JP4276901B2 - Cleaning composition for dry cleaning and cleaning method using the same - Google Patents

Description

【００１８】
一般式（１）におけるグリセリン誘導体変性シリコーン中の多価アルコール置換基Ｒ^４の含有量は３〜３０重量％が好ましく、更に、好ましくは５〜２０重量％である。多価アルコール置換基Ｒ^４の含有量が３０重量％を超えると、グリセリン誘導体変性シリコーンのシリコーン溶剤への溶解性が乏しいものとなり、３重量％未満であると洗浄力が不足するおそれがある。
【００１９】
さらに、（Ｂ）成分としての多価アルコール変性シリコーンは下記一般式（２）で表されるオルガノポリシロキサンポリグリセリンブロック共重合体が用いられる。
【化２】

【００２０】
式中のＲ^２は脂肪族不飽和結合を有しない炭素数１〜３０の１価炭化水素基である。さらにＲ^２は同一、又は異なっても良く、炭素数１〜３０のアルキル基、アリール基、アラルキル基、アミノ置換アルキル基、カルボキシル置換アルキル基（一部ハロゲンに置換されていてもよい）を表す。Ｑはエーテル結合及びエステル結合を含有しても良い炭素数３〜２０の二価有機基を表し、Ｇ^２はモノグリセリンあるいはポリグリセリン残基である。ａは２以上１００以下の整数であり、ｂは２以上１００以下の整数である。
【００２１】
Ｒ^２の具体例としては、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基、トリデシル基、テトラデシル基、ヘキサデシル基、オクタデシル基、ベヘニル基、及び一部ハロゲンで置換されたアルキル基である。シクロペンチル基、シクロヘキシル基等のシクロアルキル基、フェニル基、トリル基等のアリール基、ベンジル基、フェネチル基等のアラルキル基などを挙げることができる他、３−アミノプロピル基、３−［（２−アミノエチル）アミノ］プロピル基などのアミノ置換アルキル基、３−カルボキシプロピル基等のカルボキシ置換アルキル基などが挙げられる。また、トリフロロプロピル基やノナフロロオクチル基などのように一部の水素がハロゲンに置換された物も挙げられる。
【００２２】
Ｑはエーテル結合及びエステル結合を含有しても良い炭素数３〜２０の二価有機基を表し、具体例としては、−（ＣＨ_２）_２−、−（ＣＨ_２）_３−、−ＣＨ_２ＣＨ（ＣＨ_３）ＣＨ_２−、−（ＣＨ_２）_４−、−（ＣＨ_２）_５−、−（ＣＨ_２）_６−、−（ＣＨ_２）_７−、−（ＣＨ_２）_８−、−（ＣＨ_２）_２−ＣＨ（ＣＨ_２ＣＨ_２ＣＨ_３）−、−ＣＨ_２−ＣＨ（ＣＨ_２ＣＨ_３）−、−（ＣＨ_２）_３−Ｏ−（ＣＨ_２）_２−、−（ＣＨ_２）_３−Ｏ−（ＣＨ_２）_２−Ｏ−（ＣＨ_２）_２−、−（ＣＨ_２）_３−Ｏ−ＣＨ_２ＣＨ（ＣＨ_３）−、−ＣＨ_２−ＣＨ（ＣＨ_３）−ＣＯＯ（ＣＨ_２）_２−等を挙げることができる。
【００２３】
Ｇ^２はモノグリセリンあるいはポリグリセリン残基であり、下記一般式（３）、（４）および（５）で表される有機基で代表される。（３）、（４）および（５）式中のｓ、ｔ、ｕおよびｖは１〜２０の整数であり、モノグリセリン、ジグリセリン、トリグリセリン、テトラグリセリン、オクタグリセリン、デカグリセリン、ヘキサデカグリセリン、オクタデカグリセリン等のポリグリセリン、更に、ポリグリセリンの水酸基の一部がアルコキシ基あるいはエステル基で置換されていても良い。
【００２４】
【化３】

