JPS6121159A - Thermoplastic resin composition with sweet smell - Google Patents
Thermoplastic resin composition with sweet smellInfo
- Publication number
- JPS6121159A JPS6121159A JP14166384A JP14166384A JPS6121159A JP S6121159 A JPS6121159 A JP S6121159A JP 14166384 A JP14166384 A JP 14166384A JP 14166384 A JP14166384 A JP 14166384A JP S6121159 A JPS6121159 A JP S6121159A
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- Japan
- Prior art keywords
- fragrance
- thermoplastic resin
- resin composition
- weight
- parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は熱可塑性樹脂に香料を含有せしめ、長期間にわ
たシ、一定の香を放ち続ける芳香性熱可塑性樹脂組成物
に関する１ものである。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to an aromatic thermoplastic resin composition in which a thermoplastic resin contains a fragrance and continues to emit a constant fragrance for a long period of time. .
香料とプラスチックを一体化した芳香性プラスチックは
リンゴの香りのする流し排水管、ぶどうやいちごの勾い
のする子供用はきもの及び花びらに芳香を持たせた造花
などにみられるようにプラスチック成形品の多くの分野
に採用されつつある。そして芳香性プラスチックを得る
方法としては次のような方法が知られている。Aromatic plastics that integrate fragrance and plastic are plastic molded products, such as apple-scented sink drain pipes, children's footwear with grape or strawberry slopes, and artificial flowers with scented petals. are being adopted in many fields. The following methods are known as methods for obtaining aromatic plastics.
６１香料をサイクロデキストリンに加えて包接化合物化
してこれを熱可塑性樹脂中にねり込む方法。（特開昭！
！−９４１？ｌｊ号参照）（ロ）ポリエチレン等のワッ
クスに香料を含有せしめてプレマスターバッチを製造し
、これを熱可塑性樹脂に練シ込む方法。（特開昭５６一
−ｏｏｚｓ号参照）
〔発明が解決しようとする問題点〕
上記げ）及び（ロ）の方法で得られる成形品はいずれも
その芳香性の持続期間がｌ〜３ケ月程度の短時間で［Ｌ
その香りの調節もほとんどできない場合が多く充分満足
できるものではない。A method in which a 61 fragrance is added to cyclodextrin to form an clathrate compound, which is then kneaded into a thermoplastic resin. (Tokukai Akira!
! -941? (See No. 1j) (b) A method in which a pre-masterbatch is produced by incorporating a fragrance into a wax such as polyethylene, and the pre-masterbatch is kneaded into a thermoplastic resin. (Refer to JP-A No. 561-oozs) [Problems to be solved by the invention] The molded products obtained by the above methods (g) and (b) all have an aromatic duration of about 1 to 3 months. In a short time [L
In many cases, it is hardly possible to adjust the scent, which is not completely satisfactory.
本発明者等はかかる従来技術に鑑み、長期間にわたり一
定の香を放ち続ける芳香性熱可塑性樹脂成形品を得るべ
く鋭意検討した結果、香料を担持させた多孔質無機充填
材を特定量熱可塑性樹脂に配合してなる芳香性熱可塑性
樹脂組成物から得られる成形品はその芳香性の持続期間
が１年以上の長時間にわた）保持し得ることを見出し、
本発明を完成した。In view of such prior art, the present inventors conducted intensive studies to obtain an aromatic thermoplastic resin molded product that continues to emit a constant fragrance over a long period of time. It has been discovered that molded articles obtained from aromatic thermoplastic resin compositions blended with resin can retain their aromatic properties for a long period of time (one year or more),
The invention has been completed.
すなわち、本発明の要旨は熱可塑性樹脂ｉｏ。That is, the gist of the present invention is thermoplastic resin io.
重量部に、あらかじめ香料を担持させた多孔質無機充填
材をＯ，．５〜７１重量部配合してなることを特徴とす
る芳香性熱可塑性樹脂組成物に存する。O, . The aromatic thermoplastic resin composition is characterized in that it contains 5 to 71 parts by weight.
