JPH07157489A - Silicon derivative of beta-styrylacrylic acid and its production - Google Patents
Silicon derivative of beta-styrylacrylic acid and its productionInfo
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- JPH07157489A JPH07157489A JP5340044A JP34004493A JPH07157489A JP H07157489 A JPH07157489 A JP H07157489A JP 5340044 A JP5340044 A JP 5340044A JP 34004493 A JP34004493 A JP 34004493A JP H07157489 A JPH07157489 A JP H07157489A
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、長波長域における紫外
線吸収能を有し、特に各種油剤との相溶性を有するた
め、化粧品用紫外線吸収剤として好適に使用されるβ−
スチリルアクリル酸のシリコーン誘導体及びその製造方
法に関する。Industrial Applicability The present invention has an ultraviolet absorbing ability in a long wavelength region, and in particular, is compatible with various oil agents, and is therefore preferably used as an ultraviolet absorbent for cosmetics.
The present invention relates to a silicone derivative of styryl acrylic acid and a method for producing the same.
【０００２】[0002]
【従来の技術及び発明が解決しようとする課題】紫外線
吸収能を有する化合物、即ち紫外線吸収剤は、皮膚の日
焼け止め防止、老化防止などを目的として化粧品などに
配合されるものであり、従来、紫外線吸収剤としては、
ＰＡＢＡ系、桂皮酸系、サリチル酸系、ベンゾフェノン
系等の化合物が知られているが、いずれも液状化の度合
或いは相溶性を高めるために誘導体化がなされている。2. Description of the Related Art A compound having an ultraviolet absorbing ability, that is, an ultraviolet absorbing agent, is a compound to be incorporated into cosmetics for the purpose of preventing sunscreen and aging of the skin. As an ultraviolet absorber,
PABA-based compounds, cinnamic acid-based compounds, salicylic acid-based compounds, benzophenone-based compounds, etc. are known, but all of them are derivatized to enhance the degree of liquefaction or compatibility.
【０００３】上記化合物を誘導体化する方法として、シ
リコーン変性する方法が種々提案されており（特公昭４
４−２９８６６号公報、特開昭６０−５８９９１、６０
−１０８４３１号公報、特開平２−１６７２９１、２−
１１７６１３、３−２０４８８７号公報）、シリコーン
による変性は、特に液状化の度合、撥水性の付与、相溶
性の付与などに優れるという利点がある。As a method of derivatizing the above compound, various methods of modifying with silicone have been proposed (Japanese Patent Publication No. Sho 4).
4-29866, JP-A-60-58991, 60
-108431, JP-A-2-167291, 2-
117, pp. 3-204887), the modification with silicone has an advantage of being particularly excellent in the degree of liquefaction, imparting water repellency, imparting compatibility and the like.
【０００４】しかしながら、このシリコーン誘導体は、
一般にヒドロシリル化反応によって製造されるが、シリ
コーンそのものが酸やアルカリに弱いため、このシリコ
ーン誘導体は中性条件下又は温和な反応条件下で製造す
ることが必要とされ、このためα，β−不飽和カルボニ
ル化合物のβ−スチリルアクリル酸をシリコーンによっ
て変性した場合、収率及び純度を満足させるシリコーン
誘導体を得ることができないという問題がある。また、
シリコーン変性して得られる誘導体の純度が十分でない
ため、精製操作或いは単離操作が困難になるという問題
がある。However, this silicone derivative is
Generally, it is produced by a hydrosilylation reaction, but since silicone itself is weak against acid and alkali, it is necessary to produce this silicone derivative under neutral conditions or mild reaction conditions. When β-styryl acrylic acid which is a saturated carbonyl compound is modified with silicone, there is a problem that a silicone derivative satisfying the yield and purity cannot be obtained. Also,
Since the derivative obtained by silicone modification is not sufficiently pure, there is a problem that the purification operation or the isolation operation becomes difficult.
【０００５】なお、紫外線吸収剤を製造する場合、高収
率かつ高純度で目的生成物を与える反応方法を適用する
ことが重要である。なぜなら、目的生成物の収率が著し
く低い場合には製品のコストを高くすることにつなが
り、また、目的生成物の純度が低い場合には、紫外線吸
収能の低下、相溶性の低下、人体（皮膚）に対する刺激
の増加を引き起こすことにつながるからである。When producing an ultraviolet absorber, it is important to apply a reaction method which gives the desired product in high yield and high purity. This is because, when the yield of the target product is extremely low, it leads to an increase in the cost of the product, and when the purity of the target product is low, the ultraviolet absorption ability is reduced, the compatibility is reduced, and the human body ( This leads to an increase in irritation to the skin).
