Cyclic oligosaccharide-modified organopolysiloxane and film-forming agent

Abstract

The present invention is a cyclic oligosaccharide-modified organopolysiloxane which is an addition reaction product of (A) and (B) described below, as a result, the present invention provides: (A) an organohydrogenpolysiloxane having one or more hydrosilyl groups in one molecule, having a kinematic viscosity at 25 DEG C of 50 mm2 / s or more and a molecular weight of 8,000 or more, and having a cyclic oligosaccharide-modified organopolysiloxane that has a high molecular weight and is soluble in a solvent, and a film-forming agent that contains the polysiloxane, and also provides: (A) an organohydrogenpolysiloxane that has one or more hydrosilyl groups in one molecule, said organohydrogenpolysiloxane having a kinematic viscosity at 25 DEG C of 50 mm2 / s or more and a molecular weight of 8,000 or more; (B) is a cyclic oligosaccharide derivative having an unsaturated group represented by formula (1) (in formula (1), A is an alkenyl group having 2-12 carbon atoms, R1 is independently a group selected from the group consisting of an alkyl group having 1-4 carbon atoms, an aryl group having 6-10 carbon atoms, and an aralkyl group having 7-10 carbon atoms, R2 is an alkylene group having 1-4 carbon atoms, and R3 is an alkyl group having 1-4 carbon atoms. R1 and R2 are independently selected from alkyl with 1-4 carbon atoms or acyl with 1-4 carbon atoms, R3 is independently selected from alkyl with 1-4 carbon atoms or acyl with 1-4 carbon atoms, a is an integer of 0-8, b is an integer of 5-7, and x is 0 or 1.

Description

TECHNICAL FIELD

[0001] The present application relates to a cyclic oligosaccharide-modified organopolysiloxane and a film-forming agent containing the same. BACKGROUND

[0002] Organopolysiloxanes can be endowed with various functions by modifying various chemical structures at the terminal or side chain. On the other hand, it is also known that the cavity of the molecular structure of a cyclic oligosaccharide interacts with various compounds. Utilizing this characteristic, it is used in the industrial field of food or cosmetics, and in order to develop functional materials, it is studied to be introduced into various high molecular materials. In fact, it is studied to introduce a cyclic oligosaccharide into an organopolysiloxane, and a gel material crosslinked with a cyclic oligosaccharide derivative is disclosed (Patent Literature 1).

[0003] However, since the above-mentioned cyclic oligosaccharide-modified organopolysiloxane is a crosslinked material, although it swells in a solvent, it is difficult to dissolve it, and there are limitations in the use in applications such as film-forming agents or coating materials.

[0004] In Patent Literature 2 and Non-Patent Literature 1, a method for producing a non-crosslinked cyclic oligosaccharide-modified organopolysiloxane using a derivative in which a reactive functional group is bonded to only one hydroxyl group of a cyclic oligosaccharide is disclosed.

[0005] However, generally, since the compatibility of a cyclic oligosaccharide with an organopolysiloxane is poor, the addition thereof to a high molecular weight organopolysiloxane has not been sufficiently studied. In fact, the number average molecular weight of the organopolysiloxane used in Patent Literature 2 or Non-Patent Literature 1 is about 1,000 to 7,500, which is a relatively low molecular weight organopolysiloxane.

[0006] PRIOR ART DOCUMENTS PATENT LITERATURE Patent Literature 1: Japanese Patent Application Laid-Open No. 2022-503533 Patent Literature 2: International Publication No. 2021 / 172468 NON-PATENT LITERATURE Non-Patent Literature 1: Ahlem Noomen, et al., Emulsions of β-cyclodextrins grafted to silicone for the transport of antifungal drugs, Materials Science and Engineering C, 2008, 28, p. 705-715 SUMMARY

[0007] (I) Technical Problem to be Solved The present application has been made in view of the above circumstances, and its object is to provide a cyclic oligosaccharide-modified organopolysiloxane which is high in molecular weight and soluble in a solvent, and a film-forming agent containing the same.

[0008] (II) Technical Solution To achieve the above object, the present application provides the following cyclic oligosaccharide-modified organopolysiloxane and film-forming agent.

[0009] That is, the present application provides a cyclic oligosaccharide-modified organopolysiloxane which is an addition reaction product of at least the following (A) and (B), (A) is an organohydrogenpolysiloxane having one or more silicon-bonded hydrogen atoms in one molecule, which has a kinematic viscosity at 25°C of 50 mm 2 or more and a number average molecular weight of 8,000 or more, (B) is a cyclic oligosaccharide derivative having an unsaturated group represented by the following general formula (1), [Chemical Formula 1]

[0010] In general formula (1), A is an alkenyl group having 2 to 12 carbon atoms, R 1 independently is a group selected from an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms, R 2 is an alkylene group having 1 to 4 carbon atoms, R 3 independently is a group selected from an alkyl group having 1 to 4 carbon atoms or an acyl group having 1 to 4 carbon atoms, a is an integer of 0 to 8, b is an integer of 5 to 7, and x is 0 or 1.

