WO2023195626A1 - Polysiloxane composition amd hydrophilic silicone prepared therefrom - Google Patents

Abstract

The present invention relates to a polysiloxane composition comprising a polyol-modified crosslinking agent, an organohydrogenpolysiloxane, an alkenyl group-containing organopolysiloxane, and a diluent, wherein the polyol-modified crosslinking agent is prepared by reacting a compound containing a vinyl group and a glycidyl group with a polyol compound in a molar ratio of 2:1 to 5:1, and the polyol compound includes 5 or more hydroxyl groups.

Description

Polysiloxane compositions and hydrophilic silicones made therefrom

This application claims the benefit of priority based on Korean Patent Application No. 10-2022-0043002 filed on April 6, 2022, and all contents disclosed in the Korean Patent Application document are included as part of this specification.

The present invention relates to a polysiloxane composition containing a polyol-modified crosslinking agent, and a hydrophilic silicone prepared therefrom and having excellent emulsification performance, storage stability, and feeling of use.

Silicone is used as a raw material in various fields due to its excellent stability and usability. In particular, silicones applied to cosmetic compositions are typically produced by reacting polysiloxane containing alkenyl groups and hydrogenpolysiloxane containing Si-H groups. However, silicone manufactured as described above lacks hydrophilicity, which has limitations in deteriorating the storage stability and processability of cosmetics containing it.

As an alternative to this, a method for producing hydrophilic silicone using a composition containing polyglycerol or glucose has been proposed as described above. Specifically, Korean Patent No. 1833959 (Patent Document 1) discloses a gelling agent for oil-based raw materials comprising (A) a co-modified organopolysiloxane having a hydrophilic group and a group having a siloxane dendron structure. The co-modified organopolysiloxane is obtained by reacting (a) organohydrogensiloxane, (b) a hydrophilic derivative having a reactive unsaturated group, and (c) a siloxane dendron having a reactive unsaturated group. However, as in Patent Document 1, silicone modified with polyglycerol or glucose has problems such as phase separation and unpleasant odor due to the remaining unreacted glycerol or raw material glucose generated during production. In addition, when the degree of polymerization of glycerol is high, workability is reduced due to the high viscosity of the manufactured silicone, and stickiness occurs when applied to the skin, making it impossible to obtain a moist and smooth feeling. In addition, there was a problem of insufficient improvement in hydrophilicity due to the use of glycerol or glucose, which are hydrophilic raw materials, and yellowing phenomenon due to low storage properties of the produced silicone.

Therefore, there is a need for research and development on compositions capable of producing silicone with excellent hydrophilicity, emulsification performance, storage stability, and usability, as well as hydrophilic silicone manufactured therefrom.

The present invention provides a composition capable of producing silicone with excellent hydrophilicity, emulsification performance, storage stability, and feeling of use, and a hydrophilic silicone prepared therefrom.

In order to achieve the above object, the present invention includes a polyol-modified crosslinking agent, organohydrogenpolysiloxane, organopolysiloxane containing an alkenyl group, and a diluent,

The polyol-modified crosslinking agent is prepared by reacting a vinyl group-containing glycidyl group-containing compound and a polyol compound at a molar ratio of 2:1 to 5:1,

The polyol compound provides a polysiloxane composition containing 5 or more hydroxyl groups.

Additionally, the present invention provides a hydrophilic silicone prepared from the polysiloxane composition.

The polysiloxane composition according to the present invention can produce silicone with excellent hydrophilicity and emulsification performance by including a polyol-modified crosslinking agent. In addition, the silicone prepared from the composition has excellent hydrophilicity, emulsification performance, storage stability, and feeling of use, making it very suitable for use as an emulsifier in cosmetic compositions.

Hereinafter, the present invention will be described in detail.

The “weight average molecular weight” used herein is measured by a common method known in the art, and can be measured, for example, by a GPC (gel permeation chromatograph) method.

Functional group content, such as 'hydroxyl content', can be measured by methods well known in the art and can be calculated, for example, through structural analysis such as H-NMR and C-NMR.

In addition, “viscosity” is measured by a common method known in the art, and can be measured, for example, by the Brookfield viscometer method. Specifically, the viscosity at 25°C can be measured using a viscometer (HBDV Brookfield viscometer, spindle #93, 2.5rpm).

In this specification, “parts by weight” refers to the weight ratio between each component and may also mean “% by weight.”

Polysiloxane composition

The polysiloxane composition according to the present invention includes a polyol-modified crosslinking agent, organopolysiloxane, organohydrogenpolysiloxane, and diluent.

Polyol modified crosslinking agent

The polyol-modified crosslinking agent serves to crosslink the components in the composition and improve the emulsification performance of the manufactured silicone.