【００２５】
【化４】

【００２６】
【化５】

【００２７】
ｓ、ｔ、ｕおよびｖは１〜２０の整数であり、好ましくは１〜４の整数であり、さらに好ましくはｓ、ｔおよびｕ＋ｖの合計が２であるトリグリセリンである。
【００２８】
前記ａは２以上１００以下の整数であり、好ましくは１０〜６０である。またｂは０以上１００以下の整数である。ｃは２以上１００以下の整数であるが、繰り返し単位のｃが大きいと粘度が高くなり使用性が悪くなることから、好ましくは３〜３０である。
【００２９】
一般式（２）におけるグリセリン誘導体変性シリコーン中のモノグリセリンあるいはポリグリセリン残基Ｇ^２の含有量は３〜３０重量％が好ましく、更に、好ましくは５〜２０重量％である。モノグリセリンあるいはポリグリセリン残基Ｇ^２のの含有量が３０重量％を超えると、グリセリン誘導体変性シリコーンのシリコーン溶剤への溶解性が乏しいものとなり、３重量％未満であると洗浄力が不足するおそれがある。
【００３０】
本発明の一般式（１）の多価アルコール変性シリコーン化合物は、下記一般式（６）で示されるオルガノハイドロジェンポリシロキサンと、たとえば（ａ）または（ｂ）で表されるトリグリセリンアリルエーテル化合物、白金触媒又はロジウム触媒の存在下に付加反応させることにより容易に合成することができる。
Ｒ^１ _ｐＨ_ｑＳｉＯ_{（４−ｐ−ｑ）／２} （６）
【００３１】
ＣＨ_２＝ＣＨＣＨ_２ＯＣＨ（ＣＨ_２ＯＣＨ_２ＣＨ（ＯＨ）ＣＨ_２ＯＨ）_２ （ａ）
ＣＨ_２＝ＣＨＣＨ_２ＯＣＨ_２ＣＨ（ＯＨ）ＣＨ_２Ｏ（ＣＨ_２ＣＨ（ＯＨ）ＣＨ_２Ｏ）_３ＣＨ_２ＣＨ＝ＣＨ_２ （ｂ）
【００３２】
なお、触媒の使用量は触媒量とすることができるが、白金又はロジウム量で５０ｐｐｍ以下であることが好ましく特に２０ｐｐｍ以下であることが好ましい。上記付加反応は、必要に応じて有機溶剤中で行ってもよい。
【００３３】
有機溶剤としては、例えばメタノール、エタノール、２−プロパノール、ブタノール等の脂肪族アルコール、トルエン、キシレン等の芳香族炭化水素、ｎ−ペンタン、ｎ−ヘキサン、シクロヘキサン等の脂肪族または脂環式炭化水素、ジクロロメタン、クロロホルム、四塩化炭素等のハロゲン化炭化水素等が挙げられる。付加反応条件は特に限定されるものではないが、８０〜１２０℃で１〜１０時間反応させることが好ましい。
【００３４】
本発明の一般式（２）の多価アルコール変性シリコーン化合物は、例えば下記式（７）で示されるα、ω−オルガノハイドロジェンポリシロキサンと、下記式（ｉ）あるいは（ｉｉ）で表されるトリグリセリンジアリルエーテル化合物を、白金触媒又はロジウム触媒の存在下に付加反応させることにより容易に合成することができる。
【００３５】
【化６】