[0011] If it is such a cyclic oligosaccharide-modified organopolysiloxane, it is soluble in a solvent while being high in molecular weight.

[0012] In this case, it is preferable that it is an addition reaction product of the above (A) and (B) and (C), and (C) is an α-olefin having 2 to 16 carbon atoms.

[0013] In such a cyclic oligosaccharide-modified organopolysiloxane, the compatibility with a cyclic oligosaccharide is increased.

[0014] Further, the present application provides a cyclic oligosaccharide-modified organopolysiloxane characterized by being a substance represented by general formula (2).

[0015] [Chemical Formula 2]

[0016] In general formula (2), R4 independently a group selected from an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms, R 5 independently an alkyl group having 5 to 16 carbon atoms, R 6 independently a group represented by the following general formula (3) having a cyclic oligosaccharide structure, R 7 independently a group selected from R 4 or R 6 , c is an integer of 100 to 600, d is an integer of 0 to 50, e is an integer of 1 to 50, wherein c+d+e satisfies the range of 101 to 700, and the bonding order of the siloxane units in parentheses of c, d, and e is optionally block or random, [Chemical Formula 3]

[0017] In the general formula (3), A' is an alkylene group having 2 to 12 carbon atoms, R 1 , R 2 , R 3 , a, b, and x are the same as R 1 , R 2 , R 3 , a, b, and x in the above general formula (1), is a free radical bonded to a silicon atom of a siloxane unit.

[0018] In this case, it is preferable that, in the general formula (2), R 1 is a methyl group, R 3 is an acetyl group, and R 4 is a methyl group.

[0019] Further, it is further preferable that, in the general formula (2), x is 1.

[0020] If it is such a substance, the effect of the present application can be more surely exerted.

[0021] A cyclic oligosaccharide-modified organopolysiloxane can be provided, characterized in that a glass transition temperature measured by dynamic viscoelasticity measurement is 50 to 100°C.

[0022] A cyclic oligosaccharide-modified organopolysiloxane having a glass transition temperature of 50 to 100°C can have sufficient physical properties and soft film-forming ability at room temperature.

[0023] The cyclic oligosaccharide-modified organopolysiloxane of the present application can be used as a film-forming agent because it forms a film that is high in transparency, soft and non-sticky, and tough.

[0024] (III) Advantageous Effects The cyclic oligosaccharide-modified organopolysiloxane of the present application has a structure in which a cyclic oligosaccharide is stably bonded, is of high molecular weight, and is soluble in a solvent, and after evaporation of the solvent, forms a coating film that is highly transparent, soft, not sticky, and strong, and is a novel film-forming agent. DETAILED DESCRIPTION

[0025] Hereinafter, the present application will be described in detail, but the present application is not limited by the following description.

[0026] In order to achieve the above object, the present inventors have conducted earnest research, and as a result, have found that by imparting a short-chain alkyl structure or a dimethylsiloxane structure having high compatibility with an organopolysiloxane to a cyclic oligosaccharide, it is possible to stably add the cyclic oligosaccharide to the organopolysiloxane. The cyclic oligosaccharide-modified organopolysiloxane of the present application has a specific structure, and thus even if it is of high molecular weight, it can be uniformly dissolved in a solvent, and can be added as a coating agent for cosmetics or paints. Furthermore, it has been found that after evaporation of the solvent, a coating film that is highly transparent, soft, not sticky, and strong is formed, and thus the present application has been completed.

[0027] That is, the cyclic oligosaccharide-modified organopolysiloxane of the present application is an adduct of at least the following (A) and (B), (A) is an organohydrogenpolysiloxane having one or more silicon-bonded hydrogen atoms in one molecule, and has a kinematic viscosity at 25°C of 50 mm 2 or more, and a number average molecular weight of 8,000 or more, (B) is a cyclic oligosaccharide derivative having an unsaturated group represented by the following general formula (1), [Chemical Formula 4]

[0028] In the general formula (1), A is an alkenyl group having 2 to 12 carbon atoms, R 1 is independently a group selected from an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms, R 2 is an alkylene group having 1 to 4 carbon atoms, R 3 is independently a group selected from an alkyl group having 1 to 4 carbon atoms or an acyl group having 1 to 4 carbon atoms, a is an integer of 0 to 8, b is an integer of 5 to 7, and x is 0 or 1.

[0029] In the (A), the kinematic viscosity at 25°C is 50 mm 2 or more, from the viewpoint of ease of handling, it is preferably 50 to 25,000 mm 2 or more, from the viewpoint of ease of handling, it is preferably 50 to 25,000 mm 2 / s. Furthermore, in this invention, the kinematic viscosity is the value measured at 25°C using a Cannon-Fenske viscometer as described in JIS Z8803:2011.