The polyol-modified crosslinking agent is prepared by reacting a vinyl group, a glycidyl group-containing compound, and a polyol compound. The polyol-modified crosslinking agent prepared as described above contains a vinyl group derived from a vinyl group and a glycidyl group-containing compound at the terminal, and has the advantage of imparting excellent emulsification performance to the manufactured silicone and providing a soft and moist feeling when used. In addition, the polyol-modified crosslinking agent complements the limitations of silicone through a crosslinking reaction between the terminal vinyl group and organohydrogenpolysiloxane, thereby imparting hydrophilicity and emulsification performance to the manufactured silicone and improving compatibility with cosmetic raw materials and formulation stability. It has advantages.

For example, the polyol-modified crosslinking agent includes a vinyl group- and glycidyl group-containing compound and a polyol compound at a molar ratio of 2:1 to 5:1, a molar ratio of 2:1 to 4:1, or a molar ratio of 2:1 to 3:1. It may be manufactured by reacting with . At this time, the molar ratio of the compound containing a vinyl group and a glycidyl group, and the polyol compound may be the ratio of the number of moles of glycidyl groups in the compound containing a vinyl group and a glycidyl group and the number of moles of hydroxyl groups in the polyol compound. If the molar ratio of the vinyl group, the glycidyl group-containing compound, and the polyol compound is less than the above range, that is, when reacting a small amount of the mole number of the glycidyl group relative to the mole number of the hydroxyl group, the compatibility with silicon is poor and the unreacted polyol compound content is reduced. A problem occurs in which the emulsification performance and stability deteriorate due to the increase, and if it exceeds the above range, that is, when reacting with an excess number of moles of glycidyl groups compared to the number of moles of hydroxyl groups, the hydroxyl group content of the polyol-modified crosslinking agent is lowered, thereby reducing the emulsification performance of the produced silicone. This problem may occur.

The compound containing a vinyl group and a glycidyl group may be a compound containing a vinyl group at one end and a glycidyl group at the other end. Specifically, the compound containing a vinyl group and a glycidyl group may be represented by the following formula (3).

In Formula 3, R ¹⁵ may be an oxyalkylene group. For example, R ¹⁵ may be an oxyalkylene group having 1 to 15 carbon atoms, or an oxyalkylene group having 1 to 5 carbon atoms. Specifically, R ¹⁵ is oxymethyl (-O-CH ₂ -), oxyethylene (-O-CH ₂ -CH ₂ -, -CH ₂ -O-CH ₂ -), or oxypropylene (-O-CH ₂ It may be -CH ₂ -CH ₂ -, -CH ₂ -CH ₂ -O-CH ₂ -, -CH(CH ₃ )-O-CH ₂ -). Additionally, R ¹⁵ may be an oxyalkylene group in which an oxygen atom is bonded to a vinyl group. For example, R ¹⁵ may be oxyethylene (-O-CH ₂ -CH ₂ -, -CH ₂ -O-CH ₂ -).

The polyol compound contains 5 or more hydroxyl groups. For example, the polyol compound may include 5 to 7 hydroxyl groups, or 5 or 6 hydroxyl groups. Specifically, the polyol compound may include xylitol.

If the polyol compound contains four or less hydroxyl groups, the emulsification performance may be limited due to insufficient hydrophilic components such as hydroxyl group content. In addition, in the case of a polyol compound containing 5 or more hydroxyl groups, the reaction between the hydroxyl group of the polyol compound and the glycidyl group of the glycidyl group-containing compound occurs appropriately and the melting point of the polyol compound is lowered, providing an advantage in the process.

The polyol-modified crosslinking agent may be represented by the following formula (1).

In Formula 1, R ¹ to R ⁵ are each independently a hydrogen group or represented by the following Formula 2, and at least two of R ¹ to R ⁵ are represented by the following Formula 2. That is, in Formula 1, R ¹ to R ⁵ may be a hydrogen group or a group derived from a compound containing the vinyl group and glycidyl group, and at least two of R ¹ to R ⁵ contain the vinyl group and glycidyl group. It is a group derived from a compound.

In Formula 2,

R ¹⁰ is hydroxyalkylene having 2 to 10 carbon atoms,

R ¹¹ is alkenyl having 2 to 10 carbon atoms,

* is a joining hand.

For example, R ¹⁰ may be C _2-7 hydroxyalkylene or C _2-5 hydroxyalkylene, and R ¹¹ may be C _2-8 alkenyl or C _2-4 alkenyl. At this time, the alkylene and alkenyl may be linear or branched.

