JP2002265724A - Sticky perfuming material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To solve the problems that, in an airtight narrow space, such as in an automobile, a malodor stays, making the space unpleasant; that, though a liquid-type perfuming agent used in such a space is excellent in perfuming capability, it is liable to leak and hence is unsuitable for the use in a vigorously jolty place; that, though a gelatinous perfuming agent is solid and is not liable to leak, its perfuming persistence is short; and that a perfuming agent which does not require a large space, does not leak even under vigorous jolting, and has a long perfuming persistence has been desired. SOLUTION: A perfuming material prepared by incorporating a perfume into a thermoplastic styrene elastomer composition is provided. The elastomer composition comprises a block copolymer consisting of a polymer block derived from an aromatic vinyl compound and a polymer block derived from a conjugated diene compound, and a random copolymer of an aromatic vinyl compound and a conjugated diene compound. Preferably, the perfume is limonene or benzyl benzoate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a sticky fragrance containing a fragrance contained in a styrenic thermoplastic elastomer composition.

[0002]

2. Description of the Related Art In small airtight spaces such as automobiles, unpleasant odors and bad odors stay in the interior for a long time, and the desire to obtain a more comfortable space increases. It is common. Various fragrances have been developed and used to satisfy such needs. Conventional fragrances are liquid-type fragrances or gel-type fragrances, and liquid-type fragrances have excellent fragrance. But
If the container falls down due to the use of the liquid fragrance, the fragrance may leak, and is not suitable for use in a place with strong sway such as an automobile. Also, since the gel-like fragrance is a solidified fragrance, there is no risk of the fragrance leaking out, but it generally has a short-lived fragrance.

[0003]

As described above, it does not take up space even in a small airtight space such as an automobile, and does not leak fragrances despite violent shaking, and has a long lasting fragrance. Development of fragrance was desired.

[0004]

Means for Solving the Problems The present inventors have conducted various studies to solve these problems, and as a result, by using a styrene-based thermoplastic elastomer composition,
It has led to the provision of sticky fragrances. That is, an adhesive fragrance characterized in that a fragrance is contained in a styrene-based thermoplastic elastomer composition, wherein the styrene-based thermoplastic elastomer composition has at least one polymer block comprising a vinyl aromatic compound. , And at least one polymer block composed of a conjugated diene compound, preferably a block copolymer containing at least one, and preferably a random copolymer of a vinyl aromatic compound and a conjugated diene compound as a main component, It is particularly preferable that 35% or more of the conjugated diene portion of the conjugated diene compound is a hydrogenated block copolymer. Preferably, the fragrance is limonene or benzyl benzoate.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The sticky fragrance referred to in the present invention is
It refers to a sticky fragrance that can be attached to a flat surface by allowing the fragrance to be contained in a styrene-based thermoplastic elastomer composition formed into a sheet or block. Therefore, by attaching it to a glass surface or a dashboard inside an automobile, fragrance can be enjoyed for a long period of time.

The styrene-based thermoplastic elastomer composition used in the present invention contains at least one polymer block composed of a vinyl aromatic compound and at least one polymer block composed of a conjugated diene compound. A composition mainly composed of a block copolymer or a composition mainly composed of a random copolymer of a vinyl aromatic compound and a conjugated diene compound, wherein 35% or more of the conjugated diene portion of the conjugated diene compound is hydrogenated. It is preferably a block copolymer.

[0007] Vinyl aromatic compounds include styrene and α-
The conjugated diene compound is, for example, isoprene or butadiene. The content of the vinyl aromatic compound in the block copolymer or the random copolymer is 5 to 75% by weight, and when the content of the vinyl aromatic compound is out of this range, the block copolymer or the random copolymer is removed. A thermoplastic elastomer composition as a main component is not preferable because sufficient rubber elasticity cannot be obtained.

The number average molecular weight of the block copolymer or random copolymer is in the range of 30,000 to 500,000. When the molecular weight is smaller than the above range, the mechanical strength becomes insufficient, and when the molecular weight is larger than the above range, the mechanical strength becomes insufficient. Is not preferable because molding processability is insufficient.

The above-mentioned block copolymers and random copolymers may be used alone or in combination of two or more in order to carry out the present invention. The mixing ratio can be arbitrarily selected depending on the properties of the obtained resin.

