KR102170712B1 - Silicone elastomers composition and preparation method thereof - Google Patents

Abstract

The present invention relates to a silicone elastomer composition and a method for producing the same, and more particularly to a silicone elastomer composition and a method for producing the same that can be used for thickening a silicone fluid and an organic solvent. The silicone elastomer composition of the present invention comprises a main crosslinking portion prepared by addition reaction of a first organohydrogenpolysiloxane and an α,ω-diene compound, a second organohydrogenpolysiloxane as a main chain, and a diluent.

Description

Silicone elastomers composition and preparation method thereof TECHNICAL FIELD

The present invention relates to a silicone elastomer composition, and more particularly to a method for preparing a silicone elastomer composition that can be used for thickening of silicone fluids and organic solvents.

Recently, an attempt to manufacture a cosmetic composition by applying a silicone elastomer continues.

Silicone elastomer has a high oil absorption, so it can absorb sebum and sweat, and it is a material that has excellent swelling properties for silicone oil in cosmetics.Talc, mica, and sericite are used in cosmetics along with silicone oil. , Silica, calcium carbonate, kaolin, it is used as a dispersion medium for extender pigments such as starch.

In addition, in order to provide a silicone elastomer that can be used in cosmetics, attempts to prepare a silicone elastomer using organopolysiloxane and various binders are continuing, and among them, silicone elastomers prepared using organic compounds as a crosslinking agent are excellent. Although it shows a feeling of use, it is not possible to manufacture raw materials with excellent sensory properties due to unpleasant odor.

Accordingly, the inventors of the present invention completed the present invention by discovering a silicone elastomer with an excellent feeling of use and a reduction in unpleasant odor to a degree applicable to cosmetic compositions and a method for producing the silicone elastomer prepared by using an organic compound as a crosslinking agent.

An object of the present invention is to provide a silicone elastomer with improved feeling of use and improved unpleasant odor while using an organic compound as a crosslinking agent, and a method for manufacturing the same.

More specifically, it is an object of the present invention to provide a silicone elastomer with improved feeling of use and improved unpleasant odor to be used in cosmetic compositions, and a method for manufacturing the same.

In addition, by including the silicone elastomer composition according to the present invention, it is intended to provide a cosmetic composition having excellent dispersibility of raw materials, improved storage stability, and excellent sensory properties.

In order to achieve the above object, the present invention provides a main crosslinking part prepared by addition reaction of a first organohydrogenpolysiloxane and an α,ω-diene compound, a second organohydrogenpolysiloxane as a main chain, and a diluent. A silicone elastomer composition comprising, wherein the first organohydrogenpolysiloxane is a compound containing a hydrogen atom bonded to silicon at both ends, represented by the following formula (1), and the second organohydrogenpolysiloxane comprises silicon and It provides a silicone elastomer composition that is represented by the following formula (2) as a compound containing a bonded hydrogen atom.

[Formula 1]

HR ₂ SiO(R´ ₂ SiO) _a SiR ₂ H

[Formula 2]

R ₃ SiO(R´ ₂ SiO) _b (R˝HSiO) _c SiR ₃

(In Formulas 1 and 2,

R, R'and R" are each independently selected from C ₁ to C ₁₅ alkyl groups,

a

250, 0

b

250, 1

c

250 임)0

a

250, 0

b

250, 1

c

250)

In another aspect, the present invention (a) by mixing the first organohydrogenpolysiloxane and an α,ω-diene compound to prepare a main crosslinking portion in which α,ω-diene is additionally bonded to the terminal of the first organohydrogenpolysiloxane (B) mixing the main crosslinking part, the second organohydrogenpolysiloxane, and the first diluent to prepare a silicone gel, and (c) mixing the silicone gel with a second diluent to shear and swell the silicone gel. It provides a method for producing a silicone elastomer composition comprising the step of.

In another aspect, the present invention provides a cosmetic composition comprising the silicone elastomer composition according to the present invention.

The silicone elastomer composition of the present invention can exhibit an effect of improving unpleasant odor and excellent feeling of use, and according to the manufacturing method of the silicone elastomer composition of the present invention, an organic compound can be used as a crosslinking agent while excellently improving the resulting unpleasant odor. It works.

In addition, by including such a silicone elastomer composition, it is possible to provide a cosmetic composition having excellent sensory properties such as spreadability.

Hereinafter, the present invention will be described in detail.

[Silicone elastomer composition]

In one aspect, the present invention provides a silicone elastomer composition comprising a main crosslinking part prepared by addition reaction of a first organohydrogenpolysiloxane and an α,ω-diene compound, a second organohydrogenpolysiloxane as a main chain, and a diluent. do.

