Curable composition, cured coating, article, and coating formation method using the same.

Abstract

This curable composition has a weight average molecular weight of 3,000-10,000 and a number average molecular weight of 2,000-8,000, and contains a polysiloxazane compound (A) component having a specific structure, and a silicone compound (B) having a hydrolysable silyl group or a hydroxyl group.　The present invention provides a curable composition from which it is possible to form a coating film having excellent water repellency and sliding properties, and which provides excellent stability to a coating film at the initial stage of being applied.

Description

[Technical Field]

[0001] The present invention relates to a curable composition capable of forming a cured film having excellent water repellency and slipperiness, as well as a cured film, article, and film-forming method using the same. [Background technology]

[0002] Conventionally, curable compositions have been applied to painted steel sheets of automobile bodies and other materials for the purpose of protection and aesthetic improvement. For example, Japanese Patent Publication No. 2014-139301 discloses a curable composition mainly composed of a polysilazane compound that has excellent water repellency and slipperiness. [Overview of the project]

[0003] However, even with the curable composition described in Japanese Patent Publication No. 2014-139301, it was difficult to achieve a good balance of all three requirements: film stability in the initial stages of application (stability of the contact angle of the film in the initial stages of application), sufficient water repellency (i.e., a sufficiently large contact angle for water droplets), and sliding properties (i.e., a sufficiently small sliding angle for water droplets).

[0004] The present invention has been made in view of the above circumstances, and aims to provide a curable composition that can form a coating with excellent water repellency and slipperiness, and furthermore, has excellent coating stability in the initial stages of application. Another object of the present invention is to provide a cured coating, an article, and a method for forming a coating using the above curable composition.

[0005] As a result of diligent research to achieve the above objective, the inventors of the present invention discovered that the curable composition described in detail below can form a coating with excellent water repellency and slipperiness, and furthermore, it exhibits excellent coating stability in the initial stages of application, thus completing the present invention.

[0006] The gist of this invention is described below.

[0007] 1. The material comprises a polysiloxazane compound (A) having a weight-average molecular weight of 3,000 to 10,000 and a number-average molecular weight of 2,000 to 8,000, and a silicone compound (B) having a hydrolyzable silyl group or hydroxyl group. A curable composition in which component (A) contains constituent units a to d represented by formula (1), and the molar ratio a:b:c:d of each constituent unit is 5 to 15:1 to 3:6 to 10:0.5 to 1.5.

[0008] [ka]

[0009] (In formula (1), R 1 R represents an unsubstituted monovalent alkyl group having 3 to 10 carbon atoms. 2 and R 3 Each of these independently represents an unsubstituted monovalent alkyl group having 1 to 6 carbon atoms. m is 0 or 1, and n is an integer between 30 and 100.

[0010] 2. The curable composition according to 1, wherein m of component (A) is 0.

[0011] 3. R ​​of component (A) 1 The curable composition according to 1. or 2., wherein is an unsubstituted monovalent alkyl group having 4 to 8 carbon atoms.

[0012] 4. The kinematic viscosity of component (B) at 25°C is 1 to 500 mm². 2 A curable composition as described in any of 1. to 3., wherein the value is / s.

[0013] 5. The curable composition according to any one of 1 to 4, wherein component (B) comprises a silicone compound having one or more functional groups selected from the group consisting of a dialkoxysilyl group, a trialkoxysilyl group, a silanol group, and a carbinol group at its terminal end.

[0014] 6. A curable composition according to any one of 1 to 5, comprising 0.1 to 500 parts by mass of component (B) per 100 parts by mass of component (A).

[0015] 7. A curable composition according to any one of 1 to 6, further comprising a catalyst as component (C).

[0016] 8. The curable composition according to 7, wherein component (C) contains one or more compounds selected from the group consisting of organotin compounds, organotitanium compounds, organoaluminum compounds, aluminum salt compounds, organozinc compounds, organozirconium compounds, inorganic acid compounds, organic acid compounds, inorganic base compounds, and organic base compounds.

[0017] 9. A curable composition according to any one of 1 to 8, further comprising an organic solvent as component (D).

[0018] 10. The curable composition according to 9, wherein component (D) is an aromatic hydrocarbon solvent or an aliphatic hydrocarbon solvent.

[0019] 11. The curable composition according to 9. or 10., comprising 200 to 15,000 parts by mass of component (D) per 100 parts by mass of component (A).

[0020] 12. The curable composition according to any one of 1 to 11, wherein the curable composition is used to form a film on the surface of a substrate selected from metal, glass, ceramics, plastic, fiber, steel sheet, and exterior steel sheet.

[0021] A cured film obtained by curing a curable composition described in any of sections 13.1 to 13.2.

[0022] Article having a cured coating as described in 14.13, wherein the article is selected from the group consisting of automobiles, motorcycles, bicycles, railway vehicles, solar panels, vending machines, and buildings.

[0023] A method for forming a coating, comprising applying a curable composition described in any of sections 15.1 to 15.11 to the surface of a substrate and curing it on the substrate. [Brief explanation of the drawing]

[0024] [Figure 1] This is the IR spectrum of polysiloxane 1 used in the example. [Modes for carrying out the invention]

[0025] The details of the present invention are described below. However, this disclosure is not limited to the embodiments described below. In this specification, "X~Y" is used to mean that the numerical values ​​(X and Y) described before and after it are the lower limit and upper limit, respectively, and means "X or more and Y or less". Furthermore, concentration and % represent mass concentration and mass %, respectively, unless otherwise specified, and ratios represent mass ratios unless otherwise specified. Furthermore, unless otherwise specified, operations and measurements of physical properties, etc., are performed under conditions of room temperature (20~25℃) / relative humidity 40~55%RH. Furthermore, "A and / or B" means that A and B, each of them, and combinations thereof are included.

[0026] [Curable composition] A curable composition according to one aspect of the present invention (hereinafter also referred to as "curable composition" or simply "composition") comprises a polysiloxazane compound (A) component having a weight-average molecular weight of 3,000 to 10,000 and a number-average molecular weight of 2,000 to 8,000, and a silicone compound (B) component having a hydrolyzable silyl group or a hydroxyl group, wherein component (A) comprises constituent units a to d represented by formula (1), and the molar ratio a:b:c:d of each constituent unit is 5 to 15:1 to 3:6 to 10:0.5 to 1.5.

[0027] [ka]

[0028] (In formula (1), R 1 R represents an unsubstituted monovalent alkyl group having 3 to 10 carbon atoms. 2 and R 3 Each of these independently represents an unsubstituted monovalent alkyl group having 1 to 6 carbon atoms. m is 0 or 1, and n is an integer between 30 and 100.

[0029] In other words, the curable composition contains components (A) and (B) described in detail below. By including these components, the curable composition according to the present invention can form a film with excellent water repellency and slipperiness, and furthermore, it has excellent film stability in the initial stages of application.

[0030] The following describes each component contained in the curable composition.

[0031] <(A) component> Component (A) contained in the curable composition of the present invention is a polysiloxane compound having a weight-average molecular weight of 3,000 to 10,000 and a number-average molecular weight of 2,000 to 8,000, and containing constituent units a to d represented by the following formula (1), wherein the molar ratio of each constituent unit a:b:c:d is 5 to 15:1 to 3:6 to 10:0.5 to 1.5.

[0032] Component (A) is a polysiloxane compound having constituent units represented by the average composition formula with subscripts a to d, as shown in the following formula (1) (average composition formula (1)). When a coating film containing the polysiloxane compound is formed on an adherend such as a substrate, water repellency, slipperiness, etc., can be imparted to the surface of the adherend.

