactant having an HLB value of 9.5 to 15 is added in an amount of 21 parts by mass to 63 parts by mass based on 100 parts by mass of the fragrance component, the fragrance odor intensity is 2. However, when a surfactant having an HLB value of 9.5 to 15 is added in an amount of 66 parts by mass to 80 parts by mass based on 100 parts by mass of the fragrance component (Examples 17 to 20), the intensity of the fragrance odor becomes 1. When the fragrance odor intensity becomes low, the fragrance imparted to the product becomes insufficient, which is not good.

[0054] Furthermore, when a surfactant having an HLB value of 9.5 to 15 is added in an amount of 85 parts by mass to 110 parts by mass based on 100 parts by mass of the fragrance component (Comparative Examples 6 to 9), the fragrance odor intensity becomes 0, which is not suitable.

Industrial Applicability

[0055] The present invention is suitable as a method for imparting fragrance to polymer articles.

[0056] A preferred embodiment (1) of the present invention is a method for imparting fragrance to a polymer article, which comprises immersing the polymer article in an aqueous dispersion of a fragrance and drying the polymer article taken out from the aqueous dispersion of the fragrance.

[0057] A preferred embodiment (2) of the present invention is a method for imparting fragrance to a polymer article according to embodiment (1), wherein the aqueous dispersion of the fragrance contains 7 parts by mass to 80 parts by mass of a nonionic surfactant based on 100 parts by mass of the fragrance component.

[0058] A preferred embodiment (3) of the present invention is a method for imparting fragrance to a polymer article according to embodiment (1) or (2), wherein the aqueous dispersion of the fragrance contains 21 parts by mass to 63 parts by mass of a nonionic surfactant based on 100 parts by mass of the fragrance component.

[0059] A preferred embodiment (4) of the present invention is a method for flavoring a polymer article according to any one of embodiments (1) to (3), wherein the nonionic surfactant has an HLB of 9.5 or more and 15 or less.

[0060] A preferred embodiment (5) of the present invention is a method for flavoring a polymer article according to any one of embodiments (1) to (4), wherein, as the aqueous dispersion of the fragrance, a composition containing 7 to 80 parts by mass of a nonionic surfactant having an HLB of 9.5 or more and 15 or less with respect to 100 parts by mass of the fragrance component is used.

Claims

**Claim 1** A method for flavoring a polymer article, comprising immersing the polymer article in an aqueous dispersion of a fragrance and drying the polymer article taken out from the aqueous dispersion of the fragrance. **Claim 2** The method for flavoring a polymer article according to claim 1, wherein the aqueous dispersion of the fragrance contains 7 to 80 parts by mass of a nonionic surfactant with respect to 100 parts by mass of the fragrance component. **Claim 3** The method for flavoring a polymer article according to claim 1, wherein the aqueous dispersion of the fragrance contains 21 to 63 parts by mass of a nonionic surfactant with respect to 100 parts by mass of the fragrance component. **Claim 4** The method for flavoring a polymer article according to claim 1, wherein the nonionic surfactant has an HLB of 9.5 or more and 15 or less. **Claim 5** The method for flavoring a polymer article according to claim 1, wherein the aqueous dispersion of the fragrance contains 7 to 80 parts by mass of a nonionic surfactant having an HLB of 9.5 or more and 15 or less with respect to 100 parts by mass of the fragrance component.

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