【００３６】
【化７】

【００３７】
【化８】

【００３８】
（ｉ）あるいは（ｉｉ）で表されるトリグリセリンジアリルエーテル化合物はグリセリンにアルカリ触媒存在下、グリシドールを徐々に滴下することで得ることができる。反応温度は６０〜１２０℃に制御することが好ましく、反応後触媒を中和した後、低沸分を留去することによって得ることができる。
【００３９】
このような方法によって得られたトリグリセリンジアリルエーテルは式（ｉ）および（ｉｉ）構造の混合物と考えられ、代表的な物性値は粘度３３０ｍｍ^２／ｓ であり、水酸基価５２３ＫＯＨｍｇ／ｇ、不飽和度が６．１３ｍｅｑ／ｇの淡黄色液状物である。水酸基価および不飽和度はほぼ理論値（それぞれ５２５、６．２４）通りとなっており、この方法で得られるジアリルエーテル体は精度の良い２官能のグリセリン誘導体である。
【００４０】
さらに高重合度のジアリルエーテル体を得るためにはグリセリンの代わりにジグリセリンあるいはトリグリセリンを使用することで合成が可能である。
【００４１】
α、ω−オルガノハイドロジェンポリシロキサン（５）と上記一般式（ｉ）あるいは（ｉｉ）などで表されるポリグリセリンジアリルエーテル化合物との合計の混合割合は、α、ω−オルガノハイドロジェンポリシロキサンのＳｉＨ基とポリグリセリンジアリルエーテル化合物のＣＨ＝ＣＨ_２基とのモル比で０．５≦α、ω−オルガノハイドロジェンポリシロキサン／ポリグリセリンジアリルエーテル化合物＜１．０、好ましくは０．８≦α、ω−オルガノハイドロジェンポリシロキサン／ポリグリセリンジアリルエーテル化合物＜１．０である。
【００４２】
上記付加反応は、白金触媒又はロジウム触媒の存在下で行なうことが好ましく、具体的には塩化白金酸、アルコール変性塩化白金酸、塩化白金酸−ビニルシロキサン錯体等の触媒が好適に使用される。
【００４３】
なお、触媒の使用量は触媒量とすることができるが、白金又はロジウム量で５０ｐｐｍ以下であることが好ましく特に２０ｐｐｍ以下であることが好ましい。上記付加反応は、必要に応じて有機溶剤中で行ってもよい。有機溶剤としては、例えばメタノール、エタノール、２−プロパノール、ブタノール等の脂肪族アルコール、トルエン、キシレン等の芳香族炭化水素、ｎ−ペンタン、ｎ−ヘキサン、シクロヘキサン等の脂肪族または脂環式炭化水素、ジクロロメタン、クロロホルム、四塩化炭素等のハロゲン化炭化水素等が挙げられる。付加反応条件は特に限定されるものではないが、還流下で１〜１０時間反応させることが好ましい。
【００４４】
本発明のドライクリーニング用洗浄剤組成物にはシリコーン溶剤、多価アルコール変性シリコーンの他に必要に応じて公知の界面活性剤を併用しても差し支えない。この場合、シリコーン溶剤との相溶性を考慮してシリコーン系界面活性剤が好ましい。シリコーン系界面活性剤としてはアニオン系シリコーン界面活性剤、ノニオン系シリコーン界面活性剤、カチオン系シリコーン界面活性剤及び両性シリコーン界面活性剤が挙げられる。
【００４５】
アニオン系シリコーン界面活性剤としてはカルボン酸塩変性シリコーン、スルホン酸塩変性シリコーン，硫酸エステル塩変性シリコーン及びリン酸エステル塩等が挙げられる。ノニオン系シリコーン界面活性剤としては、ポリオキシアルキレンアルキルエーテル変性シリコーン，ポリオキシアルキレン脂肪酸エステル変性シリコーンなどが挙げられる。カチオン系シリコーン界面活性剤の例としては４級アンモニウム変性シリコーンが挙げられ、両性シリコーン界面活性剤としてはベタイン変性シリコーンを挙げることができる。
【００４６】
本発明のドライクリーニング用洗浄剤組成物において、シリコーンと相溶するシリコーン系界面活性剤は０．１〜５重量％含有されることが必要である。０．１重量％未満では洗浄力が不足したり、被洗浄物にシミを生じる可能性がある。５重量％を超えて含有させると界面活性剤が被洗浄物に残存付着し、仕上り品の風合いが損なわれる可能性がある。
【００４７】
本発明のドライクリーニング用洗浄剤組成物は、溶剤に浸漬して衣料の洗浄を行いその後、脱液、乾燥する、従来の石油系炭化水素溶剤を使用するドライクリーニング方法に使用可能である。洗浄方法としては浸漬、洗浄の他、噴霧洗浄、超音波洗浄などが挙げられ、脱液方法としては遠心脱液、ローラーによる絞り脱液等が挙げられ、乾燥法としては風乾、減圧乾燥、温風乾燥及び加熱乾燥などが挙げられる。
【００４８】
本発明のドライクリーニング用洗浄剤組成物においては、ドライクリーニング後の衣類への溶剤臭の残存量を極力低減させるために、使用する多価アルコール変性シリコーンに無臭化処理を施した後、ドライクリーニング用洗浄剤組成物として使用してもよい。無臭化の方法は公知の手法で行えばよく、その方法は特願平２００１−００２５５８に記載されている。
【００４９】
【発明の効果】
【発明の効果】
本発明のドライクリーニング用洗浄剤組成物及びこれを使用するドライクリーニング方法は汚れの除去性能が良好で、その組成物は安全性に優れ、仕上がった衣類の風合いが良好で、オゾン層を破壊することがなく、皮膚刺激性も少なく、衣類のドライクリーニング用洗浄剤組成物として好適である。
【００５０】
【実施例】
下記記載されているシリコーン及び多価アルコール変性シリコーンを下記表１に記載された割合で混合して得た各組成物について、相溶性を目視観察し，その結果を表１に示した。なお、相溶性は下記の基準で評価した。
【００５１】
○：相溶した、×：相溶しなかった。
【表１】

