Resin-linear structure-containing organopolysiloxane, composition containing the same, and method for producing the same

Abstract

To provide a resin-linear structure-containing organopolysiloxane that exhibits excellent film-forming properties and non-stickiness at room temperature, and provides a cured film that balances hardness and flexibility. [Solution] A resin-linear structure-containing organopolysiloxane having a constituent unit ratio represented by the following formula (1) and a weight-average molecular weight of 1,000,000 to 20,000,000. TIFF2026085882000010.tif19169 (in the formula, R 1 , R 2 , R 3 , R 4 and R 5 Each of the following is independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, m is an integer from 0 to 50, a, b, c, d, and e are numbers satisfying 0 ≤ a ≤ 0.25, 0.05 ≤ b × (m + 2) ≤ 0.3, 0 ≤ c ≤ 0.25, 0.7 ≤ d ≤ 0.95, 0 ≤ e ≤ 0.25, and a + b × (m + 2) + c + d + e = 1, and x is 0

Description

[Technical Field]

[0001] The present invention relates to a resin-linear structure-containing organopolysiloxane, a composition containing the same, and a method for producing the same. [Background technology]

[0002] Silicone resins containing silanol groups in their polymer structure have traditionally been used as heat-resistant and weather-resistant coatings, taking advantage of their excellent heat resistance, weather resistance, and rigidity. Furthermore, these silicone resins are also useful as modification raw materials for producing hybrid resins by reacting them with various organic resins, and have been used in a wide range of fields.

[0003] Especially SiO 4 / 2 Units (Q units) and RSiO 3 / 2 Organopolysiloxanes, which have a three-dimensional crosslinked structure and are mainly composed of units (T units) (where R is an organic group such as an alkyl group or aryl group), are called silicone resins and are widely used in paints, coatings, and binders, etc., by utilizing the formation of siloxane bonds through the dehydration condensation reaction of silanol groups and their crosslinking curability.

[0004] However, while such silicone resins have the advantage of good curability and high surface hardness due to their three-dimensional crosslinking structure, they also have the problem of insufficient flexibility and bending resistance due to their high crosslinking density, which can lead to cracks forming in the cured product over time after film formation or when external stress is applied.

[0005] To improve this flexibility and bending resistance, diorganosiloxane (R2SiO2) is added to the polymer structure of the silicone resin. 2 / 2 A commonly known method involves incorporating units (D units). However, in this case, since D units are randomly incorporated into the structure, a large number of D units must be added to impart flexibility, which leads to a decrease in the excellent curability and surface hardness that are advantages of silicone resin.

[0006] Furthermore, as a method for introducing D units, a method has been proposed in which silicone oil, whose molecular ends are sealed with tetraethoxysilane which has reactivity with silanol groups, is added to silicone resin (Non-Patent Literature 1). However, silicone oil has low compatibility with silicone resin, which has caused clouding and repelling of the coating film.

[0007] To solve these problems, a technique has been proposed to chemically bond a silicone resin structure and a linear silicone structure to form an organopolysiloxane. For example, Patent Document 1 proposes a resin-linear structure-containing organopolysiloxane obtained by hydrosilylation reaction between a linear polysiloxane having a hydrosilyl group at its terminus and a silicone resin having an olefin group and an alkoxysilyl group. Furthermore, Patent Document 2 proposes a resin-linear structure-containing organopolysiloxane obtained by hydrolyzing and condensing a polydimethylsiloxane having silanol groups at both ends with a highly reactive 3-4 functional hydrolyzable silane monomer.

[0008] However, the organopolysiloxane described in Patent Document 1 has a relatively long-chain, high-molecular-weight linear structure. While it is effective when added as a crack-resistant agent, its hardness is insufficient when cured on its own, making it difficult to use alone for coating applications. Furthermore, while Patent Document 2 introduces a linear structure with the aim of reducing stickiness derived from the resin component, it does not take into account factors such as crack prevention through improved flexibility and improved curability, leaving room for improvement in those properties.