[0030] Furthermore, the number average molecular weight is 8,000 or higher, preferably 8,000 to 50,000, and more preferably 8,000 to 35,000, from the perspective of ease of operation. The number of hydrosilyl groups contained in one molecule of organohydropolysiloxane is one or more, preferably 1 to 40, and more preferably 1 to 20, from the perspective of the resulting coating properties. In addition, in this invention, the number average molecular weight is a value obtained by GPC (gel permeation chromatography) analysis using polystyrene as a standard under the following conditions.

[0031] [Measurement Conditions] Developing solvent: Toluene Flow rate: 0.6 mL / min Detector: Differential Refractive Index Detector (RI) Chromatographic column: TSK Guard column Super HH TSKgel Super H5000 (6.0mm ID ×15cm×1) TSKgel Super H4000 (6.0mm ID ×15cm ×1) TSKgel Super H3000 (6.0mm ID ×15cm×1) TSKgel Super H2000 (6.0mm ID ×15cm ×1) (All manufactured by TOSOH CORPORATION) Column temperature: 40℃ Sample injection volume: 50 μL (0.3% by mass toluene solution) In the general formula (1) of (B), A is an alkenyl group with 2 to 12 carbon atoms. From the perspective of providing raw materials for synthesis, an alkenyl group with 2 to 4 carbon atoms is preferred, and a vinyl group is more preferred. R 1 The group is independently selected from alkyl groups having 1 to 4 carbon atoms, aryl groups having 6 to 10 carbon atoms, and aralkyl groups having 7 to 10 carbon atoms. From the perspective of the availability of synthetic raw materials, methyl or ethyl is preferred, and methyl is more preferred. 2It is an alkylene group having 1 to 4 carbon atoms; from the perspective of providing synthetic raw materials, it is preferably an alkylene group having 2 to 3 carbon atoms, and more preferably a propenyl group. R 3 Independently, it is a group selected from alkyl groups having 1 to 4 carbon atoms or acyl groups having 1 to 4 carbon atoms. From the perspective of reaction conditions, it is preferably an acyl group having 1 to 4 carbon atoms, and more preferably an acetyl group. a is an integer from 0 to 8. From the perspective of the supply of synthetic raw materials, it is preferably 0 to 2, and more preferably 0. b is an integer from 5 to 7. x is 0 or 1. For excellent compatibility with the component (A), x is preferably 1.

[0032] In addition to (A) and (B) described above, the cyclic oligosaccharide-modified organopolysiloxane of the present invention can also add to (C) an α-olefin having 2 to 16 carbon atoms. From the perspective of compatibility with cyclic oligosaccharides, the α-olefin having 2 to 16 carbon atoms is preferably an alkyl group having 5 to 8 carbon atoms, and more preferably an octyl group. The ratio of (A) and (B) is preferably: relative to 1 mole of the hydrosilyl group in the organohydropolysiloxane (A), the alkenyl group in the cyclic oligosaccharide derivative (B) is 0.8 to 1.2 moles. Furthermore, when the (C) component is also included, it is preferable that: relative to 1 mole of the hydrosilyl group in the organohydropolysiloxane (A), the alkenyl group in the cyclic oligosaccharide derivative (B) is 0.02 to 1.2 moles, and the alkenyl group in the α-olefin (C) is 0.02 to 1.98 moles. Of which, relative to 1 mole of the hydrosilicon-based component (A), the total amount of components (B) and (C) is preferably in the range of 0.8 to 2.0 moles.

[0033] The above addition reaction is preferably carried out in the presence of a platinum or rhodium catalyst. Specifically, catalysts such as platinum chloride, alcohol-modified platinum chloride, and platinum chloride-vinylsiloxane complexes can be suitably used. Furthermore, the amount of catalyst used can be defined as the catalyst amount, but from the perspective of the appearance of the cyclic oligosaccharide-modified organopolysiloxane, it is preferably 100 ppm or less, and particularly preferably 50 ppm or less, based on the amount of platinum or rhodium.

[0034] The above addition reaction can be carried out in an organic solvent as needed. Examples of suitable organic solvents include aliphatic alcohols such as methanol, ethanol, 2-propanol, and butanol; aromatic hydrocarbons such as toluene and xylene; aliphatic or alicyclic hydrocarbons such as n-pentane, n-hexane, and cyclohexane; and halogenated hydrocarbons such as dichloromethane, chloroform, and carbon tetrachloride. From the perspective of compatibility with the starting materials, toluene is preferred.

[0035] There are no particular limitations on the conditions for the addition reaction, but it is preferred to carry out the reaction at 70~110℃ for 1~10 hours.

[0036] The cyclic oligosaccharide-modified organopolysiloxane obtained by the addition reactions of (A), (B) and (C) is preferably the substance represented by the following formula (2).

