JPS6019888B2 - hair cosmetics - Google Patents

Description

Detailed Description of the Invention The present invention uses polyglycerin with an average degree of polymerization of 3, that is, triglycerin or higher, and 20 to 100 moles of propylene oxide (hereinafter abbreviated as PO) (average number of moles: hereinafter, unless otherwise specified, moles). (all numbers are the average number of moles) addition-polymerized polyether compound, and the polyglycerin P
040 to 120 moles and 1 to 20 moles of ethylene oxide (hereinafter abbreviated as EO). It is something.

The purpose of this product is to provide appropriate hair styling power and hair styling feel with moderate oiliness, not be sticky to the hands, have good affinity for hair, and have excellent hair styling retention properties. To provide a new and useful hair cosmetic that is less irritable, easier to wash, washes stains from clothes better, and is less irritating and less toxic.
Traditionally, the raw materials for hair cosmetics or liquid hair styling products include:
Polypropylene oxide monobutyl ether (hereinafter referred to as P
(abbreviated as PBE), polypropylene oxide glycerin ether (hereinafter abbreviated as PPGE), and their phosphate esters and salts include the phosphate ester of PPBE (Ko Hakama, 1977-11955), the phosphate ester of PPGE (Special Publication, 1977-11). 29141) type is known.
However, none of the above compounds satisfy all of the conditions that must be met as raw materials for hair cosmetics. Nonionic type PPBEPPG
E and the like are extremely excellent raw materials that satisfy a number of properties including hair styling power and feel when used due to their moderate oiliness, and were the main raw materials for liquid hair styling products in the early days.

However, since it has only a propylene oxide polymer as its main chain, it has a relatively oily polar region, and although it has no drawbacks in alcohol-water-based product formulation systems, these solvent systems After the hair has dispersed, the hair washing performance is slightly inferior, and at the same time, it becomes a staining factor that causes oil stains on clothes, etc. Another disadvantage is that dirt on hands cannot be easily washed off with tap water.

In order to improve this drawback, it is known that a hydrophilic ethylene oxide polymer is added to the propylene oxide polymer chain to avoid the drawback, but these generally have increased water solubility and the above-mentioned Although this improves the drawbacks, on the other hand, it has a new drawback of increasing celluloid erosiveness. In addition, various polypropylene oxide phosphate ester compounds have been developed, but although these have improved the original drawbacks, ie, factors such as hair staining, they have new and contradictory drawbacks.

That is, the hair styling ability tends to deteriorate under humid conditions because it exceeds the oil-based property that is appropriate and becomes closer to the hydrophilic side, increasing the number of hydrophilic polar groups too much. Furthermore, the addition of an unterminated phosphate ester group promotes intermolecular or intramolecular crosslinking, which makes it difficult to freely control the viscosity, and improves the feel of hair styling due to the physical properties of volatile residue, which is an important factor for liquid hair styling products. There are some significant disadvantages.

Furthermore, by converting a nonionic type into a phosphate ester to make it anionic, the irritation to animals is clearly increased.

Furthermore, polyether compounds made by addition-polymerizing polyhydric alcohols (glycerin, bentaerythritol, sorbitan) with PO and further adding-polymerizing EO in an appropriate ratio are also known, but they do not corrode celluloid and stain stains on shirts. Although it is an excellent raw material for hair cosmetics with good properties, it still has poor water solubility and has the disadvantage that stains on hands caused by this compound cannot be easily washed off with tap water. In addition, polyoxyalkylene ether compounds of various saccharides are also known in Mochiseki No. 126841/1989, but they suffer from many intramolecular and intermolecular dehydration condensation side reactions during the alkylene oxide addition reaction, resulting in uniform quality. is difficult to obtain. In particular, variations in color tone, odor, and viscosity are large from lot to lot, making it impossible to consider the application of these compound groups to hair cosmetics. As a result of intensive research aimed at determining the above-mentioned contradictory facts, the present inventors discovered a group of compounds that have all the characteristic factors as raw materials for hair cosmetics, and obtained a new and useful hair cosmetic.