[0033] In this specification, the "polysiloxazane compound" means a compound having both Si-N bonds and Si-O bonds. Generally, such a compound undergoes a hydrolysis reaction with moisture present in the air, the nitrogen atom in the molecule detaches to form ammonia, and this acts as a catalyst to further promote the reaction, thereby forming three-dimensional Si-O bonds. Generally, a "polysilazane compound" is a compound having a plurality of Si-N bonds. However, in this specification, for the purpose of distinguishing from polysiloxazane compounds, a compound having only Si-N bonds and no Si-O bonds is referred to as a "polysilazane compound". Further, in formula (1), the structural units each appended with subscripts a to d (hereinafter sometimes simply referred to as "structural unit a", "structural unit b", "structural unit c", and "structural unit d", respectively) are assumed to be bonded by silazane bonds (≡Si-NH-Si≡). That is, the silicon atoms contained in each structural unit are bonded via silazane bonds. In the following formula (1), the structural units a to d are described in this order, but the order in which each structural unit binds is not limited to this order, and the structural units to be bound are also not limited to the description in formula (1). For example, not all of structural unit a need to be bonded to structural unit b via silazane bonds, and any of structural units b to d may be bonded via the above bonds.

[0034]

Chemical formula

[0035] (In formula (1), R 1 represents an unsubstituted monovalent alkyl group having 3 to 10 carbon atoms, and R 2 and R 3 each independently represent an unsubstituted monovalent alkyl group having 1 to 6 carbon atoms. m is 0 or 1, and n is an integer from 30 to 100.)

[0036] R 1Examples of unsubstituted monovalent alkyl groups having 3 to 10 carbon atoms include linear, branched, or cyclic alkyl groups. Examples of these include, for example, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isoamyl group, tert-pentyl group, neopentyl group, 3-methylpentan-2-yl group, 3-methylpentan-3-yl group, 4-methylpentyl group, 4-methylpentan-2-yl group, 1,3-dimethylbutyl group, 3,3-dimethylbutyl group, Examples include 3,3-dimethylbutan-2-yl group, 1-methylhexyl group, 3-methylhexyl group, 4-methylhexyl group, 5-methylhexyl group, 1-ethylpentyl group, 1-(n-propyl)butyl group, 1,1-dimethylpentyl group, 1,4-dimethylpentyl group, 1,1-diethylpropyl group, 1,3,3-trimethylbutyl group, 1-ethyl-2,2-dimethylpropyl group; cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group; and others.

[0037] In equation (1), R 1 Preferably, it is an unsubstituted monovalent alkyl group having 4 to 8 carbon atoms, more preferably an unsubstituted monovalent alkyl group having 5 to 7 carbon atoms, particularly preferably an unsubstituted linear or branched alkyl group having 5 to 7 carbon atoms, and most preferably an unsubstituted linear or branched alkyl group having 6 carbon atoms.

[0038] Also, R 2 and R 3 These may be the same or different. 2 and R 3Examples of unsubstituted monovalent alkyl groups having 1 to 6 carbon atoms include linear, branched, or cyclic alkyl groups (provided that branched and cyclic alkyl groups have 3 to 6 carbon atoms). Examples of these include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, isopropyl, isobutyl, and cyclohexyl groups. In addition to these, alkyl groups having 3 to 6 carbon atoms are similarly exemplified from the specific examples of unsubstituted monovalent alkyl groups having 3 to 10 carbon atoms mentioned above.

[0039] In equation (1), R 2 and R 3 The element is preferably an unsubstituted monovalent alkyl group having 1 to 3 carbon atoms, more preferably 1 or 2 carbon atoms.

[0040] In formula (1), m is particularly preferably 0 from the viewpoint of excellent film stability in the initial stages of application. Furthermore, n is more preferably an integer between 33 and 80, particularly preferably an integer between 35 and 60, and most preferably an integer between 38 and 45.

[0041] In the above-mentioned (A) component of formula (1), the content ratio of each constituent unit a to d (molar ratio of each constituent unit a to d (a:b:c:d)) is 5 to 15:1 to 3:6 to 10:0.5 to 1.5. Here, it is preferable that the content ratio of constituent unit d is 0.5. In that case, the molar ratio of each constituent unit a to d (a:b:c:d), assuming the content ratio of constituent unit d is 0.5, is preferably 5 to 15:1 to 3:6 to 10:0.5, and more preferably 7.5 to 12.5:1.5 to 2.5:7 to 9:0.5. That is, the molar ratio of each constituent unit a to d (a:b:c:d) is preferably 10 to 30:2 to 6:12 to 20:1, and more preferably 15 to 25:3 to 5:14 to 18:1. Within the above range, a curable composition can be obtained that forms a coating with excellent water repellency and slipperiness, and also exhibits excellent coating stability in the initial stages of application.

[0042] Furthermore, regarding the content ratio of each constituent unit a to d (molar ratio of each constituent unit a to d (a:b:c:d)), other preferred forms include 5 to 15:1 to 3:6 to 10:1, and more preferably 7 to 13:1 to 3:6 to 10:1. Within the above range, a curable composition can be obtained that forms a coating with excellent water repellency and slipperiness, and also has excellent coating stability in the initial stages of application.

[0043] The content ratio of each of the above constituent units a to d (the molar ratio of each constituent unit a to d (a:b:c:d)) can be measured by GC / MS. Furthermore, this content ratio can be controlled by setting the amount of compound used as a raw material for component (A) within an appropriate range.

[0044] Furthermore, component (A) may further contain constituent units other than the above-mentioned constituent units a to d. However, from the viewpoint of obtaining a curable composition that can form a film with excellent water repellency and slipperiness, and has excellent film stability in the initial stages of application, it is preferable that component (A) consists only of the above-mentioned constituent units a to d.

[0045] The component (A) is a polysiloxazane compound that contains the constituent units a to d represented by the above formula (1) in specific ratios, and has a weight-average molecular weight of 3,000 to 10,000 and a number-average molecular weight of 2,000 to 8,000. The weight-average molecular weight of the polysiloxazane compound as component (A) is more preferably 3,500 to 8,000, even more preferably 4,000 to 7,000, and particularly preferably 4,500 to 6,000. In this specification, "weight-average molecular weight" refers to the weight-average molecular weight (Mw) in polystyrene terms measured by gel permeation chromatography (GPC). Furthermore, the number-average molecular weight of the polysiloxazane compound as component (A) is more preferably 2,100 to 7,000, even more preferably 2,200 to 6,000, and particularly preferably 2,300 to 5,000. In this specification, "number-average molecular weight" refers to the number-average molecular weight (Mn) in polystyrene equivalent, measured by gel permeation chromatography (GPC). By having the weight-average molecular weight and / or number-average molecular weight within the above range, a curable composition can be obtained that forms a coating with excellent water repellency and slipperiness, and also exhibits excellent coating stability in the initial stages of application.

[0046] Furthermore, the polydispersity (Mw / Mn) of the polysiloxane compound as component (A) is preferably 1.10 to 5.00, more preferably 1.20 to 3.00, and particularly preferably 1.50 to 2.50. The above polydispersity (Mw / Mn) is calculated by dividing the weight-average molecular weight (Mw) by the number-average molecular weight (Mn) measured by the above method.

[0047] Next, a method for producing a polysiloxane compound having constituent units a to d represented by formula (1) (average composition formula (1)) as component (A) (hereinafter referred to as polysiloxane (1)) will be described. The alkoxysilyl group-containing polysiloxane compound of the present invention can be obtained, for example, by a production method using an unsaturated bond (ethylenically unsaturated bond)-containing polysiloxane compound having constituent units a, b' and d represented by the following formula (8) (average composition formula (8)) (hereinafter referred to as unsaturated bond-containing polysiloxane compound (8)) as a starting material.

[0048] [ka]

[0049] (In formula (8), R 1 and n are R in equation (1) 1 (And are synonymous with n, respectively.)

[0050] In the above formula (8), the content ratio of each constituent unit a, b', and d (molar ratio of each constituent unit a, b', and d (a:b':d)) is preferably 5-15:1-16:0.5-1.5. Here, the content ratio of constituent unit d is preferably 0.5. In this case, the molar ratio of each constituent unit a, b', and d (a:b':d), assuming the content ratio of constituent unit d is 0.5, is preferably 5-15:7-13:0.5, and more preferably 7.5-12.5:8.5-11.5:0.5. That is, the molar ratio of each constituent unit a, b', and d (a:b':d) is preferably 10-30:14-26:1, and more preferably 15-25:17-23:1.