First organohydrogenpolysiloxane

Si-H의 구조의 수소 원자를 의미한다.The first organohydrogenpolysiloxane may be an organohydrogenpolysiloxane compound containing a hydrogen atom bonded to silicon at both ends, wherein the hydrogen atom bonded to silicon is

It means a hydrogen atom in the structure of Si-H.

The first organohydrogenpolysiloxane may be represented by Formula 1 below.

[Formula 1]

HR ₂ SiO(R´ ₂ SiO) _a SiR ₂ H

a

250 이다.In Formula 1, R and R'are each independently selected from C ₁ to C ₁₅ alkyl groups, and 0

a

250.

The alkyl group includes a linear or branched chain, and may be further substituted by other substituents. The number of carbon atoms of the alkyl group may be 1 to 15, specifically 1 to 10, and more specifically 1 to 6. The alkyl group is not limited thereto, for example, methyl group, ethyl group, propyl group, n-propyl group, isopropyl group, butyl group, n-butyl group, isobutyl group, tert-butyl group, sec-butyl group, 1-methylbutyl group, 1-ethylbutyl group, pentyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, hexyl group, n-hexyl group, 1-methylpentyl group, 2-methyl Pentyl group, 3,3-dimethylbutyl group, 2-ethylbutyl group, heptyl group, n-heptyl group, 1-methylhexyl group, cyclopentylmethyl group, octyl group, n-octyl group, tert-octyl group, 1- Methylheptyl group, 2-ethylhexyl group, 2-propylpentyl group, n-nonyl group, 2,2-dimethylheptyl group, 1-ethylpropyl group, 1,1-dimethylpropyl group, isohexyl group, 2-methyl Pentyl group, 4-methylhexyl group, 5-methylhexyl group, and the like, but are not limited thereto.

a

50 인 제1 오르가노하이드로겐폴리실록산을 사용할 수 있다.In one embodiment, R and R'is a methyl group, 40

a

A first organohydrogenpolysiloxane of 50 can be used.

The viscosity of the first organohydrogenpolysiloxane is not limited thereto, but for example, 30 to 100 cP, specifically 30 to 50 cP at 25°C may be used.

The weight average molecular weight of the first organohydrogenpolysiloxane is not limited thereto, but, for example, 2,000 to 5,000 g/mol may be used, and specifically 3,000 to 4,000 g/mol may be used.

The total H content of the first organohydrogenpolysiloxane is not limited thereto, but may be, for example, 0.3 to 2 mmol/g, specifically 0.5 to 0.8 mmol/g.

In the present invention, the viscosity may represent a value measured at 25° C. and 90% or more of Torque using a Brookfield viscometer LV type spindle #18. In addition, the H content of the first organohydrogenpolysiloxane can be calculated as {(2/molecular weight of the first organohydrogenpolysiloxane)*1,000mmol/g}.

The first organohydrogenpolysiloxane may be included in an amount of 75 to 95 parts by weight, specifically 80 to 90 parts by weight, based on 100 parts by weight of the main crosslinking part, but is not limited thereto.

α,ω-diene compounds

The α,ω-diene compound is a compound containing two alkene groups so as to be additionally bonded to the first organohydrogenpolysiloxane.

The α,ω-diene compound may be a compound represented by Formula 3 below.

[Formula 3]

CH ₂ =CH(CH ₂ ) _x CH=CH ₂

20 일 수 있다.In Chemical Formula 3, 1

Can be 20

The α,ω-diene compound is not limited thereto, for example, 1,4-pentadiene, 1,5-hexadiene; 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1,11-dodecadiene, 1,13-tetradecadiene and 1,10-ecosa At least one compound selected from the group consisting of diene may be used.

In one embodiment, the α,ω-diene compound may be 1,7-octadiene.

In the silicone elastomer composition of the present invention, the main crosslinking portion is prepared by an addition reaction by mixing the first organohydrogenpolysiloxane and an α,ω-diene compound. More specifically, the main crosslinking part may be in a form in which the α,ω-diene compound is added to the terminal of the first organohydrogenpolysiloxane.

The Vi content of the main crosslinked portion prepared by the addition reaction is not limited thereto, but may be, for example, 0.3 to 3.6 mmol/g, specifically 0.4 to 2 mmol/g.

The α,ω-diene compound may be included in an amount of 5 to 25 parts by weight, specifically 10 to 20 parts by weight based on 100 parts by weight of the main crosslinking part, but is not limited thereto.

The mixing molar ratio of the first organohydrogenpolysiloxane and the α,ω-diene compound is the first organohydrogenpolysiloxane: as an α,ω-diene compound, 1: 2 to 1: 10, specifically 1: 3 to 1 : May be 8, in one embodiment may be 1: 5, but is not limited thereto. When mixed at the molar ratio, the effect of reducing unpleasant odor may be more excellent.