Specifically, as is clear from Table 1, we focused on physiologically mild nonionic types and discovered the following compound group. The compound used in the present invention is polyglycerin;
That is, a polyether compound obtained by addition polymerizing 20 to 100 moles of PO, preferably 40 to 80 moles, to polyglycerin having an average degree of polymerization of 3 (triglycerin) or more, and 40 to 120 moles of PO and ~20 moles of EOI. A polyether compound subjected to addition polymerization, preferably addition polymerization with 3 to 10 moles of E0, with a viscosity of 500 at 25 qo.
The hair cosmetic of the present invention having a PS of ~150 may contain one or more of the above polyether compounds, and has excellent hair styling ability and is non-sticky. A suitable blending amount is 5 to 50%. The degree of polymerization of the polyglycerin used in the present invention needs to be selected so that the viscosity of the compound obtained by adding PO or EO to PS is 500 to 150.

The lower limit of the degree of polymerization is the average trimer (hereinafter, the degree of polymerization refers to the average unless otherwise specified), and it cannot be obtained below this. Regarding the upper limit, the viscosity of polyglycerin increases as the degree of polymerization increases, but P○ or P
By adding O and EO, the viscosity decreases, P○,
Alternatively, the viscosity of the polyether compound can be suppressed to 150 PS or less by controlling the number of moles of PO and EO added, so there is no particular limitation. The number of moles of PO and EO added to polyglycerin is PO
In the case of 20 to 100 moles, in the case of PO and EO, P
O is 40 to 120 moles, and EO is 1 to 20 moles.

Addition of low molar amount of PO causes strong celluloid corrosion, and P02
By adding 0 mole or more, celluloid corrosiveness can be eliminated, and the viscosity can be moderated, making it necessary for hair styling oils.
It shows PS viscosity in the range of 00 to 150, and even if up to 100 moles of PO is added, the polar groups of the hydroxyl groups in polyglycerin work effectively, resulting in good water dispersibility and dirt on hands can be easily washed off with tap water. A compound characterized by the following properties is obtained. In addition, if PO is added to polyglycerin beyond the above-mentioned optimum addition range, the compound becomes oily and has poor water dispersibility, but by adding 1 to 20 moles of EO, it has excellent hair styling ability and does not corrode celluloid. , a compound with good water solubility can be obtained. This also applies to polyglycerin in which 1 to 20 moles of EO is added and then PO is added and polymerized in an amount greater than the optimum number of moles added. All of the compounds according to the present invention are easy to manufacture and control quality, and are extremely advantageous industrially. I of these polyether compounds
Research was also conducted on J-acid ester, and it was confirmed that it was unfavorable in hair styling retention and usability (stickiness on hands) compared to the polyether compound used in the present invention.

The production of these polyether compounds can be carried out according to conventional production methods, but to give an example, granular caustic soda is mixed with polyglycerin in N2 gas, and PO is heated to a reaction temperature of 100%.
~120oo, internal pressure 5~7k9/mass G, slowly add, then add EO as needed to make polyglycerin.

A pyrene oxide, propylene oxide, or ethylene oxide addition polymer compound is obtained. All parts are by weight. Reference Example 1: Mix polyglycerin (average molecular weight 350) and 100% woven granular caustic soda in nitrogen gas, charge 95 to 100 qo of PO into the reaction system, and set the pressure in the system to 5 kg/G. When this pressure is reached, the PO preparation is stopped. If the chanting is continued, the reaction will start after 1 to 2 hours and the pressure will drop. The reaction temperature was raised to 120° C., and addition polymerization was carried out using the required amount of PO, totaling 6,628 sites, to obtain a polyglycerol polyether compound. The viscosity of this compound was 70 ps (25° C.). The viscosity was measured using a B-type viscometer (rotor M.3, lapm, 6$ec.
) was measured. (All of the following viscosities were also measured using the same machine.)
Reference example 2: Mix granular caustic soda with 1,000 parts of polyglycerin (average molecular weight 350) in nitrogen gas,
Charge PO into the reaction system at ~10,000 ℃, and reduce the pressure in the system to 5
Let it be G of kg.

