JPS62240335A - Silicone oil composition - Google Patents

Abstract

PURPOSE:To provide a composition composed of a silicone oil and PVA, etc., having a specific triorganosilyl group on a side chain as a substituent group, having uniform viscosity, giving an oxygen-permeable coating film having high strength and useful in the field of cosmetic, medicine, etc. CONSTITUTION:The objective composition can be produced by dissolving (A) a polymer selected from PVA, a water-soluble nonionic natural polysaccharide (e.g. pullulan) and their derivatives and having a triorganosilyl group of formula I (R1-R3 are 1-6C hydrocarbon group) on a side chain as a substituent group in (B) a silicone oil of formula II or III (m is 0-5; n is 3-7) (e.g. octamethylcyclotetrasiloxane). The content of the triorganosilyl group in the polymer A is preferably >=50wt%.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention has excellent solubility and thickening properties for polysiloxane such as silicone oil, and is useful in -i! III Rut" m I 4 sz 11-1- ・No h l +L m rh It1w+ L= I
Q10 It's a bus thing.

(Prior art and problems) In recent years, organic solvents conventionally used as solvents or dispersion media in various fields, such as acetone, methanol, ethanol, methyl ethyl ketone, toluene, and liquid paraffin, have been replaced by silicone oil. It's starting to look like this.

This is because the silicone oil is colorless, transparent, tasteless and odorless, and has excellent properties such as non-toxicity, low biological irritation, and little change in viscosity due to temperature.

This is due to its excellent dielectric properties, mold releasability, water repellency, antifoaming action, heat and cold resistance, and good compatibility with other solvents.

A composition that thickens and/or gels such silicone oil is 4! It is useful in the cosmetics, food, and medical fields, and is expected to be used more and more in the future.

However, conventional polymeric substances dissolved in silicone oil mainly consist of siloxane bonds.

It has not been found in anything other than so-called silicone resins.

Even if this silicone resin can form a film, the strength of the film is extremely weak, and it thickens and gels the silicone oil [even if it is mixed alone,
The thickening effect was only very small.

In addition, commercially available and known organic solvent-soluble thickeners include cellulose derivatives such as nitrocellulose and ethylcellulose, and fatty acid esters of polysaccharides, but these compounds swell in silicone oil but do not dissolve. Therefore, it cannot be used as a thickener for silicone oil.

(Structure of the Invention) As a result of extensive research by the present inventors to develop a silicone oil composition that dissolves in silicone oil, imparts a thickening effect, and has good film formability after drying,
It was discovered that the conventional problems could be solved by a composition consisting of a silicone oil and a polymer having a specific triorganosilyl group as a substituent in the side chain, leading to the present invention.

That is, the gist of the present invention is (a) to provide a trioxycarbonate compound represented by the general formula (wherein R1, R2, and R3 may be the same or different and are hydrocarbon nors having 1 to 6 carbon atoms); At least one polymer selected from polyvinyl alcohol having a substituent on the side chain of an organosilyl group or a water-soluble nonionic natural polysaccharide and its derivative; dFf=1+ (in the formula, n represents an integer from 3 to 7).

Polyvinyl alcohol, polyvinyl alcohol derivatives, water-soluble nonionic natural polysaccharides, and polysaccharide derivatives thereof, which are used as raw materials for the triorganosilyl group-containing polymer used in the present invention, are all triorganosilyl. It is a polymer containing a hydroxyl group into which a group can be introduced to form a silyl ether bond.

Here, examples of polyvinyl alcohol derivatives include, for example,
Examples include vinyl ether-based vinyl alcohol copolymers, ethylene/vinyl alcohol copolymers, and vinyl acetate/vinyl alcohol copolymers. There is no particular restriction on the hydroxyl group content of these derivatives, but it is preferable that the hydroxyl group content is 30 moles or more.If the hydroxyl group content is less than this, it will be impossible to increase the content of triorganosilyl groups, and it will not dissolve in silicone oil. There is a risk that it will disappear.