以下、本発明をさらに詳細に説明する。The present invention will be explained in more detail below.
本発明において用いられる熱可塑性樹脂としてはポリエ
チレン、ポリプロピレン、エチレンープ四ピレン共重合
体、ポリブテン−７１エチレン−酢酸ビニル共重合体等
のオレフィン系樹脂、ポリ塩化ビニル、ポリ塩化ビニリ
デン、塩化ビニル−酢酸ビニル共重合体等の塩化ビニル
系樹脂、ポリスチレン、アクリロニトリル−スチレン共
重合体等のスチレン系樹脂、ナイロン−６、ナイロン６
−６、ナイロン１１等のポリアミド系樹脂、ポリエチレ
ンテレフタレート。Thermoplastic resins used in the present invention include polyethylene, polypropylene, ethylene-tetrapyrene copolymer, olefin resin such as polybutene-71 ethylene-vinyl acetate copolymer, polyvinyl chloride, polyvinylidene chloride, vinyl chloride-vinyl acetate. Vinyl chloride resins such as copolymers, polystyrene, styrene resins such as acrylonitrile-styrene copolymers, nylon-6, nylon-6
-6, polyamide resin such as nylon 11, polyethylene terephthalate.
ポリブチレンテレフタレート等のポリエステル系樹脂等
通常押出成形に用いられる熱可塑性合成樹脂が挙げられ
る。Examples include thermoplastic synthetic resins commonly used in extrusion molding, such as polyester resins such as polybutylene terephthalate.
本発明において香料を担持させるのに用いる多孔質無機
充填材としては天然シリカ、合成シリカ、ゼオライト、
炭酸カルシウム、硫酸カルシウム、沸石、滑石及び長石
等の粉末が挙けられる。これらの多孔質無機充填材はそ
の平均粒径が１０μ以下、好ましくは０．１％１０μの
範囲で、且つ比表面積が／ゴ／１／以上、好ましくはＪ
ｒｒｊ ／ １１以上のものが用いられる。特に本発
明の熱可塑性樹脂組成物をフィルム成形品に用いる場合
には平均粒径が０．／−／θμ、粒子径が０、／−／！
；ｉｔで、且つ比表面積が／ ｄ ７７７以上の物性を
有する多孔質無機充填材を用いるとフィルムのブロッキ
ング性が改良されるので望ましい。In the present invention, the porous inorganic fillers used to support fragrances include natural silica, synthetic silica, zeolite,
Examples include powders of calcium carbonate, calcium sulfate, zeolite, talc, feldspar, and the like. These porous inorganic fillers have an average particle diameter of 10μ or less, preferably in the range of 0.1%10μ, and a specific surface area of /G/1/ or more, preferably J
rrj/11 or more is used. In particular, when the thermoplastic resin composition of the present invention is used for film molded products, the average particle size is 0. /-/θμ, particle size is 0, /-/!
It is desirable to use a porous inorganic filler having the physical properties of /d and a specific surface area of 777 or more because the blocking properties of the film are improved.
また、香料としては液体状香料が用いられ。In addition, liquid fragrances are used as fragrances.
香料の原料である天然香料および合成香料またはこれら
の調合香料によって目的の香シの香料原油を調製したも
のなどが用いられる。Natural fragrances and synthetic fragrances, which are raw materials for fragrances, or fragrance crude oils prepared from blended fragrances thereof are used.
上記香料を多孔質無機充填材に担持させる方法としては
通常の液体を固体に担持させる慣用法を採用することが
できる。例えば、上記充填材に香料原油を添加し混合す
る方法、上記充填材の一部に香料原油を添加、混合して
高濃度の香料マスターバッチを製造し、これに上記充填
材の残部を添加し混合する方法等が好適に用いられる。As a method for supporting the perfume on the porous inorganic filler, a conventional method of supporting a liquid on a solid can be adopted. For example, a method of adding flavor crude oil to the filler and mixing it, or adding flavor crude oil to a part of the filler and mixing to produce a highly concentrated flavor masterbatch, and adding the remainder of the filler to this. A method of mixing, etc. is preferably used.