【０００６】本発明は上記事情に鑑みなされたもので、
長波長域における紫外線吸収能を有し、紫外線吸収剤と
して好適な化合物、及びこの化合物を高収率かつ高純度
で製造し得る製造方法を提供することを目的とする。The present invention has been made in view of the above circumstances.
An object of the present invention is to provide a compound having an ultraviolet absorbing ability in a long wavelength region and suitable as an ultraviolet absorber, and a production method capable of producing this compound in a high yield and a high purity.
【０００７】[0007]
【課題を解決するための手段及び作用】本発明者は上記
目的を達成するため鋭意検討を行った結果、下記一般式
（４）で表される化合物と下記一般式（５）で表される
化合物とを脱酸剤の存在下で反応させる方法、即ちβ−
スチリルアクリル酸化合物とアルコール変性シリコーン
とのエステル化反応によって、下記一般式（１）で表さ
れるシロキサン化合物を得ることができ、しかも、この
反応は低温で行われるためシリコーン鎖が分解すること
がなく、このため高収率かつ高純度（９０％以上）で式
（１）のシロキサン化合物（β−スチリルアクリル酸の
シリコーン誘導体）を得ることができることを見い出し
た。また、得られたβ−スチリルアクリル酸のシリコー
ン誘導体の紫外線吸収能はλMAX［アルコール］＝３０
５ｎｍ以上であり、従来の無置換基の桂皮酸誘導体（λ
MAX［アルコール］＝２７０ｎｍ付近）よりも長波長域
での紫外線吸収能が向上し、ＵＶＢ波（２９０〜３２０
ｎｍ）のみを吸収する従来の桂皮酸系紫外線吸収剤より
も広い吸収帯（ＵＶＢ波からＵＶＡ波（３２０〜３５０
ｎｍ）まで）を持ち、また、各種油剤に対する相溶性も
炭化水素系油剤からシリコーン系油剤に至る広範囲での
相溶性を有するため、皮膚の日焼け止めや老化防止など
を目的として化粧品などに添加し、紫外線吸収剤として
好適に使用し得ることを知見し、本発明をなすに至った
ものである。Means and Actions for Solving the Problems As a result of intensive studies for achieving the above-mentioned object, the present inventor has shown that the compound represented by the following general formula (4) and the compound represented by the following general formula (5). A method of reacting a compound with a deoxidizing agent, that is, β-
A siloxane compound represented by the following general formula (1) can be obtained by an esterification reaction between a styryl acrylic acid compound and an alcohol-modified silicone, and since this reaction is performed at a low temperature, the silicone chain may be decomposed. Therefore, it was found that the siloxane compound of formula (1) (silicone derivative of β-styrylacrylic acid) can be obtained in high yield and high purity (90% or more). The ultraviolet absorption capacity of the obtained silicone derivative of β-styrylacrylic acid was λ MAX [alcohol] = 30
5 nm or more, the conventional unsubstituted cinnamic acid derivative (λ
UV absorption in the long wavelength range is improved compared to MAX [alcohol] = around 270 nm), and UVB waves (290 to 320)
a wider absorption band (UVB wave to UVA wave (320 to 350) than that of a conventional cinnamic acid type ultraviolet absorber that absorbs only nm).
Since it has a wide range of compatibility from hydrocarbon-based oil agents to silicone-based oil agents, it is added to cosmetics for the purpose of preventing sunscreen and aging of the skin. The present invention has been completed by finding that it can be suitably used as an ultraviolet absorber.