In addition, the addition reaction is not limited thereto, but may be performed in the presence of a platinum-based catalyst. The platinum-based catalyst may be, for example, a Karstedt catalyst disclosed in US Patent Nos. 3,715,334 and 3,814,730. The Karstedt catalyst represents platinum divinyl tetramethyl disiloxane containing about 1% by weight of platinum in a solvent such as toluene. In addition, as the platinum-based catalyst, a reaction product of platinum chloric acid and an organosilicone compound containing an unsaturated fatty chain at the terminal may be used.

The platinum-based catalyst may be used in an amount of 0.001 to 1 part by weight based on 100 parts by weight of the main crosslinking part.

In addition, the main crosslinking unit may be preferably prepared by mixing the first organohydrogenpolysiloxane and an α,ω-diene compound and then heating, and the heating is performed at 50 to 120° C. for 30 minutes to 10 hours, more specifically It may be performed at 60 to 100 °C for 1 hour to 5 hours. The main crosslinking part is prepared by mixing the first organohydrogenpolysiloxane and an α,ω-diene compound and then heating it, thereby remaining α,ω-diene without being added to the end of the first organohydrogenpolysiloxane By volatilizing the compound, it is possible to exhibit an effect of reducing an unpleasant odor in the finally prepared silicone elastomer composition.

As described above, the main crosslinking portion formed by adding an α,ω-diene compound to the first organohydrogenpolysiloxane is additionally mixed with a second organohydrogenpolysiloxane as a main chain to be described later and a diluent (specifically, a first diluent). The addition crosslinking can form a silicone gel.

Second organohydrogenpolysiloxane

Si-H의 구조의 수소 원자를 의미한다.The second organohydrogenpolysiloxane may be an organohydrogenpolysiloxane compound containing a hydrogen atom bonded to silicon in a side chain, wherein the hydrogen atom bonded to silicon is

It means a hydrogen atom in the structure of Si-H.

The second organohydrogenpolysiloxane may be represented by Formula 2 below.

[Formula 2]

R ₃ SiO(R´ ₂ SiO) _b (R˝HSiO)cSiR ₃

b

250, 1

c

250 이다.In Formula 2, R, R'and R" are each independently selected from a C ₁ to C ₁₅ alkyl group, and 0

b

250, 1

c

250.

The alkyl group includes a linear or branched chain, and may be further substituted by other substituents. The number of carbon atoms of the alkyl group may be 1 to 15, specifically 1 to 10, and more specifically 1 to 6. The alkyl group is not limited thereto, for example, methyl group, ethyl group, propyl group, n-propyl group, isopropyl group, butyl group, n-butyl group, isobutyl group, tert-butyl group, sec-butyl group, 1-methylbutyl group, 1-ethylbutyl group, pentyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, hexyl group, n-hexyl group, 1-methylpentyl group, 2-methyl Pentyl group, 3,3-dimethylbutyl group, 2-ethylbutyl group, heptyl group, n-heptyl group, 1-methylhexyl group, cyclopentylmethyl group, octyl group, n-octyl group, tert-octyl group, 1- Methylheptyl group, 2-ethylhexyl group, 2-propylpentyl group, n-nonyl group, 2,2-dimethylheptyl group, 1-ethylpropyl group, 1,1-dimethylpropyl group, isohexyl group, 2-methyl Pentyl group, 4-methylhexyl group, 5-methylhexyl group, and the like, but are not limited thereto.

b

230, 2

c

5 인 제2 오르가노하이드로겐폴리실록산을 사용할 수 있다.In one embodiment, the R, R'and R" is a methyl group, 30

b

230, 2

c

It is possible to use a 5 phosphorus second organohydrogenpolysiloxane.

The viscosity of the second organohydrogenpolysiloxane is not limited thereto, but may be, for example, 1 to 10,000 cP, specifically 1 to 1,000 cP at 25°C. The viscosity may represent a value measured at 25° C. and 90% or more of Torque using a Brookfield viscometer LV type spindle #18.

The weight average molecular weight of the second organohydrogenpolysiloxane is not limited thereto, but, for example, 1,000 to 20,000 g/mol may be used, and specifically 2,500 to 18,000 g/mol may be used.

The total H content of the second organohydrogenpolysiloxane is not limited thereto, but, for example, 0.1 to 2 mmol/g, 0.11 to 2 mmol/g, 0.5 to 2 mmol/g, specifically 0.6 to 1.7 mmol/ g can be used.