特に上記充填材は香料原油を担持させる前にあらかじめ
乾燥等の方法によって上記充填剤中の水分を除去してお
くことにより、得られる樹脂組成物の成形時における水
分蒸発による発泡現象を防止することができるので好ま
しい。In particular, the moisture in the filler is removed by a method such as drying in advance before supporting the fragrance crude oil to prevent foaming caused by moisture evaporation during molding of the resulting resin composition. This is preferable because it allows
上記充填材に担持させる香料原油（香料と溶剤の混合物
）の−°は上記充填剤ｉｏｏ電量部に対して５〜３０重
量部、好ましくは１０−１０重量部の範囲である。香料
原油の量が上記範囲より多すぎると成形の際発泡現象を
生起しフィルム成形不可能となるので好ましくなく、ま
た十＾己範囲よシ少ないと充分な芳香性が付与できない
ので好ましくない。-° of the fragrance crude oil (mixture of fragrance and solvent) supported on the filler is in the range of 5 to 30 parts by weight, preferably 10-10 parts by weight, based on ioo coulometric parts of the filler. If the amount of the fragrance crude oil is more than the above range, foaming occurs during molding, making it impossible to form a film, which is undesirable, and if it is less than the above range, sufficient fragrance cannot be imparted, which is undesirable.
本発明における芳香性熱可塑性樹脂組成物は前記した熱
可塑性樹脂１００重開゛に対し、上記した香料原油を多
孔質無機充填材１０θ重量部に３〜３０重甘部をせ持し
たものを０．５〜７重量部、好ましくは／ −ｊ−ｉｉ
’量部置部合したものである。香料を担持した多孔質無
機充填材の童が上記範囲より多すぎると成形の際、上記
充填材の樹脂への分散性が不良となり、成形品にゲルが
発生するので好ましくなく、また上記範囲より少ないと
香料の揮散蓋が多く、その芳香性の持続期間が短くなる
ので好ましくない。The aromatic thermoplastic resin composition of the present invention is made by adding the above-mentioned fragrance crude oil to 10θ parts by weight of a porous inorganic filler and 3 to 30 parts by weight of the above-mentioned thermoplastic resin. .5 to 7 parts by weight, preferably / -j-ii
'It is a combination of quantity and part. If the number of particles of the porous inorganic filler carrying the fragrance is larger than the above range, the dispersibility of the filler into the resin will be poor during molding, and gel will occur in the molded product, which is undesirable. If it is too low, a lot of the fragrance will volatilize and the duration of the fragrance will be shortened, which is not preferable.
上記香料を担持した多孔質無機充填材を熱可塑性樹脂に
配合するには通常の溶融混線法に従い、例えばバンバリ
ーミキサ−、コンティニュアスミキサー、混練押出機等
を用い、１１７０〜２３０℃で溶融混合すればよい。ま
た所謂マスターバッチ方式により、高濃度の香料を担持
した上記充填材を含有するマスターバッチを調整し、こ
れを成形時に熱可塑性樹脂と混合してもよい。The porous inorganic filler carrying the fragrance mentioned above is blended into the thermoplastic resin using the usual melt mixing method, for example, using a Banbury mixer, continuous mixer, kneading extruder, etc., at 1170 to 230°C. do it. Alternatively, a masterbatch containing the filler carrying a high concentration of fragrance may be prepared by a so-called masterbatch method, and this may be mixed with a thermoplastic resin during molding.
以上のようにして調製した芳香性熱可塑性樹脂組成物を
用いて溶融成形して得られた各種成形品はその芳香性を
長時にわたり賦与させることができ、且つ製品の物性を
低下させない。Various molded products obtained by melt-molding the aromatic thermoplastic resin composition prepared as described above can retain their aromatic properties for a long time, and do not deteriorate the physical properties of the product.
それ故、本発明の芳香性熱可塑性樹脂組成物はフィルム
製品、フラットヤーン製品、モノフィラメント製品、ラ
ミネート製品、各種成形品等のあらゆる分野に利用する
ことができる。Therefore, the aromatic thermoplastic resin composition of the present invention can be used in all fields such as film products, flat yarn products, monofilament products, laminate products, and various molded products.