【０００８】[0008]
【化５】 （式中、Ｒ1は炭素数１〜１８のアルキル基又はアリー
ル基、Ｒ2は下記式（２）、（３）で表される基及びＲ1
と同様の基から選択される基であるが、Ｒ2のうち少な
くとも一つは下記式（２）又は（３）で表される基であ
る。ｍ及びｎは０〜１０００の整数である。）[Chemical 5] (In the formula, R 1 is an alkyl group or aryl group having 1 to 18 carbon atoms, R 2 is a group represented by the following formulas (2) and (3), or R 1
A group selected from the same groups as in, but at least one of R 2 is a group represented by the following formula (2) or (3). m and n are integers of 0 to 1000. )
【０００９】[0009]
【化６】 （式中、Ｒ3は炭素数１〜１１のアルキレン基、Ｒ4はＣ
Ｈ3、ＣＨ3Ｏ、Ｆ、Ｃｌ、Ｂｒ及びＩから選択される基
であり、ｋは０〜５の整数である。）[Chemical 6] (In the formula, R 3 is an alkylene group having 1 to 11 carbon atoms, and R 4 is C
It is a group selected from H 3 , CH 3 O, F, Cl, Br and I, and k is an integer of 0-5. )
【００１０】[0010]
【化７】 （式中、Ｒ4及びｋは上記と同様の意味を示し、ＸはＣ
ｌ、Ｂｒ及びＣＦ3ＣＯから選択される基である。）[Chemical 7] (In the formula, R 4 and k have the same meanings as described above, and X is C
It is a group selected from 1, Br and CF 3 CO. )
【００１１】[0011]
【化８】 （式中、Ｒ1、ｍ及びｎは上記と同様の意味を示し、Ｒ5
は−Ｒ3 ＯＨ、−Ｒ3 ＯＣＨ2ＣＨ2ＯＨ（Ｒ3は上記と同
様の意味を示す）及びＲ1と同様の基から選択される基
であり、Ｒ5のうち少なくとも一つは−Ｒ3 ＯＨ又は−Ｒ
3 ＯＣＨ2ＣＨ2ＯＨである。）[Chemical 8](In the formula, R1, M and n have the same meanings as described above, and RFive
Is -R3 OH, -R3 OCH2CH2OH (R3Is the same as above
And R)1Groups selected from groups similar to
And RFiveAt least one is -R3 OH or -R
3 OCH2CH2It is OH. )
【００１２】従って、本発明は、上記一般式（１）で表
されるβ−スチリルアクリル酸のシリコーン誘導体、並
びに、上記一般式（４）で表されるβ−スチリルアクリ
ル酸化合物と下記一般式（５）で表されるアルコール変
性シリコーン化合物とを脱酸剤の存在下で反応させるこ
とを特徴とする上記一般式（１）で表されるβ−スチリ
ルアクリル酸のシリコーン誘導体の製造方法を提供す
る。Therefore, the present invention provides a silicone derivative of β-styrylacrylic acid represented by the above general formula (1), a β-styrylacrylic acid compound represented by the above general formula (4) and the following general formula: A method for producing a silicone derivative of β-styrylacrylic acid represented by the above general formula (1), which comprises reacting the alcohol-modified silicone compound represented by (5) in the presence of a deoxidizing agent. To do.
【００１３】以下、本発明を更に詳しく説明すると、本
発明のシロキサン化合物は下記一般式（１）で表される
ものである。The present invention will be described in more detail below. The siloxane compound of the present invention is represented by the following general formula (1).
【００１４】[0014]
【化９】 [Chemical 9]
【００１５】ここで、Ｒ1は炭素数１〜１８、好ましく
は１〜８のアルキル基又はアリール基であり、アルキル
基としてはメチル基、エチル基、プロピル基、ブチル
基、ヘキシル基などが挙げられ、アリール基としてはフ
ェニル基、トリル基などが挙げられる。Ｒ2は下記式
（２）、（３）で表される基及びＲ1と同様の基から選
択される基であるが、Ｒ2のうち少なくとも一つは下記
式（２）又は（３）で表される基である。Here, R 1 is an alkyl group or an aryl group having 1 to 18 carbon atoms, preferably 1 to 8 carbon atoms, and examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group and a hexyl group. Examples of the aryl group include a phenyl group and a tolyl group. R 2 is a group selected from the groups represented by the following formulas (2) and (3) and the same group as R 1, and at least one of R 2 is represented by the following formula (2) or (3) Is a group represented by.