When this pressure is reached, the PO preparation is stopped. If Takaazusa is continued, the reaction will start after 1 to 2 hours and the pressure will drop. Raise the reaction temperature to 120 oo, add the required amount of PO, total amount 8,
285 parts were added, and then E063 was added and polymerized to obtain a polyglycerol polyether compound. The viscosity of this compound was 90 ps (25 CO). Reference example 3: Polyglycerin (average molecular weight 350) 1,000 in nitrogen gas
Mix granular caustic soda with the water and PO at 95-100 pm.
is charged into the reaction system, and the pressure in the system is set to 5k9/Sakaki G.
When this pressure is reached, the PO preparation is stopped. If the reaction is continued for 1 to 2 hours, the reaction will start and the pressure will drop.
Raise the reaction temperature to 120°C, add the required amount of PO, total amount 13
, 256 parts, and then addition polymerization of EO1,26 was carried out to obtain a polyglycerin polyether compound. The viscosity of this compound was 1.10 ps (290). In the same manner, 1,00 parts of polyglycerin (average molecular weight 350) is added to 1,26 parts of EO, and then 3,256 parts of POI are added and polymerized to obtain a polyglycerol polyether compound. The viscosity of the compound is 1,10 ps (2
5°C).

Reference Example 4: In the same manner as in Reference Example 1, polyglycerin (average molecular weight 500) of 1,00 $ class POll, 60 anchor parts was subjected to addition polymerization to obtain a polyglycerin polyether compound.

The viscosity of this compound was 80 ps (25 qo).
Reference Example 5: In the same manner as in Reference Example 1, 1000 parts of polyglycerin (average molecular weight 750) is subjected to addition polymerization of 13 parts of P05 to obtain a polyglycerin polyether compound. The viscosity of this compound was 85 PS (25 qo). Reference example
6: Same as Reference Example 1, polyglycerin (average molecular weight 75
0) Add P06960 copies to 1000 copies, then E0
A polyglycerol polyether compound can be obtained by addition polymerizing 293 parts, and the viscosity of this compound is 88 P.
It was S (25 qo). Reference Example 7: Same as Reference Example 1, 100 $ parts of polyglycerin (average molecular weight 1125)
125 parts of this P04 is subjected to addition polymerization to obtain a polyglycerol polyether compound. The viscosity of this compound is about 95 (2
5qC). Table 1 <Reference Example Compounds> Comparative Examples 1 and 2 were manufactured according to Reference Example IK) Table 2 Existing and Invention Raw Material Evaluation Test Results Test Method 1. A sample of one bird is applied to a celluloid plate and left in a 390 constant temperature bath overnight, and the surface condition is observed after washing.

○: No abnormality ×: Whitening to swelling of the surface 2. Hair styling power sample preparation - Add 2 parts of each compound, 5 parts of ethyl alcohol, and 3 parts of ion exchange water, and dissolve uniformly.

o Hair set test method - Try the above on hair strands (4 evenings) 2.Apply the skin and adjust the shape with Well, after drying for an hour, the hair sets. View.

o Hair set evaluation method ◎: Excellent setting power ○: Average ×: Poor 3. Sticky hair after hair styling Apply 3 parts of various bases (2 parts by weight) [50 parts ethyl alcohol, 3 parts deionized water] solution to the hair strands (2 parts by weight).
In the evening, apply on 3 skins x 15 skins, comb through and leave at room temperature for 1 hour (
Wind string at 25q0, 50%RH).

Thereafter, the stickiness of the coated hair was sensory evaluated. ○: Hardly sticky ×: Sticky 4. Shirt stain stain washing method Staining method - 2 parts by weight of various bases [5 parts ethyl alcohol, 3 parts ion-exchanged water] 50 ml of solution was applied to the test cloth and kept at room temperature overnight. Leave to dry.

Washing method - Add 250 ml of tap water and 40 ml of commercially available synthetic detergent, dissolve, add stained test cloth, wash in a commercially available washing machine for 10 minutes, spin dry, rinse for 10 minutes, dehydrate, and make a judgment after drying. One.

○: Dirt stains are completely removed ×: 〃 remains 5. Add one sample to tap water with a water solubility of 2500 or 100, shake it, let it stand, and observe the state of dissolution or dispersion.

○：Transparent melting ×: It becomes cloudy and looks like an oil bottle. Next, examples of hair cosmetics will be described.