In the present invention, the block copolymer or the random copolymer may be used alone, but may be used by adding another compounding agent thereto. For example, it is more preferable to use a composition in which a softener such as a polyolefin resin such as polypropylene or polyethylene or a hydrocarbon-based oil or a lubricant such as a fatty acid salt, a fatty acid amide, or a silicone oil is mixed. By using a composition to which such other additives are added, it is possible to change physical properties such as hardness, strength, fluidity, and surface friction coefficient in a wide range.

In order to easily form the adhesive fragrance of the present invention, the hardness is preferably adjusted to 1 to 90 degrees in JIS-E type hardness. Above all, it is more preferable to adjust the angle to 1 to 50 degrees. The MFR value (190 ° C., 2.16 kg load) is preferably 0.5 g / 10 min or more. Above all, 1-6
It is more preferable to adjust to 0 g / 10 minutes.

As another compounding agent to be added to the block copolymer or the random copolymer, a softening agent is particularly frequently used for adjusting the hardness of the thermoplastic elastomer composition. Generally, hydrocarbon compounds are used, and examples thereof include paraffin hydrocarbons, naphthenic hydrocarbons, aromatic hydrocarbons, and liquid paraffin. One of these softeners is usually used, but two or more may be used in combination. In that case, the mixing ratio can be arbitrarily selected.

The content of the softening agent added to the block copolymer or the random copolymer can be used in the range of 0 to 95% by weight, and preferably 30 to 85% by weight in terms of flowability at the time of molding. Are better.

The styrenic thermoplastic elastomer composition used in the present invention comprises a single-screw extruder, a twin-screw extruder,
It is obtained by kneading the raw materials in a heated and molten state using a kneader or a mixer such as a Banbury mixer, a Brabender, a Henschel mixer, an open roll, or a kneader. As a method for molding the obtained composition, a conventionally known molding method can be selected. For example,
Examples include an injection molding method, an extrusion molding method, a hollow molding method, a compression molding method, and a calendar molding method. Also, after forming into a sheet shape, it can be die-cut into an arbitrary shape. The thickness of the sheet can be set arbitrarily, but is set in consideration of the area to be attached. Accordingly, the thickness can be set in the range of 50 μm to 20 mm, but is preferably 1 to 5 mm for practical use.

The term "perfume" as used herein refers to a substance that emits a pleasant odor. In order to carry out the present invention, a synthetic perfume produced by an organic synthesis reaction is preferable in view of its properties and cost. That is, solubility in a softener,
It can be arbitrarily selected from the desired odor properties and price. For example, limonene as a hydrocarbon compound,
Dipentene, terpinolene, allocymene, ocimene, p-cymene were converted to cis-3 as an aliphatic alcohol.
-Hexenol, 9-decenol, as chain terpene alcohols linalool, geraniol, nerol,
Citronellol, Rosinol, Dimethyloctanol,
Hydroxycitronellol, tetrahydro linalool, mugol, myrcenol, α-terpineol, isopulegol as cyclic terpene alcohol, farnesol, nerolidol, Santalol, vetiverol as sesquiterpene alcohol, benzyl alcohol, β-phenylethyl as aromatic alcohol Alcohol, γ-phenylpropyl alcohol, dimethylbenzylcarbinol, methylphenylcarbinol,
β-phenylethyldimethylcarbinol, β-phenylethylmethylethylcarbinol, phenol and its derivatives as anisole, p-cresol methyl ether, anethole, dihydroanethole, eugenol, isoeugenol, methyleugenol, methylisoeugenol, fat N-octyl aldehyde, n-nonyl aldehyde, n-decyl aldehyde, methyl nonylacetaldehyde as an aromatic aldehyde, citral, citronellal, hydroxycitronellol, perilaldehyde as a terpene aldehyde, and benzaldehyde, phenylacetaldehyde, phenylpropyl aldehyde as an aromatic aldehyde , Cinnamic aldehyde, α-amylcinnamic aldehyde, α-hexylcinnamic Aldehyde, anisaldehyde, cycler Men aldehyde, p- tert-butyl -α- methylhydrosiloxane cinnamic aldehyde, the hydro Toro path aldehyde, ethyl -n- amyl ketone as aliphatic ketone,
Methyl-n-nonyl ketone, diacetyl, terpene-based cyclic ketone, l-carboxyl, menthone, d-pulegone, cyclic ketone as acetophenone, yonone, iron, jasmon, dihydrojasmon, fatty acid ester geranyl formate, benzyl formate, Phenylethyl formate, isoamyl acetate, citronellyl acetate, geranyl acetate, linalyl acetate, menthyl acetate, benzyl acetate, phenylethyl acetate, methylphenylcarbinyl acetate, ethyl propionate, isoamyl propionate, citronellyl propionate, linalyl propionate, propionate Geranyl, terpinyl propionate, benzyl propionate, cinnamyl propionate, ethyl butyrate, isoamyl butyrate, geranyl butyrate, linalyl butyrate, linalyl isobutyrate, citro butyrate Ryl, citronellyl isobutyrate, benzyl butyrate, benzyl isobutyrate, n-propyl isovalerate, isoamyl isovalerate, geranyl isovalerate, benzyl isovalerate, cinnamyl isovalerate, ethyl benzoate as an ester of an aromatic acid , Isobutyl benzoate,
Mention may be made of linalyl benzoate, benzyl benzoate, phenylethyl benzoate, methyl salicylate, ethyl salicylate, isoamyl salicylate, ethyl anisate, ethyl anthranilate. Also, a compounded fragrance prepared by mixing the above fragrances can be used.