Among the hydroxyalkylene and oxyalkylene, alkylene refers to a branched, straight-chain, or cyclic divalent radical derived by removing one hydrogen atom from the carbon atom of an alkyl group. For example, the alkylene is methylene (-CH ₂ -), 1,1-ethylene (-CH(CH ₃ )-), 1,2-ethylene (-CH ₂ CH ₂ -), 1,1-propylene (-CH(CH ₂ CH ₃ )-), 1,2-propylene (-CH ₂ CH(CH ₃ )-), 1,3-propylene (-CH ₂ CH ₂ CH ₂ -), 1,4-butyl Examples include, but are not limited to, lene (-CH ₂ CH ₂ CH ₂ CH ₂ -) and 2,4-butylene (-CH ₂ (CH ₃ )CH ₂ CH ₂ -).

Additionally, the polyol-modified crosslinking agent may have a hydroxyl group (-OH) content of 1 to 15% by weight, 7 to 15% by weight, or 8 to 13% by weight based on the total weight of the compound. When the hydroxyl content of the polyol-modified crosslinking agent is within the above range, it acts as an emulsifying aid during silicone production, improves compatibility with aqueous systems, and provides excellent moisturizing effect. If the hydroxyl group content of the polyol-modified crosslinking agent is less than the above range, the hydrophilic group content of the produced silicone may be lowered, resulting in poor emulsification performance and low emulsion stability. In addition, if the hydroxyl group content of the polyol-modified crosslinking agent exceeds the above range, the lipophilic group content of the produced silicone may be relatively low, resulting in poor compatibility with oil, resulting in poor emulsification performance and low emulsion stability.

The polyol-modified crosslinking agent may have a weight average molecular weight (Mw) of 150 to 700 g/mol, or 300 to 600 g/mol. If the weight average molecular weight of the polyol-modified crosslinking agent is less than the above range, unreacted substances remain among the polyol compounds or compounds containing vinyl and glycidyl groups, which inhibits the silicone crosslinking reaction and may cause phase separation of the product in the future. If the weight average molecular weight of the polyol-modified cross-linking agent exceeds the above range, the hydroxyl group of the polyol compound causes an additional ring-opening reaction, and the hydrophilic group content of the prepared polyol-modified cross-linking agent may be lowered, thereby reducing emulsification performance.

Additionally, the polyol-modified crosslinking agent may have a viscosity of 1,000 to 30,000 cP, or 5,000 to 15,000 cP at 25°C. If the viscosity of the polyol-modified cross-linking agent at 25°C is less than the above range, the degree of polymerization of the polyol-modified cross-linking agent is increased, and the emulsification performance and emulsion stability of the produced silicone are poor due to the low content of hydrophilic groups. If the viscosity is above the above range, the cross-linking agent Unused polyol compounds may remain in the polyol-modified crosslinking agent, which may increase the content of hydrophilic groups, inhibiting the crosslinking reaction of the manufactured silicone and lowering compatibility with silicone.

The polyol-modified crosslinking agent may be included in the composition in an amount of 0.5 to 15 parts by weight, 0.5 to 8 parts by weight, or 3 to 5 parts by weight based on 0.1 to 15 parts by weight of organopolysiloxane. If the content of the polyol-modified crosslinking agent is less than the above range, the emulsification performance of the produced silicone is lowered and compatibility with the aqueous system is lowered, and if it exceeds the above range, the feeling of use of the produced silicone, such as softness and spreadability, is decreased. Problems of insufficient performance and poor workability may occur due to the high viscosity of silicone.

Organopolysiloxane

Organopolysiloxane is a substance that crosslinks with organohydrogenpolysiloxane.

The organopolysiloxane contains alkenyl groups and does not contain Si-H groups. For example, the organopolysiloxane may include alkenyl groups at both ends. Specifically, the organopolysiloxane may be represented by the following formula (4).

In Formula 4,

R ²⁰ to R ²³ are each independently a substituted or unsubstituted C _1-10 alkyl group or C _2-10 alkenyl group,

R ²⁴ and R ²⁵ are each independently a substituted or unsubstituted C _2-10 alkenyl group,

m is 5 to 1000.

Specifically, R ²⁰ to R ²³ may each independently be a substituted or unsubstituted C _1-6 alkyl group or C _1-3 alkyl group, or a C _2-8 alkenyl group or a C _2-4 alkenyl group.

Specifically, R ²⁴ and R ²⁵ may each independently be a substituted or unsubstituted C _2-8 alkenyl group, or a C _2-4 alkenyl group.

Specifically, m may be 30 to 300 or 50 to 100.

At this time, the alkyl group and alkenyl group may be linear or branched.

The organopolysiloxane may have an alkenyl group content of 0.1 to 1.0 mmol/g, or 0.2 to 0.7 mmol/g. At this time, the alkenyl group may be a vinyl group. If the alkenyl group content of the organopolysiloxane is less than the above range, the crosslink density of the prepared silicone is lowered and the thickening effect is unsatisfactory when applied to cosmetic formulations, and if it exceeds the above range, the crosslink density of the prepared silicone excessively increases. As a result, the oil absorption capacity may be lowered and the usability may be inferior.