In addition, as a water-soluble nonionic natural polysaccharide, 1
Examples include starch, pullulan, guar gum, and locust bean gum, and their derivatives include furkyl groups such as methyl, ethyl, and propyl; hydroxyfurkyl groups such as bitroxyethyl, hydroxypropyl, and hydroxybutyl; and/or partially etherified products substituted with carboxyalkyl groups such as carboxymethyl and carboxyethyl, and 7 cetyl,
Examples include partially esterified products substituted with aliphatic acyl groups such as flopionyl and butyryl.

The degree of substitution of these derivatives is not particularly limited, but for alkyl groups, carboxyalkyl groups, and aliphatic acyl groups, it is preferably 1 or less. As the degree of substitution increases, the number of active wood groups in the polysaccharide return unit decreases. , it becomes impossible to increase the content of triorganosilyl groups, and there is a risk that the composition will not dissolve in silicone oil.

Nonionic polysaccharides are considered nonionic because they have about three hydroxyl groups in the saccharide unit, whereas ionic polysaccharides (e.g. alginic acid, chitin, etc.) have about three hydroxyl groups. This is because there are only two of them, and the content of triorganosilyl groups cannot be increased, which prevents them from dissolving in silicone oil. In addition, triorganosilyl derivatives of cellulose that are not water-soluble cannot be used because they do not dissolve in silicone oil, perhaps because the cellulose of j[4 is highly crystalline and the L substituent cannot be uniformly introduced. 1
゜The above-mentioned -11 that the polymer used in the present invention has in the side chain
The mono-deficient hydrogen group having 1 to 6 carbon atoms in the triorganosilyl group of formula Q (I) is a linear or branched alkyl group, such as methyl, ethyl, propyl, isopropyl, butyl, tert-butyl. , pentyl,
Dichloroalkyl groups such as hexyl, such as cyclopentyl, cyclohexyl, etc.; V1 button or branched alkenyl groups 1 Examples include vinyl, allyl, impropenyl, l-butenyl, l-pentenyl, l-hexenyl, etc. As the number of carbon atoms in a hydrocarbon group increases, the hydrocarbon group becomes bulkier and becomes difficult to effectively introduce into a polymer. ter
T-butyl is preferred.

Specific examples of the triorganosilyl of the general formula (I) having a chemical group at 1 include trimethylsilyl group, triethylsilyl group, tripropylsilyl group, dimethylpropylsilyl group, butyldimethylsilyl group) -t
Examples include ert-butyldimethylsilyl group and cyclohexyldimethylsilyl group.

The triorganosilyl group of general formula (1) is preferably contained in the polymer used in an amount of 40% by weight or more, especially 50% by weight or more. If the average weight is less than 40 layers,
The solubility of polymers containing triorganosilyl groups in silicone oil is extremely poor.

As a method for producing the polymer used in the present invention by introducing a triorganosilyl group of general formula (O) into a raw material polymer, a silylating agent corresponding to the required triorganosilyl group can be used.For example, a hydroxyl group can be used. Examples of the silylation method of a polymer having the following include a method using a triorganochlorosilane-pyridine system, a method using a triorganosilylacetamide-N-methylpyrrolidone system, and a method using a hexaorganosilyldisilazane-pyridine system, which are known. In addition, a method using a triorganosilyl peroxide ester, which is a known alcohol silylation method, can also be used.However, 1
In the present invention, the manufacturing method is not particularly limited.

The silicone oil used in the present invention is dimethylpolysiloxane, and has a siloxane median number of 7 or less. When the number of siloxane units is 7 or more, it becomes difficult to uniformly dissolve the polymer having the triorganosilyl group as a substituent in the side chain.

Such cyclic and chain silicone oils include:
For example, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, hexamethyldisiloxane, octamethyltrisiloxane,
Examples include decamethyltetrasiloxane, dodecamethylpentasiloxane, and tetradecamethylhexasiloxane, but a combination of these can also be used.

The composition ratio of the polymer having the triorganosilyl group as a substituent in the side chain and the silicone oil in the silicone oil composition of the present invention may be selected as appropriate depending on the purpose;
The weight ratio is preferably 0.05:99.95 to 70:30.6 If the composition ratio exceeds the value shown above, a sufficiently uniform viscous solution cannot be obtained.6 It is still below the value shown above. Otherwise, a sufficiently viscous solution cannot be obtained.