[0037] [Chemical Formula 5]

[0038] In equation (2), R 4 Independently, R is a group selected from alkyl groups having 1 to 4 carbon atoms, aryl groups having 6 to 10 carbon atoms, and aralkyl groups having 7 to 10 carbon atoms. 5 Independently, it is an alkyl group having 5 to 16 carbon atoms, R 6 R is independently a group having a cyclic oligosaccharide structure as represented by the following formula (3). 7 Independently selected from R 4 、or R 6 In the group, c is an integer from 100 to 600, d is an integer from 0 to 50, and e is an integer from 1 to 50. Among them, c+d+e satisfy the range of 101 to 700, and the bonding order of the siloxane units enclosed in parentheses by c, d, and e can be arbitrarily chosen as block or random.

[0039] [Chemical Formula 6]

[0040] In formula (3), A' is an alkylene group with 2 to 12 carbon atoms, and R 1 R 2 R 3 a, b, and x are related to R in the above general formula (1). 1 R 2 R 3 a, b, and x are the same. It is a free radical that bonds to the silicon atom of the siloxane unit.

[0041] In equation (2), R 4 The group is independently selected from alkyl groups having 1 to 4 carbon atoms, aryl groups having 6 to 10 carbon atoms, and aralkyl groups having 7 to 10 carbon atoms. From the perspective of compatibility with cyclic oligosaccharides, methyl or ethyl groups are preferred, and methyl groups are more preferred. R 5The alkyl group is independently an alkyl group with 5 to 16 carbon atoms. From the perspective of compatibility with cyclic oligosaccharides, it is preferably an alkyl group with 5 to 8 carbon atoms, and more preferably an octyl group. c is an integer from 100 to 600. From the perspective of coating properties, it is preferably 300 to 600, and more preferably 400 to 500. d is an integer from 0 to 50. From the perspective of coating properties, it is preferably 0 to 20, and more preferably 0 to 10. e is an integer from 1 to 50. From the perspective of coating properties, it is preferably 1 to 20, and more preferably 1 to 10. Furthermore, c+d+e satisfies the range of 101 to 700, and preferably the range of 300 to 600.

[0042] Furthermore, the R 6 Independently, it refers to a group having a cyclic oligosaccharide structure represented by the general formula (3), in which A' is an alkylene group having 2 to 12 carbon atoms, preferably having 2 to 4 carbon atoms, and more preferably a vinyl group having 2 carbon atoms. R 7 Independently selected from R 4 Or R 6 The groups in.

[0043] The glass transition temperature of the cyclic oligosaccharide-modified organopolysiloxane obtained by the above method is preferably 50~100℃, more preferably 60~95℃ from the perspective of the properties of the formed coating, and even more preferably 65~90℃. If it is within the above range, it has sufficient physical properties at room temperature and forms a soft coating.

[0044] Furthermore, the glass transition temperature of the present invention is a value obtained by dynamic viscoelasticity measurement under the conditions shown in the embodiments described later.

[0045] Film-forming agent The cyclic oligosaccharide-modified organopolysiloxane of the present invention forms a highly transparent, soft, non-sticky, and tough coating, and therefore can be used as a film-forming agent.

[0046] Although the above-mentioned cyclic oligosaccharide-modified organopolysiloxanes can be used alone as film-forming agents, from the perspective of film-forming properties or operability, it is preferable to use them after dilution with an organic solvent.

[0047] As an organic solvent, it can be selected from volatile siloxanes, saturated aliphatic hydrocarbons, saturated alicyclic hydrocarbons, aromatic hydrocarbons, chlorinated hydrocarbons, fluorinated hydrocarbons, alcohols, etc. Volatile organosiloxanes and light liquid isoalkanes with boiling points of 100~270℃ at atmospheric pressure (1013hPa) are particularly preferred. Examples of volatile siloxanes include cyclic siloxanes such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecylcyclohexasiloxane, trimethyltriethylcyclotrisiloxane, hexaethyltricyclosiloxane, diethyltetramethylcyclotrisiloxane, dimethyltetraethylcyclotrisiloxane, diethylhexamethylcyclotetrasiloxane, and tetraethyltetramethylcyclotetrasiloxane; linear siloxanes such as hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, dodecylpentasiloxane, hexaethyldisiloxane, and octaethyltrisiloxane; and branched siloxanes such as methyltris(trimethylsiloxane)silane and phenyltris(trimethylsiloxane)silane. Furthermore, examples of light liquid isoalkanes include light liquid isoalkanes whose main component is an isoalkane with 8 to 16 carbon atoms.

[0048] The preferred content of the cyclic oligosaccharide-modified organopolysiloxane when using an organic solvent is 0.1-80%, more preferably 0.5-20%.

[0049] The coating method can employ known methods corresponding to the type of coating substrate.

[0050] Applications of the cyclic oligosaccharide-modified organopolysiloxane film-forming agent of the present invention include damage protectants, hydrophobic agents, and release agents for cosmetics, coatings, paper, plastic sheets, and rubber articles; damage protectants, hydrophobic agents, waterproofing agents, texture modifiers, and fillers for fabrics; and hydrophobic agents, waterproofing agents, and release agents for concrete, mortar, and wood. It can be used to impart properties such as durability, slip resistance, and hydrophobicity to cosmetics.