[0009] As methods for producing silanol-containing silicone resins with ensured reactivity, continuous and batch hydrolysis condensation methods (sol-gel methods) are widely known. For example, Patent Documents 3 and 4 disclose a continuous hydrolysis process, while Patent Document 5 discloses a batch hydrolysis process.

[0010] Generally, in these patent documents, chlorosilane or alkoxysilane is used as the reactive silane monomer. Especially in a system with a high resin component ratio that provides three-dimensional crosslinking such as Q units or T units, it is difficult to control the reaction during hydrolysis. In the patent documents related to the aforementioned manufacturing method, efforts are made to suppress the generation of gel components insoluble in the solvent by means such as setting the reaction temperature, using alcohol in combination, and setting the target molecular weight of the resin structure to a lower value. However, when trying to increase the resin component ratio and make the target molecular weight higher, further improvement of manufacturing conditions is required to suppress gelation and improve the stability of the generated resin.

Prior Art Documents

Patent Documents

[0011]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

Non-Patent Documents

[0012]

Non-Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0013] The present invention has been made in view of the above circumstances, and provides a resin-linear structure-containing organopolysiloxane that exhibits excellent film-forming properties and no stickiness at room temperature, and gives a cured film capable of achieving both hardness and flexibility, a composition containing the same, and a method for producing the same.

Means for Solving the Problems

[0014] As a result of intensive studies to solve the above problems, the present inventors have found that a predetermined resin-linear structure-containing organopolysiloxane gives the target film properties, and have also found that this resin-linear structure-containing organopolysiloxane can be stably obtained by hydrolytic condensation of an organopolysiloxane having chlorosilane and chlorosilyl groups in a predetermined reaction solvent composition, thereby completing the present invention.

[0015] That is, the present invention provides: 1. A resin-linear structure-containing organopolysiloxane having a structural unit ratio represented by the following formula (1) and a weight average molecular weight of 1,000,000 to 20,000,000,

Chemical Formula

[0016] The resin-linear structure-containing organopolysiloxane of the present invention exhibits excellent film-forming properties, efficiently demonstrating flexibility through the introduction of a linear structure despite having a high T-unit ratio. Furthermore, the film obtained from a composition containing the resin-linear structure-containing organopolysiloxane of the present invention is suitable as a coating agent because it can achieve both hardness and flexibility (crack resistance). [Modes for carrying out the invention]

[0017] The present invention will be described in detail below. [Resin-Linear Structure-Containing Organopolysiloxane] The resin-linear structure-containing organopolysiloxane according to the present invention has a constituent unit ratio represented by the following general formula (1).

[0018] [ka]

[0019] In equation (1), R 1 , R 2 , R 3 , R 4 and R 5 Each of these is independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms. R 1 , R 2 , R 3 and R 4Specific examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms in [reference] include alkyl groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, and n-decyl groups; cycloalkyl groups such as cyclopentyl and cyclohexyl groups; alkenyl groups such as vinyl, allyl, butenyl, hexenyl, and octenyl groups; and aryl groups such as phenyl and naphthyl groups. Among these, methyl, ethyl, n-propyl, and phenyl groups are preferred, methyl and ethyl groups are more preferred, and the methyl group is even more preferred. R 5 Specific examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms in [reference] are the same as those described above. Among them, alkyl groups having 1 to 4 carbon atoms such as methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, i-butyl, and t-butyl groups are preferred, and n-butyl, s-butyl, i-butyl, and t-butyl groups are more preferred.

[0020] In formula (1), m is an integer from 0 to 50, and an integer from 10 to 40 is preferred from the viewpoint of achieving the desired flexibility. a, b, c, d, and e represent the molar ratios of the respective structural units, and are numbers that satisfy 0 ≤ a ≤ 0.25, 0.05 ≤ b×(m + 2) ≤ 0.3, 0 ≤ c ≤ 0.25, 0.7 ≤ d ≤ 0.95, 0 ≤ e ≤ 0.25, and a + b×(m + 2) + c + d + e = 1. From the viewpoint of achieving both hardness and flexibility, it is preferable that c and e are 0, and it is more preferable that a, c, and e are 0.