また、本発明の芳香性熱可塑性樹脂組成物はその使用目
的に応じ、紫外線吸収剤、熱安定剤、帯電防止剤、顔料
等の添加剤を適宜配合することができる。Furthermore, additives such as ultraviolet absorbers, heat stabilizers, antistatic agents, pigments, etc. can be appropriately blended into the aromatic thermoplastic resin composition of the present invention, depending on the purpose of use.
本発明において、香料を多孔質無機充填材に相持したも
のを熱可塑性樹脂に配合させることにより、その芳香性
を長時間にわた９持続する理由は明らかではないが、お
そらく該充填材の細孔内に吸着された香料はその揮散速
度が遅く徐々に揮発するため、その芳香性は長時間にわ
たり持続することができるものと推定される。In the present invention, the reason why the aromatic property is maintained for a long time by blending the fragrance with the porous inorganic filler into the thermoplastic resin is not clear, but it is probably due to the pores of the filler. Since the fragrance adsorbed in the liquid has a slow volatilization rate and gradually evaporates, it is presumed that its fragrance can be maintained for a long period of time.
以下、実施例により本発明を更に詳細に説明するが、本
発明はその要旨を越えない限り以下の実施例に限定され
るものではない。Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to the following Examples unless the gist thereof is exceeded.
実施例／
（イ１ 香料を担持した多孔質無機充填材の調製シリカ
粉末（ジョンマンビル社製、商品名スーパーフロス、平
均粒径１．５μ、比表面積ｊ、ｊゴ／、！ｉ＋）をあら
かじめ１００℃で２ダ時間真空乾燥したもの１００重量
部と香料として金木セイの香りのする合成香料油７０重
量部をコｊ ’Ｃで７時間混合してシリカ粉末の表面に
香料を担持させた。Example / (1) Preparation of porous inorganic filler supporting fragrance Silica powder (manufactured by John Manville, trade name Super Floss, average particle size 1.5μ, specific surface area j, jgo/,!i+) 100 parts by weight of a product previously vacuum-dried at 100°C for 2 hours and 70 parts by weight of a synthetic fragrance oil with the scent of Sei Kaneki as a fragrance were mixed in Coj'C for 7 hours to support the fragrance on the surface of the silica powder. Ta.
（ロ）芳香性熱可塑性樹脂組成物及びフィルムの製造
低密度ポリエチレン（メルトインデックス：２１／／１
０分、密度二〇、タコ” Ｉｔ ／ ｃｒｌ ） ｉｏ
。(b) Production of aromatic thermoplastic resin composition and film Low density polyethylene (melt index: 21//1
0 minutes, density 20, octopus” It / crl) io
.
重量部に対し、上記（イ）で得られた香料を担持したシ
リカ粉末９重量部を配合し、バンバリー 望 −
一ミキサーでｌダＯ℃において混線、ペレット化して低
密度ポリエチレン樹脂組成物のペレットを得た。9 parts by weight of the silica powder supporting the fragrance obtained in (a) above was blended with each part by weight, mixed in a Banbury mixer at 0°C, and pelletized to form pellets of the low-density polyethylene resin composition. I got it.
上記ペレットをモダンマシナリー社製ｅＯＨｄ押出機に
環状スリット径１００酊ダ、リップクリアランスθ、７
龍のインフレーションダイ及び冷却用エアーリングを取
付けたインフレーション成形機を用い、押出温度１６０
℃、・押出−ｉｉ ？ ｋＶｈｒ 、 ブローアツプ
比／、ｊ、７１：ＩＸトライン高さコｊ ＣＩｒ１ ｂ
引取速度り、−ｍ７分の条件下にインフレーション成形
し、厚さＳθμノインフレーションフイルムヲ得り。The above pellets were placed in an eOHd extruder manufactured by Modern Machinery with an annular slit diameter of 100 mm and a lip clearance of θ of 7.
Using an inflation molding machine equipped with a dragon inflation die and a cooling air ring, the extrusion temperature was 160℃.
