WO2002015850A1

WO2002015850A1 - Cosmetic preparation and basic cosmetic product

Info

Publication number: WO2002015850A1
Application number: PCT/JP2001/007151
Authority: WO
Inventors: Tamiko Suga; Mitsuo Okamoto; Yuichi Tokumoto
Original assignee: Nippon Petrochemicals Company Limited
Priority date: 2000-08-23
Filing date: 2001-08-21
Publication date: 2002-02-28
Also published as: JP2002068928A; JP4562882B2

Abstract

A cosmetic preparation containing a product of hydrogenation of a polymer of a C4 olefin, characterized in that the hydrogenation product in 13C-NMR spectrometry gives a signal at 7 to 60 ppm, the proportion of the integrated value for the signal attributable to a tertiary carbon atom to the integrated value for that signal being less than 0.08, and that the hydrogenation product comprises as a major ingredient at least one member selected from the group consisting of olefin polymers having 20, 24, 28, and 32 carbon atoms, respectively; and a basic cosmetic product containing the cosmetic preparation. The cosmetic preparation and basic cosmetic product have excellent stability, contain no ingredients irritating the skin, are colorless and odorless, and are inexpensive.

Description

Description Cosmetics and basic cosmetics Technical field

The present invention includes a hydrogenated product of a putene polymer having a specific chemical structure, has excellent oxidation stability and low skin irritation, and is further characterized by being colorless, odorless, and inexpensive, and is particularly used as a basic cosmetic. Related to cosmetics with excellent properties. Background art

JP A 4 9 one 8 5 2 4 3 JP, 1 0 0 ° F 〇 ₄ Orefuin heavy which is hydrogenation treatment having a kinematic viscosity of 1 5 to 3 5 cSt at (3 7. 8 ° C) A cosmetic composition blended with a synthetic oil for cosmetics consisting of coalescing is disclosed, and its properties include odorlessness, low cost, low irritation to animals and humans, and storage stability.

However, in the above C ₄ olefin polymer, since the C ₄ olefin is a spent ₄ fraction containing isobutylene, n-butene, 2-butene, etc., even if post-distillation or hydrogenation treatment is performed, Even if a standard such as 15 to 35 cSt is set at 100 ° F (37.8 ° C), (1) oxidation stability due to the structure containing a tertiary carbon atom in the molecule poor sex, and (2) since the carbon atoms from the polymer during the polymerization reaction is a side reaction which leaves occurs, the number of carbon atoms of 〇 ₄ Orefuin polymer is not only a multiple of 4, various carbon having a boiling point adjacent Since it is a mixture of a number of polymers, it is difficult to purify and separate a specific molecular weight component by distillation. Therefore, there is room for improvement in that components having poor oxidation stability and components having a carbon number of 19 or less that have skin irritation properties cannot be completely removed.

Therefore, it is difficult to satisfy the requirement that the cosmetic composition containing the above synthetic oil for cosmetics contains no component exhibiting skin irritation and is stable in long-term storage or outdoor use. In particular, when used as a cosmetic for basic cosmetics, this drawback becomes a serious problem. Disclosure of the invention

The present inventors have made intensive studies on the above points, molecular weight and molecular weight distribution of the polymer in c ₄ unsaturated compounds containing Murrell hydrogenation treatment in cosmetic compositions

By limiting the chemical structure, raw materials used, polymerization method, etc. to specific ones, it has excellent oxidation stability, very low oxidative degradation rate, and does not contain any components that show skin irritation. They found that a colorless, odorless and inexpensive cosmetic composition could be obtained, and completed the present invention.

That is, in the first aspect of the present invention, in a cosmetic containing a treated product of a ォ₄ olefin polymer, the hydrogenated product has a signal of 7 to 6 Oppm detected in ¹³ C-NMR measurement. The ratio of the integrated value of the signal of the tertiary carbon atom to the integrated value of is 0.