【００５２】
多価アルコール変性シリコーン１
【化９】

（多価アルコール置換基含有量 １６％）
【００５３】
多価アルコール変性シリコーン２
【化１０】

（多価アルコール置換基含有量 １０％）
【００５４】
多価アルコール変性シリコーン３
【化１１】

（多価アルコール置換基含有量 １７％）
多価アルコール変性シリコーン４
【化１２】

（多価アルコール置換基含有量 ４０％）
【００５５】
ポリオキシエチレン変性シリコーン１
【化１３】

【００５６】
シリコーンの記号はそれぞれ下記に示すとおりである。
Ｄ５：オクタメチルシクロペンタシロキサン
Ｍ２Ｄ：オクタメチルトリシロキサン
Ｍ２Ｄ２：デカメチルテトラシロキサン
Ｍ２Ｄ３：ドデカメチルペンタシロキサン
Ｍ３Ｔ：トリス（トリメチルシロキシ）メチルシラン
Ｍ４Ｑ：テトラキス（トリメチルシロキシ）シラン
【００５７】
（実施例２及び比較例２、洗浄性試験）
０．５ｇの食用油を付着させたポリエステル布または綿布（１５ｃｍ×１５ｃｍ）を表１の組成物１〜８の組成物及び比較例２の組成物の各１リットル中に浸し、錨型攪拌羽で、４０℃で１５分間，１００ｒｐｍで攪拌、洗浄した。洗浄後、遠心脱水機で脱水後、６０℃の乾燥機で１時間かけて乾燥した。乾燥後の被洗浄物の洗浄結果を表２に示した。洗浄効果の評価は目視で付着物（汚れ）の残存の有無を洗浄性として評価し、風合い及び溶剤臭（残臭）については官能性試験により評価した。なお、食用油を付着させた場合の洗浄試験結果を表２に示した。洗浄後の素材の変色および変質はいずれの揚合も観察されなかった。洗浄効果（目視）、風合い、残存溶剤臭の有無は下記の基準で評価した。
【００５８】
【表２】

