Composition for forming polysiloxane resins, and MQ resins manufactured therefrom

Abstract

The present invention provides a composition for forming a polysiloxane resin, and an MQ resin having excellent moisturizing properties manufactured therefrom. Specifically, the composition for forming a polysiloxane resin comprises a first siloxane monomer, a second siloxane monomer, a third siloxane monomer, and a monomer containing a Q unit represented by chemical formula 1, wherein the first siloxane monomer may include a siloxane monomer containing a C1-C15 hydroxyalkyl group, the second siloxane monomer may include a siloxane monomer containing a C5-C30 alkyl group, and the third siloxane monomer may include a siloxane monomer containing a C1-C4 alkyl group directly bonded to silicon. [Chemical formula 1] SiO4 / 2

Description

Composition for forming polysiloxane resin and MQ resin produced therefrom

[0001] The present invention relates to a composition for forming a polysiloxane resin capable of producing an MQ resin with improved moisture retention properties, and an MQ resin produced therefrom.

[0002] Polysiloxane, a silicone polymer, is excellent in stability and usability, and is used as a material for polymer products such as plastics, rubber, and wax, as well as surface treatment materials for paper and glass. It is also used as a raw material in various fields such as hair products such as shampoo and conditioner, and cosmetics. Polysiloxane applied to hair products or cosmetics can form a film on the surface without the stickiness characteristic of silicone, and imparts excellent gloss and usability.

[0003] Meanwhile, MQ resin, one of the polysiloxanes, is a triorganosiloxy (R3SiO 1 / 2 ) structure and the M unit and tetrasiloxy (SiO 4 / 2 ) is a three-dimensional resin containing Q units in a structure. This MQ resin has excellent heat resistance, cold resistance, film formation, flexibility, water resistance, and adhesiveness, as well as excellent film forming ability and compatibility, and is therefore mainly used as a liquid injection molding material, a release agent, a filler for silicone oxygen-based adhesives, a tackifier, a reinforcing filler for liquid silicone addition, and a cosmetic material.

[0004] The MQ resin is typically prepared by adding a triorganohalosilane, which is a monomer of M units, to a composition containing sodium silicate, an acid, and an oxygen-containing solvent such as isobutyl alcohol, methyl isobutyl ketone, or 1-pentanol, and reacting them.

[0005] For example, Japanese Patent No. 6620101 (Patent Document 1) discloses a method for producing an MQ resin, comprising a step of reacting an MQ-type silicone resin, a halosilane capping agent, and a polar organic compound. However, the conventional MQ resin disclosed in Patent Document 1 has a drawback of poor moisture retention, limiting the improvement in moisture retention properties of products containing it.

[0006] Accordingly, research and development of materials capable of manufacturing MQ resin with improved moisture retention is necessary.

[0007] The present invention is intended to solve the above problems, and provides a composition for forming a polysiloxane resin capable of producing an MQ resin with improved moisture retention properties.

[0008] In addition, the present invention provides an MQ resin manufactured from the composition for forming the polysiloxane resin.

[0009] The present invention comprises a first siloxane monomer, a second siloxane monomer, a third siloxane monomer, and a monomer containing a Q unit represented by the following chemical formula 1,

[0010] The above first siloxane monomer comprises a siloxane monomer containing a hydroxyalkyl group having 1 to 15 carbon atoms,

[0011] The above second siloxane monomer comprises a siloxane monomer containing an alkyl group having 5 to 30 carbon atoms,

[0012] The third siloxane monomer provides a composition for forming a polysiloxane resin comprising a siloxane monomer containing an alkyl group having 1 to 4 carbon atoms directly bonded to silicon.

[0013] [Chemical Formula 1]

[0014] SiO 4 / 2

[0015]

[0016] In addition, the present invention provides an MQ resin including a Q unit represented by the following chemical formula 1, an M unit represented by the following chemical formula 2, and an M' unit represented by the following chemical formula 3:

[0017] [Chemical Formula 1]

[0018] SiO 4 / 2

[0019] [Chemical Formula 2]

[0020] R 1 R 2 R 3 SiO 1 / 2

[0021] In the above chemical formula 2,

[0022] R 1 , R 2 and R 3 Each independently has 1 to 15 carbon atoms. Hydroxyalkyl group, alkyl group having 5 to 30 carbon atoms or alkyl group having 1 to 15 carbon atoms It is an alkoxy group, and R 1 , R 2 and R 3 At least one of them has 1 to 15 carbon atoms. It is a hydroxyalkyl group.

[0023] [Chemical Formula 3]

[0024] R 1’ R 2’ R 3’ SiO 1 / 2

[0025] In the above chemical formula 3,

[0026] R 1’ , R 2’ and R 3’ are each independently an alkyl group having 1 to 30 carbon atoms.

[0027] The composition for forming a polysiloxane resin according to the present invention comprises a siloxane monomer having a specific structure, thereby enabling the production of an MQ resin having excellent moisture retention properties, storage stability, and thixotropic properties. When the MQ resin of the present invention is applied, a film can be formed that is non-sticky, has an excellent appearance, and has improved moisture retention properties, gloss, coatability, stability, long-term durability, and uniformity.