【００１６】[0016]
【化１０】 [Chemical 10]
【００１７】上記式（２）及び（３）においてＲ3は炭
素数１〜１１、好ましくは炭素数３〜８のアルキレン基
であり、アルキレン基としてはエチレン基、トリメチレ
ン基、プロピレン基などが挙げられる。Ｒ3は少なくと
も一つの不斉炭素を有することが好ましく、この点か
ら、Ｒ3としては特に−ＣＨ2ＣＨ（ＣＨ3）ＣＨ2ＣＨ2
−、−ＣＨ2ＣＨ（ＣＨ3）ＣＨ−が好ましい。In the above formulas (2) and (3), R 3 is an alkylene group having 1 to 11 carbon atoms, preferably 3 to 8 carbon atoms. Examples of the alkylene group include ethylene group, trimethylene group and propylene group. To be R 3 preferably has at least one asymmetric carbon, and in this respect, R 3 is particularly —CH 2 CH (CH 3 ) CH 2 CH 2
-, - CH 2 CH (CH 3) CH- are preferred.
【００１８】Ｒ4はＣＨ3、ＣＨ3Ｏ、Ｆ、Ｃｌ、Ｂｒ及
びＩから選択される基である。また、上記式（１）にお
いてｍ及びｎは０〜１０００、好ましくはｍ及びｎは０
〜１００の整数であり、上記式（２）及び（３）におい
てｋは０〜５の整数である。R 4 is a group selected from CH 3 , CH 3 O, F, Cl, Br and I. In the above formula (1), m and n are 0 to 1000, preferably m and n are 0.
Is an integer of 100, and k is an integer of 0 to 5 in the above formulas (2) and (3).
【００１９】上記式（１）で表されるβ−スチリルアク
リル酸のシリコーン誘導体を得るための製造方法は、下
記一般式（４）で表されるβ−スチリルアクリル酸化合
物と、下記一般式（５）で表されるアルコール変性シリ
コーン化合物とを脱酸剤の存在下で反応させるものであ
る。The production method for obtaining the silicone derivative of β-styrylacrylic acid represented by the above formula (1) is as follows: a β-styrylacrylic acid compound represented by the following general formula (4); An alcohol-modified silicone compound represented by 5) is reacted in the presence of a deoxidizing agent.
【００２０】[0020]
【化１１】 （式中、Ｒ4及びｋは上記と同様の意味を示し、ＸはＣ
ｌ、Ｂｒ及びＣＦ3ＣＯから選択される基である。）[Chemical 11] (In the formula, R 4 and k have the same meanings as described above, and X is C
It is a group selected from 1, Br and CF 3 CO. )
【００２１】[0021]
【化１２】 （式中、Ｒ1、ｍ及びｎは上記と同様の意味を示し、Ｒ5
は−Ｒ3 ＯＨ、−Ｒ3 ＯＣＨ2ＣＨ2ＯＨ（Ｒ3は上記と同
様の意味を示す）及びＲ1と同様の基から選択される基
であり、Ｒ5のうち少なくとも一つは−Ｒ3 ＯＨ又は−Ｒ
3 ＯＣＨ2ＣＨ2ＯＨである。）[Chemical 12](In the formula, R1, M and n have the same meanings as described above, and RFive
Is -R3 OH, -R3 OCH2CH2OH (R3Is the same as above
And R)1Groups selected from groups similar to
And RFiveAt least one is -R3 OH or -R
3 OCH2CH2It is OH. )
【００２２】ここで、上記式（４）で表される化合物と
しては下記のものが例示される。Examples of the compound represented by the above formula (4) include the following.
【００２３】[0023]
【化１３】 [Chemical 13]
【００２４】また、上記式（５）で表される化合物とし
ては下記のものが例示される。The following are examples of compounds represented by the above formula (5).
【００２５】[0025]
【化１４】 [Chemical 14]
【００２６】上記式（４）で表される化合物と上記式
（５）で表される化合物の使用割合は、モル比で１：１
〜３とすることが好ましい。The compound represented by the above formula (4) and the compound represented by the above formula (5) are used in a molar ratio of 1: 1.
It is preferable to set to 3.
【００２７】脱酸剤としては、ピリジン、トリエチルア
ミン、４−ジメチルアミノピリジン、Ｎ，Ｎ−ジメチル
ベンジルアミン、酢酸ナトリウム及び酢酸カリウムから
選択される有機塩基を使用することができ、特にピリジ
ンを用いることが好ましい。As the deoxidizing agent, an organic base selected from pyridine, triethylamine, 4-dimethylaminopyridine, N, N-dimethylbenzylamine, sodium acetate and potassium acetate can be used, and pyridine is particularly preferably used. Is preferred.
【００２８】この脱酸剤の使用量は式（４）で表される
化合物１モルに対して１〜２モルとすることが好まし
い。The amount of the deoxidizing agent used is preferably 1 to 2 mol per 1 mol of the compound represented by the formula (4).