℃、・Extrusion-ii? kVhr, blow-up ratio/, j, 71: IX trine height coj CIr1 b
Inflation molding was performed at a take-up speed of -m7 minutes to obtain a blown film having a thickness of Sθμ.
（／ｉ 芳香性の持続時間の測定
上記仲）で得られたフィルムなコ３℃の恒温室に放置し
、その芳香性の香如が消滅する時間を測定した。結果を
第７表に示す。(/i Measurement of duration of aromatic property) The film obtained in the above procedure was left in a constant temperature room at 3°C, and the time taken for the aromatic fragrance to disappear was measured. The results are shown in Table 7.
実施例コ
実施例１（イ１において、香料をバニラの香りのする合
成香料油にかえたこと以外は実施例１と同様に行った。Example 1 The same procedure as in Example 1 was carried out except that in Example 1, the fragrance was changed to a synthetic fragrance oil with a vanilla scent.
結果を第１表に示す。The results are shown in Table 1.
−日 一
実施例３〜Ｓ
実施例１（イ）において、香料をバターの香りのする合
成香料油（実施例３）、コーヒーの香如のする合成香料
油（実施例ダ）、カレーの香りのする合成香料油（実施
例Ｓ）にそれぞれかえたこと以外は実施例１と同様に行
った。結果を第１表に示す。- Day 1 Examples 3 to S In Example 1 (A), the fragrances were a synthetic fragrance oil with a buttery fragrance (Example 3), a synthetic fragrance oil with a coffee fragrance (Example D), and a curry fragrance. The same procedure as in Example 1 was carried out except that the synthetic fragrance oil (Example S) was used. The results are shown in Table 1.
比較例１
実施例１（イ）において、香料油の量をＳＯ重量部にか
えたこと以外は実施例１と同様に行ったところフィルム
成形時に発泡現象を起し、成形不可能であった。Comparative Example 1 The same procedure as in Example 1 was carried out in Example 1 (a) except that the amount of perfume oil was changed to parts by weight of SO, but a foaming phenomenon occurred during film molding, and molding was impossible.
比較例コ
実施例１（ロ）において、香料を担持したシリカ粉末の
量をｉｏ重量部にかえたこと以外は実施例１と同様に行
ったところ、フィルム成形品に細かい砂地状のゲルが多
量発生し、且つ透明性が著しくそこなわれ、フィルム製
品としては使用不可能であった。Comparative Example When the same procedure as in Example 1 was carried out in Example 1 (b) except that the amount of silica powder supporting the fragrance was changed to io parts by weight, a large amount of fine sandy gel was found in the film molded product. and the transparency was significantly impaired, making it impossible to use as a film product.
比較例３
実施例／（ロ）において、サイクロデキストリン粉末ｉ
ｏｏ重量部と金木セイの香りのする合成香料油−０重量
部をコＳ℃混合して得た該香料油のサイクロデキストリ
ン包接化合物粉末化合物を前記低密度ポリエチレン１０
θ重量部に対して／θ重量部配合したことｖ外は実施例
１（ロ）及び（／→と同様に行った。結果を第７表に示
す。Comparative Example 3 In Example/(b), cyclodextrin powder i
The cyclodextrin clathrate compound powder compound of the fragrance oil obtained by mixing 0 parts by weight of synthetic fragrance oil with the scent of Sei Kaneki and 0 parts by weight of the synthetic fragrance oil with the scent of Sei Kaneki was added to the low-density polyethylene 10
The same procedures as in Example 1 (B) and (/→) were carried out except that /θ weight parts were blended with respect to θ weight parts. The results are shown in Table 7.
