Elastomer having a CO-Si bond between the polyester main chain and the crosslinking agent.

Abstract

A composition containing an elastomer, wherein the elastomer has a polyester backbone crosslinked with a crosslinking agent and has a carbon-oxygen-silicon bond between the ester group and the crosslinking agent.

Description

[Technical Field]

[0001] The present invention relates to elastomers and gels and pastes containing elastomers.

[0002] (Introduction) Polysiloxane elastomer materials are desirable in the cosmetics industry for thickening carrier fluids while imparting desirable sensory properties to cosmetics. Polysiloxane elastomers are crosslinked gel materials that thicken carrier fluids while providing the smooth, dry, and fine texture desired in many cosmetics. Polysiloxane elastomers contain polysiloxane backbone chains crosslinked by polysiloxane crosslinking agents.

[0003] There is interest in identifying elastomer materials that can provide similar sensory and thickening properties to polysiloxane elastomers, but also have a higher organic content. Increasing the organic content can increase compatibility with non-aqueous solvents, which may be desirable to increase the versatility of the elastomer in useful formulations. In this regard, it is desirable to identify elastomers that have the thickening and sensory properties of polysiloxane elastomer materials, but contain a siloxane-free main chain.

[0004] Furthermore, it is desirable to increase the environmentally friendly properties of elastomers by, for example, reducing their hydrolysis stability so that they decompose more easily over time. Degradability, particularly between the main chain polymer and the crosslinking agent, can accelerate the degradation of the polymer over time.

[0005] Cosmetics rely on polysiloxane elastomers for their thickening and sensory properties, and can further benefit from wash resistance, so that they remain on the skin for a longer period of time once applied. One way to help increase the durability of cosmetics is to identify elastomer gels that can be processed into pastes with desired sensory properties and are wash-resistant (durable).

[0006] It is desirable to identify an elastomer that provides similar thickening and sensory properties to polysiloxane elastomers, but has a non-siloxane main chain polymer bonded to the crosslinking agent via a bond that is less hydrolytically stable than a carbon-oxygen-carbon (COC) bond, and has at least as good or better washability than polysiloxane elastomers. [Overview of the Initiative]

[0007] The present invention provides a solution to the problem of identifying an elastomer that offers similar thickening and sensory properties as polysiloxane elastomers, but has a non-siloxane main-chain polymer bonded to the crosslinking agent via a bond that is less hydrolytically stable than a carbon-oxygen-carbon (COC) bond, and has at least as good or better washability as polysiloxane elastomers.

[0008] This invention is the result of discovering a method for preparing an elastomer having a polyester main chain that does not contain siloxane bonds and is crosslinked via carbon-oxygen-silicon (CO-Si) bonds, which are less hydrolytically stable than COC bonds, thereby yielding an elastomer with the desired properties described above.

[0009] In a first aspect, the present invention is a composition comprising an elastomer, wherein the elastomer has a polyester main chain crosslinked with a crosslinking agent, and has a carbon-oxygen-silicon bond between the ester group and the crosslinking agent.

[0010] In a second aspect, the present invention is a process for preparing a composition of any one of the preceding claims, the method comprising: (a) a backbone polymer having at least two terminal unsaturated carbon-carbon bonds separated from any polyester groups by carbon-oxygen-silicon bonds, and a crosslinking agent material containing a plurality of silyl hydride groups, provided that at least one of the backbone polymer or the crosslinking agent has 3 or more average unsaturated carbon-carbon bond functional groups and / or the crosslinking agent has 3 or more average silyl hydride functional groups, providing the backbone polymer and the crosslinking agent material; (b) crosslinking the backbone polymer with the crosslinking agent material by hydrosilylation addition between the unsaturated carbon-carbon bonds of the backbone polymer and the silyl hydride groups of the crosslinking agent material to form an elastomer.

[0011] The elastomers of the present invention are useful as additives for cosmetics in order to achieve the desired sensory properties for cosmetics, particularly to achieve a smooth, dry, fine texture while achieving durability with respect to wash resistance.

BRIEF DESCRIPTION OF THE INVENTION

[0012] The test method refers to the most recent test method at the priority date of this document if the date is not indicated together with the test method number. References to test methods include both a reference to the association of the test and the test method number. In this specification, the following abbreviations and identifiers for test methods apply. ASTM refers to the test methods of the American Society for Testing and Materials, END refers to the European Norm, DIN refers to the Deutsches Institut fur Normung, ISO refers to the International Organization for Standards, and UL refers to the Underwriters Laboratory.

[0013] Products identified by trade names refer to the compositions available under those trade names at the priority date of this document.

[0014] "Plural" means two or more. "And / or" means "and, or alternatively". All ranges include endpoints unless otherwise indicated.

[0015] "Unsaturated carbon-carbon bond" can be a carbon-carbon triple bond or preferably a carbon-carbon double bond (C=C).

[0016] In one aspect, the present invention is a composition comprising an elastomer. The composition can be an elastomer or a combination of components comprising an elastomer. Desirably, the composition is a solvent-swollen gel comprising an elastomer swollen in a solvent, typically a non-aqueous solvent (i.e., a solvent-swollen elastomer). The solvent-swollen elastomer can be in particulate form in a solvent, particularly a non-aqueous solvent, so as to form a paste. The paste can be formed by subjecting the solvent-swollen elastomer gel to shearing, typically while in an excess of solvent, to grind the elastomer gel into fine particles. The degree of shearing can determine the particle size of the elastomer gel in the paste. Typically, the finer the particle size, the smoother the resulting paste feels, and thus a finer particle size is desirable for applications such as cosmetics involving application to the skin.