Additionally, the organopolysiloxane may have a viscosity of 50 to 10,000 mPa·s, or 50 to 1,000 mPa·s at 25°C. If the viscosity of the organopolysiloxane at 25°C is less than the above range, the crosslinking density of the manufactured silicone increases, resulting in lower oil absorption and stiffness, resulting in low adhesion, resulting in an unsatisfactory feeling of use. If it exceeds the above range, the viscosity of the organopolysiloxane increases. , the crosslinking density and viscosity of the manufactured silicone is lowered, which may cause problems such as an unsatisfactory feeling of use, such as a sticky feeling.

The organopolysiloxane may have a weight average molecular weight (Mw) of 2,000 to 20,000 g/mol, or 3,000 to 10,000 g/mol. If the weight average molecular weight of the organopolysiloxane is less than the above range, the cross-linking density of the manufactured silicone increases, resulting in lower oil absorption and stiffness, resulting in low adhesion, resulting in an unsatisfactory feeling of use. If it exceeds the above range, the manufactured silicone The crosslinking density of the silicone is lowered and the hydroxyl group content is lowered, which may cause problems with insufficient emulsification performance.

Additionally, the organopolysiloxane may be included in the composition in an amount of 0.1 to 15 parts by weight, 0.5 to 5 parts by weight, or 1 to 3 parts by weight based on 0.5 to 15 parts by weight of the polyol-modified crosslinking agent. If the content of organopolysiloxane is less than the above range, the crosslink density of the produced silicone is lowered, resulting in low viscosity, and the thickening effect is unsatisfactory when applied to cosmetic formulations, and if it exceeds the above range, the hydrophilic group content of the produced silicone is lowered. Emulsification performance decreases, emulsion stability decreases, and cross-linking density increases excessively, which lowers oil absorption and may also result in inferior feeling of use.

The polyol-modified crosslinking agent and organopolysiloxane may be included in a weight ratio of 0.1:1 to 10:1, 0.5:1 to 7.0:1, or 1.0:1 to 4.0:1. For example, the polysiloxane composition may contain more polyol-modified crosslinking agent than organopolysiloxane. If the weight ratio of the polyol-modified cross-linking agent and the organopolysiloxane is less than the above range, that is, if a small amount of the polyol-modified cross-linking agent is included relative to the weight of the organopolysiloxane, the emulsification performance is insufficient, resulting in a decrease in the emulsification power and emulsion stability of the manufactured silicone. If it exceeds the above range, that is, if it contains an excessive amount of polyol-modified crosslinking agent relative to the weight of the organopolysiloxane, the compatibility with silicon is insufficient, so the stability of the polysiloxane composition is reduced and problems of phase separation may occur. .

Organohydrogenpolysiloxane

Organohydrogenpolysiloxane is a substance that crosslinks with polyol-modified crosslinking agents and organopolysiloxane, and is the main resin of polysiloxane compositions.

The organohydrogenpolysiloxane may include a hydrogen group (SiH) directly bonded to silicon in the side chain. Additionally, the organohydrogenpolysiloxane may be represented by the following formula (5).

In Formula 5,

R ³⁰ to R ³⁸ are each independently a substituted or unsubstituted C _1-10 alkyl group or a C _2-10 alkenyl group,

a is 1 to 50,

b is 20 to 250.

Specifically, R ³⁰ to R ³⁸ are each independently a substituted or unsubstituted C _1-6 alkyl group or C _1-3 alkyl group, a is 1 to 30 or 1 to 10, and b is 50 to 250 or 150 to 240. It can be.

At this time, the alkyl group and alkenyl group may be linear or branched.

The organohydrogenpolysiloxane may have a hydrogen group (SiH) content directly bonded to silicon of 0.01 to 10 mmol/g, 0.05 to 5.0 mmol/g, or 0.05 to 1.0 mmol/g. When the content of hydrogen groups (SiH) directly bonded to silicon of the organohydrogenpolysiloxane is within the above range, the crosslinking density of the produced silicon is appropriately adjusted, and subsequent mixing with the diluent is good, making it possible to produce a uniform paste. . If the content of hydrogen groups (SiH) directly bonded to the silicon of the organohydrogenpolysiloxane is less than the above range, there are problems with use such as the crosslink density of the manufactured silicone is low, the viscosity is low, and it is excessively sticky, and if the content exceeds the above range, In this case, the cross-linking density of the manufactured silicone may be excessively high, making it difficult to absorb oil and becoming stiff, resulting in poor adhesion, which may cause problems with use.