[0051] Example The following examples illustrate the present invention in detail, but the present invention is not limited to the following examples.

[0052] [Determination Method] Various measurements were performed using the following methods.

[0053] <Glass transition temperature> The glass transition temperature can be obtained as follows: A 0.25 mm thick coating is prepared, and dynamic viscoelastic data measured in the range of 25–120 °C at a heating rate of 5 °C / min under tensile mode and a frequency of 1 Hz are analyzed using a "DMA7100" manufactured by Hitachi High-Tech Science CORPORATION. The temperature at which tanδ (loss tangent), expressed as E'' (loss modulus) / E' (storage modulus), is maximized is determined and taken as the glass transition temperature.

[0054] < 1 H-NMR> The determination was performed using an AVANCE-III 400MHz microscope (manufactured by Bruker Corporation) with deuterated chloroform as the determination solvent.

[0055] [Synthetic Example 1: Synthesis of Cyclic Oligosaccharide Derivatives with Unsaturated Bonds] In a four-necked flask equipped with a stirrer, thermometer, reflux cooler, and dropping funnel, 50.0 g of mono-6-O-(p-toluenesulfonyl)-β-cyclodextrin (C6-Ts-β-CD) and 500.0 g of allylamine were added. After purging the flask with nitrogen, the mixture was stirred at 53°C for 7 hours, cooled to room temperature, and stirred overnight. The mixture was concentrated using an evaporator, and 1,000 mL of acetonitrile was added to the resulting solid. The precipitate was recovered by filtration. The precipitate was dissolved in 1,000 mL of distilled water, and the solution was added dropwise to 1,000 mL of acetonitrile. The precipitate was recovered by filtration. After washing the precipitate with acetone, it was dried in a vacuum dryer at 40°C to obtain vinyl-modified compound A (white solid, 42.7 g).

[0056] [Chemical Formula 7]

[0057] [Synthetic Example 2: Synthesis of Cyclic Oligosaccharide Derivatives with Unsaturated Bonds] In a four-necked flask equipped with a stirrer, thermometer, reflux cooler, and dropping funnel, 30.0 g of the vinyl-modified compound A, 110.0 g of acetic anhydride, and 170.0 g of pyridine were added. After purging the flask with nitrogen, the mixture was stirred at 60°C for 7 hours, cooled to room temperature, and stirred overnight. 170 mL of toluene was added to the solution in the flask, and the mixture was washed twice with 170 mL of 1 mM hydrochloric acid and once with 170 mL of saturated saline solution. The solution obtained by separation was concentrated using an evaporator. The recovered solid was then dissolved in 50 mL of acetone, and the solution was added dropwise to 500 mL of distilled water. The precipitate was recovered by filtration. The precipitate was dried in a vacuum dryer at 40°C to obtain vinyl-modified compound B (white solid, 31.8 g).

[0058] [Chemical Formula 8]

[0059] [Synthetic Example 3: Synthesis of Cyclic Oligosaccharide Derivatives with Unsaturated Bonds] In a four-necked flask equipped with a stirrer, thermometer, reflux cooler, and dropping funnel, 48.0 g of mono-6-O-(p-toluenesulfonyl)-β-cyclodextrin (C6-Ts-β-CD), 300.0 g of 1-vinyl,3-(3-aminopropyl)tetramethyldisiloxane, and 60.0 g of N,N-dimethylformamide were added. After purging the flask with nitrogen, the mixture was stirred at 75°C for 7 hours, cooled to room temperature, and stirred overnight. The solution in the flask was added dropwise to 1,200 mL of acetonitrile, and the precipitate was recovered by filtration. 60.0 g of N,N-dimethylformamide was added to the resulting precipitate to dissolve it, and the solution was added dropwise to 1,200 mL of toluene, and the precipitate was recovered by filtration. After washing the precipitate with acetone, it was dried using a vacuum dryer at 40°C to obtain vinyl-modified compound C (white solid, 42.5 g).

[0060] [Chemical Formula 9]

[0061] [Synthetic Example 4: Synthesis of Cyclic Oligosaccharide Derivatives with Unsaturated Bonds] In a four-necked flask equipped with a stirrer, thermometer, reflux cooler, and dropping funnel, 42.0 g of the vinyl-modified compound C, 134.4 g of acetic anhydride, and 210.0 g of pyridine were added. After purging the flask with nitrogen, the mixture was stirred at 60°C for 7 hours, cooled to room temperature, and stirred overnight. 210 mL of toluene was added to the solution in the flask, and the mixture was washed twice with 210 mL of 1 mM hydrochloric acid and once with 210 mL of saturated saline solution. The solution obtained by separation was concentrated using an evaporator. The recovered solid was then dissolved in 150 mL of toluene, and the solution was added dropwise to 300 mL of hexane. The precipitate was recovered by filtration. The precipitate was dried using a vacuum dryer at 40°C to obtain vinyl-modified compound D (white solid, 50.1 g).