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a novel cleaning composition for dry cleaning that is excellent in cleaning effect, does not destroy the ozone layer, and is excellent in safety, and a dry cleaning method using the same.
[0002]
[Prior art]
In a dry cleaning cleaning method for cleaning clothes and the like using a solvent, a chlorine-based solvent represented by Freon, perchlorethylene, and trichloroethane, and a petroleum-based solvent represented by paraffin and naphthene have been widely used. However, chlorofluorocarbon and chlorinated solvents are nonflammable and have excellent properties such as high drying speed. However, they are a cause of ozone depletion and groundwater contamination, and are used from the standpoint of protecting the global environment. Is in a severely restricted direction.
[0003]
In addition, the allowable concentration of petroleum-based solvents is set strictly from the viewpoint of the working environment, and sufficient attention must be paid to solvent poisoning. Therefore, a solvent system using volatile silicone as an alternative cleaning agent has been studied.
[0004]
For example, Japanese Patent Laid-Open No. 61-119765 (Patent Document 1) describes that a cyclic siloxane alone or a mixture of this with a petroleum hydrocarbon solvent is used as a cleaning solvent, and Japanese Patent Laid-Open No. 6-327888 (Patent Document 2). ) Describes a dry cleaning method using volatile linear polysiloxane. However, it has been pointed out that silicone is a cause of electrostatic ignition due to its large volume resistivity. Therefore, JP 2000-290689 A (Patent Document 3) proposes to add an ether carboxylic acid type anionic surfactant as a surfactant to be dissolved in silicone in order to prevent electrostatic ignition. Among them, it is described that oil-based dirt such as motor oil adhering to clothing is excellent, but it is insufficient for removing water-soluble dirt such as sweat.
[0005]
In addition, surfactants usually used for dry cleaning do not usually dissolve in silicone solvents, and there is a concern about irritation to the skin, etc., and there is a need for surfactants that are milder and capable of dissolving in silicone. It was done. Therefore, in order to solve these problems, the use of polyoxyalkylene-modified silicone surfactants is disclosed in Japanese Patent Nos. 3338429, 3294596, 2000-313900, 2000-319694, and 2002-180091 (patent). Documents 4 to 8) are proposed. However, although cleaning using these surfactants shows improvement in cleaning properties, the finish of the clothes after dry cleaning is not limited to Japanese Patent Laid-Open No. 2002-180091 (Patent Document 8) proposed by the present inventor. There was no description, and further improvements were desired.
[0006]
[Patent Document 1]
Japanese Patent Laid-Open No. 61-119765 [Patent Document 2]
JP-A-6-327888 [Patent Document 3]
JP 2000-290689 A [Patent Document 4]
Japanese Patent No. 3338429 (International Publication No. 00/04221)
[Patent Document 5]
Japanese Patent No. 3294596 (International Publication No. 00/04222)
[Patent Document 6]
JP 2000-313900 A [Patent Document 7]
JP 2000-319694 A [Patent Document 8]
JP, 2002-180091, A [Problems to be solved by the invention]
[0007]
The object of the present invention is to improve the above-mentioned problems, good removal performance of oily and fat stains and water-soluble stains, excellent safety, little residual solvent odor to clothing, good texture of finished clothing, ozone layer An object of the present invention is to provide a cleaning composition for dry cleaning with less skin irritation and a dry cleaning method using the same.
[Means for Solving the Problems]
[0008]
The present invention provides (A) at least one silicone selected from the group consisting of decamethylcyclopentasiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, tris (trimethylsiloxy) methylsilane and tetrakis (trimethylsiloxy) silane. Solvent 95-99.9% by weight, and (B) a polyhydric alcohol-modified silicone dissolved in component (A) and modified with a glycerin derivative, the content of the polyhydric alcohol substituent derived from the glycerin derivative 0.1 to 5% by weight of polyhydric alcohol-modified silicone which is 3 to 30% by weight of the weight of component (B)
And a dry cleaning method using the same.
[0009]
DETAILED DESCRIPTION OF THE INVENTION
The present invention will be described in detail below.
(A) Silicone solvent The silicone solvent as the component (A) of the present invention may be volatile, and examples thereof include linear organopolysiloxanes, cyclic organopolysiloxanes, and branched organopolysiloxanes. Examples of linear organopolysiloxanes include hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, tetradecamethylhexasiloxane, 1,3-dipropyltetramethyldisiloxane, 3- Examples thereof include propylheptamethyltrisiloxane and 3-hexylheptamethyltrisiloxane.
[0010]
Examples of the cyclic organopolysiloxane include octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, propylheptamethylcyclotetrasiloxane, 1,5-dipropylhexamethylcyclotetrasiloxane, and the like. Examples of branched organopolysiloxanes include tristrimethylsiloxyethylsilane, tristrimethylsiloxypropylsilane, tristrimethylsiloxybutylsilane, tristrimethylsiloxypentylsilane, tristrimethylsiloxyhexylsilane, tristrimethylsiloxyheptylsilane, tristrimethylsiloxyoctyl. Examples include silane, tristrimethylsiloxynonylsilane, tristrimethylsiloxydecylsilane, tristrimethylsiloxydodecylsilane, tristrimethylsiloxytetradecylsilane, tristrimethylsiloxyhexadecylsilane, tristrimethylsiloxyoctadecylsilane, tetrakis (trimethylsiloxy) silane .
[0011]
Of these, decamethylcyclopentasiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, tris (trimethylsiloxy) methylsilane, and tetrakis (trimethyl) from the viewpoint of availability of raw materials and economy. Siloxy) silane is preferred.
[0012]
As a use form, it can be used by 1 type in these or the combination of 2 or more types. If necessary, ethanol such as ethanol and 2-propanol, ethers such as butyl cellosolve and butyl carbitol acetate, and petroleum solvents such as naphthene and isoparaffin may be used in combination.
[0013]
(B) Polyhydric alcohol-modified silicone The polyhydric alcohol-modified silicone as the component (B) in the present invention requires a silicone compound having a polyhydric alcohol such as a glycerin derivative or a sugar derivative in its structure. ) Or (2) is particularly preferred.
R ¹ _p G ¹ _q SiO _{(4-pq) / 2} (1)
[R ¹ is a monovalent hydrocarbon group having 1 to 10 carbon atoms which does not have an aliphatic unsaturated bond, G ¹ is a glycerol derivative substituent represented by the general formula —R ³ —O—R ⁴ , and R ³ is an ether bond. And a divalent hydrocarbon group having 2 to 20 carbon atoms which may contain an ester bond, R ⁴ represents a polyhydric alcohol substituent having at least two hydroxyl groups, and p and q are 0 ≦ p <3. 0, 0 <q <3.0, and a positive number satisfying 0 <p + q ≦ 3.0. ]
[0014]
Specific examples of R ¹ include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, Other examples include alkyl groups such as hexadecyl group, octadecyl group and behenyl group, cycloalkyl groups such as cyclopentyl group and cyclohexyl group, aryl groups such as phenyl group and tolyl group, aralkyl groups such as benzyl group and phenethyl group, etc. And amino-substituted alkyl groups such as 3-aminopropyl group and 3-[(2-aminoethyl) amino] propyl group, and carboxy-substituted alkyl groups such as 3-carboxypropyl group. Moreover, the thing by which some hydrogen was substituted by the halogen like a trifluoropropyl group, a nonafluoro octyl group, etc. is mentioned.
[0015]
Specific examples of R ³ include — (CH ₂ ) ₂ —, — (CH ₂ ) ₃ —, —CH ₂ CH (CH ₃ ) CH ₂ —, — (CH ₂ ) ₄ —, — (CH ₂ ) ₅ —. ,-(CH ₂ ) ₆ -,-(CH ₂ ) ₇ -,-(CH ₂ ) ₈ -,-(CH ₂ ) ₂ -CH (CH ₂ CH ₂ CH ₃ )-, -CH ₂ -CH (CH _{2 CH 3) -, - (} CH 2) 3 -O- (CH 2) 2 -, - (CH 2) 3 -O- (CH 2) 2 -O- (CH 2) 2 -, - (CH 2 ) ₃ —O—CH ₂ CH (CH ₃ ) —, —CH ₂ —CH (CH ₃ ) —COO (CH ₂ ) ₂ — and the like are exemplified, but not limited thereto.
[0016]
Specific examples of G ¹ include, but are not limited to, substituents represented by the following general formula. S and t in a formula are the integers of 1-20. In addition, a part of the hydroxyl groups in the following substituents may be substituted with an alkoxy group or an ester group.
[0017]
[Chemical 1]