In the silicone elastomer composition of the present invention, the molar ratio of the second organohydrogenpolysiloxane and the first organohydrogenpolysiloxane may be 1:0.5 to 1:6, specifically 1:1 to 1:5, and more Specifically, it may be 1:1 to 1:3.

In addition, in order to achieve excellent physical properties of the finally prepared silicone elastomer composition, the content of the second organohydrogenpolysiloxane is the Vi content of the main crosslinking part and the H content of the second organohydrogenpolysiloxane in the following formula 1 When calculated by, these values may be included to be 0.5 to 2, specifically 0.6 to 1.8, more specifically 1.2 to 1.8, and more specifically 1.2 to 1.5. When included in the above content, the degree of improvement in physical properties such as viscosity and hardness of the finally prepared silicone elastomer composition is excellent, and when the silicone elastomer composition according to the silicone elastomer composition is used for a cosmetic composition, it can exhibit an effect that shows excellent feeling of use.

The Vi content of the main crosslinked part can be calculated as {(2/molecular weight of the main crosslinked part)*1,000 mmol/g}, and the main crosslinked part contains a vinyl group (Vi) at both ends.

The H content of the second organohydrogenpolysiloxane can be calculated as {(number of H/molecular weight of the second organohydrogenpolysiloxane)*1,000 mmol/g}, wherein the number of H is'c' in Formula 2 It represents the value of.

[Equation 1]

(Vi content of the main crosslinking part)/(H content of the second organohydrogenpolysiloxane)

In addition, the silicone gel may be prepared by mixing the main crosslinking part with the main chain and a diluent (specifically, a first diluent) and then performing an addition crosslinking reaction in the presence of a platinum-based catalyst, wherein the platinum-based catalyst is 100 weight of the total composition It may be included to be used in an amount of 0.001 to 1 part by weight based on parts.

Further, mixing of the main crosslinking portion and the second organohydrogenpolysiloxane is carried out using a diluent as a solvent.

diluent

The silicone elastomer composition of the present invention includes a diluent used as a solvent for the addition crosslinking reaction of the main crosslinking portion and the main chain, and a diluent for shearing and swelling of the silicone gel. In the present specification, a diluent used as a solvent for the addition crosslinking reaction of the main crosslinking portion and the main chain in order to explain the diluent used as a solvent for the addition crosslinking reaction between the main crosslinking portion and the main chain and the diluent used for shearing and swelling of the silicone gel. Is also referred to as a first diluent, and a diluent used for shearing and swelling of the silicone gel is also referred to as a second diluent.

The first and second diluents may each independently be a low molecular weight silicone oil, and may be a low molecular weight linear or cyclic polysiloxane. Specifically, the low molecular weight silicone oil is a group consisting of low molecular weight linear and cyclic volatile methylsiloxanes, low molecular weight linear and cyclic volatile and nonvolatile alkyl and aryl siloxanes, and low molecular weight linear and cyclic substituted siloxanes It may be at least one compound selected from. More specifically, the low molecular weight silicone oil may be a low molecular weight linear and cyclic volatile methylsiloxane.

The linear volatile methylsiloxane may have a formula of (CH ₃ ) ₃ SiO{(CH ₃ ) ₂ SiO} _y Si(CH ₃ ) ₃ , where y is a number from 0 to 15, specifically y is 2 It may be to 10, and the viscosity may be 1 to 10 cP at 25 ℃.

In one embodiment, the first diluent and the second diluent may be, for example, cyclopentasiloxane, low molecular weight poly(dimethylsiloxane), or a mixture thereof.

The first diluent may be included in an amount of 1 to 50 parts by weight based on 100 parts by weight of the total silicone elastomer composition, and specifically, may be included in an amount of 1 to 20 parts by weight, but is not limited thereto. The second diluent may be included in an amount of 50 to 90 parts by weight, and specifically 55 to 80 parts by weight, based on 100 parts by weight of the total silicone elastomer composition, but is not limited thereto.

The silicone elastomer composition according to the present invention may have a gel content of 10 to 30 parts by weight based on 100 parts by weight of the total silicone elastomer composition, wherein the gel content is the total sum of the content of the main crosslinking part and the second organohydrogenpolysiloxane as the main chain It may be to represent.

The silicone elastomer composition may have a viscosity of 100,000 to 600,000 cP, wherein the viscosity may be a value measured for 10 minutes at 2.5 rpm using a Brookfield viscometer HBDVT2 spindle #93.

In one aspect, the present invention provides a method for preparing a silicone elastomer composition.

[Method for preparing silicon elastomer composition]

The method for preparing the silicone elastomer composition of the present invention includes (a) a stock price in which α,ω-diene is additionally bonded to the terminal of the first organohydrogenpolysiloxane by mixing the first organohydrogenpolysiloxane and an α,ω-diene compound. (B) preparing a silicone gel by mixing the main crosslinking part, the second organohydrogenpolysiloxane, and a first diluent, and (c) mixing the silicone gel with a second diluent to prepare a silicone gel. Shearing and swelling.