[0017] The solvent is preferably a non-aqueous solvent and can be a non-polar solvent. The solvent can be any one or any combination of fluids selected from the group consisting of hydrocarbons, ethers, esters, alcohols, and siloxane fluids. Examples of suitable hydrocarbon fluids include farnesane, squalane, isohexadecane, undecane, tridecane, and isododecane. Examples of suitable ether fluids include the material sold by BASF under the name CETIOL® OE (CETIOL is a trademark of Cognis IP Management GmbH), ethyl 3-(2,4-dimethyl-1,3-dioxolan-2-yl)propanoate, ethyl glycerin acetal levulinate, ethyl phenethyl acetal, and isopropylidene glyceryl cocoate. Examples of suitable ester fluids include isodecyl neopentanoate, isostearyl neopentanoate, isononyl isononanoate, ethyl acetate, capric triglyceride, caprylic triglyceride, triheptanoin, triisostearin, diisopropyl acetate, diisopropyl adipate, diisobutyl adipate, diethylhexyl adipate, n-propyl acetate, isobutyl acetate, n-butyl acetate, trimethylolpropane tricaprylate, trimethylolpropane tricaprate, dipentaerythritylhexacinate C5-9, C12-15 alkyl benzoate, triethylhexanoin, and neopentyl Examples include glycol diheptanoate, diheptyl succinate, heptyl undecylate, propylene glycol dibenzoate, dipropylene glycol dibenzoate, ethylhexyl palmitate, ethylhexyl stearate, isopropyl laurate, hexyl laurate, isopropyl myristate, isopropyl palmitate, n-butyl stearate, propylene glycol dicaprylate, propylene glycol dicarelate, cococaprylate, cococaprate, ethylhexyl cocoate, oleyl ethyl acetate, propyl butyl caprylate, decyl oleate, hexyl decyl stearate, and propylene glycol laurate.Suitable examples of siloxane fluids include cyclic siloxanes, e.g., cyclotetrasiloxane available as DOWSIL® 244 Fluid (DOWSIL is a registered trademark of The Dow Chemical Company), cyclopentasiloxane available as DOWSIL® 245 Fluid, or cyclohexasiloxane available as DOWSIL® 246 Fluid; linear and branched alkyl and arylsiloxanes, e.g., caprylmethicone available as DOWSIL® FZ-3196; and linear dimethylsiloxanes, e.g., linear dimethylsiloxane available as DOWSIL® 200 Fluids; and phenyltrimethicone available as DOWSIL® 556 Fluid. If the solvent contains a siloxane fluid, it may also contain additional solvents. The solvent may also not contain siloxanes.

[0018] The solvent can be a "highly volatile" solvent selected from isododecane (boiling point 210°C at a pressure of 101 megapascals), farnesane (boiling point 252°C at a pressure of 101 megapascals), undecane (boiling point 195°C at a pressure of 101 megapascals), n-dodecane (boiling point 216°C at a pressure of 101 megapascals), and tridecane (boiling point 234°C at a pressure of 101 megapascals). These solvents form gels that can be transformed into pastes with higher washability than pastes made from typical pure silicone elastomers.

[0019] The concentration of the solvent in the solvent-swelled elastomer composition is preferably 25 weight percent (weight-percent) or more, more preferably 30 weight or more, 35 weight or more, 40 weight or more, 45 weight or more, 50 weight or more, 55 weight or more, 60 weight or more, 65 weight or more, 70 weight or more, 75 weight or more, and even more than 80 weight or more, and at the same time, typically 85 weight or less, 80 weight or less, 75 weight or less, 70 weight or less, 65 weight or less, 60 weight or less, 55 weight or less, 50 weight or less, 45 weight or less, 40 weight or less, and 35 weight or less.

[0020] The elastomer is a crosslinked polymer comprising a main chain polymer ("main chain") interconnected with other main chain polymers via a crosslinking agent polymer ("crosslinking agent"). Preferably, each main chain polymer has at least three bonds with the crosslinking agent, and / or each crosslinking agent has at least three bonds with the main chain polymer.

[0021] The main chain is polyester and is a molecule containing multiple polyester groups. The main chain polyester cannot contain siloxane (Si-O-Si) bonds between ester groups. The elastomer may or may not contain polysaccharide components.

[0022] Crosslinking agents contain carbon-oxygen-silicon (CO-Si) bonds and attach to the main chain via bonding groups that can be such bonds. These bonding groups are located between the ester group in the main chain and the crosslinking agent. Crosslinking agents are typically polysiloxanes, molecules containing multiple Si-O-Si bonds.

[0023] Preferably, the elastomer comprises a main chain that does not contain Si-O-Si bonds but contains ester bonds, and a crosslinking agent that contains Si-O-Si bonds. In such an elastomer, the main chain is clearly defined as a component between ester groups that do not contain Si-O-Si bonds, while the crosslinking agent is clearly defined as a component between CO-Si bonds that contain Si-O-Si bonds. Preferably, at least one CO-Si bond exists between any polyester and any Si-O-Si bond in the elastomer.