[0018]
The content of the polyhydric alcohol substituent R ⁴ in the glycerin derivative-modified silicone in the general formula (1) is preferably 3 to 30% by weight, and more preferably 5 to 20% by weight. If the content of the polyhydric alcohol substituent R ⁴ exceeds 30% by weight, the solubility of the glycerin derivative-modified silicone in the silicone solvent becomes poor, and if it is less than 3% by weight, the detergency may be insufficient.
[0019]
Furthermore, as the polyhydric alcohol-modified silicone as the component (B), an organopolysiloxane polyglycerin block copolymer represented by the following general formula (2) is used.
[Chemical formula 2]

[0020]
R ² in the formula is a monovalent hydrocarbon group having 1 to 30 carbon atoms that does not have an aliphatic unsaturated bond. Further, R ² may be the same or different and represents an alkyl group having 1 to 30 carbon atoms, an aryl group, an aralkyl group, an amino-substituted alkyl group, or a carboxyl-substituted alkyl group (which may be partially substituted with a halogen). . Q represents a divalent organic radical of 3 to 20 carbon atoms which may contain an ether bond and an ester bond, G ² is a monoglycerol or polyglycerol residues. a is an integer of 2 to 100, and b is an integer of 2 to 100.
[0021]
Specific examples of R ² include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, Hexadecyl group, octadecyl group, behenyl group, and alkyl group partially substituted with halogen. Other examples include cycloalkyl groups such as cyclopentyl group and cyclohexyl group, aryl groups such as phenyl group and tolyl group, aralkyl groups such as benzyl group and phenethyl group, 3-aminopropyl group, 3-[(2- Amino-substituted alkyl groups such as aminoethyl) amino] propyl group and carboxy-substituted alkyl groups such as 3-carboxypropyl group. Moreover, the thing by which some hydrogen was substituted by the halogen like a trifluoropropyl group, a nonafluoro octyl group, etc. is mentioned.
[0022]
Q represents a C3-C20 divalent organic group which may contain an ether bond and an ester bond. Specific examples thereof include — (CH ₂ ) ₂ —, — (CH ₂ ) ₃ —, and —CH _2. CH (CH ₃ ) CH ₂ —, — (CH ₂ ) ₄ —, — (CH ₂ ) ₅ —, — (CH ₂ ) ₆ —, — (CH ₂ ) ₇ —, — (CH ₂ ) ₈ —, — _{(CH 2) 2 -CH (CH} 2 CH 2 CH 3) -, - CH 2 -CH (CH 2 CH 3) -, - (CH 2) 3 -O- (CH 2) 2 -, - (CH 2 _{) 3 -O- (CH 2) 2} -O- (CH 2) 2 -, - (CH 2) 3 -O-CH 2 CH (CH 3) -, - CH 2 -CH (CH 3) -COO ( CH ₂ ) ₂ — and the like.
[0023]
G ² is a monoglycerin or polyglycerin residue, and is represented by an organic group represented by the following general formulas (3), (4) and (5). In the formulas (3), (4) and (5), s, t, u and v are integers of 1 to 20, and monoglycerin, diglycerin, triglycerin, tetraglycerin, octaglycerin, decaglycerin, hexadeca Polyglycerin such as glycerin and octadecaglycerin, and part of the hydroxyl group of polyglycerin may be substituted with an alkoxy group or an ester group.
[0024]
[Chemical 3]

[0025]
[Formula 4]

[0026]
[Chemical formula 5]