[0051] Furthermore, regarding the content ratio of each constituent unit a, b', and d (molar ratio of each constituent unit a, b', and d (a:b':d)), other preferred forms include 5-15:7-13:0.5-1.5, more preferably 5-15:7-13:1, and particularly preferably 7-13:7-13:1.

[0052] The weight-average molecular weight of these unsaturated bond-containing polysiloxanes (8) in terms of polystyrene, calculated by GPC, is not particularly limited, but is preferably 1,000 to 8,000.

[0053] First, a method for producing the unsaturated bond-containing polysiloxane compound (8) will be described. The unsaturated bond-containing polysiloxane compound (8) can be obtained, for example, by mixing a double-ended OH-modified silicone oil represented by formula (4) below (hereinafter referred to as double-ended OH-modified silicone oil (4)) with a chlorosilane compound represented by formula (5) (hereinafter referred to as chlorosilane compound (5)), then adding a chlorosilane compound represented by formula (7) (hereinafter referred to as chlorosilane compound (7)), introducing ammonia, and carrying out ammonia monolith polymerization.

[0054] [ka]

[0055] (In the above reaction equation, R 1 and n are R in equation (1) 1 (And are synonymous with n, respectively.)

[0056] The OH-modified silicone oil (4) at both ends has a kinematic viscosity at 25°C, preferably 20 to 5,000 mm². 2 / s, more preferably 30~1,500mm 2 The interval is / s, and is particularly preferably 50-100 mm. 2 The value is / s. Note that there is a correlation between kinematic viscosity and n in equation (4), specifically, when the kinematic viscosity is 20 to 5,000 mm². 2 When the value is / s, then 11 ≤ n ≤ 400, and the kinematic viscosity is 30 to 1,500 mm². 2 When the value is / s, then 13 ≤ n ≤ 300. Note that "kinematic viscosity" can be measured in accordance with JIS K2283:2000, and the kinematic viscosity values ​​in this specification are measured using an Ubbelohde viscometer.

[0057] Specific examples of chlorosilane compounds (5) include n-propyltrichlorosilane, n-hexyltrichlorosilane, cyclohexyltrichlorosilane, n-octyltrichlorosilane, n-nonyltrichlorosilane, and n-decyltrichlorosilane.

[0058] The mixing ratio of the terminally OH-modified silicone oil (4) and the chlorosilane compound (5) is not particularly limited, but from the viewpoint of imparting water-repellent properties to the resulting cured product, the amount of chlorosilane compound (5) is preferably 5 to 30 moles, more preferably 5 to 20 moles, even more preferably 7 to 15 moles, and particularly preferably 8 to 12 moles, per mole of OH groups in the terminally OH-modified silicone oil (4). That is, the amount of chlorosilane compound (5) added is preferably 10 to 60 moles, more preferably 10 to 40 moles, even more preferably 14 to 30 moles, and particularly preferably 16 to 24 moles, per mole of terminally OH-modified silicone oil (4).

[0059] Specific examples of the chlorosilane compound (7) include unsaturated bond-containing alkyldichlorosilane compounds such as methylvinyldichlorosilane. The amount of chlorosilane compound (7) added (used) is not particularly limited, but is preferably 0.3 to 10 moles, more preferably 0.5 to 5 moles, even more preferably 0.8 to 3 moles, and particularly preferably 0.9 to 1.5 moles per mole of chlorosilane compound (5).

[0060] Ammonolithic polymerization can proceed without a solvent, but as the reaction progresses, ammonium chloride is produced as a by-product, making stirring difficult; therefore, it is preferable to use a solvent. Examples of solvents include hydrocarbon solvents such as pentane, hexane, cyclohexane, isooctane, benzene, toluene, and xylene; and ether solvents such as diethyl ether, tetrahydrofuran, 4-methyltetrahydropyran, cyclopentyl methyl ether, dioxane, and dipropylene glycol dimethyl ether. These solvents may be used individually or in mixtures of two or more. If any solvent remains after the synthesis of component (A), it will be treated as component (D) described later.

[0061] Ammonolithic polymerization can also have its reaction time shortened by adding a catalyst. Specific examples of catalysts include Brønsted acids such as methanesulfonic acid, benzenesulfonic acid, dodecylbenzenesulfonic acid, trifluoromethanesulfonic acid, acetic acid, propionic acid, benzoic acid, and trifluoroacetic acid. The amount of catalyst to be added is not particularly limited, but from the viewpoint of the effect of catalyst addition or suppression of side reactions, it is preferably 0.001 to 0.1 moles, more preferably 0.005 to 0.1 moles, per mole of chlorosilane compound (5).

[0062] The reaction temperature is not particularly limited, but from the viewpoint of sublimation of ammonium chloride or reaction rate, it is preferably -85 to 100°C, more preferably -78 to 50°C, and even more preferably -10 to 20°C. The reaction time is preferably 30 minutes to 24 hours, more preferably 3 hours to 15 hours, from the viewpoint of reaction rate or suppression of side reactions. Furthermore, the atmosphere in which the reaction is carried out is not particularly limited, but in an inert gas atmosphere such as nitrogen or argon is preferred in order to avoid hydrolysis of the raw materials.

[0063] After the reaction is complete, the unsaturated bond-containing polysiloxazane compound (8) can be recovered by removing the by-product ammonium chloride from the reaction solution and, if necessary, the solvent. Filtration is a preferred method for removing ammonium chloride.

[0064] Next, polysiloxazane compound (1) is produced from the unsaturated bond-containing polysiloxazane compound (8) obtained in this manner. One method of production involves an addition reaction of a mercapto group-containing silane compound represented by the following formula (9) (hereinafter referred to as mercapto group-containing silane compound (9)) in the presence of a radical generator.

[0065] A method for producing a polysiloxane compound (1) is described, which involves introducing an alkoxysilyl group to an unsaturated bond-containing polysiloxane compound (8) by an addition reaction with a mercapto group-containing silane compound (9) in the presence of a radical generator.

[0066] [ka]

[0067] (In the above reaction equation, R 2 and R 3 , and m are R in equation (1). 2 and R 3 ) These are synonymous with m, respectively.

[0068] Specific examples of mercapto group-containing silane compounds (9) include mercaptoalkyltrialkoxysilane compounds such as mercaptopropyltrimethoxysilane, and mercaptoalkylalkyldialkoxysilane compounds such as mercaptopropylmethyldimethoxysilane.

[0069] Furthermore, as described above, a radical generator is used in the addition reaction between the unsaturated bond-containing polysiloxane compound (8) and the mercapto group-containing silane compound (9). Specific examples of this radical generator include organic peroxides such as tert-butyl hydroperoxide, di-tert-butyl peroxide, and benzoyl peroxide; azo compounds such as azobisisobutyronitrile and 2,2'-azobis(2-methylbutyronitrile); however, azo compounds are particularly preferred. The amount of radical generator used is not particularly limited, but from the viewpoint of productivity, 0.00001 to 0.2 moles is preferred, 0.0001 to 0.1 moles is more preferred, and 0.001 to 0.01 moles is particularly preferred, per mole of unsaturated bond contained in the unsaturated bond-containing polysiloxane compound (8).

[0070] The mixing ratio of the unsaturated bond-containing polysiloxane compound (8) and the mercapto group-containing silane compound (9) is not particularly limited, but from the viewpoint of product usefulness and reactivity, it is preferable that the ratio of the mercapto group-containing silane compound (9) is 0.1 to 1.5 moles, more preferably 0.15 to 1.2 moles, even more preferably 0.2 to 1.0 moles, and particularly preferably 0.3 to 0.9 moles per mole of unsaturated bond contained in the unsaturated bond-containing organic polysiloxane compound (8).