[0021] In formula (1), x is the number of moles of a hydroxy group or an organoxy group bonded to 1 mole of Si atoms, and is a number that satisfies 0 < x ≤ 0.1. When x is 0, it does not contain a structural group that undergoes dehydration or dealcoholization condensation crosslinking. Although it is excellent in terms of the stability of the polymer, it does not have curability, so it is not preferable because it reduces the durability of the cured film formed. On the other hand, when x is greater than 0.1, the curability is excellent, but there is a risk that the stability of the polymer will decrease.

[0022] The weight-average molecular weight of the resin-linear structure-containing organopolysiloxane of the present invention is 1,000,000 to 20,000,000, from the viewpoint of film-forming properties and non-stickiness of the cured film obtained. More preferably, it is 1,500,000 to 10,000,000, and even more preferably 2,000,000 to 8,000,000. The weight-average molecular weight in this invention is the standard polystyrene equivalent value obtained by gel permeation chromatography (GPC) under the conditions shown below. [Measurement conditions] Developing solvent: Tetrahydrofuran (THF) Flow rate: 0.5mL / min Detector: Differential refractive index detector (RI) Columns: Use two of the following columns directly connected together. TSKgel GMH HR -H(30)(7.8mmI.D.×30cm×1) (Manufactured by Tosoh Corporation) Column temperature: 40℃ Sample injection volume: 200 μL (THF solution with a concentration of 20 g / L)

[0023] The resin-linear structure-containing organopolysiloxane of the present invention has a linear organopolysiloxane structure, and as an indicator thereof 29 This can be determined by detecting signals in the Si-NMR spectrum that belong to structures within a predetermined range of chemical shifts. in general 29 In Si-NMR spectra, signals originating from D units are detected in the range of -10 to -50 ppm. However, in the resin-linear structure-containing organopolysiloxane of the present invention, the chemical shift of the signal attributed to D units originating from the linear organopolysiloxane structure is detected in the range of -15 to -25 ppm. Furthermore, the detection width of the signal peak (the difference between the chemical shift at the detection start point and the chemical shift at the detection end point) is in the range of 3 to 8 ppm. A narrower detection width of the signal peak indicates that the linear siloxane structure is maintained while being introduced into the polymer, while a larger detection width means that the proportion of continuous D units in the polymer is small. Furthermore, in the present invention 29 The Si-NMR spectra were obtained by measuring a solution sample with a sample concentration of 20% by mass using a 300MHz-NMR spectrometer manufactured by JEOL Ltd., under conditions of 25°C.

[0024] [Composition containing resin-linear structure-containing organopolysiloxane] The resin-linear structure-containing organopolysiloxane of the present invention can be prepared as a composition dissolved in an organic solvent, but the pH of the extracted water must be in the acidic range of 3.5 to 6. By adjusting the pH of the extracted water to this range, it is possible to obtain a stable composition that does not cause gelation or other problems over a long period of time.

[0025] To adjust the pH of the extracted water, for example, an acid can be used. Examples of acids include inorganic acids such as hydrochloric acid, nitric acid, and sulfuric acid; carboxylic acids such as formic acid, acetic acid, propionic acid, citric acid, succinic acid, and maleic acid; and sulfonic acids such as methanesulfonic acid and trifluoromethanesulfonic acid. Among these, carboxylic acids are preferred.

[0026] The organic solvent in the composition of the present invention is not particularly limited, but examples include aliphatic hydrocarbons such as hexane, heptane, octane, cyclohexane, methylcyclohexane, ethylcyclohexane, decane, isododecane, and isoparaffin compounds, and aromatic hydrocarbons such as toluene and xylene. From the viewpoint of environmental impact, aliphatic hydrocarbons are preferred, hexane, heptane, octane, cyclohexane, methylcyclohexane, and ethylcyclohexane are more preferred, and hexane, heptane, and ethylcyclohexane are even more preferred.