Additionally, the organohydrogenpolysiloxane may have a weight average molecular weight (Mw) of 300 to 25,000 g/mol, 3,000 to 20,000 g/mol, or 10,000 to 20,000 g/mol. When the weight average molecular weight of the organohydrogenpolysiloxane is within the above range, the viscosity of the manufactured silicone is appropriate and the applicability may be light and less sticky in terms of feeling of use. If the weight average molecular weight of the organohydrogenpolysiloxane is less than the above range, the cross-linking density of the manufactured silicone increases, making it difficult to absorb oil, and it becomes stiff, resulting in poor adhesion, leading to problems in use, and if it exceeds the above range, the manufactured silicone Problems with use may occur, such as lower crosslinking density, lower viscosity, and excessive stickiness.

The organohydrogenpolysiloxane may be included in the composition in an amount of 10 to 35 parts by weight, 10 to 25 parts by weight, or 11 to 17 parts by weight based on 0.5 to 15 parts by weight of the polyol-modified crosslinking agent. When the content of organohydrogenpolysiloxane is within the above range, unreacted products with organopolysiloxane are small, and the crosslinking density of the produced silicone is appropriate, so the physical properties and feeling of use of the silicone can be good. If the content of organohydrogenpolysiloxane is less than the above range, the crosslink density of the produced silicone is lowered, the viscosity is low, and the stickiness is increased, which results in unsatisfactory feeling of use. If the content is more than the above range, the crosslink density of the silicone increases and the hydrophilic group As the content of is lowered, problems with lowering emulsification performance and emulsion stability may occur.

diluent

The diluent is not particularly limited as long as it can be added as a diluent to the polysiloxane composition, and examples include organic solvents and silicone oil.

The organic solvent includes, for example, ethanol, isopropanol, sorbitol, maltose, cholesterol, sitosterol, phytosterol, lanosterol, butylene glycol, propylene glycol, dibutylene glycol, pentyl glycol, triethylhexanoin, etc. I can hear it. In addition, the silicone oil includes dimethylpolysiloxane, methylphenylpolysiloxane, dimethylsiloxane·methylphenylsiloxane copolymer, organopolysiloxane, octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6). ), tetramethyltetraphenylcyclotetrasiloxane, tritrimethylsiloxysilane (M3T), tetrakistrimethylsiloxysilane (M4Q), tritrimethylsiloxyphenylsilane, stearoxy silicone, alkyl modified silicone, amino modified silicone , fluorine-modified silicon, etc. Additionally, the organic solvent may be a naturally derived oil.

The diluent may be included in the composition in an amount of 55 to 98 parts by weight, 70 to 90 parts by weight, or 75 to 85 parts by weight based on 0.5 to 15 parts by weight of the polyol-modified crosslinking agent. If the content of the diluent is less than or exceeds the above range, a uniform polysiloxane composition may not be obtained and is undesirable in terms of viscosity or feeling of use of the produced silicone.

The polysiloxane composition according to the present invention may further include additives such as catalysts and antioxidants.

additive

The catalyst is not particularly limited as long as it can be added to the polysiloxane composition, and includes, for example, a hydrosilylation catalyst, specifically, chloroplatinic acid, platinum metal, platinum supported on alumina, platinum supported on silica, Examples include platinum supported on carbon black, platinum-vinylsiloxane complex, platinum phosphorus complex, platinum-phosphite complex, and platinum alcoholate catalyst.

Additionally, the catalyst may be included in the composition in an amount of 0.001 to 0.1 parts by weight, or 0.01 to 0.09 parts by weight, based on 0.5 to 15 parts by weight of the polyol-modified crosslinking agent. If the catalyst content is less than the above range, the crosslinking reaction may not occur and silicon may not be produced, and if it exceeds the above range, the catalyst may remain in the product of the crosslinking reaction, darkening the color of the produced silicon.

The antioxidant is not particularly limited as long as it can be added to the polysiloxane composition to improve storage stability, and may be, for example, a benzopyran-based compound.

Additionally, the antioxidant may be included in the composition in an amount of 0.001 to 0.2 parts by weight, or 0.01 to 0.1 parts by weight, based on 0.5 to 15 parts by weight of the polyol-modified crosslinking agent. If the content of the antioxidant is less than the above range, the storage stability of the polysiloxane composition may decrease, causing phase separation and lowering the emulsion stability of the composition, and if it exceeds the above range, the appearance of the polysiloxane composition may turn yellow.

As described above, the polysiloxane composition according to the present invention includes a polyol-modified crosslinking agent prepared by reacting a vinyl group and a glycidyl group-containing compound and a polyol compound, and can produce silicone with excellent hydrophilicity, emulsification performance, storage stability, and feeling of use. .

hydrophilic silicone

Additionally, the hydrophilic silicone according to the present invention is prepared from the polysiloxane composition.

The hydrophilic silicone may have a solid content of 10 to 30% by weight or 10 to 20% by weight based on the total weight. Additionally, the hydrophilic silicone may have a viscosity of 50,000 to 500,000 cP or 100,000 to 300,000 cP at 25°C.