[0071] The reaction temperature for the above addition reaction is not particularly limited, but from the viewpoint of avoiding unwanted side reactions, 0 to 200°C is preferred, and 20 to 150°C is more preferred. Similarly, the reaction time is not particularly limited, but from the viewpoint of avoiding unwanted side reactions, 1 to 40 hours is preferred, and 1 to 20 hours is more preferred. Furthermore, the above addition reaction is preferably carried out under an inert gas atmosphere such as nitrogen or argon to prevent hydrolysis of the mercapto group-containing silane compound (9).

[0072] The above addition reaction can proceed without a solvent, but a solvent may also be used. Specific examples of solvents include aliphatic hydrocarbon solvents with 5 to 20 carbon atoms such as pentane, hexane, cyclohexane, heptane, octane, nonane, decane, isooctane, and isododecane; aromatic hydrocarbon solvents with 6 to 10 carbon atoms such as benzene, toluene, and xylene; ether solvents such as diethyl ether, tetrahydrofuran, dioxane, and dipropylene glycol dimethyl ether; ester solvents such as ethyl acetate and butyl acetate; aprotic polar solvents such as acetonitrile, N,N-dimethylformamide, and N-methylpyrrolidone; and silicone solvents such as hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, tris(trimethylsiloxy)methylsilane, octamethylcyclotetrasiloxane, and decamethylcyclopentasiloxane. These solvents may be used individually or in combination of two or more. In particular, when using azo compounds as catalysts, toluene and xylene are preferred from the viewpoint of catalyst solubility.

[0073] Based on the above, another aspect of the present invention is to add the terminally OH-modified silicone oil represented by formula (4) and the chlorosilane compound represented by formula (5) in a molar ratio of 1:10 to 60 (terminally OH-modified silicone oil (4): chlorosilane compound (5)); to add 0.3 to 10 moles of the chlorosilane compound represented by formula (7) to 1 mole of the chlorosilane compound (5), introduce ammonia, and carry out ammonia monolith polymerization to obtain the unsaturated bond-containing polysiloxane compound represented by formula (8); and the unsaturated bond-containing polysiloxane The present invention provides a method for producing a curable composition, comprising: adding 0.1 to 1.5 moles of a mercapto group-containing silane compound represented by formula (9) to 1 mole of xazanine compound (8), and reacting it with the unsaturated bond-containing polysiloxazanine compound (8) in the presence of a radical generator; in this order, preparing a polysiloxazanine compound (component (A)) having a weight-average molecular weight of 3,000 to 10,000 and a number-average molecular weight of 2,000 to 8,000; and adding a silicone compound (component (B)) having a hydrolyzable silyl group or hydroxyl group.

[0074] For preferred conditions in the above manufacturing method, refer to the description in the section <(A) component> above. Similarly, for preferred forms of component (B), refer to the description in the section <(B) component> below.

[0075] <(B) component> Component (B) contained in the curable composition of the present invention is a silicone compound having a hydrolyzable silyl group or a hydroxyl group (-OH). By combining component (B) of the present invention with component (A) above, a curable composition can be obtained that can form a film with excellent water repellency and slipperiness, and that has excellent film stability in the initial stages of application.

[0076] Here, "hydrolyzable silyl group" refers to a silicon atom to which 1 to 3 hydrolyzable groups are bonded. Preferred examples of hydrolyzable groups include halogen atoms (fluorine, chlorine, bromine, iodine), alkoxy groups, acyl oxide groups, ketoximate groups, and alkenyl oxide groups. From the viewpoint of good compatibility with component (A) and good film stability in the initial stages of application, alkoxy groups are particularly preferred as hydrolyzable groups, and hereafter, hydrolyzable silyl groups having alkoxy groups will also be referred to as alkoxysilyl groups. That is, component (B) preferably contains alkoxysilyl groups as hydrolyzable silyl groups.

[0077] Examples of alkoxysilyl groups included in component (B) above include monoalkoxysilyl groups, dialkoxysilyl groups, and trialkoxysilyl groups. Dialkoxysilyl groups and trialkoxysilyl groups are preferred, and trialkoxysilyl groups are particularly preferred, due to their excellent film stability in the initial stages of application.

[0078] The alkoxy group included in the alkoxysilyl group is preferably an alkoxy group having 1 to 20 carbon atoms. The alkoxy group may be linear or branched, but preferably a linear alkoxy group having 1 to 20 carbon atoms or a branched alkoxy group having 3 to 20 carbon atoms is mentioned. Examples include methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group, undecyloxy group, dodecyloxy group, tridecyloxy group, tetradecyloxy group, pentadecyloxy group, hexadecyloxy group, heptadecyloxy group, octadecyloxy group, 2-ethylhexyloxy group, and 3-ethylpentyloxy group. Among these, a linear alkoxy group having 1 to 5 carbon atoms or a branched alkoxy group having 3 to 5 carbon atoms is preferred, and a linear alkoxy group having 1 to 3 carbon atoms is more preferred.

[0079] Therefore, preferred monoalkoxysilyl groups include dimethylmethoxysilyl group, dimethylethoxysilyl group, and dimethylpropoxysilyl group; preferred dialkoxysilyl groups include methyldimethoxysilyl group, methyldiethoxysilyl group, and methyldipropoxysilyl group; and preferred trialkoxysilyl groups include trimethoxysilyl group, triethoxysilyl group, and tripropoxysilyl group. Among these, alkoxysilyl groups having a methoxy group are preferred from the viewpoint of high reactivity and easy film formation, and trimethoxysilyl group is particularly preferred.

[0080] The hydroxyl group (-OH) in component (B) may be directly bonded to the silicon atom or bonded to the silicon atom via an organic group. That is, the hydroxyl group in component (B) may be present in the form of a silanol group or in the form of a carbinol group. In this specification, "carbinol group" means a group having a hydroxyl group linked to an organic group.

[0081] The silicone compound as component (B) may contain either a hydrolyzable silyl group or a hydroxyl group, or both. The position of the hydrolyzable silyl group or hydroxyl group in the molecular chain of component (B) is not particularly limited, such as at the end or in a side chain, but it is preferably at the end. Particularly preferred as component (B) is a silicone compound having a hydrolyzable silyl group or hydroxyl group at one or both ends, and most preferably a silicone compound having a hydrolyzable silyl group or hydroxyl group at both ends.

[0082] Component (B) is preferably a silicone compound having a hydroxyl group, from the viewpoint of obtaining a curable composition with excellent film stability in the initial stages of application. That is, from the viewpoint of film stability in the initial stages of application, component (B) is preferably a silicone compound having a silanol group and / or a carbinol group. Furthermore, from the same viewpoint, component (B) is preferably a silicone compound having a silanol group and / or a carbinol group represented by formula (11) or formula (12), which will be described in detail below. In addition, the carbinol group is preferably located at one end or both ends of the silicone compound, and most preferably at both ends.

[0083] From the viewpoint of excellent film stability in the initial stages of application, component (B) is preferably a silicone compound having a carbinol group represented by the following formula (11) at one or both ends. Furthermore, from the viewpoint of improving water repellency and slipperiness, component (B) is preferably a silicone compound having a carbinol group represented by the following formula (12) at one or both ends. In particular, for the reason that slipperiness can be improved, it is preferable that the carbinol group represented by the following formula (12) contained in component (B) is located at both ends.

[0084] Furthermore, as mentioned above, from the viewpoint of improving the film stability in the initial stages of application, the hydrolyzable silyl groups included in the silicone compound as component (B) are preferably dialkoxysilyl groups and trialkoxysilyl groups. Therefore, in order to obtain excellent film stability in the initial stages of application, component (B) in the present invention is preferably a silicone compound having one or more functional groups selected from the group consisting of dialkoxysilyl groups, trialkoxysilyl groups, silanol groups, and carbinol groups at its terminal end.