【００２９】上記式（４）の化合物と上記式（５）の化
合物の反応は、有機溶媒中で加熱することによって行う
ことができ、この場合、有機溶媒としては脂肪族炭化水
素系溶媒及び芳香族系溶媒のいずれも使用することがで
きるが、特にトルエン、ヘキサンを用いることが好まし
い。The reaction of the compound of the above formula (4) with the compound of the above formula (5) can be carried out by heating in an organic solvent. In this case, the organic solvent is an aliphatic hydrocarbon solvent or an aromatic compound. Although any of the group-based solvents can be used, it is particularly preferable to use toluene or hexane.
【００３０】この有機溶媒の使用量は全量に対して３０
〜２００重量％とすることが好ましい。また、反応は温
度６０〜１００℃、４〜８時間の条件で行うことができ
る。The amount of this organic solvent used is 30 with respect to the total amount.
It is preferable to be set to ˜200 wt%. Further, the reaction can be carried out under the conditions of a temperature of 60 to 100 ° C. and a time of 4 to 8 hours.
【００３１】[0031]
【発明の効果】本発明によれば、広い範囲の長波長域に
おいて紫外線吸収能を有する高純度のβ−スチリルアク
リル酸のシリコーン誘導体を高収率で製造することがで
き、得られたβ−スチリルアクリル酸のシリコーン誘導
体は各種油剤との相溶性に優れるため、化粧品用の紫外
線吸収剤などとして好適に使用される。According to the present invention, a high-purity silicone derivative of β-styrylacrylic acid having an ultraviolet absorption ability in a wide range of long wavelengths can be produced in a high yield, and the obtained β- Since the silicone derivative of styryl acrylic acid has excellent compatibility with various oil agents, it is preferably used as an ultraviolet absorber for cosmetics.
【００３２】[0032]
【実施例】以下、実施例を示し、本発明を具体的に説明
するが、本発明は下記の実施例に制限されるものではな
い。EXAMPLES The present invention will now be specifically described with reference to examples, but the present invention is not limited to the following examples.
【００３３】［実施例］３−メチル−３−ブテン−１−
オール１０６ｇ（１．２モル）、トルエン８６０ｇ、白
金触媒２．９ｇ（白金換算１１ｐｐｍ）の溶液を８０℃
に加熱しながら、下記式（６）で表される化合物３２８
ｇ（１．５モル）を滴下し、５時間かけて付加反応を行
った。反応後、溶液を活性炭処理し、減圧蒸留すること
により下記式（７）で表されるアルコール変性シリコー
ン２９７ｇを得た（収率７８％、沸点９０〜９４℃／２
ｍｍＨｇ）。[Example] 3-Methyl-3-butene-1-
A solution of 106 g (1.2 mol) of all, 860 g of toluene, and 2.9 g of platinum catalyst (11 ppm in terms of platinum) at 80 ° C.
Compound 328 represented by the following formula (6) while being heated to
g (1.5 mol) was added dropwise, and the addition reaction was performed for 5 hours. After the reaction, the solution was treated with activated carbon and distilled under reduced pressure to obtain 297 g of an alcohol-modified silicone represented by the following formula (7) (yield 78%, boiling point 90 to 94 ° C / 2.
mmHg).
【００３４】[0034]
【化１５】 [Chemical 15]
【００３５】次に、β−スチリルアクリル酸２０ｇ
（０．１１モル）をトルエン８０ｇに溶解した溶液を７
０℃に加熱、撹拌しながら、塩化チオニル２０ｇ（０．
１７モル）を滴下し、１時間反応させた後、過剰の塩化
チオニルを留出し、そこに上記式（７）のアルコール変
性シリコーン３９ｇ（０．１３モル）、ピリジン１０ｇ
（０．１３モル）の溶液を滴下し、１時間熟成させた。
熟成後、ピリジン塩酸塩を瀘過により取り除き、瀘液を
減圧蒸留することによって、目的とする生成物２８．９
ｇを得た（収率５４％、沸点１９４〜２０５℃／０．５
ｍｍＨｇ）。Next, 20 g of β-styryl acrylic acid
A solution of (0.11 mol) in 80 g of toluene was added to 7
20 g of thionyl chloride (0.