[0028] Figure 1 is a graph showing the change in viscosity according to shear rate of MQ resins manufactured in Experimental Examples 1 to 8 and Comparative Experimental Examples 1 to 5.

[0029] Terms or words used in this specification and claims should not be interpreted as limited to their usual or dictionary meanings, but should be interpreted as meanings and concepts that conform to the technical spirit of the present invention, based on the principle that the inventor can appropriately define the concept of the term to explain his or her own invention in the best possible manner.

[0030] It should be understood that the terms “include,” “comprising,” or “having” in this specification are intended to specify the presence of a feature, number, step, component, or combination thereof, but do not preclude the possibility of the presence or addition of one or more other features, numbers, steps, components, or combinations thereof.

[0031] Meanwhile, before explaining the present invention, unless otherwise specified, “*” in the present invention means a connected portion (bonding site) between the terminals of the same or different atoms or chemical formulas.

[0032] In addition, in the description of “carbon atoms a to b” in the present specification, “a” and “b” refer to the number of carbon atoms included in a specific functional group. That is, the functional group may include “a” to “b” carbon atoms. For example, “an alkyl group having 1 to 5 carbon atoms” refers to an alkyl group including 1 to 5 carbon atoms, that is, CH3-, CH3CH2-, CH3CH2CH2-, (CH3)2CH-, CH3CH2CH2CH2-, (CH3)2CHCH2-, CH3CH2CH2CH2CH2-, (CH3)2CHCH2CH2CH2-, etc.

[0033] In addition, in this specification, unless otherwise defined, “substitution” means that at least one hydrogen bonded to carbon is replaced by another element such as fluorine, and at least one or more hydrogen bonded to carbon is replaced by an element other than hydrogen, for example, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, or a halogen atom (particularly, fluorine).

[0034] Additionally, in this specification, “%” means weight percent unless explicitly indicated otherwise.

[0035] In addition, in the present specification, “weight average molecular weight” and “number average molecular weight” can be measured by a method well known in the art, and may be values ​​measured by, for example, a GPC (gel permeation chromatograph) method.

[0036] Additionally, in this specification, “polydispersity index (PDI)” is a value obtained by dividing the weight average molecular weight (Mw) by the number average molecular weight (Mn), and refers to molecular weight distribution or dispersion.

[0037] In addition, in the present specification, the thixotropic index (TI) of the MQ resin is measured at a total of 30 points per second for 30 seconds while gradually increasing the shear rate from 0.1 / s to 10 / s at 25°C using a rheometer (model name: MCR301) from Anton Paar, and the viscosity change value according to the shear rate is obtained, and then the value can be calculated using the following [Formula 1].

[0038] [Formula 1]

[0039] TI = A / B

[0040] A: Viscosity at shear rate of 0.1 / s

[0041] B: Viscosity at shear rate 10 / s

[0042] Furthermore, each unit constituting the resin in this specification can be represented by the following chemical formula, where R, R 1 , R 1’ , R 2 , R 2’ , R 3 , R 3’ , R 4 and R 5 Each represents a substituted or unsubstituted hydrocarbon group, and R, R 1’ , R 2 , R 2’ , R 3 , R 3’ , R 4 and R 5 may be identical or different.

[0043] M Unit: (R 1 R 2 R 3 SiO 1 / 2 ) unit

[0044] M'unit: (R 1’ R 2’ R 3’ SiO 1 / 2 ) unit

[0045] D Unit: (R4 R 5 SiO 2 / 2 ) unit

[0046] T Unit: (RSiO 3 / 2 ) unit

[0047] Q Unit: (SiO 4 / 2 ) unit

[0048]

[0049] Hereinafter, the present invention will be described in more detail.

[0050] The composition for forming a polysiloxane resin according to the present invention and the MQ resin prepared therefrom comprise at least one of the following disclosed configurations, and may comprise any combination between technically possible configurations among the following configurations.

[0051]

[0052] [Composition for forming polysiloxane resin]

[0053] The present invention provides a composition for forming a polysiloxane resin.

[0054] The composition for forming the above polysiloxane resin is

[0055] It comprises a first siloxane monomer, a second siloxane monomer, a third siloxane monomer, and a monomer containing a Q unit represented by the following chemical formula 1,

[0056] The above first siloxane monomer comprises a siloxane monomer containing a hydroxyalkyl group having 1 to 15 carbon atoms,

[0057] The above second siloxane monomer comprises a siloxane monomer containing an alkyl group having 5 to 30 carbon atoms,

[0058] The above third siloxane monomer may include a siloxane monomer containing an alkyl group having 1 to 4 carbon atoms directly bonded to silicon.

[0059] [Chemical Formula 1]

[0060] SiO 4 / 2

[0061]

[0062] (A) First siloxane monomer

[0063] The composition for forming a polysiloxane resin of the present invention can introduce a first siloxane monomer containing a hydroxyalkyl group, which is a hydrophilic group, to improve the moisture retention of the MQ resin.

[0064] The above first siloxane monomer may include a siloxane monomer containing a hydroxyalkyl group having 1 to 15 carbon atoms in its structure.