比較例１
実施例１（ロ）において、高圧法ポリエチレン製造時に
副生する数平均分子量約１ｏｏｏｏの低重合度ポリエチ
レン（グリースワックス） １００重普部と金木セイの
香りのする合成香料油３０重量部を１００℃で溶融混合
したものを前記低密度ポリエチレン１００重量部に対し
て１０重量部配合したこと以外は実施例／（ロ）及び（
／１と同様に行った。結果を第１表に示す。Comparative Example 1 In Example 1 (b), 100 parts by weight of low polymerization degree polyethylene (grease wax) with a number average molecular weight of about 1oooo produced as a by-product during the production of high-pressure polyethylene and 30 parts by weight of synthetic fragrance oil with the scent of Kanagi Sei Example/(B) and (B) except that 10 parts by weight of the mixture of 100 parts by weight of the low-density polyethylene was melt-mixed at 100°C.
/1 was carried out in the same manner. The results are shown in Table 1.
−１１＝
〔発明の効果〕
本発明の芳香性熱可塑性樹脂組成物から得られる成形品
はその芳香性の香りを長時間にわたυ保持することがで
きる。-11= [Effects of the Invention] The molded article obtained from the aromatic thermoplastic resin composition of the present invention can retain its aromatic scent υ for a long time.
それ故、本発明の芳香性熱可塑性樹脂組成物はその芳香
性の香りを必要される用途にフィルム、フラットヤーン
、モノフラメントラミネート等の成形品として利用する
ことができる。Therefore, the aromatic thermoplastic resin composition of the present invention can be used as a molded article such as a film, flat yarn, monofilament laminate, etc. for applications that require its aromatic scent.
出 願 人 三菱化成工業株式会社 代 理 人 弁理士 長谷用 − ほか１名Sender: Mitsubishi Chemical Industries, Ltd. Representative Patent Attorney Hase - 1 other person
Claims (1)
担持させた多孔質無機充填材を０．５〜７重量部配合し
てなることを特徴とする芳香性熱可塑性樹脂組成物。(1) An aromatic thermoplastic resin composition comprising 100 parts by weight of a thermoplastic resin and 0.5 to 7 parts by weight of a porous inorganic filler preliminarily loaded with a fragrance.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14166384A JPS6121159A (en) | 1984-07-09 | 1984-07-09 | Thermoplastic resin composition with sweet smell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14166384A JPS6121159A (en) | 1984-07-09 | 1984-07-09 | Thermoplastic resin composition with sweet smell |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6121159A true JPS6121159A (en) | 1986-01-29 |
Family
ID=15297279
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14166384A Pending JPS6121159A (en) | 1984-07-09 | 1984-07-09 | Thermoplastic resin composition with sweet smell |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6121159A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6375045A (en) * | 1986-09-17 | 1988-04-05 | Nok Corp | Mildew-proofing resin composition |
| JPH01313533A (en) * | 1988-06-13 | 1989-12-19 | Dainippon Printing Co Ltd | Antibacterial resin sheet |
| KR20040005429A (en) * | 2002-07-10 | 2004-01-16 | 문영철 | Fragrant Resin Plastics and Manufacturing Method Thereof |
| JP2006070128A (en) * | 2004-09-01 | 2006-03-16 | Nippon Unicar Co Ltd | Ethylenic resin composition in which unpleasant odor is masked and film obtained therefrom |
| JP2007137922A (en) * | 2005-11-15 | 2007-06-07 | Tajima Roofing Co Ltd | Deodorant composition for molten asphalt, and method for reducing odor of molten asphalt using the composition |
-
1984
- 1984-07-09 JP JP14166384A patent/JPS6121159A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6375045A (en) * | 1986-09-17 | 1988-04-05 | Nok Corp | Mildew-proofing resin composition |
| JPH01313533A (en) * | 1988-06-13 | 1989-12-19 | Dainippon Printing Co Ltd | Antibacterial resin sheet |
| KR20040005429A (en) * | 2002-07-10 | 2004-01-16 | 문영철 | Fragrant Resin Plastics and Manufacturing Method Thereof |
| JP2006070128A (en) * | 2004-09-01 | 2006-03-16 | Nippon Unicar Co Ltd | Ethylenic resin composition in which unpleasant odor is masked and film obtained therefrom |
| JP2007137922A (en) * | 2005-11-15 | 2007-06-07 | Tajima Roofing Co Ltd | Deodorant composition for molten asphalt, and method for reducing odor of molten asphalt using the composition |
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