An outline of the present invention will be described. A softening agent is added to the styrene-based thermoplastic elastomer composition and kneaded well. At this time, a coloring agent can be added as needed. The styrene-based thermoplastic elastomer composition kneaded with the softener is molded into a sheet or an arbitrary shape by an arbitrary molding method. In order to make the obtained molded product contain a fragrance, the adhesive fragrance is immersed in a solution containing the fragrance or by applying a solution containing the fragrance to the surface of the molded product to remove the sticky fragrance. Obtainable. The immersion time of the molded article in the perfume-containing solution varies depending on the type of perfume and the combination of the styrene-based thermoplastic elastomer composition. When a solution containing a fragrance is applied to the surface of a molded article, the time required for impregnation after the fragrance is applied varies depending on the type of the fragrance and the combination of the styrene-based thermoplastic elastomer composition. Is usually 4 hours to 14 days, and preferably 5 to 10 days in the case of a compounded fragrance.

As the colorant according to the present invention, it is preferable to use dyes and pigments used for general-purpose plastics in view of their properties and cost. That is, the solubility in the copolymer or softener constituting the styrene-based thermoplastic elastomer composition is good, the discoloration is small, and a material having good weather resistance is selected. Is preferably a dye rather than a pigment. The color tone of the colorant can be arbitrarily selected depending on the purpose, such as black, white, gray, orange, pink, and purple. The amount of the colorant to be added varies depending on the density of the target color, but the weight ratio is 0.01 to 10.0% of the styrene-based thermoplastic elastomer composition, and the general use is 0.1 to 2%. 0.0% is preferred.

[0018]

EXAMPLES Next, the details of the present invention will be described based on examples, but the gist of the present invention is not limited to these examples.

Example 1 As a styrene-based thermoplastic elastomer composition, hydrogenated styrene having a styrene content of 30% by weight, a number average molecular weight of 140,000 and a hydrogenation rate of 97% was used.
30% by weight of an isoprene-styrene type triblock copolymer, a paraffinic oil (PW-9 manufactured by Idemitsu Kosan Co., Ltd.)
0) was mixed at a ratio of 70% by weight, and this mixture was melt-kneaded with a small twin-screw extruder to a hardness of JIS-E type 20 ° and an MFR value (190 ° C., 2.16 kg load) of 40.
A pellet compound of g / 10 minutes was prepared. Using the obtained pellet compound as a material, a leaf-shaped sheet piece was molded using an injection molding machine FE120 manufactured by Nissei Plastics Co., Ltd. Natural limonene (product of Brazil) was applied to the surface of the obtained sheet piece and allowed to stand for 6 hours to impregnate the fragrance, thereby obtaining a sticky aromatic material on the leaf-shaped surface. Leave this fragrance on the window glass in the car and leave
The fragrance persistence and the tackiness of the glass surface were examined. As a result, it was recognized that the fragrance continued for 60 days, and it was found that excellent fragrance persistence was obtained and that the tackiness was maintained without peeling off from the glass surface.