[0065] Specifically, the first siloxane monomer may be a diol compound containing two hydroxyalkyl groups having 1 to 15 carbon atoms in its structure. In addition, the first siloxane monomer may be a polyol compound containing two or more hydroxyalkyl groups having 1 to 15 carbon atoms in its structure. In addition, the first siloxane monomer may be a diol compound containing a hydroxyalkyl group having 1 to 15 carbon atoms and a hydroxyalkyl group having 1 to 15 carbon atoms. It may be a siloxane compound containing an ether group. In addition, the first siloxane monomer may include a hydroxyalkyl group having 5 to 15 carbon atoms and a hydroxyalkyl group having 5 to 15 carbon atoms. It may be a siloxane compound containing an ether group. In addition, the first siloxane monomer may be a siloxane compound containing a hydroxyalkyl group having 6 to 12 carbon atoms and an ether group having 6 to 12 carbon atoms. In addition, the first siloxane monomer may be a siloxane compound containing a hydroxyalkyl group having 7 to 11 carbon atoms and an ether group having 7 to 11 carbon atoms.

[0066] The first siloxane monomer may be included in an amount of 0.1 to 4.0 wt% based on the total weight of the composition for forming the polysiloxane resin. Specifically, the first siloxane monomer may be included in an amount of 0.1 wt% or more, or 0.3 wt% or more, or 0.5 wt% or more, based on the total weight of the composition for forming the polysiloxane resin. In addition, the first siloxane monomer may be included in an amount of 4.0 wt% or less, or 3.0 wt% or less, and preferably 2.0 wt% or less, based on the total weight of the composition for forming the polysiloxane resin.

[0067] When the content range of the first siloxane monomer satisfies the above range, an MQ resin with improved moisture retention can be manufactured. When the content of the first siloxane monomer is less than the above range, gelation of the MQ resin may occur during the manufacturing process. In addition, when the content of the first siloxane monomer exceeds the above range, unreacted monomer remains due to the use of an excessive amount of monomer, which may lower the viscosity of the manufactured resin or deteriorate the appearance characteristics of the manufactured coating film.

[0068]

[0069] (B) Second siloxane monomer

[0070] The composition for forming a polysiloxane resin of the present invention may use a second siloxane monomer containing an alkyl group having 5 to 30 carbon atoms in combination to improve the usability, such as adhesion and spreadability.

[0071] Specifically, the second siloxane monomer may include an alkyl group having 5 to 30 carbon atoms directly bonded to silicon. Specifically, the terminal of the second siloxane monomer may be represented by the following chemical formula A.

[0072] [Chemical Formula A]

[0073]

[0074] (In the above chemical formula A, n is an integer from 2 to 27)

[0075] Additionally, the second siloxane monomer may include an alkyl group having 7 to 16 carbon atoms directly bonded to silicon, or may include an alkyl group having 10 to 16 carbon atoms.

[0076] The second siloxane monomer may be included in an amount of 0.01 to 4.0 wt% based on the total weight of the composition for forming the polysiloxane resin. Specifically, the second siloxane monomer may be included in an amount of 0.01 wt% or more, or 0.05 wt% or more, or 0.1 wt% or more, or 0.5 wt% or more based on the total weight of the composition for forming the polysiloxane resin. In addition, the second siloxane monomer may be included in an amount of 4.0 wt% or less, or 3.0 wt% or less, or 2.0 wt% or less, or 1.0 wt% or less based on the total weight of the composition for forming the polysiloxane resin.

[0077] When the content range of the second siloxane monomer satisfies the above range, an MQ resin having improved adhesion and spreadability along with moisturizing properties can be manufactured. When the content of the second siloxane monomer is less than the above range, the effect of improving adhesion and spreadability intended to be achieved by additionally including the second siloxane monomer may be minimal, and when the content of the second siloxane monomer exceeds the above range, unreacted monomer may remain due to the use of an excessive amount of monomer, which may lower the viscosity of the manufactured resin or deteriorate the appearance characteristics of the manufactured coating film.

[0078]

[0079] (C) Third siloxane monomer

[0080] The composition for forming a polysiloxane resin of the present invention may include a third siloxane monomer containing an alkyl group having 1 to 4 carbon atoms directly bonded to silicon as a component for MQ resin end capping.

[0081] The third siloxane monomer may include an alkyl group having 1 to 4 carbon atoms, or an alkyl group having 1 to 3 carbon atoms. It may include an alkyl group. Specifically, the terminal of the third siloxane monomer may be represented by the following chemical formula B.

[0082] [Chemical Formula B]

[0083]

[0084] Specifically, the third siloxane monomer may use hexamethyldisiloxane.

[0085] If necessary, the third siloxane monomer may additionally contain an alkoxy group having 1 to 4 carbon atoms.

[0086] The third siloxane monomer may be included in an amount of 3.5 to 7.0 wt% based on the total weight of the composition for forming a polysiloxane resin.