[0027]
s, t, u and v are integers of 1 to 20, preferably an integer of 1 to 4, and more preferably triglycerin in which the sum of s, t and u + v is 2.
[0028]
The a is an integer of 2 or more and 100 or less, preferably 10-60. B is an integer of 0 or more and 100 or less. c is an integer of 2 or more and 100 or less, but when c of the repeating unit is large, the viscosity is increased and the usability is deteriorated.
[0029]
Formula (2) the content of monoglycerol or polyglycerol residues G ² glycerin derivative-modified silicone in preferably 3 to 30 wt%, further preferably from 5 to 20 wt%. When the content of the monoglycerol or polyglycerol residues G ² is more than 30 wt%, a fear that becomes as solubility in silicone solvents glycerin derivative-modified silicone is poor, insufficient detergency is less than 3 wt% There is.
[0030]
The polyhydric alcohol-modified silicone compound of the general formula (1) of the present invention includes an organohydrogenpolysiloxane represented by the following general formula (6) and a triglyceryl allyl ether compound represented by, for example, (a) or (b) It can be easily synthesized by an addition reaction in the presence of a platinum catalyst or a rhodium catalyst.
R ¹ _{pH Hq} SiO _{(4-pq) / 2} (6)
[0031]
CH ₂ = CHCH ₂ OCH (CH ₂ OCH ₂ CH (OH) CH ₂ OH) ₂ (a)
_{CH 2 = CHCH 2 OCH 2 CH} (OH) CH 2 O (CH 2 CH (OH) CH 2 O) 3 CH 2 CH = CH 2 (b)
[0032]
In addition, although the usage-amount of a catalyst can be made into a catalytic amount, it is preferable that it is 50 ppm or less by platinum or rhodium amount, and it is especially preferable that it is 20 ppm or less. You may perform the said addition reaction in an organic solvent as needed.
[0033]
Examples of the organic solvent include aliphatic alcohols such as methanol, ethanol, 2-propanol and butanol, aromatic hydrocarbons such as toluene and xylene, and aliphatic or alicyclic hydrocarbons such as n-pentane, n-hexane and cyclohexane. , Halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride and the like. Although addition reaction conditions are not specifically limited, It is preferable to make it react at 80-120 degreeC for 1 to 10 hours.
[0034]
The polyhydric alcohol-modified silicone compound of the general formula (2) of the present invention is represented by, for example, an α, ω-organohydrogenpolysiloxane represented by the following formula (7) and the following formula (i) or (ii): A triglyceryl diallyl ether compound can be easily synthesized by addition reaction in the presence of a platinum catalyst or a rhodium catalyst.
[0035]
[Chemical 6]

[0036]
[Chemical 7]

[0037]
[Chemical 8]

[0038]
The triglyceryl diallyl ether compound represented by (i) or (ii) can be obtained by gradually dropping glycidol into glycerin in the presence of an alkali catalyst. The reaction temperature is preferably controlled to 60 to 120 ° C., and can be obtained by distilling off the low boiling point after neutralizing the post-reaction catalyst.
[0039]
The triglyceryl diallyl ether obtained by such a method is considered to be a mixture of the structures of formulas (i) and (ii), a typical physical property value is a viscosity of 330 mm ² / s, a hydroxyl value of 523 KOHmg / g, unsaturated It is a pale yellow liquid having a degree of 6.13 meq / g. The hydroxyl value and the degree of unsaturation are almost as theoretical values (525 and 6.24, respectively), and the diallyl ether obtained by this method is a highly accurate bifunctional glycerin derivative.
[0040]
Furthermore, in order to obtain a diallyl ether having a high degree of polymerization, synthesis can be performed by using diglycerin or triglycerin instead of glycerin.
[0041]
The total mixing ratio of the α, ω-organohydrogenpolysiloxane (5) and the polyglyceryl diallyl ether compound represented by the general formula (i) or (ii) is α, ω-organohydrogenpolysiloxane. The molar ratio of the SiH group of the polyglycerin diallyl ether compound to CH = CH ₂ group is 0.5 ≦ α, ω-organohydrogenpolysiloxane / polyglyceryl diallyl ether compound <1.0, preferably 0.8 ≦ α, ω-organohydrogenpolysiloxane / polyglycerol diallyl ether compound <1.0.
[0042]
The addition reaction is preferably carried out in the presence of a platinum catalyst or a rhodium catalyst. Specifically, a catalyst such as chloroplatinic acid, alcohol-modified chloroplatinic acid, or chloroplatinic acid-vinylsiloxane complex is preferably used.
[0043]
In addition, although the usage-amount of a catalyst can be made into a catalytic amount, it is preferable that it is 50 ppm or less by platinum or rhodium amount, and it is especially preferable that it is 20 ppm or less. You may perform the said addition reaction in an organic solvent as needed. Examples of the organic solvent include aliphatic alcohols such as methanol, ethanol, 2-propanol and butanol, aromatic hydrocarbons such as toluene and xylene, and aliphatic or alicyclic hydrocarbons such as n-pentane, n-hexane and cyclohexane. , Halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride and the like. Although the addition reaction conditions are not particularly limited, the reaction is preferably performed for 1 to 10 hours under reflux.
[0044]
In addition to the silicone solvent and the polyhydric alcohol-modified silicone, a known surfactant may be used in combination with the cleaning composition for dry cleaning of the present invention as necessary. In this case, a silicone surfactant is preferable in consideration of compatibility with the silicone solvent. Examples of the silicone surfactant include an anionic silicone surfactant, a nonionic silicone surfactant, a cationic silicone surfactant, and an amphoteric silicone surfactant.
[0045]
Examples of the anionic silicone surfactant include carboxylate-modified silicone, sulfonate-modified silicone, sulfate ester-modified silicone, and phosphate ester salt. Nonionic silicone surfactants include polyoxyalkylene alkyl ether-modified silicones, polyoxyalkylene fatty acid ester-modified silicones, and the like. Examples of the cationic silicone surfactant include quaternary ammonium-modified silicone, and examples of the amphoteric silicone surfactant include betaine-modified silicone.
[0046]
In the cleaning composition for dry cleaning of the present invention, it is necessary that the silicone surfactant compatible with silicone is contained in an amount of 0.1 to 5% by weight. If it is less than 0.1% by weight, the cleaning power may be insufficient or the object to be cleaned may be stained. If the content exceeds 5% by weight, the surfactant remains on the object to be cleaned, and the texture of the finished product may be impaired.
[0047]
The cleaning composition for dry cleaning of the present invention can be used in a conventional dry cleaning method using a petroleum hydrocarbon solvent that is immersed in a solvent to wash clothes, and then drained and dried. Examples of the cleaning method include immersion, cleaning, spray cleaning, ultrasonic cleaning, and the like. Examples of the liquid removal method include centrifugal liquid removal and squeezing liquid removal using a roller. Examples of the drying method include air drying, vacuum drying, and warming. Examples include air drying and heat drying.
[0048]
In the cleaning composition for dry cleaning of the present invention, the polyhydric alcohol-modified silicone to be used is subjected to a non-bromide treatment in order to reduce the residual amount of solvent odor to the clothing after dry cleaning, and then dry cleaning is performed. It may be used as a cleaning composition. The bromide-free method may be carried out by a known method, and the method is described in Japanese Patent Application No. 2001-002558.
[0049]
【The invention's effect】
【The invention's effect】
The cleaning composition for dry cleaning of the present invention and the dry cleaning method using the same have good dirt removal performance, the composition is excellent in safety, the texture of the finished clothing is good, and the ozone layer is destroyed. This is suitable as a cleaning composition for dry cleaning of clothing.
[0050]
【Example】
The compatibility of each composition obtained by mixing the following silicone and polyhydric alcohol-modified silicone in the proportions shown in Table 1 was visually observed, and the results are shown in Table 1. The compatibility was evaluated according to the following criteria.
[0051]
○: compatible, ×: not compatible.
[Table 1]