[0024] The main chain components of the elastomer have unbonded bonds, indicated by "--", which then bond with the crosslinking agent. or one or more of the chemical structures (I), (II), and (III) A segment may include or consist of any combination of the following: -CH(CH3)-SiR2O-[(CH2) m OC(O)CH2(CH2) n CH2 C(O)O-] o (CH2) m -OSiR2-CH(CH3)-- (I) C(R)[CH2OX]3(II) CH3CH(OX)CH2CH2OX (III) During the ceremony, R independently originates from a hydrocarbyl group having 1 to 8 carbon atoms in each occurrence. They can be selected and all be the same, or they can be different from one another. Buildings can be 1 or more, 2 or more, 3 or more, 4 or more, 5 or more, 6 or more, or even 7 or more. It may have carbon atoms as shown above, but typically contains eight or fewer carbon atoms at the same time. And, 7 or fewer, 6 or fewer, 5 or fewer, 4 or fewer, 3 or fewer, and even 2 or fewer carbon atoms It may contain. Preferably, the R group is methyl, ethyl, propyl, and phenyl Selected from a group consisting of elements. X independently, in each occurrence, -H, -C(O)-(CH2)4C(O)OH and -C(O)-(CH2)4C(O)OSiR2-CH2CH2-- is selected, and R is, As stated above, however, at least two X groups are -C(O)-(CH2)4C( O)OSiR2-CH2CH2--group The subscript 'm' independently has an average value in the range of 1 to 8 in each occurrence, preferably It has a value of 2 or more, and also has a value of 3 or more, 4 or more, 5 or more, 6 or more, and even 7 or more. It is possible, but at the same time, typically 8 or less, 7 or less, 6 or less, 5 or less, 4 or less, 3 or less, and It has a value of 2 or less. Preferably, the subscript m is 2 in each occurrence. The subscript n has an average value within the range of 2 to 5. The subscript n is 2 or greater, 3 or greater. , 4 or more, 5 or more, 10 or more, 15 or more, 20 or more, 25 or more, 30 or more, 35 or more, It can have a value of 40 or more, but at the same time, typically 50 below , 45 below , 40 below ,35 below , 31 below ,twenty five below , 20 below , 10 below Furthermore, 5 below It has the value. The subscript o has an average value in the range of 2 to 10. The subscript o is 2 or greater, 3 or greater. It can have values ​​of 4 or more, 5 or more, 6 or more, 7 or more, 8 or more, and even 9 or more. At the same time, typically, 10 below , 9 below , 8 below , 7 below , 6 below , 5 below , 4 below Furthermore, 3 below It has the value of .

[0025] The crosslinking agent segment of the elastomer contains any one or any combination of two or more of the following segments (IV) and (V), or consists of them, where “--” corresponds to the bond connecting to the carbon atom of the main chain and can correspond to the same bond indicated by “--” in structures (I), (II) and (III). It can contain any one or any combination of two or more of the following segments (IV) and (V), or consist of them, where “--” corresponds to the bond connecting to the carbon atom of the main chain and can correspond to the same bond indicated by “--” in structures (I), (II) and (III). ((CH3)2SiO )2((CH3)SiO ) 1 / 2 ((CH3)3SiO 2 / 2 )2((CH3)2SiO b ) ((CH3)3SiO 1 / 2 )2((CH3)2SiO 2 / 2 ) c (--(CH3)S iO 2 / 2 ) d (V) In the formula The subscript b corresponds to the average number of ((CH\(_3\))SiO 2 / 2 ) groups per crosslinking agent segment having structure (IV), typically has a value of 5 or more, can have a value of 10 or more, 15 or more, and further can have a value of 16 or more, and at the same time, typically has a value of 30 or less, 25 or less , 20 or less, and further can be 17 or less. The subscript c corresponds to the average number of ((CH\(_3\))2SiO 2 / 2 ) per crosslinking agent segment having structure (V), typically has a value of 2 or more, can have a value of 3 or more, 5 or more, 10 or more , 15 or more, 20 or more, 25 or more, 30 or more, 40 or more, 50 or more, 60 or more, 70 or more , 80 or more, and further can be 90 or more, and at the same time, typically is 100 below , 95 below , 92 below , 90 below , 80 below , 70 below , 60 below , 50 below , 40 below , 30 below , 25 below , 20 below , 10 below Furthermore, 5 below It can be, The subscript d indicates the amount of (--(CH3)Si per crosslinking agent segment having structure (V). O 2 / 2 Corresponding to the average number of ), it typically has a value of 2 or more, and is 3 or more, 4 or more, 5 or more, Furthermore, it can be a value of 6 or greater, and at the same time, typically it has a value of 10 or less, and 9 or less. It can be 8 or less, 7 or less, and even 6 or less.

[0026] In a second aspect, the present invention is a method for preparing a composition of the first aspect of the present invention. The method includes preparing an elastomer of the first aspect by (a) providing a main chain polymer having at least two terminally unsaturated carbon-carbon bonds separated from any polyester group by carbon-oxygen-silicon bonds, and a crosslinking agent material containing a plurality of silyl hydride groups, wherein at least one of the main chain polymer or the crosslinking agent has three or more average unsaturated carbon-carbon bond functional groups, and / or the crosslinking agent has three or more average silyl hydride functional groups; and (b) forming an elastomer by crosslinking the main chain polymer with the crosslinking agent material by hydrosilylation addition between the unsaturated carbon-carbon bonds of the main chain polymer and the silyl hydride groups of the crosslinking agent material. "Functional group" refers to a terminally unsaturated carbon-carbon bond in the main chain polymer and to a silyl hydride group in the crosslinking material.

[0027] The main chain polymer is preferably an organosilyl functional polyester comprising at least two organosilyl functional groups, each having at least one terminal unsaturated carbon-carbon bond. "Organosilyl functional" means having at least one -SiR3 group, preferably multiple -SiR3 groups, where each R is independently selected from a hydrocarbyl group, including alkyl groups, alkenyl groups, and aryl groups.