[0087] Specifically, the third siloxane monomer may be included in an amount of 3.5 wt% or more, or 4.0 wt% or more, or 5.0 wt% or more, and preferably 6.0 wt% or more, based on the total weight of the composition for forming a polysiloxane resin. In addition, the third siloxane monomer may be included in an amount of 7.0 wt% or less, or 6.9 wt% or less, based on the total weight of the composition for forming a polysiloxane resin.

[0088] When the content range of the third siloxane monomer satisfies the above range, a stabilized MQ resin can be manufactured by preventing side reactions. When the content of the third siloxane monomer is less than the above range, gelation of the manufactured resin may be induced, and when the content of the third siloxane monomer exceeds the above range, the viscosity of the manufactured resin may be lowered or the appearance characteristics of the manufactured coating film may be deteriorated due to the residual unreacted monomer.

[0089]

[0090] (D) Monomer containing tetrasiloxy unit (Q unit)

[0091] The composition for forming a polysiloxane resin of the present invention may include a monomer containing a Q unit represented by the following chemical formula 1.

[0092] [Chemical Formula 1]

[0093] SiO 4 / 2

[0094] The monomer containing the above Q unit is typically SiO in MQ resin during the manufacture of polysiloxane. 4 / 2 Monomers commonly used to form Q units represented by may be used, and a representative example thereof may include sodium silicate.

[0095] The monomer containing the Q unit represented by the above chemical formula 1 may be included in an amount of 10 to 25 wt% based on the total weight of the composition for forming a polysiloxane resin. Specifically, the monomer containing the Q unit represented by the chemical formula 1 may be included in an amount of 10 wt% or more, or 11 wt% or more, or 13 wt% or more, based on the total weight of the composition for forming a polysiloxane resin. In addition, the monomer containing the Q unit represented by the above chemical formula 1 may be included in an amount of 25 wt% or less, or 23 wt% or less, or 20 wt% or less, based on the total weight of the composition for forming a polysiloxane resin.

[0096] If the content of the above Q unit monomer is outside the above range, it may be difficult to manufacture the resin.

[0097]

[0098] Meanwhile, in the composition for forming a polysiloxane resin of the present invention, the molar ratio of the monomer containing the Q unit represented by the chemical formula 1 and the total siloxane monomer (the total of the first to third siloxane monomers) may be 1:0.61 to 1:0.68, or 1:0.65 to 1:0.68.

[0099] As described above, when the molar ratio of the siloxane monomer (the entire first to third siloxane monomers) to the monomer containing the Q unit represented by the chemical formula 1 in the composition for forming a polysiloxane resin according to the present invention satisfies the above range, an MQ resin having improved moisturizing properties, spreadability, and thixotropic properties can be produced. That is, when the molar ratio of the siloxane monomer (the entire first to third siloxane monomers) based on the monomer containing the Q unit represented by the chemical formula 1 is 0.61 or more, the composition for forming a polysiloxane resin can be prevented from being excessively cured or formed into an uneven structure during the synthesis of the MQ resin, thereby suppressing gelation. In addition, when the molar ratio of the siloxane monomer (the entire first to third siloxane monomers) based on the monomer containing the Q unit represented by the chemical formula 1 is 0.68 or less, the weight average molecular weight of the MQ resin to be produced can be appropriately controlled, thereby ensuring desired viscosity and texture. Therefore, an MQ resin having moisturizing properties, spreadability, and thixotropic properties (resistance to flow and resilience) suitable for use in cosmetics can be manufactured. Meanwhile, the molar ratio of the monomer containing the Q unit represented by the above chemical formula 1 and the total siloxane monomer can be confirmed through NMR analysis.

[0100]

[0101] (D) Solvent

[0102] Meanwhile, the composition for forming a polysiloxane resin according to the present invention may include a solvent commonly used in the production of MQ resin.

[0103] The above solvent may be at least one selected from aromatic hydrocarbons, aliphatic hydrocarbons, and silicone-based solvents.

[0104] Specifically, the aromatic hydrocarbon may include xylene. The aliphatic hydrocarbon may include isododecane (IDD) or isopropyl alcohol (IPA). The silicone-based solvent may include polydimethylsiloxane.

[0105]

[0106] [MQ Suji]

[0107] The present invention provides an MQ resin.

[0108] The MQ resin can be prepared from a composition for forming a polysiloxane resin according to the present invention, and includes a Q unit represented by the following chemical formula 1, an M unit represented by the following chemical formula 2, and an M' unit represented by the following chemical formula 3. That is, the MQ resin can secure excellent moisturizing properties, adhesion, and spreadability by including a unit including a hydroxyalkyl group, which is a hydrophilic group, and an alkyl group having 1 to 30 carbon atoms at the terminal.

[0109] [Chemical Formula 1]

[0110] SiO 4 / 2

[0111] [Chemical Formula 2]

[0112] R 1 R 2 R 3 SiO 1 / 2

[0113] In the above chemical formula 2,

[0114] R 1 , R 2 and R 3 Each independently has 1 to 15 carbon atoms. Hydroxyalkyl group, alkyl group having 5 to 30 carbon atoms or alkyl group having 1 to 15 carbon atoms It is an alkoxy group, and R 1 , R 2 , and R 3 At least one of them has 1 to 15 carbon atoms. It may contain a hydroxyalkyl group.