The present invention relates to a cosmetic characterized in that at least one selected from the group consisting of olefin polymers having a carbon number of less than 0 and having 20, 24, 28 and 32 carbon atoms is a main component. .

The second of the present invention, in the first invention, C ₄ Orefin polymer, C ₄ Monoo Refuin such a result by polymerizing containing Isobuten alone or Isoputen using a fluorine-containing compound as a polymerization catalyst, and the polymer 60% by mole or more of the cosmetic has a vinylidene terminal structure.

A third aspect of the present invention relates to the cosmetic according to the first or second aspect of the present invention, wherein the fluorine content of the C ₄ olefin polymer is 1 O ppm or less.

A fourth aspect of the present invention relates to the cosmetic according to any one of the first to third aspects of the present invention, wherein the cosmetic mainly comprises a hydrogenated product having 24 and / or 28 carbon atoms. You.

A fifth aspect of the present invention relates to the cosmetic according to any one of the first to third aspects of the present invention, wherein the cosmetic mainly comprises a hydrogenated product having 20 and ぴ Z or 24 carbon atoms. You.

A sixth aspect of the present invention relates to a basic cosmetic using the cosmetic according to any one of the first to fifth aspects of the present invention.

Further, the present invention will be described in detail.

The polymer of the C ₄ unsaturated compound according to the present invention has a carbon number of 20, 24, 28 and At least one selected from the group consisting of the 32 olefin polymers is the main component, and the hydrogenated one is the integral of the signal of 7-6 O ppm detected in the ¹³ C—NMR measurement. The ratio of the integrated value of the signal of the tertiary carbon atom to the value is less than 0.08. (Hereinafter referred to as “butene oligomer hydride”)

1 ³ C-NM and R ratio of the integrated value of the signals of the tertiary carbon atoms against the integrated value of 7 and 6 O ppm of signal detected in the measurement, for example, can be determined by the following procedure. The instrument used was a 400 MHz NMR (manufactured by JEOL Ltd.), and an analysis sample: deuterated chromate form = 40:60 (weight) was mixed in an NMR sample tube with an inner diameter of 5 mm. The mixed solution was put into a measurement sample. Tertiary carbon atoms were determined by DEPT measurements. The trimethylaminosilane (TMS) was defined as O ppm, and the integral value of signonole at 7 to 60 ppm was calculated. The content of tertiary carbon atoms was calculated by the following equation.

(Tertiary carbon atom content)

= (Integral value of signal of tertiary carbon atom) Z (integral value of signal of 7 to 6 ppm) In order to obtain the effect of the present invention, it is essential that this value is less than 0.08. is there . The ratio of the integral value of the signal of the tertiary carbon atom being less than 0.08 means that the butene oligomer hydride of the present invention has, for example, 20 or 24 carbon atoms, such as heat or ultraviolet light. It means that it does not contain more than two tertiary carbon atoms per mole that are unstable to energy and easily decomposed or oxidized. As a result, the butene oligomer hydride of the present invention exhibits excellent oxidation stability.

Flop Ten oligomer hydride according to the present invention, for example, isobutene alone or petroleum, naphtha, and a butadiene raffinate was divided butadiene _0-4 fractions produced by thermal decomposition of butane polymerized in a fluorine-containing catalysts as butene polymer, It can be obtained by hydrogenating the oligomer component contained therein.

The carbon number of the butene polymer according to the present invention obtained by this method is represented by 4n (n≥2, where n is a natural number) since no side reaction occurs in which a carbon atom is eliminated during the polymerization reaction. Therefore, it is possible to purify and separate those with a specific molecular weight by distillation without using any special equipment or technology. Therefore, since the butene oligomer hydride of the present invention does not contain any component having a carbon number of 19 or less that exhibits skin irritation, it has excellent oxidative stability as described above, has a low oxidative degradation rate, and has a low skin irritation. I have to show it It has the following features.