As described above, the hydrophilic silicone according to the present invention has excellent hydrophilicity, emulsification performance, storage stability, and feeling of use, and is suitable for use as an emulsifier in cosmetic compositions.

Hereinafter, the present invention will be described in more detail through examples. However, these examples are only intended to aid understanding of the present invention, and the scope of the present invention is not limited to these examples in any way.

Preparation Example 1. Preparation of polyol modified crosslinking agent-1

20.13 parts by weight of xylitol and 2.97 parts by weight of potassium hydroxide (KOH) were added to the reaction vessel, the temperature was raised to 110°C and maintained for 30 minutes. After water was removed by dehydration under reduced pressure, 31.72 parts by weight of allyl glycidyl ether was added dropwise for 6 hours to cause reaction. Afterwards, the temperature was reduced to 60°C, 1.71 parts by weight of phosphoric acid and 39.7 parts by weight of ethanol were added and stirred. Afterwards, 0.68 parts by weight of neutralizer (KYOWAAD-700, Kyowa Chemical Industry Co., Ltd.), 2.74 parts by weight of activated carbon, and 0.35 parts by weight of water were added and stirred. Afterwards, it was filtered through filter paper and distilled under reduced pressure at 120°C for 3 hours to remove the solvent (ethanol and water) and unreacted remaining substances to prepare polyol-modified crosslinking agent-1. At this time, the reaction molar ratio between the glycidyl group in allyl glycidyl ether, a vinyl group and a glycidyl group-containing compound, and the hydroxyl group in xylitol, a polyol compound, was about 2:1.

The prepared polyol-modified crosslinking agent-1 was represented by the following formula (6), had a weight average molecular weight (Mw) of 420 g/mol, and a viscosity at 25°C of 12,000 cP.

Preparation Examples 2 to 4. Preparation of polyol modified crosslinking agent-2 to 4

A crosslinking agent was prepared in the same manner as Preparation Example 1, except that the content of each component was adjusted as shown in Table 1.

Ingredient name (parts by weight) Manufacturing Example 1 Production example 2 Production example 3 Production example 4 Allyl glycidyl ether 31.72 38.25 45.22 6.05 xylitol 20.13 18.21 15.07 26.87 potassium hydroxide 2.97 2.69 2.22 3.96 phosphoric acid 1.71 1.54 3.88 6.92 ethanol 39.7 35.90 29.71 52.98 corrector 0.68 0.61 0.51 0.91 activated carbon 2.74 2.48 3.13 1.84 water 0.35 0.32 0.26 0.47 total 100.00 100.00 100.00 100.00 Physical properties of the prepared crosslinking agent Molar ratio of glycidyl group/hydroxyl group 2.1 2.8 4.1 0.9 Weight average molecular weight (g/mol) 420 520 712 230 Viscosity at 25℃ (cP) 12,000 7,000 3,100 40,800 Hydroxyl content (% by weight) 12 9.2 6.7 18.1

Experimental Example 1. Preparation of hydrophilic silicone

In a reaction vessel, 16.3 parts by weight of organohydrogenpolysiloxane, 4.87 parts by weight of the polyol-modified crosslinking agent of Preparation Example 1, 1.25 parts by weight of organopolysiloxane-1, and 15.0 parts by weight of dimethylpolysiloxane (Dimethicone-2cSt) as a diluent were added and stirred. Afterwards, 0.03 parts by weight of catalyst and 0.02 parts by weight of antioxidant were added, the temperature was raised to 80°C, and reaction was performed for 2 hours. After cooling to room temperature and performing the 3-roll mill process three times, 62.53 parts by weight of dimethylpolysiloxane (Dimethicone-2cSt) was added and diluted to prepare hydrophilic silicone with a solid content of 22% by weight.

The produced hydrophilic silicone had a viscosity of 250,000 cP at 25°C and appeared as a milky white paste.

Experimental Examples 2 to 18.

Hydrophilic silicone was prepared in the same manner as in Experimental Example 1, except that the same amounts of ingredients as shown in Tables 2 and 3 were used.