[0028] Suitable examples of organosilyl functional polyesters include those having average chemical structures (VI), (VII), or (VIII). Ru O One of the following lucanosilyl functional polyesters Does it include or Two or more Includes any combination, CH2=CH-SiR2O-[(CH2)] m OC(O)CH2(CH2) n CH2C( O)O-] o (CH2) m -OSiR2-CH=CH2(VI) C(R)[CH2OX]3(VII) CH3CH(OX)CH2CH2OX (VIII) During the ceremony, R independently originates from a hydrocarbyl group having 1 to 8 carbon atoms in each occurrence. They can be selected and all be the same, or they can be different from one another. Buildings can be 1 or more, 2 or more, 3 or more, 4 or more, 5 or more, 6 or more, or even 7 or more. It may have carbon atoms as shown above, but typically contains eight or fewer carbon atoms at the same time. And, 7 or fewer, 6 or fewer, 5 or fewer, 4 or fewer, 3 or fewer, and even 2 or fewer carbon atoms It may contain. Preferably, the R group is methyl, ethyl, propyl, and phenyl Selected from a group consisting of elements. X independently, in each occurrence, is -H, -C(O)-(CH2)4C(O)OH, and The selection is made from -C(O)-(CH2)4C(O)OSiR2-CH=CH2, where R is above As noted, however, at least two X groups are -C(O)-(CH2)4C(O It is an OSiR2-CH=CH2 group. The subscript 'm' independently has an average value in the range of 1 to 8 in each occurrence, preferably It has a value of 2 or more, and also has a value of 3 or more, 4 or more, 5 or more, 6 or more, and even 7 or more. It is possible, but at the same time, typically 8 or less, 7 or less, 6 or less, 5 or less, 4 or less, 3 or less, and It has a value of 2 or less. Preferably, the subscript m is 2 in each occurrence. The subscript n has an average value within the range of 2 to 5. The subscript n is 2 or greater, 3 or greater. , 4 or more, 5 or more, 10 or more, 15 or more, 20 or more, 25 or more, 30 or more, 35 or more, It can have a value of 40 or more, but at the same time, typically 50 below , 45 below , 40 below ,35 below , 31 below ,twenty five below , 20 below , 10 below Furthermore, it has a value less than 5. The subscript o has an average value in the range of 2 to 10. The subscript o is 2 or greater, 3 or greater. It can have values ​​of 4 or more, 5 or more, 6 or more, 7 or more, 8 or more, and even 9 or more. At the same time, typically, 10 below , 9 below , 8 below , 7 below , 6 below , 5 below , 4 below Furthermore, 3 below It has the value of .

[0029] Organosilyl functionalized polyesters preferably have a molecular weight (Mw) in the range of 1,000 to 5,000 grams per mole (g / mol), more preferably in the range of 1,200 to 2,500, and can be in the range of 1,400 to 2,300. The molecular weight of the organosilyl functionalized polyesters is determined using gel transmission chromatography with a Waters 2695 Separation Module equipped with a vacuum degasser and a Waters 2410 differential refractive index detector. Two (300 mm × 7.5 mm) Polymer Laboratories PLgel 5 micrometer Mixed-C columns (molecular weight separation range 200 to 2,000,000) are used, preceded by a PLgel 5 micrometer guard column (50 mm × 7.5 mm). High-grade tetrahydrofuran (THF) is used as the eluent for polyester samples, and toluene for crosslinking agent samples, flowing at 1.0 ml / min, while maintaining the columns and detector at 35°C. Polyester samples were prepared in THF and crosslinking agent samples in toluene at a concentration of approximately 0.15 volume percent. These were solvated for 2 hours with occasional shaking, and filtered through a 0.45 micrometer polytetrafluoroethylene syringe filter before analysis. 100 microliters of the sample were injected for analysis, and data were collected for 30 minutes. ThermoLabsystems Atlas chromatography software and Polymer Laboratories Cirrus GPC software were used to collect data and perform the analysis. Average molecular weights were relative to a cubic calibration curve created using standard polystyrene with a molecular weight range of 580–2,750,000.

[0030] The crosslinking agent material is a silylhydride-functional (SiH-functional) compound, preferably a SiH-functional polysiloxane. The crosslinking agent material contains at least two SiH functional groups. The SiH-functional polysiloxane can be branched or linear, but is preferably linear. The SiH-functional polysiloxane may have one or more terminal SiH groups without pendant SiH groups, or may have one or more pendant SiH groups without terminal SiH groups, or may have a combination of one or more terminal SiH groups and one or more pendant SiH groups.

[0031] Preferably, the SiH-functionalized polysiloxane is linear and selected from those having the following average chemical formulas. ru-ka Compound 1 Tsu Is it or Two or more Any combination, (R'3SiO 1 / 2 )2(R'2SiO 2 / 2 ) b During the ceremony, R' is independently selected in each occurrence from the group consisting of hydrogen and R groups, and R is above As noted, however, at least two R' groups are hydrogen. The subscript b indicates the amount per molecule (R'2SiO 2 / 2 This is the average number of ) and typically, Having a value of 5 or higher, 10 or higher, 15 or higher, 20 or higher, 30 or higher, 50 or higher, 70 or higher, and more It can be 90 or more, and at the same time, typically 120 below Furthermore, 100 below And, 70 below , 50 below , 30 below , 20 below , 15 below Furthermore, 10 below It can be.

[0032] Suitable examples of silylhydride-functionalized polysiloxanes include those having the following average molecular formulas: (H(CH3)2SiO 1 / 2 )2((CH3)SiO 2 / 2 ) 20 , ((CH3)3SiO 1 / 2 )2((CH3)2SiO 2 / 2 ) 25 (H(CH3)SiO 2 / 2 )6, ((CH3)3SiO 1 / 2 )2((CH3)2SiO 2 / 2 ) 92 (H(CH3)SiO 2 / 2 )6, and ((CH3)3SiO 1 / 2 )2((CH3)2SiO 2 / 2 ) 3.3 (H(CH3)SiO 2 / 2 )6.