The method for obtaining the butene oligomer hydride of the present invention will be described in more detail.

First tertiary carbon atoms is less carbon atoms 4 n to (n≥ 2 n is a natural number) of a Butenpori mer, Isoputen alone is are in the polymerisation zone with the reactor (reaction zone) is C ₄ containing Isoputen The fraction is supplied and polymerization is carried out using a fluorinated catalyst. As the polymerization reactor, a stirring type or a loop type can be arbitrarily selected, and a plurality of reactors may be provided.

Raw materials for polymerization can be used isobutene alone or naphtha in ethylene plants, kerosene, gas oil, butadiene raffinate butadiene were excluded from C ₄ fraction obtained from the cracker, such as butane. This butadiene rafte is a hydrocarbon mixture comprising 1-butene, 2-butene, isopthene and butanes. More specifically, 1-butene is about 10 to 40% by weight, and 2-butene is about 1 to 10% by weight. 40 weight. / _0, Isoputen about 3 for 5-7 0% by weight, butadiene approximately 0. 5 wt ^_0/0 or less, and butanes to those containing from about 1 0 to 3 0% by weight. The other monomer is not particularly limited as long as it is within this composition range, and may be _four fractions contained in a decomposition component from a fluid catalytic cracking (FCC) unit.

Alternatively, butadiene raffinate having the above composition may be used. For example, the composition can be changed by distillation or by adding isopten to increase the concentration of isopten, or by reducing the concentration of 1-butene by a reaction such as catalytic hydroisomerization, or by chemical or physical manipulation. it can. In any case, it is preferable that the content of isopten is large, and the water content in the polymerization raw material inhibits the activity of the catalyst, so that it is usually adjusted to 1 O ppm or less.

It is preferable to use a fluorinated catalyst for the polymerization reaction.

Examples of the fluorinated catalyst include boron trifluoride-based catalysts and catalysts obtained by contacting a divalent nickel compound with a hydrocarbylaluminum halide and trifluoroacetic acid, such as nickel-heptanoate, dichloroethylethyl and trifluorochloro. And those formed by interaction with acetic acid. This divalent nickel-based fluorinated catalyst has been proposed in Japanese Patent Application Laid-Open No. 57-87366. In the present invention, a boron trifluoride-based catalyst is used, but more preferably a complex catalyst using an oxygen-containing compound as a complexing agent.

Preferred as a complexing agent for boron trifluoride are water, alcohols, and dialkyl ethers, which may be used alone or in a mixture at an appropriate ratio. As the alcohols, aliphatic or aromatic alcohols having 1 to 21 carbon atoms are suitable. The hydrocarbon group may be linear, branched, alicyclic, or include a ring. Specific examples include methanol, ethanol, propanol, n-butanol, pentanole, hexanolone, heptanol, n-year-old lanthanum, n-nonanol, decanolone, benzyl alcohol, 1,4-butanediol, and the like. .

As the dialkyl ethers, dialkyl ethers having the same or different aliphatic or aromatic hydrocarbon groups having 1 to 20 carbon atoms are preferable. The hydrocarbon group may be linear, branched, alicyclic, or include a ring. Specifically, dimethinooleethenore, methinoleethenoreethenore, getinoreethenore, meth7 repropinoleate nore, etinolepropinoleatel, dipropinoleatenole, dibutinoreetenele, methyl petite / Reetet / Les, Etchinolebutinoleethenore, Propinolebutynoleethenore, Dipentinole ethenore, Phenoinolemethinoleether, Phenyletinoletethenore, Difeninoleetether, Cyclohexinolemethinoleether, Cyclohex Xyllechnoletertel and the like.

The supply amount of the complexing agent is preferably 0.01 to 1, OO Om mol based on 1 mol of isopten in the raw material. If it is less than 0.03 mmol, the reaction hardly proceeds, and if it is more than 1, OO O mmol, side reactions such as isomerization and conversion occur, which is not preferable.