(part by weight) Experimental Example 1 Experimental Example 2 Experimental Example 3 Experimental Example 4 Experimental Example 5 Experimental Example 6 Experimental Example 7 Experimental Example 8 Experimental Example 9 Organohydrogen polysiloxane 16.3 11.6 16.3 16.3 16.3 16.3 24.3 10.5 10.5 diluent 77.53 82.32 81.77 74.62 78.06 73.94 70.55 87.3 87.3 antioxidant 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 catalyst 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 Organopolysiloxane-1 1.25 2.78 1.25 1.25 0.72 4.84 1.8 1.05 1.05 Polyol modified crosslinking agent-1 4.87 - 0.63 7.78 4.87 4.87 3.3 1.1 - Polyol modified crosslinking agent-2 - 3.25 - - - - - - - Polyol modified crosslinking agent-3 - - - - - - - - 1.1 Polyol modified crosslinking agent-4 - - - - - - - - - Organopolysiloxane-2 - - - - - - - - - Organopolysiloxane-3 - - - - - - - - - total 100 100 100 100 100 100 100 100 100

(part by weight) Experimental Example 10 Experimental Example 11 Experimental Example 12 Experimental Example 13 Experimental Example 14 Experimental Example 15 Experimental Example 16 Experimental Example 17 Experimental Example 18 Organohydrogenpolysiloxane 10.5 16.3 16.3 8.6 40.6 16.3 16.3 14.3 5.4 diluent 87.3 65.1 65.1 85.23 53.23 77.53 77.53 68.0 24.8 antioxidant 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 catalyst 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 Organopolysiloxane-1 1.05 1.25 17.3 1.25 1.25 - 6.12 1.1 0.4 Polyol modified crosslinking agent-1 - 17.3 1.25 4.87 4.87 6.12 - - - Polyol modified crosslinking agent-2 - - - - - - - - - Polyol modified crosslinking agent-3 - - - - - - - - - Polyol modified crosslinking agent-4 1.1 - - - - - - - - Organopolysiloxane-2 - - - - - - - 16.55 - Organopolysiloxane-3 - - - - - - - - 69.35 total 100 100 100 100 100 100 100 100 100

Below, the manufacturer, product name, or ingredient name of each ingredient used in the experimental example is shown in Table 4.

ingredient note Organopolysiloxane-1

비닐기 함량: 0.4mmol/g, m: 59, 25℃에서의 점도: 100mPa·s, Mw: 5,000g/mol

Vinyl group content: 0.4mmol/g, m: 59, viscosity at 25℃: 100mPa·s, Mw: 5,000g/mol Organopolysiloxane-2

Vinyl group content: 1.2mmol/g, m: 20, viscosity at 25℃: 20mPa·s, Mw: 1,700g/mol Organopolysiloxane-3

Vinyl group content: 0.08mmol/g, m: 330, viscosity at 25℃: 20,000mPa·s, Mw: 25,000g/mol Organohydrogen polysiloxane

Content of hydrogen (SiH) bonded to silicon: 0.1 mmol/g, Mw: 17,000 g/mol, a: 2, b: 230 antioxidant 3,4-Dihydro-2,5,7,8-tetramethyl-2-(4,8,12-trimethyltridecyl)-2H-benzopyran-6-ol catalyst PT-VTSC-1.0PS (complex of platinum and (0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane, Platinum-(0)-1,3-divinyl-1,1 ,3,3- tetramethyldisiloxane) (platinum content: 1% by weight)

Test example. Characteristic evaluation

The physical properties of the hydrophilic silicone prepared in the experimental example were measured in the following manner, and the results are shown in Table 5 below.

(1) Emulsifying power

The hydrophilic silicone of the experimental example was prepared as a water-in-oil emulsion corresponding to the following formulation, and the emulsification performance was evaluated.

Specifically, phase A was prepared by mixing 8% by weight of hydrophilic silicone and 10% by weight of dimethylpolysiloxane (Dimethicone-2cSt). Additionally, phase B was prepared by mixing 80% by weight of ionized water and 2% by weight of sodium chloride. Thereafter, phase B was added in small amounts while stirring the phase A at a gradually increasing stirring speed of 480 to 2,300 rpm to prepare a water-in-oil emulsion.

The evaluation criteria is 5 levels: very good (5 points) if the silicone and ionic water are emulsified without phase separation and easily dissolved in water; excellent (4 points) if they are emulsified without phase separation or take some time to dissolve in water; It is not visible to the naked eye, but if a small amount of silicone residue remains when touched with a finger or a small oily band is formed when dissolved in water, it is average (3 points). If the silicone and ionized water are not partially emulsified, it is slightly insufficient (3 points). 2 points), and if the silicon and ionized water remained completely unmixed, it was evaluated as very insufficient (1 point).

(2) Emulsion stability

The water-in-oil emulsion prepared in item (1) was stored at 50°C for 7 days, and then the agglomeration of silicone and oil separation phenomena were observed with the naked eye. At this time, the evaluation criteria is very good (5 points) if there is no oil separation in the emulsion and it is good, excellent (4 points) if there is some clumping, and if there is clumping and some oil separation occurs and a few drops of oil are floating on the surface. In this case, it was rated as average (3 points), if oil separation occurred and the oil was somewhat separated, it was rated as slightly insufficient (2 points), and if oil separation was very severe and water and oil were completely separated, it was rated as very insufficient (1 point). .