[0033] If present, the silyl hydride-functionalized polysiloxane is present in a concentration sufficient to provide, preferably, a molar ratio of SiH functional groups from the crosslinking agent material to unsaturated carbon-carbon bonds from the main chain polymer of 0.7 or higher, preferably 0.90 or higher, and at the same time, typically 1.5 or lower, preferably 1.0 or lower, and more preferably 0.95 or lower.

[0034] The first embodiment of the present invention is formed by crosslinking the main chain polymer with a crosslinking agent material through hydrosilylation addition between the unsaturated carbon-carbon bonds of the main chain polymer and the silyl hydride groups of the crosslinking agent material.

[0035] Typically, it is desirable to carry out the hydrosilylation reaction in the presence of a hydrosilylation catalyst. Typically, the hydrosilylation catalyst is ,white One of the gold-based hydrosilylation catalysts Is it or Two or moreAny combination is acceptable. Examples of platinum-based hydrosilylation catalysts include compounds and complexes, such as platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane (karstedt catalyst), H2PtCl6, di-μ-carbonyldi-π-cyclopentadienyldinickel, platinum-carbonyl complexes, platinum-divinyltetramethyldisiloxane complexes, platinum-cyclovinylmethylsiloxane complexes, platinum acetylacetonate (acac), platinum black, platinum compounds, such as chloroplatinic acid, chloroplatinic acid hexahydrate, reaction products of chloroplatinic acid and monohydric alcohols, platinum bis(ethylacetoacetate), platinum bis(acetylacetonate), platinum dichloride, and complexes of platinum compounds with olefins or low molecular weight organopolysiloxanes, or platinum compounds microencapsulated in a matrix or core-shell structure. The hydrosilylation catalyst may be part of a solution containing a complex of platinum and a low molecular weight organopolysiloxane, including a 1,3-diethenyl-1,1,3,3-tetramethyldisiloxane complex with platinum. These complexes may be microencapsulated in a resin matrix. The catalyst may be a 1,3-diethenyl-1,1,3,3-tetramethyldisiloxane complex with platinum.

[0036] The concentration of the platinum-based hydrosilylation catalyst is typically 5 parts per million (ppm) or more, preferably 10 ppm or more, and can be 25 ppm or more, 50 ppm or more, and even 75 ppm or more, based on the total weight of the crosslinking agent material and the main chain polymer. At the same time, it is typically 500 ppm or less, 400 ppm or less, 300 ppm or less, 200 ppm or less, preferably 100 ppm or less, and can be 90 ppm or less, 80 ppm or less, 70 ppm or less, 60 ppm or less, and even 50 ppm or less.

[0037] It is desirable to carry out the hydrosilylation reaction in a non-aqueous solvent to produce a solvent-swollen elastomer. Examples of suitable solvents include the solvents mentioned herein, including nonpolar solvents. Preferably, when the solvent is a polysiloxane and the organosilyl functionalized polyester contains more than two terminal carbon-carbon double bonds, the molecular weight of the crosslinking agent is less than 7500, can have a molecular weight of 7400 or less, preferably 2400 or less, more preferably 2390 or less, more preferably 1400 or less, and even more preferably 1390 or less. The molecular weight of the crosslinking agent material is determined using the method described herein for the organosilyl functionalized polyester.

[0038] The method may include forming a solvent-swollen elastomer as described, and then subjecting the solvent-swollen elastomer to shearing to pulverize it into fine particles to produce a paste. Optionally, a non-aqueous solvent may be added to the solvent-swollen elastomer before, during, and / or after shearing. In the broadest sense, there are no limitations on the method of shearing the solvent-swollen elastomer. For example, shearing can be applied by mixing the solvent-swollen elastomer with a mixing blade to pulverize it into fine particles. The degree of shearing can determine the particle size of the elastomer gel in the paste. Typically, the finer the particle size, the smoother (less gritty) the resulting paste will feel, and therefore, finer particle sizes are desirable for applications such as cosmetics that involve application to the skin. [Examples]

[0039] The main chain polymer is prepared according to the following method, and then the samples of the Example (Ex) and Comparative Example (CEx) of the present invention are prepared according to the following subsequent procedures.

[0040] Preparation of organosilyl functional polyester main chain polymers Table 1 lists the components needed to prepare the following example.

[0041] [Table 1] PRIPLAST is a trademark of Croda International PLC. DESMOPHEN is a trademark of Covestro Intellectual Property GMBH.

[0042] Table 2 provides, for each of organosilyl-functionalized polyesters 1-3, the concentrations of polyester polyol, catalyst, and divinyldisilazane in grams used to prepare each organosilyl-functionalized polyester, as well as the reaction time (hours) and reaction temperature (°C). In addition, Table 2 lists the average OH substitution mole percent (mol%) (silylation) relative to OH moles in the polyester polyol, the weight % of vinyl groups per molecule based on the weight of the organosilyl-functionalized polyester, and the average number of vinyl groups per molecule of organosilyl-functionalized polyester.

[0043] [Table 2]

[0044] Add the polyester polyol, divinyldisilazane, and catalyst to a 500 ml (mL) round-bottom flask. Add a polytetrafluoroethylene stirring bar, purge the flask and its contents with nitrogen, and seal with a septum. Heat the contents to the reaction temperature using a heating plate while stirring during the reaction time. Cool the mixture to 23°C, and remove the residual divinyldisilazane under vacuum (1.3 kilopascals) at 130°C for 2 hours to obtain the resulting organosilyl functional polyester.