The silicone oil composition of the present invention can be obtained by stirring the polymer having the triorganosilyl group as a substituent in the side chain and the silicone oil at room temperature or at a temperature equal to or higher than the melting point of the silicone oil.

In addition, various organic and inorganic powders and pigments, solid and semi-solid waxes, pigment dispersants, plasticizers, fibers,
Flavors, preservatives, antioxidants, ultraviolet absorbers, other diluents, etc. can also be mixed.

(Effects of the Invention) The silicone oil composition according to the present invention provides a polymer film having a triorganosilyl group as a substituent in a side chain, which has uniform viscosity and has a strength of 1 when dried.

Further, according to the present invention, a silicone oil composition can be obtained in which the volatility of silicone oil having a relatively low boiling point is suppressed.

Furthermore, the polymer used in the present invention having a triorganosilyl group as a substituent in the side chain has high oxygen permeability,
Since the silicone oil composition according to the present invention has the advantage of transparency, it is expected to be applied in the fields of cosmetics, food, medical use, etc. as it has low bioirritation, and is suitable for makeup cosmetic materials for foundations, nails, etc. Lipophilic cream materials, hair mousse materials, artificial skin liniments, poultice side materials, etc., as well as various other coating materials,
It is also used as a thickener for optical fiber bonding agents, general oils, organic solvents, etc.

Example 1 Polyvinyl alcohol (manufactured by Shin-Etsu Chemical Co., Ltd.; CC-
25) 33 (0.75 ml) was dispersed in 330 g of N-methylpyrrolidone, 152.8 g (0.755 ol) of N,0-bistrimethylsilylacetamide was added to a colander, and heated at 145°C. Stir for hours. After cooling, the reaction solution was diluted with toluene 150. The polymer was diluted with water, stirred, poured into methanol, and the polymer was precipitated and collected by filtration.The polymer was then redissolved in 180 g of toluene, and foreign substances were removed using a filter with a pore size of 1O#Lm. The obtained polymer solution was precipitated with methanol and collected by filtration. Furthermore, the steps of redissolving in 180 g of toluene, precipitating with methanol, and collecting by filtration were performed twice, followed by vacuum drying at 60° C. to obtain trimethylsilyl polyvinyl alcohol No. 67.

The Si content was determined from the amount of SiO2 produced by oxidizing and then incinerating the obtained polymer, and found that the Si content was 22.0 weight tons. This polymer is soluble in octamethylcyclotetrasiloxane and at 20℃
The 101 quantity 2 viscosity measured in the Ubbelohde type viscosity liver was 97 centistokes. Further, when this solution was cast on a glass plate and octamethylcyclotetrasiloxane was volatilized, a transparent film of trimethylsilyl polyvinyl alcohol was obtained. The tensile strength of this film was 50 kg/cm' and the elongation rate was about 501.

Example 2 Polyvinyl alcohol (manufactured by Shin-Etsu Chemical Co., Ltd., r
-OWN 11) Lee-/A 6M-=1% No.-t
J11-,! , -1rs dispersed in 6g, ter
t-Butyldimethylchlorosilane 90.4g (0,8
0 mol) to toluene 86. 120°C
The mixture was stirred for 6 hours. Thereafter, purification and drying were performed in the same manner as in Example 1 to obtain tert-butyldimethylsilyl polyvinyl alcohol.

The Si content of the obtained polymer was 15.4 weight 2 (tert-butyldimethylsilyl group in the polymer; 6:1f
It was fiery. It was also soluble in decamethylcyclopentasiloxane, and its viscosity was measured in the same manner as in Example 1 and found to be 820 centistokes. Further, in the same manner as in Example 1, a transparent film of tert-butyldimethylsilyl polyvinyl alcohol was obtained. The tensile strength of this film was 250 Kg/crn' and the elongation rate was 3z, which was strong enough to satisfy practical use.