[0115] [Chemical Formula 3]

[0116] R 1’ R 2’ R 3’ SiO 1 / 2

[0117] In the above chemical formula 3,

[0118] R 1’ , R 2’ and R 3’ are each independently an alkyl group having 1 to 30 carbon atoms.

[0119]

[0120] Specifically, in the above chemical formula 2, the R 1 , R 2 and R 3 At least one of them has 1 to 15 carbon atoms. Contains a hydroxyalkyl group, and the remaining R 1 , R 2 and R 3 At least one of them may include an alkyl group having 5 to 30 carbon atoms. In addition, in the above chemical formula 2, the R 1 , R 2 and R 3 Two of them have 1 to 15 carbon atoms. One may contain a hydroxyalkyl group, and the other may contain an alkyl group having 5 to 30 carbon atoms.

[0121] In addition, in the above chemical formula 3, the R 1’ , R 2’ and R 3’ At least one of them contains an alkyl group having 5 to 30 carbon atoms, and the remaining R 1’ , R 2’ and R 3’ At least one of them has 1 to 4 carbon atoms. May contain an alkyl group.

[0122] In addition, in the above chemical formula 2, the R 1 , R 2 and R 3 At least one of them has 3 to 13 carbon atoms. Contains a hydroxyalkyl group, and the remaining R 1 , R 2 and R 3 At least one of them may contain an alkyl group having 5 to 25 carbon atoms. Specifically, in the above chemical formula 2, the R 1 , R 2 and R3 Two of them have 3 to 13 carbon atoms. One may contain a hydroxyalkyl group, and the other may contain an alkyl group having 5 to 25 carbon atoms.

[0123] In addition, in the above chemical formula 3, the R 1’ , R 2’ and R 3’ At least one of them contains an alkyl group having 5 to 25 carbon atoms, and the remaining R 1’ , R 2’ and R 3’ At least one of them has 1 to 4 carbon atoms. May contain an alkyl group.

[0124] In addition, in the above chemical formula 2, the R 1 , R 2 and R 3 At least one of them has 5 to 13 carbon atoms. Contains a hydroxyalkyl group, and the remaining R 1 , R 2 and R 3 At least one of them may include an alkyl group having 7 to 20 carbon atoms. Specifically, in the above chemical formula 2, the R 1 , R 2 and R 3 Two of them have 5 to 13 carbon atoms. One may contain a hydroxyalkyl group, and the other may contain an alkyl group having 7 to 20 carbon atoms.

[0125] In addition, in the above chemical formula 3, the R 1’ , R 2’ and R 3’ At least one of them contains an alkyl group having 7 to 20 carbon atoms, and the remaining R 1’ , R 2’ and R 3’ At least one of them has 1 to 4 carbon atoms. May contain an alkyl group.

[0126] In addition, in the above chemical formula 2, the R 1 , R 2 and R3 At least one of them has 7 to 11 carbon atoms. Contains a hydroxyalkyl group, and the remaining R 1 , R 2 and R 3 At least one of them may include an alkyl group having 10 to 15 carbon atoms. Specifically, in the above chemical formula 2, the R 1 , R 2 and R 3 Two of them have 7 to 11 carbon atoms. One may contain a hydroxyalkyl group, and the other may contain an alkyl group having 10 to 15 carbon atoms.

[0127] In addition, in the above chemical formula 3, the R 1’ , R 2’ and R 3’ At least one of them contains an alkyl group having 10 to 20 carbon atoms, and the remaining R 1’ , R 2’ and R 3’ At least one of them has 1 to 4 carbon atoms. May contain an alkyl group.

[0128] In addition, in the above chemical formula 2, the R 1 , R 2 and R 3 At least one of them has 9 to 11 carbon atoms. Contains a hydroxyalkyl group, and the remaining R 1 , R 2 and R 3 At least one of them may include an alkyl group having 10 to 13 carbon atoms. Specifically, in the above chemical formula 2, the R 1 , R 2 and R 3 Two of them have 9 to 11 carbon atoms. One may contain a hydroxyalkyl group, and the other may contain an alkyl group having 10 to 13 carbon atoms.

[0129] In addition, in the above chemical formula 3, the R 1’ , R 2’ and R 3’At least one of them contains an alkyl group having 10 to 13 carbon atoms, and the remaining R 1’ , R 2’ and R 3’ At least one of them has 1 to 4 carbon atoms. May contain an alkyl group.

[0130]

[0131] Meanwhile, in the MQ resin of the present invention, the hydroxyalkyl group having 1 to 15 carbon atoms may be included in an amount of 0.1 wt% or more, specifically 0.5 wt% or more, based on the total weight of the MQ resin. In addition, in the MQ resin, the hydroxyalkyl group having 1 to 15 carbon atoms may be included in an amount of 10 wt% or less, or 8.0 wt% or less, or 5.0 wt% or less, or 3.0 wt% or less, specifically 1 wt% or less. When the content of the hydroxyalkyl group having 1 to 15 carbon atoms in the MQ resin of the present invention is less than the above range, gelation of the MQ resin may be induced, and when it exceeds the above range, the viscosity of the MQ resin may be lowered or the appearance characteristics may be deteriorated.