[0062] [Chemical Formula 10]

[0063] [Example 1] In a four-necked flask equipped with a stirrer, thermometer, reflux cooler, and dropping funnel, add 100.0 g of the polyorganohydrosiloxane (hydrosilane content: 0.040 mol, kinematic viscosity at 25°C: 3,340 mmHg) represented by the following formula (4). 2 / s, number average molecular weight: 31,100), 24.9 g of the vinyl-modified compound B (vinyl content: 0.012 mol), and 200.0 g of toluene. After purging the flask with nitrogen, the temperature was raised to 90°C, and 1.3 g of a toluene solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum concentration: 0.5 wt%) was added to the flask, and the mixture was stirred at 90°C for 4 hours. Here, by 1 The reaction was confirmed by the disappearance of the vinyl peak (5.6–6.1 ppm) using ¹H NMR. Then, 6.4 g of 1-octene (0.057 mol) and 0.7 g of a toluene solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum concentration 0.5 wt%) were added to the flask, and the mixture was stirred at 90 °C for 4 hours. The reaction solution was then cooled to room temperature, and the toluene was removed by vacuum distillation using an evaporator. The process of adding 250 g of methanol to the resulting solid and washing it at 50 °C was repeated three times. Finally, the solid was dried using a vacuum dryer at 40 °C to obtain cyclic oligosaccharide-modified organopolysiloxane E (light brown solid, 119.7 g).

[0064] [Chemical Formula 11]

[0065] [Example 2] In a four-necked flask equipped with a stirrer, thermometer, reflux cooler, and dropping funnel, 128.3 g of the polyorganohydrosiloxane (hydrosilane content: 0.052 mol, kinematic viscosity at 25°C: 3,340 mmHg) represented by the following formula (4) was added. 2 / s, number average molecular weight: 31,100), 45.0 g of the vinyl-modified compound D (vinyl content: 0.016 mol), and 256.0 g of toluene. After purging the flask with nitrogen, the temperature was raised to 90°C, and 1.7 g of a toluene solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum concentration: 0.5 wt%) was added to the flask, and the mixture was stirred at 90°C for 2 hours. Here, by 1 The reaction was confirmed by the disappearance of the vinyl peak (5.6–6.1 ppm) using ¹H NMR. Then, 8.2 g of 1-octene (0.073 mol) and 0.9 g of a toluene solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum concentration 0.5 wt%) were added to the flask, and the mixture was stirred at 90 °C for 4 hours. The reaction solution was then cooled to room temperature, and the toluene was removed by vacuum distillation using an evaporator. The process of adding 300 g of methanol to the resulting solid and washing it at 50 °C was repeated three times. Finally, the solid was dried using a vacuum dryer at 40 °C to obtain cyclic oligosaccharide-modified organopolysiloxane F (light brown solid, 148.3 g).

[0066] [Chemical Formula 12]

[0067] [Example 3] In a four-necked flask equipped with a stirrer, thermometer, reflux cooler, and dropping funnel, 77.0 g of the polyorganohydrosiloxane (hydrosilane content: 0.031 mol, kinematic viscosity at 25°C: 3,340 mmHg) represented by the following formula (4) was added. 2 / s, number average molecular weight: 31,100), 45.0 g of the vinyl-modified compound D (vinyl content: 0.016 mol), and 154.0 g of toluene. After purging the flask with nitrogen, the temperature was raised to 90°C, and 1.1 g of a toluene solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum concentration: 0.5 wt%) was added to the flask, and the mixture was stirred at 90°C for 2 hours. Here, by 1The reaction was confirmed by the disappearance of the vinyl peak (5.6–6.1 ppm) using ¹H NMR. Then, 3.5 g of 1-octene (0.031 mol) and 0.6 g of a toluene solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum concentration 0.5 wt%) were added to the flask, and the mixture was stirred at 90 °C for 4 hours. The reaction solution was then cooled to room temperature, and the toluene was removed by vacuum distillation using an evaporator. The process of adding 240 g of methanol to the resulting solid and washing it at 50 °C was repeated three times. Finally, the solid was dried using a vacuum dryer at 40 °C to obtain cyclic oligosaccharide-modified organopolysiloxane G (light brown solid, 113.3 g).

[0068] [Chemical Formula 13]

[0069] [Example 4] In a four-necked flask equipped with a stirrer, thermometer, reflux cooler, and dropping funnel, 35.0 g of the polyorganohydrosiloxane (hydrosilane content: 0.014 mol, kinematic viscosity at 25°C: 3,340 mm) represented by the following formula (4) was added. 2 / s, number average molecular weight: 31,100), 45.0 g of the vinyl-modified compound D (vinyl content: 0.016 mol), and 70.0 g of toluene. After purging the flask with nitrogen, the temperature was raised to 90°C, and 0.6 g of a toluene solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum concentration: 0.5 wt%) was added to the flask, and the mixture was stirred at 90°C for 2 hours. Here, by 1 The reaction was confirmed by the disappearance of the vinyl peak (5.6–6.1 ppm) using ¹H NMR. The reaction mixture was then cooled to room temperature, and toluene was removed by vacuum distillation using an evaporator. The process of adding 140 g of methanol to the resulting solid and washing it at 50 °C was repeated three times. Finally, the solid was dried using a vacuum dryer at 40 °C to obtain cyclic oligosaccharide-modified organopolysiloxane H (light brown solid, 64.3 g).