[0045] The resulting organosilyl functional polyester is protonated ( 1H) Characterization is performed by nuclear magnetic resonance (NMR) spectroscopy. A 10 mg sample of organosilyl functionalized polyester is dissolved in 0.6 ml of deuterated benzene (d6-benzene) and spectroscopy is performed at 400 MHz Varian 1 Analysis is performed using a 1H NMR spectrometer. An acquisition time of 5 seconds and a relaxation delay time of 15 seconds are used. Sixteen scans are collected and averaged to obtain the resulting spectrum. The obtained spectrum is referenced to benzene at δ 7.16 ppm. The regions in the spectrum at the target group are the vinyl region ("V") integrated from δ 5.6–6.5 ppm, the methylene region adjacent to the hydroxyl ("O") integrated over δ 4.2–4.3 ppm to determine the hydroxyl substitution, the methylene exclusion adjacent to the ester region ("E") at δ 2.1–2.3 ppm, and the methyl region at δ 0.15–0.3 ppm to occupy the silylation ("S"). The integral is set based on the number of repeating units along the main chain of the polyester polymer, normalizing region "E" to 16 for polyester 1, normalizing region "E" to 30 for polyester 2, and normalizing region "E" to 24 for polyester 3. The OH substitution mole percent is calculated as the integral from the region corresponding to "V" obtained by dividing by the theoretical vinyl integral based on the OH per polyester polyol. The theoretical vinyl integral is 6 for polyesters 1 and 2, and 16.5 for polyester 3. The following calculation is used. OH substitution moles % = [(V) / (OH per polyester poly) × 3] × 100% Vinyl weight % = [Molecular weight of vinyl group] × [OH substitution mole %] / [MW / OH of polyester], where the MW / OH of polyesters 1 and 2 is 1000, and the MW / OH of polyester 3 is 260. The formula for vinyl groups per polyester is [OH substitution mole%] × [OH per polyester], where the amount of OH per polyester is 2 for polyesters 1 and 2, and 5.5 for polyester 3.

[0046] Organosilyl functional polyester 1 has the following average chemical structure. CH2=CH-Si(CH3)2O[(CH2)2OC(O)CH2(CH2) 31 CH2C(O)O-] 3.9 (CH2)2OSi(CH3)2-CH=CH2

[0047] Organosilyl functional polyester 2 has the following average chemical structure. CH2=CH-Si(CH3)2O[(CH2)2OC(O)CH2(CH2) 13 CH2C(O)O-] 7.5 (CH2)2OSi(CH3)2-CH=CH2

[0048] Organosilyl functional polyester 3 may have combinations of structures, but is expected to include materials having the following average chemical structure.

[0049] [ka]

[0050] Preparation of Ex and CEx Table 3 lists the components required to prepare the following examples (Ex) and comparative examples (CEx).

[0051] [Table 3] CETIOL is a trademark of Cognis IP Management GMBH. CRODAMOL is a trademark of Croda, Inc. CERAPHYL is a trademark of ISP Investments, Inc. DOWSIL is a trademark of The Dow Chemical Company. SYL-OFF is a trademark of Dow Corning Corporation.

[0052] Elastomer samples are prepared using the following hydrosilylation procedure. The identification of each component and its concentration in grams ("[g]") are shown in Table 4. The organosilyl-functional polyester ("OFP"), crosslinking agent, and solvent are combined in a 20 ml glass scintillation vial equipped with a magnetic stirring bar, and the components are stirred at 250 rpm to form a mixture. The mixture is heated to the reaction temperature shown in Table 4, and then the hydrosilylation catalyst is added at the concentration shown in Table 4 as parts per million of the weight of the mixture. The mixture is maintained at the reaction temperature for 3 hours and then cooled to 25°C.

[0053] Successful formation of the solvent-swollen elastomer (Rxn success = Y) is evident when the reaction product flows at a rate of less than 1 centimeter in the scintillation vial after inversion for 1 minute.

[0054] Table 4 reports the identification of each component, the amount of each component, the molar ratio of silyl hydride to carbon-carbon double bond (SiH:C=C), the reaction temperature (Temp), and whether the formation of the solvent-swollen elastomer was successful.

[0055] CEx A has shown that if the main chain polymer has an average of two unsaturated carbon-carbon bonds and the crosslinking material has an average of two SiH groups, the reaction fails to cure into an elastomer. However, other examples have shown that as long as either the main chain polymer or the crosslinking material has an average of three or more functional groups, the other can have two, and the reaction forms an elastomer.

[0056] Ex26-39 and CEx B and CEx C indicate that when using organosilyl functional polyesters with more than two terminal CC double bonds in an organosiloxane solvent, it is desirable to use a crosslinking agent with a molecular weight of less than 7400.

[0057] [Table 4]

[0058] paste sample Pastes are prepared from the example materials described above by subjecting them to shearing using a Waring Model 7012 blender. For Paste 1 and Paste 2, the solvent is gradually added while shearing is applied. Table 5 identifies exemplary compositions for preparing pastes, which example materials are used, in what quantities (grams), which solvent is added, in what quantities (grams), the resulting solid concentration as a weight % relative to the paste weight, and millipascals × second (mPa). * Determine the final paste viscosity in step s). Determine the paste viscosity at 2.5 revolutions per minute at 25°C using a Brookfield DV-II Plus Pro Programmable Viscometer with a helipad spindle (S94).

[0059] [Table 5]

[0060] Sensory sensation The tactile properties of paste samples, as well as two commercially available dimethicone materials from The Dow Chemical Company under trade names DOWSIL® 9041 (Ref 1) and DOWSIL® 3901 (Ref 2), are characterized. Ref 1 serves as a siloxane material with a desirable tactile profile. Ref 2 is a siloxane material with an undesirable tactile profile.