(a) Manufacturing step of the main crosslinking unit

In the method for preparing the silicone elastomer composition of the present invention, the first organohydrogenpolysiloxane and the α,ω-diene compound are mixed, and a main crosslinking portion is prepared by an addition reaction therebetween.

The mixing molar ratio of the first organohydrogenpolysiloxane and the α,ω-diene compound is the first organohydrogenpolysiloxane: as an α,ω-diene compound, 1: 2 to 1: 10, specifically 1: 3 to 1 : May be 8, in one embodiment may be 1: 5, but is not limited thereto. When mixed at the molar ratio, the effect of reducing unpleasant odor may be more excellent.

The platinum-based catalyst may be used in an amount of 0.001 to 1 part by weight based on 100 parts by weight of the main crosslinking part.

Preferably, the method for preparing the silicone elastomer composition according to the present invention includes a heating step after the addition reaction, so that residual α,ω-diene not participating in the addition reaction with the first organohydrogenpolysiloxane in the reactor By removing the compound, an excellent effect of reducing the unpleasant odor of the silicone elastomer composition can be exhibited.

In the heating step, the heating temperature, heating time, and pressure may be appropriately changed by a person skilled in the art depending on the specific type of α,ω-diene compound to be used, but at 50 to 120° C. 30 minutes to 10 hours, specifically 60 It may be desirable to perform at a pressure of 1 to 100 torr for 1 to 5 hours at 100°C.

(b) manufacturing step of silicone gel

The method for preparing a silicone elastomer composition according to the present invention includes preparing a silicone gel by mixing a second organohydrogenpolysiloxane in the main crosslinking portion prepared above and through an additional addition crosslinking reaction therebetween.

In the addition crosslinking reaction, the main crosslinking part and the second organohydrogenpolysiloxane were mixed using a first diluent as a solvent, and then the platinum-based catalyst was added, and at a temperature of 30 to 90°C for 3 to 9 hours. It can be carried out by stirring, but is not limited thereto.

The platinum-based catalyst may be used in an amount of 0.001 to 1 part by weight based on 100 parts by weight of the total composition.

At this time, the molar ratio of the second organohydrogenpolysiloxane and the first organohydrogenpolysiloxane is 1: 0.5 to 1: 6, specifically 1: 1 to 1: 5, more specifically 1: 1 to 1: 3 It may be desirable to mix as much as possible.

In addition, in order to achieve excellent physical properties of the finally prepared silicone elastomer composition, the content of the second organohydrogenpolysiloxane is the Vi content of the main crosslinking part and the H content of each of the second organohydrogenpolysiloxanes in the following formula: When calculated by 1, these values may be included to be 0.5 to 2, specifically 0.6 to 1.8, more specifically 1.2 to 1.8, and more specifically 1.2 to 1.5.

[Equation 1]

(Vi content of the main crosslinking part)/(H content of the second organohydrogenpolysiloxane)

In the addition crosslinking reaction for preparing the silicone gel, a first diluent may be used as a solvent, in which case the first diluent may be used in an amount of 1 to 50 parts by weight based on 100 parts by weight of the silicone elastomer composition, specifically It may be used in an amount of 1 to 20 parts by weight based on 100 parts by weight of the silicone elastomer composition, but is not limited thereto.

(c) shearing and swelling step of the silicone gel

Next, the silicone gel prepared as described above is mixed with a second diluent to shear and swell to finally prepare a silicone elastomer composition. The shearing and swelling may mean that the silicone gel prepared above swells into a diluent, more specifically, a second diluent under shear stress.

In the preparation of the silicone elastomer composition of the present invention, the silicone gel is mixed with a second diluent through step (c) so that the silicone gel infiltrates into the diluent to form a homogeneous silicone elastomer composition.

Mixing of the silicone gel with the second diluent for shearing and swelling may be performed using any mixing and shearing equipment, but is not limited thereto, for example, a batch mixer, a planetary mixer. mixer), a screw extruder, a dynamic mixer or a static mixer, a colloid mill, a homogenizer, and a sonolator. It can be carried out using at least one means.

The specific compound used as the second diluent is as described above, and the first diluent and the second diluent may be the same or different, and each is independently selected.

The second diluent may be included in an amount of 10 to 90 parts by weight based on 100 parts by weight of the silicone elastomer composition, for example, 50 to 90 parts by weight, specifically 55 to 80 parts by weight. When included in the above amount, it may be preferable in terms of physical properties of the silicone elastomer composition.