The supply amount of the catalyst is suitably 0.1 to 500 mmol as boron trifluoride with respect to 1 mol of isobutene. If the amount of catalyst supplied is less than 0.1 mmol, the reaction is difficult to proceed because the amount of catalyst is small, and if it is more than 50 O mmol, the cost of the catalyst increases and it is not economical, which is not preferable.

The boron trifluoride complex catalyst is prepared according to a conventional method. For example, it is prepared by blowing a predetermined amount of gaseous boron trifluoride while cooling a complexing agent that has been cooled to or below room temperature in advance. Alternatively, supply the catalyst and complexing agent separately into the reaction system to form a complex in the system May be.

The polymerization reaction temperature is preferably from 100 to 50 ° C, more preferably from 150 to 20 ° C. If the temperature is too low, the conversion of isobutene will be low, and if it is too high, side reactions such as isomerization and rearrangement will occur.

As the reaction mode, any of a batch system and a continuous system can be used. However, in the case of industrial production, the continuous type is more economical and more efficient, so the following is an example of the continuous type.

In the continuous method, the contact time between the raw material and the catalyst is important, and in the present invention, it is preferably 5 minutes to 4 hours. If the contact time is less than 5 minutes, a sufficient conversion of isopten cannot be obtained, and if the contact time is more than 4 hours, economical loss is large and side reactions such as isomerization and rearrangement are promoted.

For the polymerization reaction solution, the catalyst is deactivated using a suitable deactivator, for example, water, alkaline water, alcohol, or the like. After removal of the catalyze the organic layer was neutralized, and water washed to remove unreacted C ₄ components by distillation.

The butene polymer produced by the above method has few tertiary carbon atoms, 60% or more of the unsaturated bonds in the polymer have a vinylidene structure, and all carbon atoms are 4 n (n ≥ 2, where n is a natural number) Is represented by

The above-mentioned butene polymer contains residual fluorine derived from the catalyst at lppm or more in terms of fluorine atoms, and in some cases, hundreds of ppm. This residual fluorine is an organic fluorine which is difficult to remove even if it is deactivated by a conventional method and subsequent washing with water, becomes hydrogen fluoride, corrodes the apparatus, and is not used in the subsequent hydrogenation reaction. Inhibits the reaction as a catalyst. Therefore, the fluorine concentration in the butene polymer is preferably 10 ppm or less.

Therefore, the fluorine compound is removed by contacting with a treating agent containing an anolemminium atom. Fluorine atoms in the fluorine compound are fixed and removed in the treatment agent containing aluminum. The specific method of removing the fluorine compound is described in detail in the patent (International Application No. PCT / JP00 / 011036). By performing the defluorination treatment in this manner, the fluorine concentration in the butene polymer is reduced to 10 ppm or less. Next, the butene polymer is appropriately distilled to obtain a butene oligomer having 36 or less carbon atoms. The amount of butene oligomer is 5 to 30% based on the butene polymer.

The butene oligomer obtained by the above distillation is chemically unstable due to the double bond at the polymer end. Therefore, a hydrogenation reaction is carried out to prevent the formation of skin irritating substances due to oxidation, generation of odor and discoloration as a saturated hydrocarbon.

The hydrogenation reaction is carried out by reacting with hydrogen at high temperature in the presence of a metal catalyst. As the metal catalyst, a white metal, a genus of nickel, for example, copper, nickel, palladium, platinum or the like is used alone or in combination of two or more. Further, these metals may be used by adhering them to a carrier such as kieselguhr, alumina or silica.

The reaction type may be a continuous type or a batch type.The reaction conditions are as follows: temperature is 65 to 250 ° C, hydrogen pressure is normal pressure to 10 O kgf / cm ² (9.8 MPa), and catalyst is the amount as metal amount with respect Buteno oligomer, 0. 0 0 0 1 5 to 1.0 wt ^_0/0 are preferred. Whether or not the hydrogenation reaction has proceeded is determined by measuring the iodine value, and the iodine value should be less than 1.0 gI / 100 g.