Example 2 As a styrene-based thermoplastic elastomer composition, hydrogenated styrene having a styrene content of 40% by weight, a number average molecular weight of 200,000 and a hydrogenation rate of 98% was used.
25% by weight of a butadiene random copolymer, 5% by weight of polypropylene (J106W, manufactured by Grand Polymer Co., Ltd.), and a paraffinic oil (PW-38, manufactured by Idemitsu Kosan Co., Ltd.)
0) was mixed at a ratio of 70% by weight, and this mixture was melt-kneaded with a small twin-screw extruder to a hardness of JIS-E type 50 degrees and an MFR value (190 ° C., 2.16 kg load) of 15
A pellet compound of g / 10 minutes was prepared. Using the obtained pellet compound as a material, a leaf-shaped sheet having a thickness of 2 mm was formed using an injection molding machine FE120 manufactured by Nissei Plastics Co., Ltd. Benzyl benzoate (manufactured by Inoue Manufacturing Co., Ltd.) was applied to the surface of the obtained sheet and allowed to stand for 4 hours to impregnate the fragrance, thereby obtaining a sticky aromatic material on the leaf-shaped surface of the tree. The fragrance was stuck on a window glass in an automobile, and the fragrance persistence and the adhesiveness of the glass surface were examined. As a result, it was recognized that the fragrance continued for 60 days, and it was found that excellent fragrance persistence was obtained and that the tackiness was maintained without peeling off from the glass surface.

[0021]

The adhesive fragrance material of the present invention has an adhesive property on its surface, so that it can be retained in a narrow space such as an automobile by being attached to a windshield, a dashboard, a rear window, etc. without falling off. In addition, since it emits fragrance for a long period of time, it can be used for a long period of time without worrying about leakage of the fragrance despite the severe vibration. In addition, by maintaining transparency and forming a sheet, even when affixed to a windshield, the visibility is not obstructed, and safety in driving can be ensured.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 53/00 C08L 53/00 C09J 7/00 C09J 7/00 11/06 11/06 109/06 109 / 06 125/10 125/10 153/02 153/02 (72) Inventor Masashi Nakatsuruma 3-3 Doyama-cho, Kita-ku, Osaka City, Osaka Prefecture Inside Kuraray Plastics Co., Ltd. (72) Inventor ▲ Taka ▼ Tree Yasuhiko Osaka Sanwa Co., Ltd. (72) Inventor Yoshikazu Mizoguchi 2-5-1 Tamatsu, Higashinari-ku, Osaka-shi F-term (reference) in Sanwa Co., Ltd. 2-5-1 Tamatsu, Higashinari-ku, Osaka, Osaka 4C002 AA03 CC04 DD12 EE05 FF02 HH05 4J002 BC051 BP011 EA036 EC036 EE016 EE036 EH036 EH126 FD206 GB00 4J004 AA05 AA17 AB01 BA02 FA10 4J040 CA081 CA111 DB051 DB081 DM011 HB02 HB08 HB12 HB16 HB17 HB18 HB09 JA33

Claims (6)

[Claims] 1. A sticky fragrance comprising a styrene-based thermoplastic elastomer composition containing a fragrance. 2. The styrenic thermoplastic elastomer composition according to claim 1, comprising at least one polymer block comprising a vinyl aromatic compound and at least one polymer block comprising a conjugated diene compound. A sticky fragrance characterized by comprising a block copolymer as a main component. 3. The adhesive fragrance according to claim 2, wherein 35% or more of the conjugated diene portion of the conjugated diene compound is a hydrogenated block copolymer. 4. The adhesive fragrance material according to claim 1, wherein the styrenic thermoplastic elastomer composition mainly comprises a random copolymer of a vinyl aromatic compound and a conjugated diene compound. 5. The adhesive fragrance according to claim 4, wherein 35% or more of the conjugated diene portion of the conjugated diene compound is a hydrogenated copolymer. 6. A sticky fragrance, wherein the fragrance according to any one of claims 1 to 5 is limonene or benzyl benzoate.