In one embodiment, it was confirmed that a silicone elastomer composition containing 70 to 85 parts by weight of the diluent (specifically, a first diluent and a second diluent) based on 100 parts by weight of a silicone elastomer composition was prepared and exhibited excellent feeling of use.

In one aspect, the present invention provides a cosmetic composition comprising the silicone elastomer composition.

The cosmetic composition is not limited thereto, for example, foundation, solution, external ointment, cream, foam, nutrient lotion, softening lotion, pack, softening water, emulsion, makeup base, essence, sunscreen cream, sun oil, suspension, It can be prepared in the form of emulsions, pastes, gels, lotions, powders, oils, emulsion foundations, patches or sprays.

Hereinafter, examples, etc. will be described in detail to aid understanding of the present invention. However, the embodiments according to the present invention may be modified in various forms, and the scope of the present invention should not be construed as being limited to the following examples. Embodiments of the present invention are provided to more completely describe the present invention to those with average knowledge in the field to which the present invention belongs.

[Preparation of silicone elastomer composition]

Manufacture of stock crosslinking part (Production Example 1)

First, a main crosslinking part was manufactured using the composition of Table 1 below. After mixing the first organohydrogenpolysiloxane and the α,ω-diene compound, a Kastedt catalyst with a platinum content of 1% was added and stirred at 60°C for 6 hours to proceed with the addition reaction, and then the reaction was terminated at 80°C. , By heating at a pressure of 35 torr for 2 hours to volatilize the residual α,ω-diene compound that did not participate in the addition reaction to prepare a main crosslinking part.

Composition of main crosslinking part (% by weight) Manufacturing Example 1 α,ω-diene compounds 1,7-octadiene
More than 97% purity 13.68 First organohydrogenpolysiloxane HMe ₂ SiO-(Me ₂ SiO)a-SiMe ₂ H
a: 45
Viscosity: 35cP
Weight average molecular weight: 3,464 g/mol
H content: 0.57 mmol/g 86.22 catalyst Platinum catalyst (Kastedt catalyst) 0.10 α,ω-diene compound: first organohydrogenpolysiloxane molar ratio (mol ratio) 5:1 Sum 100

Preparation of silicone elastomer composition-Preparation of Examples and Comparative Examples

A silicone elastomer composition was prepared using the compositions of Tables 2 and 3. First, after mixing the main crosslinking part (Preparation Example 1) prepared above, the second organohydrogenpolysiloxane, and the first diluent, a Kastedt catalyst having a platinum content of 1% was added, followed by stirring at 80°C for 3 hours to further crosslink. The reaction proceeded to prepare a silicone gel. A silicone elastomer composition was prepared by mixing the second diluent thereto to shear and swell the silicone gel.

In addition, when preparing the silicone elastomer composition, a silicone elastomer prepared without separately preparing the main crosslinking part, that is, without the volatilization process of the residual α,ω-diene compound, was prepared in the composition of Table 4. After mixing the first and second organohydrogenpolysiloxanes and the α,ω-diene compound in the first diluent, a Kastedt catalyst having a platinum content of 1% was added and stirred at 80° C. for 3 hours to proceed with an addition crosslinking reaction. After preparing the silicone gel, a second diluent was mixed to prepare a silicone elastomer composition.

Configuration Example 1 Example 2 Example 3 Example 4 Stock exchange C ₂ H ₃ (CH ₂ ) ₆ -Me ₂ SiO-(Me ₂ SiO)a-SiMe ₂ -(CH ₂ ) ₆ C ₂ H ₃
Viscosity: 80cP
Vi content: 0.445 mmol/g 5.12 5.29 18.94 6.63 Second organohydrogenpolysiloxane Me ₃ SiO-(Me ₂ SiO)b-(MeHSiO)c-Me ₃ Si
b:230, c:2
Viscosity: 950cP
Weight average molecular weight: 17,302g/mol
H content: 0.11 mmol/g 10.68 17.74 - 13.82 Me3SiO-(Me2SiO)b-(MeHSiO)c-Me3Si
b:60, c:2.8
Viscosity: 58 cP
Weight average molecular weight: 4,667 g/mol
H content: 0.6 mmol/g 1.19 - - 1.54 Me3SiO-(Me2SiO)b-(MeHSiO)c-Me3Sib:30, c:5
Viscosity: 38 cP
Weight average molecular weight: 2941g/mol
H content: 1.7mmol/g - - 7.04 - 1st thinner Me ₃ SiO (Me ₂ SiO) x Me ₃ Si
x: 2 to 10
Viscosity: 5 cP 13.90 18.84 15.50 17.99 catalyst Platinum catalyst (Kastedt catalyst) 0.006 0.01 0.02 0.009 Second diluent Me3SiO(Me2SiO)xMe3Si
x: 2 to 10
Viscosity: 5 cP 69.11 58.12 58.50 60.02 mol ratio Second organohydrogenpolysiloxane: first organohydrogenpolysiloxane 1: 1.59 1: 1.4 1: 2.08 1: 1.59 (Vi content of the main crosslinking part)/( H content of the second organohydrogenpolysiloxane 1.2 1.2 0.7 1.80 Sum 100 100 100 100