[0027] [Method for producing a composition containing a resin-linear structure-containing organopolysiloxane] The present invention's composition containing a resin-linear structure-containing organopolysiloxane can be produced, for example, by a manufacturing method comprising the steps of hydrolyzing and condensing a silane compound having a chlorine atom bonded to a silicon atom and a linear organopolysiloxane having chlorine atoms bonded to silicon atoms at both ends of its molecular chain in a mixed medium layer consisting of water, a hydrophilic organic solvent with a water solubility of 50 to 1000 g / L at 25°C, and a hydrophobic organic solvent with a water solubility of 1 g / L or less at 25°C, and adjusting the pH of the extracted water to 3.5 to 6.0.

[0028] Specific examples of the hydrophilic organic solvents mentioned above include alcohols, ketones, esters, and ether compounds. Specifically, these include 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol (isobutanol), 2-methyl-2-propanol (t-butanol), propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl acetate, butyl acetate, methyl ethyl ketone, and cyclohexanone. Among these, 1-propanol, 2-propanol, 1-butanol, and isobutanol are preferred from the viewpoint of controlling the reaction during hydrolysis condensation and suppressing the formation of insoluble substances.

[0029] Specific examples of the hydrophobic organic solvents mentioned above include aliphatic hydrocarbons such as hexane, heptane, octane, cyclohexane, methylcyclohexane, ethylcyclohexane, decane, isododecane, and isoparaffin compounds; and aromatic hydrocarbons such as toluene and xylene. Among these, hexane, heptane, octane, cyclohexane, methylcyclohexane, and ethylcyclohexane are preferred from the viewpoint of reaction control during hydrolysis condensation, maintenance of block structure, and solubility of the resulting resin, with hexane, heptane, and ethylcyclohexane being more preferred.

[0030] The composition ratio of the above mixed media layer is preferably 10 to 30 parts by mass of hydrophilic organic solvent and preferably 10 to 30 parts by mass of hydrophobic organic solvent per 100 parts by mass of water. Within this range, insoluble matter in the solvent is suppressed and productivity is excellent.

[0031] Specific examples of silane compounds having a chlorine atom bonded to the silicon atom mentioned above include chlorosilane compounds such as tetrachlorosilane, methyltrichlorosilane, phenyltrichlorosilane, dimethyldichlorosilane, diphenyltrichlorosilane, methylphenyldichlorosilane, trimericylchlorosilane, and triphenylchlorosilane. In addition to these chlorosilane compounds, alkoxysilane compounds that can constitute each siloxane unit in formula (1), such as methyltrimethoxysilane, may also be used in combination and co-hydrolyzed and condensed.

[0032] The linear organopolysiloxane having chlorine atoms bonded to the silicon atom at both ends of the molecular chain can be any one that gives the constituent unit "b" in formula (1) above, and in particular, the linear organopolysiloxane represented by the following formula (2) is preferred.

[0033] [ka] (In the formula, m has the same meaning as above.)

[0034] The total concentration of the silane compound having a chlorine atom bonded to a silicon atom and the linear organopolysiloxane having chlorine atoms bonded to silicon atoms at both ends of the molecular chain during the hydrolysis condensation reaction is preferably 10 to 30% by mass relative to the entire reaction system. Within this range, unwanted substances in the solvent are suppressed, and productivity is excellent.

[0035] Furthermore, from the viewpoint of reaction control and productivity, the temperature during the hydrolysis condensation reaction is preferably in the range of 10 to 80°C, and the pH is preferably in the range of 1 to 3.

[0036] In the manufacturing method of the present invention, it is preferable to perform a step of allowing the reaction solution to stand to separate it into an organic phase and an aqueous phase, and then removing the aqueous phase, before the step of adjusting the pH of the extracted water to 3.5 to 6.0. This process efficiently adjusts the pH by removing hydrogen chloride and hydrochloric acid generated by the hydrolysis of silane compounds having chlorine atoms bonded to silicon atoms, and linear organopolysiloxanes having chlorine atoms bonded to silicon atoms at both ends of the molecular chain. Furthermore, it is preferable to repeatedly wash the aqueous phase with water until it becomes neutral in order to remove any remaining hydrogen chloride and hydrochloric acid in the organic phase.