The hydrogenated putene oligomer is appropriately distilled to obtain a fraction having a distillation temperature of 144 to 160 ° C / 6 to 7 nmiHg (8.0 to 9.3 hPa). When this was analyzed by gas chromatography (capillary column: HT-5, 12 m, temperature: 30 to 250 ° C, heated at 5 ° C / min), those with 20 carbon atoms were 95% or more. Occupy. When the residue at the bottom of the distillation column was analyzed by gas chromatography in the same manner, 70 were found to have 24 and 28 carbon atoms. / o or more is included.

The butene oligomers having 20 and / or 24 carbon atoms and 24 and / or 28 carbon atoms obtained by the above method can be used as cosmetics of the present invention in various cosmetic compositions. The amount is determined according to the specific purpose. In particular, when incorporated into basic cosmetics, the effect is most effectively exhibited. Examples of basic cosmetics include lotions (cleansing lotion, astringent lotion, flexible lotion, multi-layer lotion), creams (burnishing cream, moisture cream, eye cream, cleansing cream, massage cream, Mollient cream, nourishing cream, night cream, base cream, lip balm) Ningling lotion, no, lotion, body mouth, emollient lotion, milky lotion, nourishing lotion, moisture lotion, suntan lotion, cleansing milk, etc.), no. Packs (peel-off packs, powder packs, shingling packs, oil packs, wax packs, etc.), stones (cosmetic stones, transparent stones, medicinal stones, liquid stones, paper stones, shaving stones)鹼, etc.), body shampoo, face wash cream, etc. In addition to basic cosmetics, it is also used in lipsticks, eye shadows, foundations, and hair creams. BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to the following specific examples.

<Example 1> Cosmetic oil (1)

(1) Production of butene oligomer

Butadiene rice (butadiene extraction residue from ethylene crackers) containing isobutene was used as a raw material. The composition of the raw material by gas chromatography is as follows (weight / ₀ ).

Isovten 50.9

1-butene 2 3 .2

Cis _ 2—puten 2.8

Trans 2-Butene 6.4

Isobutane 5.4

― N-butane 1 1.3

Total 100.0.0

The raw material was fed at a flow rate of 4 L / h into a continuous polymerization apparatus having an inner volume of 4 L, and boron trifluoride was supplied to 8.27 mniol per 1 mol of olefin in the raw material. Getyl ether and ethanol were fed separately such that the molar ratio to boron trifluoride was 1.00 and 0.03, respectively. As a result of performing a polymerization reaction while maintaining the inside of the reactor at 110 ° C, the conversion of isobutene was 95%.

Subsequently, a 2% aqueous sodium hydroxide solution was added to the reaction mixture to deactivate the The organic layer was washed three times with deionized water, dried, and the unreacted C _{4 component} was recovered by distillation. ^The content of the bi-lidene skeleton in the unsaturated bond determined by ¹³ C-NMR was 94 mol%.

(2) Dehalogenation treatment of butene polymer

Activated alumina (trade name: PSG-D25, manufactured by PRO CATALYSE) dried under reduced pressure at 200 ° C for 2 hours in a fixed-bed container with a capacity of 10 Oml was ground to a particle size of 0.5 mm to 1. What was classified into 4 mm was filled.

With the fixed bed temperature set to 170 ° C and the WHS V set to lh- ¹ , the putten polymer described in the above (1) was brought into contact, and dehalogenation treatment was performed.

The residual fluorine concentration determined by Wickbold-colorimetry after treatment was less than 1 ppm.

(3) Recovery of butene oligomer

6,800 g of the butene polymer obtained in the above (2) was charged into a batch distillation apparatus having an internal volume of 10 L connected to a vacuum pump and a nitrogen line. The bottom of the column was heated to 220 ° C, and the putene oligomer distilled under reduced pressure of 2 minHg (2.7 hPa) was recovered. The recovered amount was 1,700 g.