Configuration Example 5 Example 6 Example 7 Stock exchange C ₂ H ₃ (CH ₂ ) ₆ -Me ₂ SiO-(Me ₂ SiO)a-SiMe ₂ -(CH ₂ ) ₆ C ₂ H ₃
Viscosity: 80cP
H content: 0.445 mmol/g 19.39 43.36 34.35 Second organohydrogenpolysiloxane Me ₃ SiO-(Me ₂ SiO)b-(MeHSiO)c-Me ₃ Si
b:230, c:2
Viscosity: 950cP
Weight average molecular weight: 17,302g/mol
H content: 0.11 mmol/g - - 9.77 Me3SiO-(Me2SiO)b-(MeHSiO)c-Me3Si
b:60, c:2.8
Viscosity: 58 cP
Weight average molecular weight: 4,667 g/mol
H content: 0.6 mmol/g 28.58 - 10.86 Me3SiO-(Me2SiO)b-(MeHSiO)c-Me3Sib:30, c:5
Viscosity: 38 cP
Weight average molecular weight: 2941g/mol
H content: 1.7mmol/g - 6.63 - 1st thinner Me ₃ SiO (Me ₂ SiO) x Me ₃ Si
x: 2 to 10
Viscosity: 5 cP 39.25 40.90 45.00 catalyst Platinum catalyst (Kastedt catalyst) 0.03 0.02 0.02 Second diluent Me3SiO(Me2SiO)xMe3Six: 2 ~ 10
Viscosity: 5 cP 12.75 9.09 0.00 mol ratio Second organohydrogenpolysiloxane: first organohydrogenpolysiloxane 1: 0.87 1: 5.13 1: 3.19 (Vi content of the main crosslinking part)/(H content of the second organohydrogenpolysiloxane 0.5 1.7 2 Sum 100 100 100

Configuration Comparative Example 1 α,ω-diene compounds 1,7-octadiene
More than 97% purity 1.19 First organohydrogenpolysiloxane HMe ₂ SiO-(Me ₂ SiO)a-SiMe ₂ H
a: 45
Viscosity: 35cP
Weight average molecular weight: 3,464 g/mol
H content: 0.57 mmol/g 7.54 Second organohydrogenpolysiloxane Me ₃ SiO-(Me ₂ SiO)b-(MeHSiO)c-Me ₃ Si
b:230, c:2
Viscosity: 950cP
Weight average molecular weight: 17,302g/mol
H content: 0.11 mmol/g 18.23 Me3SiO-(Me2SiO)b-(MeHSiO)c-Me3Si
b:60, c:2.8
Viscosity: 58 cP
Weight average molecular weight: 4,667 g/mol
H content: 0.6 mmol/g 2.03 1st thinner Me ₃ SiO (Me ₂ SiO) x Me ₃ Si
x: 2 to 10
Viscosity: 5 cP 16.57 catalyst Platinum catalyst (Kastedt catalyst) 0.03 Second diluent Me3SiO(Me2SiO)xMe3Six: 2 ~ 10
Viscosity: 5 cP 54.41 mol ratio Second organohydrogenpolysiloxane: first organohydrogenpolysiloxane 1: 1.47 (Vi content of the main crosslinking part)/( H content of the second organohydrogenpolysiloxane 1.2 Sum 100

[Evaluation of properties of silicone elastomer composition]

Using the silicone elastomer composition prepared above, physical properties, appearance, viscosity, gel content, presence of odor, and feeling of use were evaluated in the following manner, and the results are shown in Table 5.

Properties unit Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Comparative Example 1 Exterior - Transparent paste Transparent paste Opaque paste Translucent. Paste Translucent paste Opaque paste Flowable paste Translucent paste Viscosity cP 300,000 300,000 280,000 250,000 200,000 180,000 - 310,000 Gel content % 17 23 26 21.9 48 50 - 28.9 Presence or absence - X X X X X X - O Feeling rank 5 5 3 4 One One - 3

1. Appearance evaluation method

After each 100 mL of the silicone elastomer composition was put in a transparent container, the degree to which letters were visible when the A printed paper (width, length, and thickness of the letter size) was illuminated was evaluated with the naked eye.