[0132] In addition, in the MQ resin of the present invention, the alkyl group having 5 to 30 carbon atoms may be included in an amount of 0.01 wt% or more, or 0.05 wt% or more, specifically 0.1 wt% or more, based on the total weight of the MQ resin. In addition, in the MQ resin of the present invention, the alkyl group having 5 to 30 carbon atoms may be included in an amount of 10 wt% or less, or 7.0 wt% or less, specifically 5.0 wt% or less, based on the total weight of the MQ resin.

[0133]

[0134] Meanwhile, the number average molecular weight (Mn) of the MQ resin of the present invention may be 2,000 g / mol or more, and may be 2,500 g / mol or more. In addition, the number average molecular weight (Mn) of the MQ resin may be 8,000 g / mol or less, or 7,000 g / mol or less, or 6,000 g / mol or less, and specifically 5,000 g / mol or less.

[0135] In addition, the weight average molecular weight (Mw) of the MQ resin of the present invention may be 7,000 g / mol or more, or may be 8,000 g / mol or more. In addition, the weight average molecular weight (Mw) of the MQ resin of the present invention may be 30,000 g / mol or less, or may be 20,000 g / mol or less, and specifically may be 17,000 g / mol or less.

[0136] In addition, the polydispersity index (PDI) of the MQ resin of the present invention may be a value of weight average molecular weight (Mw) / number average molecular weight (Mn), and may be 3 to 5.

[0137] For MQ resins having the above-mentioned number average molecular weight (Mn), weight average molecular weight (Mw) and polydispersity index (PDI), excellent storage stability and moisture retention can be secured.

[0138]

[0139] The MQ resin according to the present invention as described above has excellent moisture retention properties and is therefore very suitable as a material for adhesives, liquid injection molding materials, release agents, and cosmetic products.

[0140]

[0141] Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the following examples are intended only to specifically illustrate specific embodiments of the present invention and are not intended to limit or restrict the scope of the present invention to the contents described in these examples.

[0142]

[0143] [Example]

[0144] Manufacturing Example 1. Manufacturing of the first siloxane monomer (diol-MM)

[0145] After liquid trimethylolpropane allyl ether (TMPME) was introduced into the reactor, some tetramethyldisiloxane (hereinafter referred to as H-MM) was introduced. The amount of tetramethyldisiloxane introduced was 10 wt% of the total amount of tetramethyldisiloxane introduced. After the temperature was raised to 55°C, a platinum (Pt) catalyst (PT-VTS-Toluene solution diluted with toluene to contain 3 wt% platinum, manufacturer: Umicore Technical Materials, product name: Pt-VTSC-3.0T) was introduced and exotherm was confirmed (step (1)). Subsequently, after exotherm was confirmed, the remaining 90 wt% of H-MM was dropped for 1 hour (step (2)), and after the dropping was completed, the reaction was conducted while stirring at 70°C for 2 hours (step (3)). Afterwards, the reactant was heated to 150°C and vacuum distilled, and after reaching 150°C, the unreacted substance was removed while maintaining vacuum distillation for 2 hours (step (4)), thereby preparing a first siloxane monomer (diol-MM) containing a hydroxyalkyl group (weight average molecular weight: 954 g / mol). At this time, the prepared first siloxane monomer (diol-MM) containing a hydroxyalkyl group can be represented by the following chemical formula 4. Meanwhile, each component used in the reaction was used as described in the contents of Table 1 below, and the process steps were performed in the order of Table 2 below.

[0146] [Chemical Formula 4]

[0147]

[0148]

[0149]

[0150]

[0151] Manufacturing Example 2. Manufacturing of 2-1 siloxane monomer (alkyl-MM)

[0152] 1-Dodecene and tetramethyldisiloxane (H-MM) were introduced into the reactor. The amount of tetramethyldisiloxane introduced was 10 wt% of the total amount of tetramethyldisiloxane introduced. After the temperature was raised to 55°C, a platinum (Pt) catalyst (PT-VTS-Toluene solution diluted with toluene to contain 3 wt% of platinum, manufacturer: Umicore Technical Materials, product name: Pt-VTSC-3.0T) was introduced and exotherm was confirmed (step (1)). After exotherm was confirmed, the remaining 90 wt% of H-MM was added dropwise over 1 hour (step (2)), and after the addition was completed, the mixture was left at 70°C for 2 hours (step (3)). Next, the reactant was heated to 150°C and vacuum distilled, and after reaching 150°C, the unreacted substance was removed while maintaining vacuum distillation for 2 hours (step (4)), thereby producing a dodecyl group-containing 2-1 siloxane monomer (alkyl-MM) (weight average molecular weight: 793 g / mol). Meanwhile, each component used in the reaction was used in the contents described in Table 3 below, and the manufacturing process was performed by the method described in Table 4 below.