The blending amount is in weight%. Example 1 Transparent liquid hair styling agent Polyglycerin (average molecular weight 350) (PO) 40 mol adduct (Reference example 1) 18% Propylene glycol 2.0 Ethyl alcohol 40.0 Fragrance
Appropriate amount of pigment. Ion-exchanged water 40.0 By temporarily adding other compounding compounds to ethyl alcohol and performing mixing, a transparent liquid hair styling agent is obtained.

A hair styling agent that gives appropriate hair styling power, is non-sticky, has good hair washability, has good water dispersibility, easily washes away dirt from hands with tap water, and has little celluloid erosivity. Example 2 Transparent liquid hair styling agent Polyglycerin (average molecular weight 350) (PO) 80 mol (EO) 10 mol adduct (Reference example 3) 40.0% polyglycerin (average molecular weight 350) (EO) 10 mol (
PO) 80 mol adduct 1.0 Glycerin 5.0 Ethyl alcohol 35.0 Perfume Appropriate amount Pigment Appropriate amount Ion-exchanged water 10.0% A transparent liquid hair styling agent was obtained in the same manner as in Example.

It is a hair styling agent that has strong hair styling power and hair setting retention power, is non-sticky, and has excellent water dispersibility. Example 3 Gel-like transparent hair styling agent polyglycerin (average molecular weight 350) (P
O) 50 mol (EO) 5 mol adduct (Reference Example 2) 2
5.0% Carbopol 940
0.1 triethanolamine
0.1 propylene glycol 8
．． 0 ethyl alcohol 35
．． 0 Fragrance, Appropriate amount of pigment, Appropriate amount of ion-exchanged water 31.8 A gel-like transparent hair styling agent that has strong hair styling and setting power, is non-sticky, has good hair washing properties, is easy to clean stains and stains on clothes, and has little celluloid corrosion properties.

Example 4 Aerosol hair styling agent polyglycerin (average molecular weight 350) (PO) 40 mol adduct (Reference Example 1)
5.0% polyglycerin (average molecular weight 500) (PO) 100 mol adduct (Reference example 4)
7.0 Propylene glycol
1.0 ethyl alcohol
10.0 Fragrance Appropriate amount of ion exchange water
10.0 Difluorodichloromethane 26.0 Tetrafluorodichloroethane 39.0 Raw materials other than difluorodichloromethane and tetrafluorodichloroethane are mixed uniformly in an aerosol can, and after a valve is attached, difluorodichloromethane and tetrafluorodichloroethane are mixed. An aerosol type liquid hair conditioner is obtained by encapsulating tongue.

It is a hair styling agent that gives appropriate hair styling power, is non-sticky, has good washing properties, does not stain stains on clothes, has good washing properties, and is slightly erosive to celluloid. Example 5 Transparent liquid hair styling agent Polyglycerin (average molecular weight 750) (PO) 70 mole adduct (Reference example 5) 10% glycerin 3 ethyl alcohol
40 fragrance, appropriate amount of pigment
Gradually add other compounding compounds to an appropriate amount of ion-exchanged water and 47 ethyl alcohol, and mix with Takaazusa to obtain a transparent liquid hair styling agent.

It is a hair styling agent that gives soft hair styling power, is non-sticky, has good hair washability, is easy to wash off dirt from hands with tap water, and is slightly erosive to celluloid. Example 6 Transparent liquid hair styling agent Polyglycerin (average molecular weight 750) 14% (P
O) 90 mol (EO) 5 mol adduct (Reference example 6) Polyg 1J serine (average molecular weight 1125) 14 (PO) 80 mol adduct (Reference example 7) 1,3 butylene glycol
2 Fragrance Appropriate amount Pigment Appropriate amount Ethyl alcohol 50 Ion exchange water 20 Example 1
A transparent liquid hair conditioner is obtained in the same manner as above.

Claims (1)

[Claims] 1. A polyether compound obtained by addition-polymerizing 20 to 100 moles (average number of moles) of propylene oxide to polyglycerin having an average degree of polymerization of 3 or more, and 40 to 120 moles (average number of moles) of propylene oxide and 1 to 100 moles of ethylene oxide to the polyglycerin. A hair cosmetic comprising one or more polyether compounds selected from polyether compounds obtained by addition polymerization of 20 moles (average number of moles) and having a viscosity of 500 to 1500 CPS at 25°C.