[0085] The above-mentioned component (B) has a kinematic viscosity of 1 to 500 mm at 25°C. 2 Preferably, it is / s, more preferably 5 to 400 mm 2 / s, and more preferably 10-200mm 2 The interval is / s, and is particularly preferably 10-60 mm. 2 The interval is / s, and most preferably 30-45mm 2 The kinematic viscosity of component (B) is within this range, which allows for the formation of a coating with excellent water repellency and slipperiness, and results in a curable composition with excellent coating stability in the initial stages of application.

[0086] The aforementioned component (B) is not particularly limited as long as it is a silicone compound having a hydrolyzable silyl group or a hydroxyl group together with the silicone skeleton. Examples of such component (B) include linear silicone compounds represented by formula (10) and silicone compounds (silicone oligomers) having a structure in which silicon atoms are bonded to each other in two or three dimensions via oxygen atoms (branched chain structure or network structure). In this specification, "silicone oligomer" refers to a silicone compound obtained by partially hydrolyzing a trifunctional alkoxysilyl compound, etc., with an acid, base, or a known catalyst such as an organotin compound or organotitanium compound, and then de-alcoholizing and condensing (also called partial hydrolysis condensation in this specification). Generally, "silicone compound" and "silicone oligomer" are terms used almost interchangeably, but in this specification, in order to distinguish them from linear silicone compounds such as the one represented by formula (10) below, silicone compounds having a branched chain structure and / or network structure may be referred to as "silicone oligomers". In this specification, the term "silicone compound" is used to include not only linear silicone compounds but also silicone oligomers. In this specification, "oligomer" refers to a polymer in which monomer units are repeated two or more times, and the upper limit of the number of monomer units is preferably 100 or less.

[0087] [ka]

[0088] (In formula (10), R 4 ~R 9 Each of these independently represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a halogen atom, X 1 and X 2 Each independently represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a hydroxyl group, a carbinol group, or a halogen atom, and X 1 and X2 At least one of these is an alkoxy group, a hydroxyl group, or a carbinol group. B (The range is 5-850.)

[0089] In equation (10), R 4 ~R 9 These may be the same or different. 4 ~R 9 Each of these is preferably an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms, and particularly preferably an alkyl group having 1 to 5 carbon atoms.

[0090] In equation (10), X 1 and X 2 They may be the same or different. 1 and X 2 Each of these is preferably independently an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a hydroxyl group, or a carbinol group. In this case, X 1 and X 2 Of these, at least one is an alkoxy group, a hydroxyl group, or a carbinol group, and is more preferably an alkoxy group or a carbinol group.

[0091] Also, X 1 and X 2 It is more preferable that both ends (both terminals) are independently an alkoxy group, a hydroxyl group, or a carbinol group having 1 to 20 carbon atoms. Furthermore, from the viewpoint of improving sliding properties, X 1 and X 2 Each of these is preferably an alkoxy group having 1 to 20 carbon atoms, or a carbinol group, and more preferably a carbinol group. Furthermore, X 1 and X 2 It is preferable that they are the same.

[0092] In equation (10), n B The formula is: -Si(R 6)(R 7 This represents the number of repeating units represented by )-O-, preferably 10 to 700.

[0093] The silicone compound represented by formula (10) has a kinematic viscosity of 1 to 500 mm at 25°C. 2 Preferably, it is / s, more preferably 5 to 400 mm 2 / s, and more preferably 10-200mm 2 The interval is / s, and is particularly preferably 10-60 mm. 2 The interval is / s, and most preferably 30-45mm 2 It is / s.

[0094] The C1-C20 alkyl group in formula (10) may be either linear or branched, but preferably a linear C1-C20 alkyl group or a branched C3-C20 alkyl group is mentioned. Specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, tert-pentyl group, neopentyl group, 1,2-dimethylpropyl group, n-hexyl group, isohexyl group, 1,3-dimethylbutyl group, 1-isopropylpropyl group, 1,2-dimethylbutyl group, n-heptyl group, 1,4-dimethylpentyl group, 3-ethylpentyl group, 2-methyl-1-isopropylpropyl group, 1-ethyl-3 Examples include methylbutyl group, n-octyl group, 2-ethylhexyl group, 3-methyl-1-isopropylbutyl group, 2-methyl-1-isopropyl group, 1-tert-butyl-2-methylpropyl group, n-nonyl group, 3,5,5-trimethylhexyl group, n-decyl group, isodecyl group, n-undecyl group, 1-methyldecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, nonadecyl group, and eicosyl group. Among them, R 4 ~R 9 The alkyl groups are preferably linear alkyl groups with 1 to 5 carbon atoms or branched alkyl groups with 3 to 5 carbon atoms, and more preferably linear alkyl groups with 1 to 3 carbon atoms. Also, X1 and X 2 The alkyl groups are preferably linear alkyl groups having 1 to 5 carbon atoms or branched alkyl groups having 3 to 5 carbon atoms, with linear alkyl groups having 1 to 3 carbon atoms being more preferred.

[0095] Examples of cycloalkyl groups having 3 to 20 carbon atoms in formula (10) include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl groups.

[0096] Examples of aryl groups having 6 to 20 carbon atoms in formula (10) include phenyl, naphthyl, biphenyl, fluorenyl, anthuryl, pyrenyl, azlenyl, acenaphthirenyl, and terphenyl groups.

[0097] Specific examples of alkoxy groups having 1 to 20 carbon atoms in formula (10) are the same as the specific examples of alkoxy groups included in the alkoxysilyl group described above. Among them, X 1 and X 2 The alkoxy groups are preferably linear alkoxy groups with 1 to 5 carbon atoms or branched alkoxy groups with 3 to 5 carbon atoms, and more preferably linear alkoxy groups with 1 to 3 carbon atoms. 4 ~R 9 The alkoxy groups are preferably linear alkoxy groups having 1 to 5 carbon atoms or branched alkoxy groups having 3 to 5 carbon atoms, with linear alkoxy groups having 1 to 3 carbon atoms being more preferred.

[0098] Examples of halogen atoms in formula (10) include fluorine, chlorine, bromine, and iodine atoms.

[0099] Examples of the carbinol group in formula (10) include organic groups represented by -CH2-OH, or organic groups having a -CH2-OH structure in part. Examples of organic groups having a -CH2-OH structure in part include the organic groups shown in formulas (11) and (12) below. Therefore, a preferred embodiment is in formula (10) above, X 1 and X2 Of these, at least one is a carbinol group represented by formula (11) or formula (12) below. Note that the silicone compound represented by formula (10) may contain these substituents individually or in combination.

[0100] [ka]

[0101] (In formula (11), R 10 , R 11 and R 12 Each of these independently represents an alkylene group having 1 to 20 carbon atoms, or an oxyalkylene group having 1 to 20 carbon atoms, and R 13 (This represents an alkyl group with 1 to 20 carbon atoms.)

[0102] R 10 , R 11 and R 12 These may be the same or different. 10 , R 11 and R 12 The alkylene group having 1 to 20 carbon atoms may be either linear or branched, but preferably a linear alkylene group having 1 to 20 carbon atoms or a branched alkylene group having 3 to 20 carbon atoms is preferred. Specifically, examples include methylene group, ethylene group, trimethylene group, tetramethylene group, propylene group, ethylethylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, etc. Of these, a linear alkylene group having 1 to 5 carbon atoms or a branched alkylene group having 3 to 5 carbon atoms is preferred, and a linear alkylene group having 1 to 3 carbon atoms is more preferred.

[0103] In addition, the oxyalkylene group having 1 to 20 carbon atoms may be either linear or branched, preferably a linear oxyalkylene group having 1 to 20 carbon atoms or a branched oxyalkylene group having 3 to 20 carbon atoms. Specifically, examples include an oxymethylene group (-OCH2-), an oxyethylene group (-OCH2CH2-), an oxypropylene group (-OCH(CH3)CH2-), an oxytrimethylene group (-OCH2CH2CH2-), an oxybutylene group (-OCH2CH2CH2CH2-), and the like. Among these, a linear oxyalkylene group having 1 to 5 carbon atoms or a branched oxyalkylene group having 3 to 5 carbon atoms is preferable, and a linear oxyalkylene group having 1 to 3 carbon atoms is more preferable.