[0153]

[0154] Manufacturing Example 3. Manufacturing of 2-2 siloxane monomer (alkyl-MM)

[0155] A hexadecyl group-containing 2-2 siloxane monomer (alkyl-MM) (weight average molecular weight: 1,057 g / mol) was prepared in the same manner as in Manufacturing Example 2, except that 1-hexadecene was used instead of 1-dodecene. Meanwhile, each component used in the reaction was used in the amounts shown in Table 3 below, and the manufacturing process was performed in the manner shown in Table 4 below.

[0156]

[0157]

[0158]

[0159] Experimental Example 1. MQ Resin Preparation

[0160] After HCl was introduced into the reactor, water glass (manufacturer: Youngil Chemical, product name: No. 3 (KS) (No. 3 KS), concentration: 35%, weight average molecular weight: 122.06 g / mol (anhydrous)) containing a Q unit represented by chemical formula 1 was diluted in distilled water to a concentration of 55 wt%, and then added dropwise to the reactor while stirring for 5 minutes. After completion of dropping, the mixture was maintained for 10 minutes (step (1))).

[0161] Next, isopropyl alcohol, a solvent, was added dropwise to the reactants while stirring for 3 minutes, and then maintained for 15 minutes (step (2)).

[0162] Then, the first to third siloxane monomers were diluted with a solvent (isododecane), and then added dropwise to the reactants while stirring for 30 minutes to prepare a composition for forming a polysiloxane resin (step (3)). The first siloxane monomer (diol-MM) prepared in Preparation Example 1 was used as the first siloxane monomer, the second-first siloxane monomer (alkyl-MM) prepared in Preparation Example 2 was used as the second siloxane monomer, and hexamethyldisiloxane (MM, 162.379 g / mol) was used as the third siloxane monomer. At this time, the molar ratio of the monomer containing the Q unit represented by the chemical formula 1 and the siloxane monomer (the entire first siloxane monomer, the second siloxane monomer, and the third siloxane monomer) was 1:0.62.

[0163] After the loading was completed, the reaction mixture was heated to 75°C and maintained for 1 hour (step (4)). Subsequently, the reaction mixture was cooled to 65°C and allowed to stand for 15 minutes to induce layer separation, after which the lower layer was separated and removed (drained) (step (5)).

[0164] Then, a neutralizing agent (CaCO3) was added to the obtained upper layer, stirred for 12 hours, and filtered to obtain a filtrate from which the neutralizing agent was removed (steps (6) and (7)).

[0165] Next, the obtained filtrate was distilled under atmospheric pressure while raising the temperature to 120°C, and after reaching 120°C, the reaction solvent was removed while maintaining the temperature for 15 minutes (step (8)), thereby preparing MQ resin.

[0166] At this time, each reactant was used in the contents described in Table 5 below, and the manufacturing process steps were performed according to the method described in Table 6 below.

[0167] Meanwhile, in Table 5 below, the molar ratio of the monomer containing the Q unit represented by Chemical Formula 1 and the total siloxane monomer (first to third siloxanes) can be calculated through NMR analysis. For example, a sample is prepared by dissolving MQ resin in CDCl3, and then the peak (Si) of the monomer containing the Q unit represented by Chemical Formula 1 is measured using NMR equipment (BRUKER, Ultrashield 400 MHz). 29 The peaks of the entire siloxane monomer (-10 ppm to 20 ppm, -120 ppm to -100 ppm) were confirmed, and their peak ratios (molar ratios) are shown in Table 5 below.

[0168]

[0169]

[0170]

[0171] Experimental Examples 2 to 8 and Comparative Experimental Examples 1 to 5. Preparation of MQ resin

[0172] MQ resin was prepared in the same manner as in Experimental Example 1, except that each component was used in the amounts indicated in Table 7 below. Here, the numerical value of each component represents weight %.

[0173]

[0174]

[0175] Test example: Physical property evaluation

[0176] The physical properties of each MQ resin manufactured in Experimental Examples 1 to 8 and Comparative Experimental Examples 1 to 5 were measured using the following methods, and the results are shown in Table 8 below.

[0177] (1) Appearance

[0178] The appearance (transparency and color) of each MQ resin manufactured in Experimental Examples 1 to 8 and Comparative Experimental Examples 1 to 5 was visually observed and evaluated, and the results are shown in Table 8 below.

[0179] (2) Number average molecular weight, weight average molecular weight, and polydispersity index (PDI)

[0180] The number average molecular weight (Mn), weight average molecular weight (Mw), and polydispersity index (PDI) of each MQ resin manufactured in Experimental Examples 1 to 8 and Comparative Experimental Examples 1 to 5 were measured using gel permeation chromatography (GPC) equipment, and the results are shown in Table 8 below.

[0181] (3) Formulation

[0182] Each MQ resin formulation manufactured in Experimental Examples 1 to 8 and Comparative Experimental Examples 1 to 5 was visually inspected, and the results are shown in Table 8 below.