[0061] A panel of 10 trained sensory evaluators was used to conduct a sensory tactile assessment. Prior to the assessment, each panelist washed their forearm, hand, and fingers with 4.3% active sodium lauryl ether sulfate in water, then rinsed with distilled water and dried with a paper towel. For the assessment, each panelist applied 50 milligrams of sample material to the inside of their forearm in a circular motion at a rate of 2 rubs per second for a maximum of 120 rubs. Panelists characterized the skin sensory parameters on a scale of 1 to 5, as shown below, where 5 was the closest to the parameter descriptive term and 1 was the least similar. Each sample was assigned a final value, which was the average of the values ​​of the 10 trained sensory evaluators for each parameter. The parameters and descriptive terms are as follows:

[0062] [Table 6]

[0063] For a "smooth, dry, and fine-grained feel," it is desirable that the sample has a smoothness value greater than 3, a fine-grained feel greater than 2, and a moisture value less than 3. Table 6 provides the sensory evaluation results for pastes 1-4, Ref 1, and Ref 2. The results show that the paste of the present invention is similar to the standard siloxane material of Ref 1 and, in contrast to Ref 2, successfully achieves the desired "smooth, dry, and fine-grained feel."

[0064] [Table 7]

[0065] durability The durability of the paste is evaluated according to the following procedure. A sample is prepared by adding 8 g of sample paste, followed by 2 g of Skolar Glare® Violet SG-7661E dye (manufactured by CQV Co. Ltd., Skolar Glare is a trademark of CQV Co. Ltd.) to a dental cup. The mixture is mixed for 20 seconds at 2000 rpm using a FlackTek DAC 150 speed mixer. 0.3 g of the resulting mixture is coated onto a 4.75 cm × 5 cm collagen-coated microscope slide. The coated sample is dried at 25°C for 24 hours. The coated slide is cleaned by applying a solution of 0.07 g of DIAL® dish soap (Henkel Corporation) in 0.07 g of water to the coated slide for 20 seconds with a damp fingertip. After cleaning, a digital image of the slide is taken and analyzed using ImageJ software to determine the area of ​​the slide where the coating remains. The area of ​​the remaining coating is reported as a percentage of the initially coated area, and this represents the durability percentage of the sample. A higher value is more desirable for durability. Table 7 reports the durability percentage for each sample.

[0066] [Table 8]

[0067] The data in Table 7 demonstrate that the paste of the present invention has higher durability than any of the siloxane reference materials. It is desirable that the paste has a greater potential to remain on the skin and provide the desired sensory feel even after washing.

[0068] Solvent compatibility The solvent compatibility of the sample is evaluated by combining 7.5 g of the sample with 2.5 g of a specific solvent (see Table 8) in a dental cup, and then mixing for 30 seconds using a FlackTek DAC 150 speed mixer at 2300 rpm. The material is transferred to a 20 ml clear glass vial and centrifuged for 20 minutes at 3000 rpm using an IEC Model K centrifuge. The samples are allowed to stand at 25°C for 24 hours, then observed and characterized using the following scale, with lower values ​​indicating better performance. 1: Transparent. The sample is clear and easily readable when text is placed behind the vial containing the sample. 2: Slight cloudiness. The sample is almost transparent, with only very slight cloudiness detectable, and letters placed behind the vial containing the sample are still easily readable through the sample. 3: Cloudy. The sample is not transparent, and while the letters placed behind the vial containing the sample can be detected, they are not legible. 4: Opaque. White solid. Light cannot pass through, making it impossible to detect what is placed behind the vial. 5: Not suitable. The sample phase separated.

[0069] The results for the samples are shown in Table 8. The data reveal that the paste of the present invention generally has broader solvent compatibility than either Ref 1 or Ref 2.

[0070] [Table 9]

[0071] Hydrolytic stability The relative hydrolysis stability of the CO-Si bond relative to the COC bond in organosilyl-functionalized polyester 1 is evaluated. 15 milligrams of organosilyl-functionalized polyester 1 is placed in a glass nuclear magnetic resonance (NMR) tube, and 0.75 milliliters of deuterated chloroform (CDCl3) is added. Then, 5 microliters of a 10:1 mixture of deionized water / trifluoroacetic acid are added. Proton NMR spectra are collected immediately after the addition of the water / acid mixture and at 5 and 25 hours. (400 megahertz Varian) 1 NMR spectra were collected using a 1H NMR spectrometer. An acquisition time of 5 seconds and a relaxation delay time of 15 seconds were used. Sixteen scans were collected and averaged for analysis to obtain the final spectrum. The reference showed a peak at δ 7.26 ppm for CDCl3. At each time point, the molar percentages of CO-Si hydrolysis and COC hydrolysis were determined. The molar percentages of CO-Si hydrolysis were determined by integrating the dimethylvinylsilyl polyester peak (CO-Si(Me)2Vi) at δ 0.16–0.18 ppm and the hydrolyzed dimethylvinylsilyl group (HO-Si(Me)2Vi) from δ 0.21–0.22. The molar percentages of CO-Si hydrolysis were determined by evaluating the growth of the resonance of the hydrolyzed dimethylvinylsilyl group (HO-Si(Me)2Vi) present at δ 0.21–0.22 in CDCl3 against the resonance of the non-hydrolyzed dimethylvinylsilyl polyester peak at δ 0.16–0.18 ppm. The molar percentage of COC hydrolysis is determined by integrating the proton resonances of the non-hydrolyzed polyester (-CH2-OC(O)-C-) present in CDCl3 at a δ of 4.21–4.26 ppm with respect to the resonances present at 9–11 ppm in the hydrolyzed composition (HO-C(O)-C) in CDCl3.

[0072] The results in Table 9 reveal that the COC bond remains stable against hydrolysis, while the CO-Si bond undergoes almost complete hydrolysis within 25 hours. This supports the idea that the CO-Si bond is less hydrolytically stable than the COC bond.