[0104] In addition, the above "oxyalkylene group" includes, in addition to the divalent substituent of the above structure (-O-(C1-C20 alkylene unit)-), an alkyleneoxyalkylene group represented by the formula: -(C1-C10 alkylene unit (1))-O-(C1-C10 alkylene unit (2))- (an alkyleneoxyalkylene group having 2 to 20 carbon atoms). Here, "C1-C10 alkylene unit (1)" is bonded to the silicon atom in formula (10) or the hydroxyl group in formula (11), and "C1-C10 alkylene unit (2)" is bonded to the carbon atom in formula (11). The number of carbon atoms contained in alkylene units (1) and (2) may be the same or different, but it is preferable that they are different.

[0105] Specific examples of alkylene units (1) and (2) are the same as the specific examples of the alkylene group having 1 to 20 carbon atoms as described above for R 10 Among these, a linear alkylene group having 1 to 5 carbon atoms or a branched alkylene group having 3 to 5 carbon atoms is preferable, and as alkylene units (1) and (2), a linear alkylene group having 1 to 4 carbon atoms is more preferable.

[0106] R 13Specific examples of the alkyl group having 1 to 20 carbon atoms as such include the same as those of the alkyl group having 1 to 20 carbon atoms in formula (10). Among them, a linear alkyl group having 1 to 5 carbon atoms or a branched alkyl group having 3 to 5 carbon atoms is preferable, and a linear alkyl group having 1 to 3 carbon atoms is more preferable.

[0107] Among the above structures, R 10 is an alkyleneoxyalkylene group having 2 to 20 carbon atoms, and R 11 and R 12 are each independently a linear alkylene group having 1 to 5 carbon atoms or a branched alkylene group having 3 to 5 carbon atoms, and R 13 is preferably a linear alkylene group having 1 to 5 carbon atoms or a branched alkyl group having 3 to 5 carbon atoms. Further, R 10 is an alkyleneoxyalkylene group represented by the formula: -(linear alkylene group having 1 to 4 carbon atoms)-O-(linear alkylene group having 1 to 4 carbon atoms)-, and R 11 and R 12 are each independently a linear alkylene group having 1 to 3 carbon atoms, and R 13 is more preferably a linear alkyl group having 1 to 3 carbon atoms.

[0108]

Chemical formula

[0109] (In formula (12), R 14 and R 15 each independently represent an alkylene group having 1 to 10 carbon atoms.)

[0110] R 14 and R 15 may be the same or different. Specific examples of the alkylene group having 1 to 10 carbon atoms as R 14 and R 15 include the same as those of the alkylene group having 1 to 10 carbon atoms in formula (11). Among them, a linear alkylene group having 1 to 8 carbon atoms or a branched alkylene group having 3 to 5 carbon atoms is preferable, and a linear alkylene group having 1 to 5 carbon atoms is more preferable.

[0111] From the standpoint of having excellent film stability in the initial stages of application, in the above formula (10), X 1 and X 2 Preferably, at least one of them is a carbinol group represented by formula (11) above. Furthermore, from the viewpoint of improving water repellency and slipperiness, in formula (10) above, X 1 and X 2 Preferably, at least one of them is a carbinol group represented by formula (12) above. In particular, for the reason that it can improve slipperiness, in formula (10) above, X 1 and X 2 Preferably, both are carbinol groups represented by the above formula (12).

[0112] Note that R in equation (11) above 10 , and R in equation (12) above 14 However, each of these bonds with the silicon atom in equation (10).

[0113] The commercially available product of component (B) of the present invention is not limited, but examples include X-40-2090 (manufactured by Shin-Etsu Chemical Co., Ltd.) as a silicone compound having an alkoxy group represented by formula (10), and KR-500 (manufactured by Shin-Etsu Chemical Co., Ltd.) as a silicone oligomer having an alkoxy group. Examples of silicone compounds having a hydroxyl group include KF-9701 (manufactured by Shin-Etsu Chemical Co., Ltd.) and XC96-C7123 (manufactured by Momentive Performance Materials Japan LLC), and examples of silicone compounds having a carbinol group include X-22-160AS, X-22-170BX, and X-22-176DX (manufactured by Shin-Etsu Chemical Co., Ltd.). These may be used individually or in combination of multiple types. When two or more types are used in combination, the content of component (B) refers to the total amount.

[0114] The content of component (B) in the curable composition according to the present invention (or the total amount if two or more types of component (B) are used in combination) is preferably in the range of 0.1 to 500 parts by mass, more preferably in the range of 0.5 to 400 parts by mass, particularly preferably in the range of 1 to 300 parts by mass, and most preferably in the range of 30 to 80 parts by mass, per 100 parts by mass of component (A). By having component (B) in this range, a coating with excellent water repellency and slipperiness can be formed, and a curable composition with excellent coating stability in the initial stages of application can be obtained.

[0115] <(C) component> The curable composition of the present invention preferably further contains a catalyst as component (C). By containing component (C), the curable composition can react with moisture in the air or the like to the hydrolyzable functional group contained in component (A) or (B) to promote the condensation reaction. Therefore, by further containing component (C) in the curable composition, the formation of a cured film can be promoted.

[0116] Examples of component (C) include organotin compounds, organotitanium compounds, organoaluminum compounds, organozinc compounds, organozirconium compounds, inorganic acid compounds, organic acid compounds, inorganic base compounds, and organic base compounds. In other words, component (C) preferably contains one or more compounds selected from the group consisting of organotin compounds, organotitanium compounds, organoaluminum compounds, aluminum salt compounds, organozinc compounds, organozirconium compounds, inorganic acid compounds, organic acid compounds, inorganic base compounds, and organic base compounds. Among these, organotitanium compounds, organoaluminum compounds, inorganic acid compounds, and organic base compounds are preferred because they have good compatibility with components (A) and (B) of the present invention, can form a coating with excellent water repellency and slipperiness, and can yield a curable composition with excellent coating stability in the initial stages of application. Particularly preferred are organotitanium compounds and organoaluminum compounds, and most preferably are organotitanium compounds. These may be used individually or in combination of multiple types.

[0117] Examples of the organotin compounds include dibutyltin dilaurate, dibutyltin dioctate, dibutyltin diacetate, dioctyltin dilaurate, dioctyltin dioctate, dioctyltin diacetate, dibutyltin bisacetylacetate, and dioctyltin bisacetyllaurate. Examples of the organotitanium compounds include titanium chelate compounds such as titanium acetylacetonate, titanium-1,3-propanedioxybis(ethylacetoacetate), and titanium ethylacetoacetate; and titanium alkoxide compounds such as tert-amyl titanate, tetratert-butyl titanate, titanium-1,3-propanedioxybis(ethylacetoacetate), tetrastearyl titanate, tetraoctyl titanate, tetran-butyl titanate, and tetraisopropyl titanate. Furthermore, the organoaluminum compounds include aluminum methoxybis(ethyl acetate), aluminum methoxybis(acetylacetonate), aluminum ethoxybis(ethyl acetate), aluminum ethoxybis(acetylacetonate), aluminum isopropoxybis(ethyl acetate), aluminum isopropoxybis(methyl acetate), aluminum isopropoxybis(t-butyl acetate), aluminum butoxybis(ethyl acetate), aluminum dimethoxy(ethyl acetate), and aluminum Examples include aluminum chelate compounds such as aluminum dimethoxy(acetylacetonate), aluminum diethoxy(ethyl acetoacetate), aluminum diethoxy(acetylacetonate), aluminum diisopropoxy(ethyl acetoacetate), aluminum diisopropoxy(methyl acetoacetate), aluminum tris(ethyl acetoacetate), and aluminum tris(acetylacetonate); and aluminum alkoxide compounds such as aluminum trimethoxide, aluminum triethoxide, aluminum triallyl oxide, and aluminum triphenoxide. Examples of aluminum salt compounds include aluminum hydroxide and aluminosilicate compounds.Examples of the organozinc compounds include zinc octylate, zinc 2-ethylhexanoate, zinc triacetylacetonate, zinc-2-ethylhexoate, zinc naphthenate, and zinc stearate. Examples of the organozirconium compounds include zirconium tetraacetylacetonate, zirconium tributoxyacetylacetonate, zirconium dibutoxydiacetylacetonate, zirconium tetran-n-propoxide, zirconium tetraisopropoxide, zirconium tetran-n-butoxide, zirconium acylate, zirconium tributoxystearate, zirconium octoate, and zirconium (2-ethylhexoate).