(4) Hydrogen tere of putene oligomer

In a 5 L autoclave, 3,068 g of butene oligomer obtained in (3) above and 5 ° /. 15 g of Pd-alumina catalyst was charged, the pressure was increased to 50 kgf / cm ² (4.9 MPa) using high-purity hydrogen, and the reaction was carried out at ²⁰⁰ ° C. for 3 hours. When the pressure decreased due to the progress of the reaction, the pressure was increased to a predetermined pressure with high-purity hydrogen each time. After completion of the reaction, the reaction solution was subjected to suction filtration to remove the catalyst.

The iodine value of the hydrogenated butene oligomer after the reaction was less than 1. Og-I / 100 g, and all peaks indicating olefins observed before the reaction in ¹³ C-NMR measurement had disappeared. From the above results, it was confirmed that the hydrogenation reaction proceeded.

(5) Purification of hydrated putene oligomer

In a batch distillation apparatus with an internal volume of i0L connected to a vacuum pump and a nitrogen line, puttenol in the above (3) as 4,410 g of hydrated putene oligomer and flux oil 2,446 g of the remaining butene polymer from which the oligomer was recovered was charged and distilled under reduced pressure. As a result, 1.316 g of a colorless, odorless liquid having a distillation temperature of 142 to: 152 ° C / 9 mmHg (1 2. O Pa) was obtained.

The oligomer hydride was analyzed by gas chromatography to find that the number of carbon atoms was all 20 and the ratio of tertiary carbon atoms determined by ¹³ C_NMR was 0.051. The kinematic viscosity at 25 ° C was 13.2 cSt.

Example 2> Cosmetic oil (2)

In the same manner as in Example 1, production of a butene oligomer, defluorination treatment of a butene polymer, recovery of the butene oligomer, and hydrogenation of the butene oligomer were performed. In the purification of the butene oligomer hydride, 7,263 g of butene oligomer hydride was charged using the same apparatus as in Example 1 and vacuum distillation was performed. Distillation temperature: 142-; Distillation was stopped when components of 15 2 ° C / 9 mmHg (1 2. OhPa) were distilled off.

When the butene oligomer hydride remaining at the bottom of the distillation column was analyzed by gas chromatography, the content of compounds having 24 and 28 carbon atoms was 79.3%, and the content of tertiary carbon atoms determined by ¹³ C-NMR was determined. The content ratio was 0.044.

The inside of a polymerization flask equipped with a stirrer, thermometer, dropping funnel, gas inlet tube and gas exhaust tube was sufficiently replaced with dry nitrogen, and 198 g of butadiene raffinate shown in Example 1 was charged. After cooling to a temperature of 20 ° C, 1.0 g of aluminum chloride powder was added to initiate polymerization. The polymerization was carried out for 1 hour while maintaining the temperature at 120 to 0 ° C. After completion of the polymerization, addition of 5% aqueous sodium hydroxide solution deactivate the catalyst by, distilling off the unreacted C ₄ component, to obtain a butene polymer 4 5 g. The content of the bilidene skeleton in the unsaturated bond of the butene polymer determined by ¹³ C-NMR was 0.

The subsequent steps were performed in the same manner as in Example 1 to obtain a putene oligomer monohydride having 16 to 35 carbon atoms. The hydride of the butene oligomer had a tertiary carbon atom ratio of 0.121 as determined by ¹³ C-NMR, and a kinematic viscosity at 25 ° C. of 20.7 cSt.

Gas chromatographic analysis was performed on the hydrogenated pentene oligomer of Example 1 and Comparative Example 1. Table 1 shows the composition of the number of carbon atoms determined by the first graph. Carbon several minutes cloth

As can be seen from Table 1, the hydrogenated pentene oligomer of Example 1 had 100 mol% of those having 20 carbon atoms, whereas in Comparative Example 1, the components other than 20 carbon atoms accounted for 40% or more. Was included.