[0073] [Table 10] This application provides, for example, the following inventions: [1] A composition comprising an elastomer, wherein the elastomer has a polyester main chain crosslinked with a crosslinking agent, and has a carbon-oxygen-silicon bond between the ester group and the crosslinking agent. [2] The composition according to [1] above, wherein the polyester main chain does not contain a silicon-oxygen-silicon bond. [3] The composition according to [1] or [2] above, wherein the crosslinking agent is a polysiloxane. [4] The composition according to any one of [1] to [3] above, wherein there is at least one carbon-oxygen-silicon bond between any polyester and any siloxane bond in the elastomer. [5] The composition according to any one of the above [1] to [4], wherein each polyester main chain has at least three bonds with a crosslinking agent, and / or each crosslinking agent has at least three bonds with a main chain polymer. [6] The composition according to any one of the above [1] to [5], wherein the elastomer is solvent-swollen with a non-aqueous solvent. [7] The composition according to [5], wherein the elastomer is present in the form of fine particles and the composition is in the form of a paste. [8] A method for preparing the composition described in any one of the above items [1] to [7], wherein the method is a. A main chain polymer having at least two terminally unsaturated carbon-carbon bonds separated from any polyester group by carbon-oxygen-silicon bonds, and a crosslinking agent material containing a plurality of silyl hydride groups, wherein at least one of the main chain polymer or the crosslinking agent has three or more average unsaturated carbon-carbon bond functional groups, and / or the crosslinking agent has three or more average silyl hydride functional groups, to provide a main chain polymer and a crosslinking agent material. b. A method for preparing the elastomer, comprising crosslinking the main chain polymer with the crosslinking agent material by hydrosilylation addition between the unsaturated carbon-carbon bonds of the main chain polymer and the silyl hydride groups of the crosslinking agent material to form an elastomer. [9] The method according to [8], wherein the hydrosilylation reaction is carried out in a non-aqueous solvent to produce a solvent-swollen elastomer, wherein the non-aqueous solvent is a polysiloxane and the organosilyl functional polyester contains three or more terminal carbon-carbon bonds, the crosslinking agent has a weight-average molecular weight less than [molecular weight for crosslinking agent 3].

[10] a. Optionally, adding an additional non-aqueous solvent to the solvent-swelled elastomer, b. The process according to [9] above, further comprising subjecting the solvent-swollen elastomer to shearing to break the solvent-swollen elastomer into granular form and produce a paste.

Claims

1. A composition containing an elastomer, The elastomer is characterized by having a main chain of organosilyl functional polyester crosslinked with a crosslinking agent material, and having a carbon-oxygen-silicon bond between the ester group and the crosslinking agent. The organosilyl functional polyester comprises one or any combination of two or more organosilyl functional polyesters having average chemical structures (VI), (VII), or (VIII). CH 2 =CH-SiR 2 O-[(CH 2 ) m OC(O)CH 2 (CH 2 ) n CH 2 C(O)O-] o (CH 2 ) m -OSiR 2 -CH=CH 2 (VI) C(R)[CH 2 OX] 3 (VII) CH 3 CH(OX)CH 2 CH 2 OX (VIII) During the ceremony, R is independently selected from hydrocarbyl groups having 1 to 8 carbon atoms in each occurrence, and they can all be the same or they can all be different from one another. X is independent in each occurrence, -H, -C(O)-(CH 2 ) 4 C(O)OH and -C(O)-(CH 2 ) 4 C(O)OSiR 2 -CH=CH 2 Selected from the above, R is as described above, however, at least two X groups are -C(O)-(CH 2 ) 4 C(O)OSiR 2 -CH=CH 2 It is the basis, The subscript m independently has a value of 2 or more and a value of 8 or less in each occurrence. The subscript n has a value of 2 or more and a value of 50 or less. The subscript o has a value of 2 or more and a value of 10 or less. The crosslinking agent material is a silyl hydride-functionalized polysiloxane, which is linear and is one or any combination of two or more compounds selected from those having the following average chemical formulas: (R’ 3 SiO 1 / 2 ) 2 (R’ 2 SiO 2 / 2 ) b During the ceremony, R' is independently selected in each occurrence from the group consisting of hydrogen and R groups, where R is as described above, except that at least two R' groups are hydrogen. The subscript b represents the (R' per numerator) 2 SiO 2 / 2 A composition having an average number of ) that is 5 or greater and 120 or less.

2. The composition according to claim 1, wherein each organosilyl functional polyester main chain has at least three bonds with a crosslinking agent material, and / or each crosslinking agent material has at least three bonds with an organosilyl functional polyester main chain polymer.

3. The composition according to claim 1 or 2, wherein the elastomer is solvent-swollen with a non-aqueous solvent.

4. The composition according to claim 3, wherein the elastomer exists in the form of fine particles, and the composition is in the form of a paste.

5. A method for preparing the composition according to claim 1 or 2, wherein the method is a. To provide the organosilyl functional polyester and the crosslinking agent material, b. Forming an elastomer by crosslinking the organosilyl functional polyester main chain with the crosslinking agent material through hydrosilylation addition between the unsaturated carbon-carbon bond of the organosilyl functional polyester and the silyl hydride group of the crosslinking agent material, A method comprising preparing the elastomer by means of the method described above.

6. The method according to claim 5, wherein the hydrosilylation reaction is carried out in a non-aqueous solvent to produce a solvent-swollen elastomer, provided that the non-aqueous solvent is a polysiloxane and the organosilyl functional polyester contains three or more terminal carbon-carbon bonds, the crosslinking agent has a weight-average molecular weight of less than 7400.

7. a. Optionally, an additional non-aqueous solvent may be added to the solvent-swollen elastomer. b. The solvent-swollen elastomer is subjected to shearing to crush the solvent-swollen elastomer into particle form and produce a paste, The method according to claim 6, further comprising:

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