[0118] Examples of the inorganic acid compounds include hydrochloric acid, phosphoric acid, sulfuric acid, and hydrofluoric acid. Examples of the organic acid compounds include p-toluenesulfonic acid, oxalic acid, citric acid, and acetic acid. Examples of the inorganic base compounds include ammonia, sodium hydroxide, and magnesium hydroxide. Examples of the organic base compounds include trimethylamine, triethylamine, tributylamine, 1,5-diazabicyclo[4.3.0]nonene-5 (DBN), and 1,8-diazabicyclo[5.4.0]undecene-7 (DBU).

[0119] These catalysts can be used individually or in combination.

[0120] Examples of commercially available organotitanium compounds include Orgatics® TA-8, TA-21, TA-23, TA-30, TC-100, TC-401, TC-710 (manufactured by Matsumoto Fine Chemical Co., Ltd.), D-20, D-25, and DX-175 (manufactured by Shin-Etsu Chemical Co., Ltd.). Examples of commercially available organoaluminum compounds include DX-9740 and CAT-AC (manufactured by Shin-Etsu Chemical Co., Ltd.). Examples of inorganic acid compounds include D-220 and X-40-2309A (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0121] The amount of component (C) added to the curable composition according to the present invention (content: if two or more types of component (C) are used in combination, the total amount thereof) is not particularly limited, but for example, it is preferably 0.01 to 50 parts by mass, more preferably 0.03 to 30 parts by mass, and particularly preferably 1 to 10 parts by mass, per 100 parts by mass of component (A). By setting it within the above range, it is possible to form a coating with even greater water repellency and slipperiness, and to obtain a curable composition with excellent coating stability in the initial stages of application.

[0122] <(D) component> The curable composition of the present invention may further contain an organic solvent as component (D). The organic solvent means one that can dissolve or uniformly disperse components (A) and (B) contained in the curable composition.

[0123] (D) The components are not particularly limited, but examples include aromatic hydrocarbon solvents such as benzene, toluene, and xylene; aliphatic hydrocarbon solvents such as paraffinic solvents, isoparaffinic solvents, and cycloparaffinic solvents; alcoholic solvents with two or more carbon atoms such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, and tert-butanol; ketone solvents such as acetone and methyl ethyl ketone; acetic acid ester solvents such as methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, and butyl acetate; halogenated solvents such as dichloromethane, chloroform, tetrachloroethane, and chlorobenzene; etheric solvents such as ethyl ether and THF; and gasoline. These may be used individually or in combination.

[0124] Examples of the paraffinic solvent include n-hexane and n-heptane; examples of the isoparaffinic solvent include isononane, isohexane, isooctane, and isododecane; and examples of the cycloparaffinic solvent include cyclohexane and methylcyclohexane.

[0125] These organic solvents can be used individually or in combination.

[0126] In the present invention, from the viewpoint of obtaining a curable composition that can form a film with excellent water repellency and slipperiness and has excellent film stability in the initial stages of application, aromatic hydrocarbon solvents and aliphatic hydrocarbon solvents are preferred, more preferably aliphatic hydrocarbon solvents, and particularly preferably isoparaffinic solvents.

[0127] There are no particular limitations on commercially available organic solvents as component (D) mentioned above, but examples include Exol D30, D40 (manufactured by TonenGeneral Sekiyu K.K.), Kyowazol® C-800, C-600M, C-900 (manufactured by HK Neochem Co., Ltd.), Isopar E® (manufactured by Maruzen Yuka Shoji Co., Ltd.), Naphthezol® 160, 200, 220 (manufactured by JXTG Energy Corporation), and IP Solvent 1620 (manufactured by Idemitsu Kosan Co., Ltd.).

[0128] In the present invention, the amount of component (D) added (content: if two or more types of component (D) are used in combination, the total amount thereof) is preferably in the range of 200 to 15,000 parts by mass per 100 parts by mass of component (A), more preferably in the range of 500 to 10,000 parts by mass, even more preferably in the range of 800 to 9,000 parts by mass, particularly preferably in the range of 1,200 to 8,500 parts by mass, and most preferably in the range of 3,000 to 5,000 parts by mass. By setting the amount within the above range, the curable composition of the present invention can ensure good storage stability and workability, and can maintain appropriate volatility. In particular, when the amount of component (D) added per 100 parts by mass of component (A) is in the range of 1,200 to 8,500 parts by mass, the workability of film formation is excellent while maintaining film properties.

[0129] <Optional ingredients> The curable composition according to the present invention may further contain any additive components, as long as they do not impair its properties. For example, components such as anti-aging agents, rust inhibitors, fungicides, colorants, surfactants, rheology modifiers, UV absorbers, fluorescent agents, abrasives, fragrances, and fillers can be selected.

[0130] <Method for producing a curable composition> The curable composition of the present invention can be manufactured by conventionally known methods. For example, the curable composition according to the present invention can be obtained by weighing predetermined amounts of component (A) and component (B), as well as other optional components, and mixing them using a mixing means such as a mixer. At this time, the mixing conditions are not particularly limited, but the mixing temperature is preferably 10 to 70°C, more preferably 20 to 50°C, and most preferably room temperature (25°C), and the mixing time is preferably 0.1 to 5 hours, more preferably 30 minutes to 3 hours, and most preferably around 60 minutes.

[0131] [Method for forming a coating and cured coating] The method for forming a film of the curable composition of the present invention is not particularly limited, but examples include the following method. First, an appropriate amount of the curable composition of the present invention is impregnated into fibers such as a brush, sponge, or cloth, and this is spread on the surface of a substrate by hand (coating step). Then, a film of the curable composition (cured film) is formed by the reaction of component (A) and component (B) (reaction step). At this time, if the curable composition further contains component (C), the above reaction is promoted by component (C), and the film of the curable composition is formed more efficiently.

[0132] In other words, another aspect of the present invention provides a method for forming a coating, which includes applying the curable composition to the surface of a substrate and curing it on the surface of the substrate.

[0133] Furthermore, if the curable composition further contains component (D), it is preferable to impregnate the fibers with an appropriate amount of the curable composition of the present invention, spread it on the substrate surface by hand, and then volatilize component (D) by natural drying, drying using a dryer, etc. (drying step). In other words, a film-forming method according to another embodiment of the present invention preferably further includes applying a curable composition containing component (D) to the substrate surface, and then drying the organic solvent as component (D).

[0134] Furthermore, after the above coating step, the coated surface may be wiped with another dry cloth or microfiber cloth to remove any excess curable composition (finishing step). In other words, a film-forming method according to another embodiment of the present invention preferably further includes wiping the coated surface after applying the curable composition to the substrate surface (wiping off any excess curable composition).

[0135] Furthermore, according to another aspect of the present invention, a cured film is provided obtained by curing the curable composition. The cured film formed using the above curable composition has excellent water repellency and slip resistance, and also exhibits good film stability in the initial stages of application.

[0136] The thickness of the coating (cured film) of the curable composition of the present invention is not particularly limited, but is preferably in the range of 0.01 to 500 μm, more preferably in the range of 0.1 to 300 μm, and even more preferably in the range of 0.5 to 100 μm. By setting the thickness of the coating of the curable composition within the above range, good water repellency can be maintained. Therefore, in the coating step of the coating formation method according to the present invention, it is preferable to appropriately adjust the thickness of the coating so that the thickness of the coating when dry is within the above range.