[0183] (4) Moisturizing

[0184] Each 0.20 g of MQ resin manufactured in Experimental Examples 1 to 8 and Comparative Experimental Examples 1 to 5 was placed on the back of the hand and spread thinly in a circular motion, and the moisturizing properties were evaluated through the touch and skin sensation during application, and the results are shown in Table 8 below. Specifically, the soft and smooth application, the low stickiness, and the degree of moisturizing properties were compared, and the evaluation results were classified into 5 levels (very good, good, average, slightly insufficient, and insufficient) and described.

[0185] (5) Thixotropic Index (TI)

[0186] The viscosity change values ​​according to the shear rate of each MQ resin manufactured in Experimental Examples 1 to 8 and Comparative Experimental Examples 1 to 5 were obtained using a rheometer (model number: MCR301) from Anton Paar. Specifically, while gradually increasing the shear rate from 0.1 / s to 10 / s at 25°C, a total of 30 points were measured in units of seconds for 30 seconds, and the viscosity change values ​​according to the shear rate of each MQ resin manufactured in Experimental Examples 1 to 8 and Comparative Experimental Examples 1 to 5 were obtained. Next, the viscosity change values ​​according to the shear rate of each MQ resin were substituted into the following [Equation 1] to derive the thixotropic index (TI) of the MQ resin, and the results are shown in Table 8 below.

[0187] [Formula 1]

[0188] TI = A / B

[0189] A: Viscosity at shear rate of 0.1 / s

[0190] B: Viscosity at shear rate 10 / s

[0191] At this time, only when the thixotropic index (TI) was 3.5 or higher, the resin was evaluated as having thixotropic properties that met the target specifications.

[0192]

[0193]

[0194]

[0195] Referring to Table 8 above, it can be seen that the MQ resins manufactured in Experimental Examples 1 to 8 have appropriate number average molecular weight (Mn), weight average molecular weight (Mw), and PDI, high moisturizing properties, and a thixotropic index (TI) of 3.5 or higher, making them suitable as raw materials for cosmetics.

[0196] In contrast, it can be seen that the MQ resin of Comparative Experimental Example 1, which does not contain both the first and second siloxane monomers, or the MQ resin of Comparative Experimental Examples 2 and 3, which does not contain the first siloxane monomer, lacks moisturizing properties and has a thixotropic index (TI) of less than 3.5, making it unsuitable as a cosmetic raw material.

[0197] In addition, in the case of the MQ resins of comparative examples 4 and 5 that do not include the second siloxane monomer, it can be seen that although the appearance and moisturizing properties are excellent, the thixotropic index (TI) is less than 3.5, making it unsuitable as a cosmetic raw material.

Claims

1. A monomer comprising a first siloxane monomer, a second siloxane monomer, a third siloxane monomer, and a Q unit represented by the following chemical formula 1, The above first siloxane monomer comprises a siloxane monomer containing a hydroxyalkyl group having 1 to 15 carbon atoms, The above second siloxane monomer comprises a siloxane monomer containing an alkyl group having 5 to 30 carbon atoms, A composition for forming a polysiloxane resin, wherein the third siloxane monomer comprises a siloxane monomer containing an alkyl group having 1 to 4 carbon atoms directly bonded to silicon. [Chemical Formula 1] Not. 4 / 2 2. In claim 1, A composition for forming a polysiloxane resin, wherein the first siloxane monomer is included in an amount of 0.1 to 4.0 wt% based on the total weight of the composition for forming a polysiloxane resin.

3. In claim 1, A composition for forming a polysiloxane resin, wherein the second siloxane monomer is included in an amount of 0.01 to 4.0 wt% based on the total weight of the composition for forming a polysiloxane resin.

4. In claim 1, A composition for forming a polysiloxane resin, wherein the third siloxane monomer is included in an amount of 3.5 wt% to 7.0 wt% based on the total weight of the composition for forming a polysiloxane resin.

5. In claim 1, A composition for forming a polysiloxane resin, wherein a monomer containing a Q unit represented by the above chemical formula 1 is included in an amount of 10 to 25 wt% based on the total weight of the composition for forming a polysiloxane resin.

6. MQ resin comprising a Q unit represented by the following chemical formula 1, an M unit represented by the following chemical formula 2, and an M' unit represented by the following chemical formula 3: [Chemical Formula 1] Not. 4 / 2 [Chemical Formula 2] R 1 R 2 R 3 SiO 1 / 2 In the above chemical formula 2, R 1 , R 2 and R 3 Each independently has 1 to 15 carbon atoms. Hydroxyalkyl group, alkyl group having 5 to 30 carbon atoms or alkyl group having 1 to 15 carbon atoms It is an alkoxy group, and R 1 , R 2 and R 3 At least one of them has 1 to 15 carbon atoms. It is a hydroxyalkyl group. [Chemical Formula 3] R 1’ R 2’ R 3’ SiO 1 / 2 In the above chemical formula 3, R 1’ , R 2’ and R 3’ are each independently an alkyl group having 1 to 30 carbon atoms.

7. In claim 6, In the above chemical formula 2, the R 1 , R 2 and R 3 At least one of them has 1 to 15 carbon atoms. Contains a hydroxyalkyl group, and the remaining R 1 , R 2 and R 3 MQ resin, wherein at least one of the groups comprises an alkyl group having 5 to 30 carbon atoms.

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