(3) Product stability

After the hydrophilic silicone of the experimental example was stored at 80°C for 7 days, agglomeration of the silicone and oil separation phenomena were observed with the naked eye. At this time, the evaluation standard is very good (5 points) if the formulation is good and there is no clumping or oil separation, and excellent (4 points) if there is slight clumping. If there is clumping and some oil separation occurs, it is excellent (4 points). If there is clumping and some oil separation occurs, a few drops of oil may appear on the surface. If the oil is floating, it is average (3 points), if oil separation occurs and the oil is somewhat separated, it is slightly insufficient (2 points), and if the oil separation is very severe and the low-viscosity oil is completely separated, it is very poor (1 point). It was evaluated as

(4) Feeling of use

1 g of the silicone of the experimental example was placed on the back of the hand and spread thinly in a circular motion, and the feeling of use was evaluated through tactile and skin sensation during application and softness and moisture after application.

Specifically, we compared whether it spreads softly and smoothly, whether it is less sticky, and the level of moisture. The evaluation results were very good (5 points), excellent (4 points), average (3 points), and slightly poor (2 points). points) and very insufficient (1 point).

Viscosity at 25℃ (cP) emulsifying power emulsion stability product stability feeling of use Experimental Example 1 250,000 5 4 4 5 Experimental Example 2 220,000 5 5 4 4 Experimental Example 3 298,000 3 3 4 3 Experimental Example 4 109,000 4 3 3 3 Experimental Example 5 120,000 3 3 3 3 Experimental Example 6 98,000 3 3 4 3 Experimental Example 7 93,800 3 3 4 3 Experimental Example 8 65,000 3 3 4 3 Experimental Example 9 248,000 3 2 2 3 Experimental Example 10 170,000 3 2 2 3 Experimental Example 11 298,000 3 2 2 2 Experimental Example 12 109,000 2 2 2 2 Experimental Example 13 120,000 3 2 2 2 Experimental Example 14 98,000 2 2 2 2 Experimental Example 15 93,800 One One One One Experimental Example 16 350,000 One One 3 One Experimental Example 17 410,000 One One 2 One Experimental Example 18 850,000 One One 2 One

As shown in Table 5, the silicones of Experimental Examples 1 to 8 were excellent in emulsifying power, emulsifying stability, product stability, and feeling of use.

On the other hand, Experimental Example 15, which did not contain vinyl group-containing organopolysiloxane, was very poor in emulsifying power, emulsifying stability, product stability, and feeling of use.

In addition, Experimental Examples 16 to 18, which did not contain a polyol-modified crosslinking agent, were very poor in emulsifying power, emulsifying stability, and feeling after use. In particular, Experimental Example 17, which does not contain a polyol-modified crosslinking agent and includes organopolysiloxane-2 with an excessive vinyl group content, and Experimental Example 18, which includes organopolysiloxane-3 with a small vinyl group content, also shows some product stability. It wasn't enough.

Claims (6)

Contains a polyol-modified crosslinking agent, organohydrogenpolysiloxane, organopolysiloxane containing an alkenyl group, and a diluent, The polyol-modified crosslinking agent is prepared by reacting a vinyl group-containing glycidyl group-containing compound and a polyol compound at a molar ratio of 2:1 to 5:1, A polysiloxane composition wherein the polyol compound contains 5 or more hydroxyl groups. In claim 1, The polyol-modified crosslinking agent has a hydroxyl group (-OH) content of 1 to 15% by weight based on the total weight of the compound, a weight average molecular weight (Mw) of 150 to 700 g/mol, and a viscosity of 1,000 to 30,000 cP at 25°C. , polysiloxane composition. In claim 1, The polyol compound includes xylitol, The polyol-modified crosslinking agent is a polysiloxane composition represented by the following formula (1): [Formula 1]

In Formula 1, R ¹ to R ⁵ are each independently a hydrogen group or represented by the following formula (2), and at least two of R ¹ to R ⁵ are represented by the following formula (2). [Formula 2]

In Formula 2, R ¹⁰ is hydroxyalkylene having 2 to 10 carbon atoms, R ¹¹ is alkenyl having 2 to 10 carbon atoms, * is a joining hand. In claim 1, The composition includes 0.5 to 15 parts by weight of a polyol-modified crosslinking agent, 0.1 to 15 parts by weight of an alkenyl group-containing organopolysiloxane, 10 to 35 parts by weight of organohydrogenpolysiloxane, and 55 to 98 parts by weight of a diluent. A polysiloxane composition. A hydrophilic silicone prepared from the polysiloxane composition of any one of claims 1 to 4. In claim 5, A hydrophilic silicone having a solids content of 10 to 30% by weight relative to the total weight and a viscosity at 25° C. of 50,000 to 500,000 cP.