[0070] [Chemical Formula 14]

[0071] [Comparative Example 1] In a four-necked flask equipped with a stirrer, thermometer, reflux cooler, and dropping funnel, add 6.9 g of the polyorganohydrosiloxane (hydrosilane content: 0.052 mol, kinematic viscosity at 25°C: 17 mm) represented by the following formula (5). 2 / s, number average molecular weight: 3,000), 45.0 g of the vinyl-modified compound D (vinyl content: 0.016 mol), and 100.0 g of toluene. After purging the flask with nitrogen, the temperature was raised to 90°C, and 0.6 g of a toluene solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum concentration: 0.5 wt%) was added to the flask, and the mixture was stirred at 90°C for 2 hours. Here, by 1 The reaction was confirmed by the disappearance of the vinyl peak (5.6–6.1 ppm) using ¹H NMR. Then, 8.2 g of 1-octene (0.073 mol) and 0.3 g of a toluene solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum concentration 0.5 wt%) were added to the flask, and the mixture was stirred at 90 °C for 4 hours. The reaction mixture was then cooled to room temperature, and the toluene was removed by vacuum distillation using an evaporator. The process of adding 100 g of methanol to the resulting solid and washing it at 50 °C was repeated three times. Finally, the solid was dried using a vacuum dryer at 40 °C to obtain cyclic oligosaccharide-modified organopolysiloxane I (light brown solid, 44.6 g).

[0072] [Chemical Formula 15]

[0073] The compounds obtained in the above examples and comparative examples were coated using the following methods and subjected to various evaluations.

[0074] [Lamination process] Various cyclic oligosaccharide-modified organopolysiloxanes obtained in the above synthetic examples, embodiments, and comparative examples were dissolved in toluene to prepare a 30% solution. The solution was poured onto a Teflon (registered trademark) coating plate with a mold having a length of 5 cm, a width of 5 cm, and a thickness of 0.25 mm. After being left at 25°C overnight, the plate was dried in a dryer at 80°C for 1 hour to produce a coating. The appearance of the resulting coating was observed visually, and it was checked by touch for any stickiness. Furthermore, dynamic viscoelasticity was measured to determine the glass transition temperature.

[0075] [Table 1]

[0076] As shown in Table 1, the cyclic oligosaccharide-modified organopolysiloxane of the present invention has a high molecular weight and is solvent-soluble, enabling the formation of a transparent, non-sticky, soft, and tough coating. On the other hand, the comparative example has a low molecular weight and lacks softness and toughness.

[0077] This manual contains the following solutions.

[0078] [1]: A cyclic oligosaccharide-modified organopolysiloxane, characterized in that it is an addition reactant of at least the following (A) and (B), (A) is an organohydrosiloxane having one or more hydrosilane groups in one molecule, and its kinematic viscosity at 25°C is 50 mm. 2 With a value of ≥ / s and a number-average molecular weight of ≥ 8,000, (B) is a cyclic oligosaccharide derivative with unsaturated groups represented by the following general formula (1). [Chemical Formula 16]

[0079] In general formula (1), A is an alkenyl group with 2 to 12 carbon atoms, and R 1 Independently, R is a group selected from alkyl groups having 1 to 4 carbon atoms, aryl groups having 6 to 10 carbon atoms, and aralkyl groups having 7 to 10 carbon atoms. 2 R is an alkylene group having 1 to 4 carbon atoms. 3 Independently, it is a group selected from alkyl groups having 1 to 4 carbon atoms or acyl groups having 1 to 4 carbon atoms, where a is an integer from 0 to 8, b is an integer from 5 to 7, and x is 0 or 1.

[0080] [2]: The cyclic oligosaccharide-modified organopolysiloxane according to [1] is characterized in that it is an addition reactant containing, in addition to (A) and (B), (C) below. (C) is an α-olefin with 2 to 16 carbon atoms.