[0037] To adjust the pH of the extracted water, for example, an acid can be used. Examples of acids include inorganic acids such as hydrochloric acid, nitric acid, and sulfuric acid; carboxylic acids such as formic acid, acetic acid, propionic acid, citric acid, succinic acid, and maleic acid; and sulfonic acids such as methanesulfonic acid and trifluoromethanesulfonic acid. Among these, carboxylic acids are preferred. The pH of the extracted water is in the acidic range of 3.5 to 6. By adjusting it to this range, a stable composition can be obtained without causing gelation or other problems over a long period of time.

[0038] [Coating agents and articles having a cured coating film of the coating agent] The present invention provides a composition containing a resin-linear structure-containing organopolysiloxane, which can be used as a coating agent. By applying it to the surface of a solid substrate and curing it, a coating layer can be formed to obtain an article having a cured film.

[0039] The application method is not particularly limited, and can be appropriately selected from known methods such as spray coating, spin coating, dip coating, roller coating, brush coating, bar coating, and flow coating.

[0040] The material and shape of the solid substrate are not particularly limited, and specific examples include epoxy resins, phenolic resins, polycarbonates and polycarbonate blends, acrylic resins such as poly(methyl methacrylate), polyester resins such as poly(ethylene terephthalate), poly(butylene terephthalate), and unsaturated polyester resins, organic polymer substrates such as polyamide resins, polyimide resins, acrylonitrile-styrene copolymers, styrene-acrylonitrile-butadiene copolymers, polyvinyl chloride resins, polystyrene resins, blends of polystyrene and polyphenylene ether, cellulose acetate butyrate, and polyethylene resins, metal substrates such as steel plates, painted surfaces, glass, ceramics, concrete, slate boards, textiles, wood, stone, roof tiles, inorganic fillers such as (hollow) silica, titania, zirconia, and alumina, and glass fiber products such as glass cloth, glass tape, glass mat, and glass paper.

[0041] The resin-linear structure-containing organopolysiloxane of the present invention has a linear siloxane structure and a high molecular weight. Therefore, a cured film made from a composition containing this has good strength and flexibility, and can be suitably used for coating, sealing, and other applications. [Examples]

[0042] The present invention will be specifically described below using examples and comparative examples, but the present invention is not limited to these. In the following examples, "parts" and "%" mean "parts by mass" and "% by mass," respectively.

[0043] [1] Synthesis of resin-linear structure-containing organopolysiloxanes [Example 1] (1) Process 1 In a 5L three-necked flask equipped with a stirrer, condenser, dropping funnel, and thermometer, 2700g of deionized water, 400g of isobutanol (solubility in water at 25°C: 87g / L), and 300g of heptane (solubility in water at 25°C: 0.05g / L) were added. While stirring at 25°C, a mixture of 650g (4.3 mol) of methyltrichlorosilane, 70g (0.9 mol equivalent of Si) of a linear organopolysiloxane represented by formula (3) below, and 300g of heptane was added dropwise over 2 hours, while controlling the temperature so that the internal temperature did not exceed 40°C.

[0044] [ka]

[0045] (2) Process 2 After step 1 was completed, the mixture was allowed to stand to separate into an organic phase and an aqueous phase, and the aqueous phase was removed. (3) Process 3 After step 2 was completed, 20 g of 36% hydrochloric acid was added to the organic phase, and the mixture was heated at 60°C for 3 hours to carry out a condensation polymerization reaction. After cooling to 25°C, heptane was added to the organic phase to adjust the concentration. (4) Process 4 After the completion of step 3, the aqueous phase was repeatedly washed with saline solution until it became neutral, and then 0.03% citric acid was added to the solution to obtain a solution of organopolysiloxane containing a resin-linear structure.

[0046] [Example 2] A solution of the resin-linear structure-containing organopolysiloxane was obtained by performing the same procedure as in Example 1, except that the condensation polymerization reaction conditions in Step 3 of Example 1 were set to 60°C for 5 hours.