(Heating test)

Example 1 and Comparative Example 1 were subjected to a heating test.

50 g of each sample was heated to 150 ° C, and air was blown at a flow rate of 21.0 to 24.0 L / h for 6 hours. Table 2 shows the results of measuring the peroxide value and the acid value before and after heating. Table 2 Measurement results of peroxide value and acid value before and after the heating test

From Table 2, it can be seen that the butene oligomer hydride of Example 1 has a lower peroxide value and a lower acid value than that of Comparative Example 1, and therefore has higher oxidation stability.

(Oxidation stability test) The oxidative stability test was performed according to the standard oil and fat analysis test method 2.5.1.2 CDM (Conductometric Determination Method) established by the Japan Oil Chemists' Society. This test method is equivalent to the AOCS Official Method Cdl2b-92 Oil Stability Index (OSI) established by the American Oil Chemists' Society (AOCS).

. The CDM value is expressed as the elapsed time until a break point at which the value of the volatile decomposition product generated by oxidation is collected in water and the value of the conductivity is measured. The higher the CDM value, the higher the oxidation stability. The test method is as follows. Connect the measurement vessel containing 5 Oml of ion-exchanged water and the reaction vessel containing 3 g of sample. 1 20 ± 0.2 Put the above reaction vessel in a thermostatic chamber adjusted to 2 ° C, leave it for 10 minutes, then blow clean air at a flow rate of 2 OL / h and start measuring conductivity at the same time. The measurement is terminated when the rate reaches 300 S / cm. The measurement temperature can be set to 100 ° C. or 140 ° C. depending on the magnitude of the CDM value.

A CDM test was performed on Example 1 and Comparative Example 1. Table 3 shows the CDM value and the time when the conductivity of water reached 40 μS / cm. Table 3 CDM test results (1 40.C)

The results in Table 3 indicate that the butene oligomer hydride of Example 1 has a higher CDM value than that of Comparative Example 1 and a longer time until the conductivity reaches 40 ^ S / cm. I understand. Therefore, taking into account the results of the above-mentioned heating test, the material of Example 1 is a material having not only excellent oxidation stability but also a low oxidation deterioration rate. This is due to the low tertiary carbon atoms.

Table 4 shows the properties of Example 1 and Comparative Example 1.

The method for measuring “acidity and alkalinity” in the table is as follows.

Add 1 Om 1 of boiling water and 1 drop of fuynolphthalein reagent to 1 Om 1 of the sample and vigorously add When shaking, the solution does not turn red. In addition, 0.2 N sodium hydroxide (0.2 Oml) is added to the mixture, and the mixture turns red when shaken.

4 Comparison of properties of Example 1 and Comparative Example 1

(1) In ¹³ C-NMR measurement, the signal of 7-6 Oppm

The ratio of the integrated value of the signal of the tertiary carbon atom to the integrated value.

Tertiary carbon atoms were determined by DEPT measurements.

(2) In the infrared spectrum absorption, the wave number MGScni- ¹ 1380cm ¹

And lSGScm- ¹ shows absorption, and δδθεηι · ¹ has no absorption.

(Human skin primary irritation test)

Forty healthy males and females (19 males and 21 females) were tested, and 0.1 ml of the cosmetic oil (1) obtained in Example 1 was applied to the circular cloth part of the bandage for patch test, and the inner part of the upper arm was used. Affixed to As a control, only a bandage was applied in parallel. After 24 hours, skin symptoms were visually observed and evaluated. For the evaluation method, the presence or absence of symptoms (erythema, edema, blisters, etc.) was confirmed according to the following criteria of the Japan Patch Test Study Group.