[0081] [3]: The cyclic oligosaccharide-modified organopolysiloxane according to [2] is characterized in that the cyclic oligosaccharide-modified organopolysiloxane is a substance represented by the following general formula (2). [Chemical Formula 17]

[0082] In general formula (2), R 4 Independently, R is a group selected from alkyl groups having 1 to 4 carbon atoms, aryl groups having 6 to 10 carbon atoms, and aralkyl groups having 7 to 10 carbon atoms. 5 Independently, it is an alkyl group having 5 to 16 carbon atoms, R 6 R is independently a group having a cyclic oligosaccharide structure as represented by the following general formula (3). 7 Independently selected from R 4 Or R 6 In the given group, c is an integer from 100 to 600, d is an integer from 0 to 50, and e is an integer from 1 to 50, where c+d+e satisfies the range of 101 to 700. The bonding order of the siloxane units enclosed in parentheses for c, d, and e can be arbitrarily chosen as block or random. [Chemical Formula 18]

[0083] In general formula (3), A' is an alkylene group with 2 to 12 carbon atoms, and R 1 R 2 R 3 a, b and x are the same as R in the general formula (1) mentioned above [1]. 1 R 2 R 3 a, b, and x are the same. It is a free radical that bonds to the silicon atom of the siloxane unit.

[0084] [4]: The cyclic oligosaccharide-modified organopolysiloxane according to [3] is characterized in that, in the general formula (2), R 1 For methyl, R 3 For acetyl, R 4 It is a methyl group.

[0085] [5]: The cyclic oligosaccharide-modified organopolysiloxane according to [3] or [4] is characterized in that x is 1 in the general formula (2).

[0086] [6]: The cyclic oligosaccharide-modified organopolysiloxane according to any one of [1] to [5] is characterized in that the glass transition temperature measured by dynamic viscoelasticity determination is 50 to 100 °C.

[0087] [7]: A film-forming agent comprising any one of the cyclic oligosaccharide-modified organopolysiloxanes described in any one of [1] to [6].

[0088] Furthermore, this invention is not limited to the above-described embodiments. The above embodiments are illustrative examples, and any technical solution having a substantially identical structure and achieving the same effect as the technical concept described in the claims of this invention is included within the technical scope of this invention.

Claims

1. A cyclic oligosaccharide-modified organopolysiloxane, characterized in that, It is an addition reactant of at least (A) and (B) below. (A) is an organohydrosiloxane having one or more hydrosilane groups in one molecule, and its kinematic viscosity at 25°C is 50 mm. 2 With a value of ≥ / s and a number-average molecular weight of ≥ 8,000, (B) is a cyclic oligosaccharide derivative with unsaturated groups represented by the following general formula (1). [Chemical Formula 1] ， In general formula (1), A is an alkenyl group with 2 to 12 carbon atoms, and R 1 Independently, R is a group selected from alkyl groups having 1 to 4 carbon atoms, aryl groups having 6 to 10 carbon atoms, and aralkyl groups having 7 to 10 carbon atoms. 2 R is an alkylene group having 1 to 4 carbon atoms. 3 Independently, it is a group selected from alkyl groups having 1 to 4 carbon atoms or acyl groups having 1 to 4 carbon atoms, where a is an integer from 0 to 8, b is an integer from 5 to 7, and x is 0 or 1.

2. The cyclic oligosaccharide-modified organopolysiloxane according to claim 1, characterized in that, It is an addition reactant that, in addition to (A) and (B) described above, also includes (C) below. (C) is an α-olefin with 2 to 16 carbon atoms.

3. The cyclic oligosaccharide-modified organopolysiloxane according to claim 2, characterized in that, The cyclic oligosaccharide-modified organopolysiloxane is a substance represented by the following general formula (2). [Chemical Formula 2] ， In general formula (2), R 4 Independently, R is a group selected from alkyl groups having 1 to 4 carbon atoms, aryl groups having 6 to 10 carbon atoms, and aralkyl groups having 7 to 10 carbon atoms. 5 Independently, it is an alkyl group having 5 to 16 carbon atoms, R 6 R is independently a group having a cyclic oligosaccharide structure as represented by the following general formula (3). 7 Independently selected from R 4 Or R 6 In the given group, c is an integer from 100 to 600, d is an integer from 0 to 50, and e is an integer from 1 to 50, where c+d+e satisfies the range of 101 to 700. The bonding order of the siloxane units enclosed in parentheses for c, d, and e can be arbitrarily chosen as block or random. [Chemical Formula 3] ， In general formula (3), A' is an alkylene group with 2 to 12 carbon atoms, and R 1 R 2 R 3 a, b, and x are the same as R in the general formula (1) of claim 1. 1 R 2 R 3 a, b, and x are the same. It is a free radical that bonds to the silicon atom of the siloxane unit.

4. The cyclic oligosaccharide-modified organopolysiloxane according to claim 3, characterized in that, In the general formula (2), R 1 For methyl, R 3 For acetyl, R 4 It is a methyl group.

5. The cyclic oligosaccharide-modified organopolysiloxane according to claim 4, characterized in that, In the general formula (2), x is 1.

6. The cyclic oligosaccharide-modified organopolysiloxane according to claim 1, characterized in that, The glass transition temperature, as measured by dynamic viscoelasticity determination, is 50–100 °C.

7. A film-forming agent comprising the cyclic oligosaccharide-modified organopolysiloxane of claim 6.

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