-Difficulty identifying letters: opaque

-Characters can be identified but not clear: translucent

-Characters can be identified, characters are clearly visible: transparent

2. Viscosity measurement method

The viscosity was measured while stirring at 2.5 rpm for 10 minutes using a Brookfield viscometer spindle #93.

3. Gel content measurement method

It was expressed as the calculated value of the total content of the main crosslinking part and the second organohydrogenpolysiloxane used in the manufacture of the silicone elastomer. It was expressed as a calculated value of the total content of genpolysiloxane.

4. How to evaluate the presence or absence of alcohol

The presence or absence of odor was evaluated by the following method, and when there was no trace of intrinsic odor and peculiar odor, it was marked as X, and in case of strong intrinsic odor, it was marked as O.

1) Move the test 　 sample to the atmosphere 　 without ventilation 　 (temperature 　25±5℃℃. 　relative humidity 　50±10%)　.

2) Smell 　 test 　 before 　 container 　 about 　 about 10 times 　 　 shake 　 and proceed 　.

3) The order of odor 　 inspection 　 proceeds in the order of 　 smell 　 strength 　 weak 　 to 　 strong 　.

4) When 　 smells 　 open 　 with the lid open 　, leave the 　 interval with the nose 　3~5　cm　 　 open the 　 lid 　 immediately 　 (within 3 seconds 　) At this time 　Too 　Depth 　Do not inhale 　　 　 Pay attention to abnormal ingredients 　Test.

5) Check the odor 　 　 1 minute 　 after rest 　 　 Total 　 3 times 　 Repetition 　 Test 　 Proceed.

6) Based on the odor 　 standard sample 　 comparison 　 and 　 judgment 　 standards below, 　 pass 　 or not 　 judge.

7) The judgment was carried out by selecting a panel of 3 members, and the average value of them was expressed as the result value.

5. How to evaluate the feeling of use

A silicone elastomer composition with a diameter of about 0.5 cm was placed on the back of the hands of three adults and applied, and the overall feeling of use such as stickiness, spreading, and feeling after application was evaluated according to the following evaluation criteria, and then expressed as the average value of the sum score.

1: not tight

2: Less feeling of adhesion

3: Less feeling of adhesion and stiffness

4: Feels a little oily and spreads thickly

5: softness. It has a sense of adhesion and is applied lightly. A small amount of oil is felt

Claims (6)

A main crosslinking part prepared by addition reaction of the first organohydrogenpolysiloxane and an α,ω-diene compound,
Including a second organohydrogenpolysiloxane as a main chain and a diluent,
As a silicone elastomer composition, the molar ratio of the first organohydrogenpolysiloxane and the α,ω-diene compound is 1:3 to 1:10,
The first organohydrogenpolysiloxane is a compound containing a hydrogen atom bonded to silicon at both ends, and is represented by Formula 1 below,
The second organohydrogenpolysiloxane is a compound containing a hydrogen atom bonded to silicon in a side chain and is represented by the following formula (2), a silicone elastomer composition.
[Formula 1]
HR ₂ SiO(R´ ₂ SiO) _a SiR ₂ H
[Formula 2]
R ₃ SiO(R´ ₂ SiO) _b (R˝HSiO) _c SiR ₃
(In Formulas 1 and 2,
R, R'and R" are each independently selected from C ₁ to C ₁₅ alkyl groups,
0

a

250, 0

b

250, 1

c

250) The method according to claim 1,
The silicone elastomer composition that the molar ratio of the second organohydrogenpolysiloxane and the first organohydrogenpolysiloxane is 1:1 to 1:5. The method according to claim 1,
The ratio of the Vi content of the main crosslinking portion and the H content of the second organohydrogenpolysiloxane is 0.6 to 1.8. (a) mixing the first organohydrogenpolysiloxane and an α,ω-diene compound to prepare a main crosslinking portion in which α,ω-diene is additionally bonded to the terminal of the first organohydrogenpolysiloxane,
(b) mixing the main crosslinking part, the second organohydrogenpolysiloxane, and the first diluent to prepare a silicone gel, and (c) mixing the silicone gel with a second diluent to shear and swell the silicone gel. Includes,
The method for producing a silicone elastomer composition wherein the molar ratio of the first organohydrogenpolysiloxane and the α,ω-diene compound is 1:3 to 1:10. The method of claim 4,
The method for producing a silicone elastomer composition wherein the molar ratio of the second organohydrogenpolysiloxane and the first organohydrogenpolysiloxane is 1:1 to 1:5. The method of claim 4,
The ratio of the Vi content of the main crosslinking portion and the H content of the second organohydrogenpolysiloxane is 0.6 to 1.8.