[0047] [Example 3] A solution of the resin-linear structure-containing organopolysiloxane was obtained by performing the same steps as in Example 1, except that heptane was replaced with isododecane (water solubility at 25°C: 0.001 g / L or less) in steps 1 and 3 of Example 1.

[0048] [Example 4] In step 1 of Example 1, the amount of linear organopolysiloxane represented by formula (3) was changed to 35 g (0.45 moles in terms of Si), but otherwise the same procedure as in Example 1 was performed to obtain a resin-linear structure-containing organopolysiloxane solution.

[0049] [Example 5] In step 1 of Example 1, the amount of linear organopolysiloxane represented by formula (3) was changed to 123 g (1.6 moles in terms of Si), but otherwise the same procedure as in Example 1 was performed to obtain a resin-linear structure-containing organopolysiloxane solution.

[0050] [Example 6] In Example 1, the same procedure was followed as in Example 1, except that heptane was replaced with isododecane (water solubility at 25°C: 0.001 g / L or less) in steps 1 and 3, and the condensation polymerization reaction conditions were set to 60°C for 5 hours, in order to obtain a solution of organopolysiloxane containing a resin-linear structure.

[0051] [Example 7] In step 1 of Example 1, a solution of the resin-linear structure-containing organopolysiloxane was obtained by performing the same procedure as in Example 1, except that a mixture of methyltrichlorosilane and heptane was added dropwise, followed by the addition of the linear organopolysiloxane represented by formula (3) above.

[0052] [Example 8] In Example 1, after the completion of step 4, 10 g (0.1 mol) of triethylamine and 8 g (0.07 mol) of trimethylchlorosilane were added to the organic phase, and the reaction was carried out by heating at 60°C for 3 hours. After that, the aqueous phase was repeatedly washed with saline solution until it became neutral, and then 0.03% citric acid was added to the solution to obtain a solution of organopolysiloxane containing a resin-linear structure.

[0053] [Example 9] In Example 1, after the completion of step 4, 10 g (0.1 mol) of triethylamine and 9 g (0.07 mol) of vinyldimethylchlorosilane were added to the organic phase, and the reaction was carried out by heating at 60°C for 3 hours. After that, the aqueous phase was repeatedly washed with saline solution until it became neutral, and then 0.03% citric acid was added to the solution to obtain a solution of organopolysiloxane containing a resin-linear structure.

[0054] [Comparative Example 1] In step 1 of Example 1, the linear organopolysiloxane represented by formula (3) above was replaced with an equimolar amount of dimethyldichlorosilane in terms of Si atoms. Otherwise, the same procedure as in Example 1 was performed to obtain a solution of organopolysiloxane.

[0055] [Comparative Example 2] In Example 1, a solution of organopolysiloxane was obtained by following the same procedure as in Example 1, except that a linear organopolysiloxane represented by formula (3) was not used in step 1, and heptane was replaced with toluene (water solubility at 25°C: 0.5 g / L) in steps 1 and 3.

[0056] [Comparative Example 3] In step 1 of Example 1, the amount of linear organopolysiloxane represented by formula (3) added was changed to 330 g (4.3 moles in terms of Si), and in steps 1 and 3, heptane was replaced with isododecane (water solubility at 25°C: 0.001 g or less / L). Otherwise, the same procedure as in Example 1 was performed to obtain a solution of resin-linear structure-containing organopolysiloxane.

[0057] [Comparative Example 4] In Example 1, a solution of the resin-linear structure-containing organopolysiloxane was obtained by performing the same steps as in Example 1, except that step 4 was performed instead of step 3.

[0058] [Comparative Example 5] A solution of the resin-linear structure-containing organopolysiloxane was obtained by performing the same procedure as in Example 1, except that the condensation polymerization reaction conditions in Step 3 of Example 1 were set to 60°C for 1 hour.

[0059] [Comparative Example 6] A solution of the resin-linear structure-containing organopolysiloxane was obtained by performing the same procedure as in Example 1, except that citric acid was not added in step 4 of Example 1.

[0060] [Comparative Example 7] In Example 1, the same procedure as in Example 1 was followed, except that step 4 was omitted, to obtain a solution of the resin-linear structure-containing organopolysiloxane.