Japan Study Group Standards:

0 No response

0 5 Light erythema

Red team

2 Erythema + edema

3 Erythema + edema + papules, serous papules, vesicles

4 large blisters

Table 5 shows the results. Table 5 Results of 24 Hour Closed Patch Test

From the results in Table 5, it can be seen that the putenoligomer hydride obtained in Example 1 is almost non-irritating.

(Production Example 1) Trial production of lotion

Using the butene oligomer hydride of the present invention, a lotion was trial-produced by the following procedure. Table 6 shows the mixing ratio.

Table 6 Mixing ratio of Production Example 1

Component B was added to Component A, and Component C was further added and mixed and dissolved. The dye was added thereto, the mixture was cooled for 2 to 3 days, and the precipitate was adsorbed and filtered using an adsorbent.

The prototype was less susceptible to oxidative degradation than the conventional product, had less skin irritation, and had a refreshing feel to the skin.

(Production Example 2) Trial production of emollient cream

An emollient cream was trial-produced using the hydrated putene oligomer of the present invention by the following procedure. Table 7 shows the mixing ratio. Table 7 Mixing ratio of Production Example 2

Component 成分 was heated to 70 to 75 ° C to dissolve it, and then filtered. While stirring this, after heating and dissolving in it at 73 to 78 ° C, the filtered component B was added. The mixture was emulsified with a high-speed homomixer, allowed to stand for defoaming, cooled, then added with a flavor at 55 to 60 ° C, and cooled to room temperature.

The prototype was less susceptible to oxidative degradation than the conventional product and had less irritation to the skin. (Production Example 3) Prototype of foundation

Using the butene oligomer hydride of the present invention, a foundation was trial-produced in the following procedure. Table 8 shows the mixing ratio. Table 8 Mixing ratio of Production Example 3

After the component A was heated to about 70 ° C. to dissolve it, the pulverized and sieved pigment was added, mixed and dispersed at about 70 ° C., and then filtered. This was heated to 70 to 75 ° G in advance and dissolved, and then filtered component B was added, followed by stirring to emulsify. After defoaming, a fragrance was added at 55 to 60 ° C, and the mixture was cooled to room temperature.

The prototype was less susceptible to oxidative degradation than the conventional product, had less irritation to the skin, and had a refreshing feel to the skin. Industrial applicability

The hydrated putene oligomer, which is a main component of the cosmetic of the present invention, is excellent in oxidative stability, has a low oxidative deterioration rate, contains no skin irritating components, and is colorless. It is odorless and inexpensive. Cosmetics containing these are particularly suitable for basic cosmetics.

Claims

The scope of the claims

1. 〇 In ₄ Orefuin polymers cosmetic comprising a hydrogenation treatment of the aqueous Moto添pressure treated product, tertiary to the product fraction value of the signal 7 and 6 O ppm to be detected in the ¹³ C-NMR measurement The main component is at least one selected from the group consisting of olefin polymers having a carbon atom signal integration value of less than 0.08 and having 20, 24, 28 and 32 carbon atoms. Cosmetics characterized by having.

2. The 〇 ₄ Orefuin polymer made by polymerizing C ₄ Monoorefin acids comprising iso heptene alone or Isobuten using a fluorine-containing compound as a polymerization catalyst, and the polymer of 6 0 mole <½ or higher terminal vinylidene structure The cosmetic according to claim 1, wherein the cosmetic comprises:

3. The 〇 ₄ Orefuin polymer cosmetics of fluorine content according to item 1 or 2 wherein the claims to feature to or less than 1 O ppm of.

4. The cosmetic according to any one of claims 1 to 3, wherein the cosmetic mainly comprises a hydrogenated product having 24 and / or 28 carbon atoms.

5. The cosmetic according to any one of claims 1 to 3, wherein the cosmetic mainly comprises a hydrogenated product having 20 and / or 24 carbon atoms.

6. Basic makeup using the cosmetic according to any one of claims 1 to 5

P