Example 3 Pullulan (Taiatsu Shoji Co., Ltd.: PF-20) 1
8.2 g (Q, IQ mol) was added to 162.2 g (Q, IQ mol) of pyridine. 58.8 g (0.30 mol) of triethylbromushila y was further added thereto, heated, and stirred at 140° C. for 7 hours. After that, Example 1
Purification and drying were performed in the same manner as above to obtain triethylsilyl pullulan.

f! The Si content of the polymer was 19.8% by weight.
(triethylsilyl groups in the polymer: 62% by weight), and was soluble in tetradecamethylhexasiloxane, and the viscosity was measured in the same manner as in Example 1 and found to be 210 centistokes.

Furthermore, a transparent film of triethylsilyl pullulan was obtained in the same manner as in Example 1. This film (7) had a tensile strength of 120 Kg/ctn'' and an elongation rate of 3%.

Example 4 Guar gum (Somar Co., Ltd.; 5upper Car)
U) 13.8g (0,085mal) of pyridine 13
Disperse in a mixed solution of 8 g and 100 g of toluene, and add 75.8 g (0,473 mol) of hexamethyldisilazane.
) and 1.0 g of pyridine hydrochloride as a catalyst were added, heated, and stirred at 140° C. for 4 hours. Thereafter, purification and drying were performed in the same manner as in Example 1 to obtain trimethylsilylguar gum.

The Si content of the obtained polymer was 21.5fi amount 2 (
The trimethylsilyl group in the polymer was 56ffiffi. Also, it is soluble in octamethylcyclotetrasiloxane, and its viscosity was measured in the same manner as in Example 1. ,
It was 800 centistokes.

In addition, a transparent film of trimethylsilylguar gum was obtained in the same manner as in Example 1.

Example 5 Hydroxypropyl guar gum (Mie Co., Ltd.; HP-1)
Hydroxypropoxylation rate of 1, 13, 3) 18.5
g (0.10 mol), N-methylpyrrolidone 180
81.0 g (0.30 mol) of N,O-bistrimethylsilylacetamide was added to the colander, heated, and stirred at 150° C. for 5 hours. Thereafter, purification and drying were performed in the same manner as in Example 1 to obtain trimethylsilylhydroxypropyl guar gum. Si of the obtained polymer
The content was 19.2 double fH (trimethylsilyl group in the polymer; 50 weight 2), and it was soluble in octamethylcyclotetrasiloxane, and when the viscosity was measured in the same manner as in Example 1, it was 5,500 centimeters. It was Stokes.

In addition, a transparent film of trimethylsilylhydroxypropyl guar gum was obtained in the same manner as in Example 1.

Comparative Example Cellulose lOg (0,081 m) was dispersed in 90 g of N-methylpyrrolidone, and 24.8 g of N,O-bistrimethylsilylacetamide (0,122 m
The mixture was heated and stirred at 150°C for 5 hours. Thereafter, purification and drying were performed in the same manner as in Example 1 to obtain trimethylsilylcellulose.

The Si content of the obtained polymer was 211 weight it (trimethylsilyl group in the polymer: 55 weight i), but this polymer did not dissolve in octamethylcyclotetrasiloxane at room temperature or even under heating.

Claims (1)

[Claims] 1. (A) General formula▲ Numerical formula, chemical formula, table, etc.▼・・・・・・(I) (In the formula, R_1, R_2, and R_3 may be the same or different, and At least one polymer selected from polyvinyl alcohol, water-soluble nonionic natural polysaccharides, and derivatives thereof, which have a triorganosilyl group as a substituent in the side chain (1 to 6 hydrocarbon groups) and (b) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ... (II) (In the formula, m indicates an integer from 0 to 5.) And/or General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼...(III) (wherein n represents an integer of 3 to 7) A silicone oil composition comprising: 2. The silicone oil composition according to claim 1, wherein the content of triorganosilyl groups in the polymer (a) is 40% by weight or more. 3. The silicone oil composition according to claim 1, wherein the triorganosilyl group of the polymer (a) is an alkyl group and/or alkenyl group having 1 to 6 carbon atoms.