[0061] [Comparative Example 8] In Step 1 of Example 1, when isobutanol was not added and the amount of heptane added was doubled, a large amount of insoluble material precipitated during the hydrolysis reaction, and it was not possible to obtain an organopolysiloxane solution.

[0062] [Comparative Example 9] In Step 1 of Example 1, when isobutanol was changed to methanol (water solubility at 25°C: over 1000 g / L) and heptane was changed to toluene (water solubility at 25°C: 0.5 g / L), a large amount of insoluble material precipitated during the hydrolysis reaction, and it was not possible to obtain an organopolysiloxane solution.

[0063] The constituent unit ratios of the organopolysiloxanes obtained in Examples 1-9 and Comparative Examples 1-7 above, 29 Information on signals attributed to D units in Si-NMR spectra, weight-average molecular weight determined by GPC, and physical properties of organopolysiloxane solutions were measured using the following methods. The results are shown in Table 1.

[0064] (1) Nuclear magnetic resonance spectrum ( 29 Si-NMR) Equipment: 300MHz-NMR manufactured by JEOL Ltd. Solvent: CDCl3 Sample concentration: 20% Internal standard: Tetramethylsilane (TMS) (2) Gel permeation chromatography (GPC) Equipment: HLC-8320GPC manufactured by Tosoh Corporation Developing solvent: Tetrahydrofuran (THF) Flow rate: 0.5mL / min Detector: Differential refractive index detector (RI) Columns: Use the following two columns directly connected. TSKgel GMH HR -H(30)(7.8mmI.D.×30cm×1) (Manufactured by Tosoh Corporation) Column temperature: 40℃ Sample injection volume: 200 μL (THF solution with a concentration of 20 g / L) Standard: Monodisperse polystyrene (3) Extract water pH 30 g of organopolysiloxane solution and 30 g of distilled water were placed in a 100 ml polyethylene bottle, stirred for 30 minutes, and then allowed to stand. The pH of the separated aqueous layer was then measured. (4) Non-volatile content The non-volatile content was calculated from the mass change before and after drying the organopolysiloxane solution at 105°C for 3 hours. (5)Kinematic viscosity In accordance with JIS Z 8803:2011, the kinematic viscosity of organopolysiloxane solutions was measured at 25°C using a Cannon-Fenske viscometer. (6) Storage stability The fluidity of the organopolysiloxane solution was checked after storage at 50°C for one month, and the following evaluations were performed. ○: Liquidity available ×: Gelated and not fluid

[0065] [Table 1]

[0066] As shown in Table 1, Comparative Example 2, which used an organopolysiloxane composed solely of T units, and Comparative Examples 6 and 7, in which the pH of the extracted water was outside the range of the present invention, showed poor storage stability.

[0067] The organopolysiloxane solutions obtained in Examples 1-9 and Comparative Examples 1-7 were applied to glass substrates (except for polished steel plates used for the flexibility test) using bar coater No. 14, and allowed to stand at 25°C for 3 hours to form a coating film. The results of the evaluation of the obtained coating films are shown in Table 2.

[0068] (1) Curability The condition of the coating was checked by touch and evaluated according to the following criteria. ◎: No tackiness, fully cured. Slippery. ○: No tackiness, fully cured. No slipperiness. ×: Hardening abnormalities such as tack are present. (2) Heat resistance The coating was stored in a 200°C oven for 12 hours, and then the surface was visually inspected to determine if there were any abnormalities. ○: No abnormalities ×: Cracks or other abnormalities present. (3) Adhesion In accordance with JIS K5600, 25 grid squares were created by making 6 vertical and 6 horizontal cuts at 2mm intervals in the paint film using a razor blade. After firmly adhering the grid with cellophane tape (registered trademark, manufactured by Nichiban Co., Ltd.), the number of squares (X) that remained without peeling off the paint film was expressed as X / 25. (4) Pencil hardness The test was conducted in accordance with the pencil scratch test described in JIS K5600-5-4, applying a load of 750g. (5) Flexibility Test specimens, in which a hardened coating was formed on polished steel plates, were measured using a cylindrical mandrel (Type 1) in accordance with the method described in JIS K 5600-5-1.