(17 mol) and allowed to react for 1 hour, then excess thionyl chloride was distilled off, and 39 g (0.13 mol) of the alcohol-modified silicone of the above formula (7) and 10 g of pyridine.
A solution of (0.13 mol) was added dropwise and aged for 1 hour.
After aging, pyridine hydrochloride was removed by filtration, and the filtrate was distilled under reduced pressure to give the desired product 28.9.
g was obtained (yield 54%, boiling point 194-1205 ° C./0.5
mmHg).
【００３６】この生成物の1Ｈ−ＮＭＲスペクトルを測
定したところ、下記式（８）で表されるβ−スチリルア
クリル酸変性シリコーンであることがわかった。When the 1 H-NMR spectrum of this product was measured, it was found to be a β-styryl acrylic acid-modified silicone represented by the following formula (8).
【００３７】[0037]
【化１６】 [Chemical 16]
【００３８】（1Ｈ−ＮＭＲスペクトル） ＣＣｌ4基準 δ＝０．１ｐｐｍ （２１Ｈ，ｓ，Ｓｉ−Ｃ
Ｈ3） δ＝０．３〜０．７ｐｐｍ （２Ｈ，ｍ，Ｓｉ−ＣＨ
2） δ＝１．０ｐｐｍ （３Ｈ，ｄ，ＣＨ3） δ＝１．３〜１．９ｐｐｍ （３Ｈ，ｍ，ＣＨ2Ｃ
Ｈ） δ＝４．１ｐｐｍ （２Ｈ，ｔ，ＯＣＨ2） δ＝５．６〜６．９ｐｐｍ （４Ｈ，ｍ，ＣＨ＝Ｃ
Ｈ） δ＝６．９〜７．５０ｐｐｍ （５Ｈ，ｍ，Ｃ6Ｈ5−
Ｈ） 得られたβ−スチリルアクリル酸変性シリコーンは、λ
MAX＝３０５ｎｍ、純度９５％であった。また、このシ
ロキサン化合物は、各種油剤（スクアラン、オレイルア
ルコール、トリ（２−エチルヘキサン酸）グリセリン、
デカメチルシクロペンタシロキサン）に対して優れた相
溶性（５％溶解性）を示した。( 1 H-NMR spectrum) CCl 4 standard δ = 0.1 ppm (21 H, s, Si-C
H 3) δ = 0.3~0.7ppm (2H , m, Si-CH
2 ) δ = 1.0 ppm (3H, d, CH 3 ) δ = 1.3 to 1.9 ppm (3H, m, CH 2 C
H) δ = 4.1 ppm (2H, t, OCH 2 ) δ = 5.6 to 6.9 ppm (4H, m, CH = C
H) δ = 6.9 to 7.50 ppm (5H, m, C 6 H 5 −
H) The obtained β-styryl acrylic acid modified silicone has a λ
MAX = 305 nm, purity 95%. Further, this siloxane compound can be used as various oil agents (squalane, oleyl alcohol, tri (2-ethylhexanoic acid) glycerin,
It showed excellent compatibility (5% solubility) with decamethylcyclopentasiloxane.
Claims (2)
ルアクリル酸のシリコーン誘導体。 【化１】 （式中、Ｒ1は炭素数１〜１８のアルキル基又はアリー
ル基、Ｒ2は下記式（２）、（３）で表される基及びＲ1
と同様の基から選択される基であるが、Ｒ2のうち少な
くとも一つは下記式（２）又は（３）で表される基であ
る。ｍ及びｎは０〜１０００の整数である。） 【化２】 （式中、Ｒ3は炭素数１〜１１のアルキレン基、Ｒ4はＣ
Ｈ3、ＣＨ3Ｏ、Ｆ、Ｃｌ、Ｂｒ及びＩから選択される基
であり、ｋは０〜５の整数である。）1. A silicone derivative of β-styrylacrylic acid represented by the following general formula (1). [Chemical 1] (In the formula, R 1 is an alkyl group or aryl group having 1 to 18 carbon atoms, R 2 is a group represented by the following formulas (2) and (3), or R 1
A group selected from the same groups as in, but at least one of R 2 is a group represented by the following formula (2) or (3). m and n are integers of 0 to 1000. ) [Chemical 2] (In the formula, R 3 is an alkylene group having 1 to 11 carbon atoms, and R 4 is C
It is a group selected from H 3 , CH 3 O, F, Cl, Br and I, and k is an integer of 0-5. )
ルアクリル酸化合物と下記一般式（５）で表されるアル
コール変性シリコーン化合物とを脱酸剤の存在下で反応
させることを特徴とする請求項１記載の一般式（１）で
表されるβ−スチリルアクリル酸のシリコーン誘導体の
製造方法。 【化３】 （式中、Ｒ4及びｋは上記と同様の意味を示し、ＸはＣ
ｌ、Ｂｒ及びＣＦ3ＣＯから選択される基である。） 【化４】 （式中、Ｒ1、ｍ及びｎは上記と同様の意味を示し、Ｒ5
は−Ｒ3 ＯＨ、−Ｒ3 ＯＣＨ2ＣＨ2ＯＨ（Ｒ3は上記と同
様の意味を示す）及びＲ1と同様の基から選択される基
であり、Ｒ5のうち少なくとも一つは−Ｒ3 ＯＨ又は−Ｒ
3 ＯＣＨ2ＣＨ2ＯＨである。）2. β-stilly represented by the following general formula (4):
And an alkyl compound represented by the following general formula (5)
React with Cole-modified silicone compound in the presence of deoxidizer
In the general formula (1) according to claim 1, characterized in that