[0052]
Polyhydric alcohol modified silicone 1
[Chemical 9]

(Polyhydric alcohol substituent content 16%)
[0053]
Polyhydric alcohol modified silicone 2
[Chemical Formula 10]

(Polyhydric alcohol substituent content 10%)
[0054]
Polyhydric alcohol modified silicone 3
Embedded image

(Polyhydric alcohol substituent content 17%)
Polyhydric alcohol modified silicone 4
Embedded image

(Polyhydric alcohol substituent content 40%)
[0055]
Polyoxyethylene-modified silicone 1
Embedded image

[0056]
The symbols for silicone are as shown below.
D5: Octamethylcyclopentasiloxane M2D: Octamethyltrisiloxane M2D2: Decamethyltetrasiloxane M2D3: Dodecamethylpentasiloxane M3T: Tris (trimethylsiloxy) methylsilane M4Q: Tetrakis (trimethylsiloxy) silane
(Example 2 and Comparative Example 2, detergency test)
A polyester cloth or cotton cloth (15 cm × 15 cm) to which 0.5 g of edible oil is adhered is immersed in 1 liter of each of the compositions 1 to 8 in Table 1 and the composition of Comparative Example 2, and a bowl-shaped stirring blade The mixture was stirred and washed at 100 rpm for 15 minutes at 40 ° C. After washing, dehydration with a centrifugal dehydrator, followed by drying with a dryer at 60 ° C. for 1 hour. Table 2 shows the results of cleaning the objects to be cleaned after drying. For the evaluation of the cleaning effect, the presence or absence of deposits (dirt) was visually evaluated as cleaning properties, and the texture and solvent odor (residual odor) were evaluated by a sensory test. In addition, Table 2 shows the cleaning test results when edible oil was adhered. Neither discoloration nor alteration of the material after washing was observed. The following criteria evaluated the washing | cleaning effect (visual observation), texture, and the presence or absence of residual solvent odor.
[0058]
[Table 2]

Claims (3)

(A) at least one silicone solvent selected from the group consisting of decamethylcyclopentasiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, tris (trimethylsiloxy) methylsilane and tetrakis (trimethylsiloxy) silane 99.9% by weight , and (B) a polyhydric alcohol-modified silicone dissolved in component (A) and modified with a glycerin derivative , wherein the content of the polyhydric alcohol substituent derived from the glycerin derivative is ( B) Polyhydric alcohol-modified silicone that is 3 to 30% by weight of the component 0.1 to 5% by weight
A cleaning composition for dry cleaning comprising: 2. The cleaning composition for dry cleaning according to claim 1, wherein the content of the polyhydric alcohol substituent in the component (B) is 5 to 20% by weight of the weight of the component (B). A dry cleaning method using the cleaning composition according to claim 1 .