[0069] [Table 2]

[0070] As shown in Table 2, the coatings obtained from the organopolysiloxane solutions of Examples 1 to 9 exhibit excellent curability, heat resistance, adhesion, hardness, and flexibility. On the other hand, Comparative Examples 1 and 2, which did not have linear organopolysiloxane moieties, showed inferior heat resistance of the coating film. In particular, the coating film of Comparative Example 2, which did not contain D units, showed significantly inferior flexibility. Furthermore, it was found that the organopolysiloxane solutions of Comparative Example 3, which contained an excess of linear organopolysiloxane moieties, and Comparative Examples 4 and 5, which had low molecular weights, exhibited poor curability. Moreover, the coating film obtained from the organopolysiloxane solution of Comparative Example 7, where the pH of the extracted water was 1.0, exhibited poor heat resistance.

Claims

1. A resin-linear structure-containing organopolysiloxane having a constituent unit ratio represented by the following formula (1) and a weight-average molecular weight of 1,000,000 to 20,000,000. 【Chemistry 1】 (In the formula, R 1 , R 2 , R 3 , R 4 and R 5 Each of the elements is independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, m is an integer from 0 to 50, a, b, c, d, and e are numbers satisfying the following conditions: 0 ≤ a ≤ 0.25, 0.05 ≤ b × (m + 2) ≤ 0.3, 0 ≤ c ≤ 0.25, 0.7 ≤ d ≤ 0.95, 0 ≤ e ≤ 0.25, and a + b × (m + 2) + c + d + e = 1, and x is a number where 0 < x ≤ 0.

1.

2. The above-mentioned R 1 , R 2 , R 3 and R 4 The resin-linear structure-containing organopolysiloxane according to claim 1, wherein the monovalent hydrocarbon group having 1 to 20 carbon atoms in R, R, R and R is a methyl group.

3. The resin-linear structure-containing organopolysiloxane according to claim 1, wherein m is an integer between 10 and 50, and a, c, and e are 0.

4. 29 The resin-linear structure-containing organopolysiloxane according to claim 1, wherein, in the Si-NMR spectrum, the chemical shift of the signal attributed to the D unit is detected in the range of -15 to -25 ppm, and the peak detection width of the signal (the difference between the chemical shift at the detection start point and the chemical shift at the detection end point) is 3 to 8 ppm.

5. A composition comprising a resin-linear structure-containing organopolysiloxane according to any one of claims 1 to 4, and an organic solvent, wherein the pH of the extracted water is in the range of 3.5 to 6.

0.

6. The composition according to claim 5, wherein the organic solvent is an aliphatic hydrocarbon.

7. The composition according to claim 5, comprising a carboxylic acid.

8. A method for producing the composition according to claim 5, A step of hydrolyzing and condensing a silane compound having chlorine atoms bonded to silicon atoms and a linear organopolysiloxane having chlorine atoms bonded to silicon atoms at both ends of its molecular chain in a mixed medium layer comprising water, a hydrophilic organic solvent with a water solubility of 50 to 1000 g / L at 25°C, and a hydrophobic organic solvent with a water solubility of 1 g / L or less at 25°C, and, A process to adjust the pH of the extracted water to 3.5 to 6.

0. A method for producing a composition containing the above.

9. A method for producing the composition according to claim 8, wherein the linear organopolysiloxane is a linear organopolysiloxane represented by the following formula (2). 【Chemistry 2】 (In the formula, m is an integer between 0 and 50.)

10. A method for producing the composition according to claim 8, wherein the hydrophilic organic solvent is one or more selected from 1-propanol, 2-propanol, 1-butanol, and isobutanol.

11. A method for producing the composition according to claim 8, wherein the hydrophobic organic solvent is one or more selected from hexane, heptane, octane, cyclohexane, methylcyclohexane, and ethylcyclohexane.

12. A coating agent comprising the composition according to claim 5.

13. An article having a cured coating film of the coating agent according to claim 12.

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