Of the silicone derivative of β-styrylacrylic acid represented
Production method. [Chemical 3](In the formula, RFourAnd k have the same meanings as above, and X is C
l, Br and CF3It is a group selected from CO. ) [Chemical 4](In the formula, R1, M and n have the same meanings as described above, and RFive
Is -R3 OH, -R3 OCH2CH2OH (R3Is the same as above
And R)1Groups selected from groups similar to
And RFiveAt least one is -R3 OH or -R
3 OCH2CH2It is OH. )
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34004493A JP2850738B2 (en) | 1993-12-07 | 1993-12-07 | Silicone derivative of β-styrylacrylic acid and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34004493A JP2850738B2 (en) | 1993-12-07 | 1993-12-07 | Silicone derivative of β-styrylacrylic acid and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07157489A true JPH07157489A (en) | 1995-06-20 |
| JP2850738B2 JP2850738B2 (en) | 1999-01-27 |
Family
ID=18333198
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP34004493A Expired - Fee Related JP2850738B2 (en) | 1993-12-07 | 1993-12-07 | Silicone derivative of β-styrylacrylic acid and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2850738B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2862640A1 (en) * | 2003-11-25 | 2005-05-27 | Oreal | New methyltrialkylsilanes with a 4,4-diarylbutadiene group e.g. UVA filters in cosmetic or dermatological compositions for sun protection of skin and hair |
| US7229609B2 (en) | 2003-11-25 | 2007-06-12 | L'oreal | Diarylbutadiene-substituted methyltrialkylsilanes and photoprotective compositions comprised thereof |
| WO2011136389A2 (en) | 2010-04-28 | 2011-11-03 | Dow Corning Toray Co., Ltd. | Cosmetic and topical skin preparation comprising higher alcohol-modified silicone |
-
1993
- 1993-12-07 JP JP34004493A patent/JP2850738B2/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2862640A1 (en) * | 2003-11-25 | 2005-05-27 | Oreal | New methyltrialkylsilanes with a 4,4-diarylbutadiene group e.g. UVA filters in cosmetic or dermatological compositions for sun protection of skin and hair |
| EP1535925A1 (en) * | 2003-11-25 | 2005-06-01 | L'oreal | 4,4-Diarylbutadiene functionalized methyltrialkylsilanes and cosmetic or photoprotective dermatological compositions containing them |
| US7229609B2 (en) | 2003-11-25 | 2007-06-12 | L'oreal | Diarylbutadiene-substituted methyltrialkylsilanes and photoprotective compositions comprised thereof |
| US7432386B2 (en) | 2003-11-25 | 2008-10-07 | L'oreal | Diarylbutadiene-substituted methyltrialkylsilanes and photoprotective compositions comprised thereof |
| WO2011136389A2 (en) | 2010-04-28 | 2011-11-03 | Dow Corning Toray Co., Ltd. | Cosmetic and topical skin preparation comprising higher alcohol-modified silicone |
| US9283164B2 (en) | 2010-04-28 | 2016-03-15 | Dow Corning Toray Co., Ltd. | Cosmetic and topical skin preparation comprising higher alcohol-modified silicone |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2850738B2 (en) | 1999-01-27 |
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