[0137] Examples of the substrate include metal, glass, ceramics, plastic, and fiber, with metal, glass, and plastic being preferred. Specifically, the metal may be a metal member in the shape of a rod, sphere, or plate. Furthermore, the metal may specifically be a steel plate (unpainted metal steel plate) or an exterior steel plate (painted steel plate). The curable composition of the present invention is suitably used for forming a film on the surface of a substrate selected from the group consisting of metal, glass, ceramics, plastic, fiber, steel plate, and exterior steel plate. More preferably, the curable composition of the present invention is used to form a film on the surface of a substrate selected from the group consisting of plastic, steel plate, and exterior steel plate.

[0138] Examples of the aforementioned plastics include (meth)acrylic resin, polycarbonate, polybutylene terephthalate, polyphenylene sulfide, polyethylene terephthalate, polyethylene naphthalate, acrylonitrile-butadiene-styrene resin, styrene-methacrylic resin, polystyrene, polyethylene, polypropylene, polyvinyl chloride, polyester, polyurethane, and the like.

[0139] Of these, the curable composition of the present invention is preferred from the viewpoint of being able to form a cured film with excellent adhesion to steel plates (unpainted metal steel plates), painted steel plates (painted steel plates), (meth)acrylic resin, polycarbonate, polybutylene terephthalate, polyethylene terephthalate, polyphenylene sulfide, polyethylene, polypropylene, styrene-methacrylic resin, etc. The term "(meth)acrylic" includes both acrylic and methacrylic.

[0140] [Application] The main uses of the curable composition of the present invention include, for example, antifouling coatings for items installed outdoors for long periods, such as automobiles, motorcycles, bicycles, construction machinery, agricultural machinery, aircraft, railway vehicles, ships, roofs and exterior walls of buildings, window glass, bridge girders, road traffic signs, traffic lights, billboards, vending machines, and solar panels; and antifouling coatings for the exteriors of equipment and parts. In particular, it is preferably used as an antifouling coating for automobiles, motorcycles, bicycles, construction machinery, agricultural machinery, aircraft, railway vehicles, and ships. For automotive antifouling coatings, for example, it is used as a coating agent for vehicles, headlamps, aluminum wheels, seats, interior parts, etc.

[0141] [Goods] Furthermore, according to another aspect of the present invention, articles having a cured coating obtained by curing the curable composition are also provided. Examples of such articles include automobiles, motorcycles, bicycles, railway vehicles, solar panels, vending machines, and buildings. That is, according to another aspect of the present invention, articles having a cured coating obtained by curing the curable composition are also provided, and such articles are selected from the group consisting of automobiles, motorcycles, bicycles, railway vehicles, solar panels, vending machines, and buildings. [Examples]

[0142] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, operations and tests were carried out in an environment of 25°C and 55% RH. Unless otherwise specified, concentration and % represent mass concentration and mass % respectively, and ratios represent mass ratios unless otherwise specified.

[0143] <Preparation of curable composition> Each component was weighed to achieve the composition shown in Table 1 (unit: parts by mass), and mixed in a mixer at room temperature for 60 minutes to obtain a curable composition. Detailed addition amounts (contents) are shown in Table 1, and all values ​​in Table 1 are expressed in parts by mass. A blank space indicates that the corresponding component was not added.

[0144] • Regarding the synthesis of polysiloxazan 1

[0145] [ka]

[0146] (In the formula, Me represents a methyl group, and n is 40. The same applies hereafter.)

[0147] The inside of a four-necked glass flask equipped with a stirrer, gas feed tube, thermometer, and reflux condenser was purged with nitrogen. While ensuring no outside air was introduced by passing nitrogen gas through the open end of the reflux condenser, 65.9 g (0.300 mol) of n-hexyltrichlorosilane (chlorosilane compound (5)) was added, and the kinematic viscosity at 25°C was 60 mmHg. 2 45.0 g (0.015 mol) of the silanol-modified silicone compound at both ends of / s (the above-mentioned OH-modified silicone oil (4)) and 295.6 g of cyclopentyl methyl ether (hereinafter referred to as "CPME") as a solvent were charged and stirred at room temperature for 1 hour. 42.3 g (0.300 mol) of methyl vinyl dichlorosilane (the above-mentioned chlorosilane compound (7)) and 76.8 g of CPME were added and stirred to obtain a homogeneous reaction solution. The reaction solution was cooled to below 10°C, and ammonia gas was fed into the reaction solution through a feed tube. The ammonia feed was continued for 6 hours while cooling the reaction solution so that its temperature did not exceed 30°C. The obtained reaction solution was filtered, and the residue was washed with CPME. The filtrate was concentrated, and 110.9 g of toluene was added to the resulting concentrate to obtain 221.8 g of a colorless, transparent solution.

[0148] Next, the inside of a four-necked glass flask equipped with a stirrer, thermometer, reflux condenser, and dropping funnel was purged with nitrogen, and 16.9 g (0.086 mol) of mercaptopropyltrimethoxysilane (the above mercapto group-containing silane compound (9)) and 16.9 g of toluene were charged and heated to 90°C. To this, 80.0 g of the colorless transparent solution obtained above and a mixture of 0.168 g (0.000874 mol) of 2,2'-azobis(2-methylbutyronitrile) were added from the dropping funnel over 2.5 hours, and the mixture was stirred for 1 hour while maintaining the same temperature to obtain polysiloxane 1.

[0149] The obtained polysiloxazan 1 was subjected to solvent replacement by adding isoparaffin solvent (IP Solvent 1620, manufactured by Idemitsu Kosan Co., Ltd., hereafter the same) to adjust the non-volatile component content to 50%. This was designated as composition 1 of polysiloxazan 1. When the obtained composition 1 was subjected to IR analysis, a peak originating from the Si-N-Si structure (932 cm⁻¹) was observed. -1 , 1,190cm -1 ), peak originating from Si-O-Si (1,092 cm²) -1 ), and a peak (3,391 cm) originating from NH. -1 ) was observed. Furthermore, GPC analysis confirmed the formation of the target polysiloxane 1, which has a weight-average molecular weight of 5,300 and a number-average molecular weight of 2,600. The IR spectrum is shown in Figure 1.

[0150] <(A) Component and comparative component> A1: Contains constituent units a to d represented by equation (1), where the molar ratio of the constituent units a:b:c:d is 18:4:16:1, m is 0, n is 40, R 1 is an n-hexyl group, and R 2 This composition (solids content 20% by mass) is obtained by dissolving and diluting polysiloxane 1, which has a methyl group, a weight-average molecular weight of 5,300, and a number-average molecular weight of 2,600, with isoparaffin solvent (IP Solvent 1620, manufactured by Idemitsu Kosan Co., Ltd.). In the table, the amount (content) of the component is listed only by mass of the solids (resin component), and the isoparaffin solvent is also listed in column (D2). A'1: The active ingredient (solid content) is 100% organic polysilazane compound (KiON® HTA1500 slow cure, manufactured by AZ Electronic Materials Co., Ltd.) <(B) Component and comparative component> B1: Kinematic viscosity at 25°C is 25 mm² 2 A silicone compound (silicone oligomer) having methoxy groups in its side chain and at both ends (manufactured by Shin-Etsu Chemical Co., Ltd., KR-500) B2: Kinematic viscosity at 25℃ is 14 mm³ 2 / s, and R in equation (10) 4 , R 5 , R 8 and R 9 Each of these is a methoxy group, and R 6 and R 7 Each of these is a methyl group, X 1 and X 2 These are silicone compounds (manufactured by Shin-Etsu Chemical Co., Ltd., X-40-2090) each containing a methoxy group. B3: Kinematic viscosity at 25℃: 60 mm² 2 / s, and R in equation (10) 4 ~R 9 Each of these is a methyl group, X 1 and X 2 These are hydroxyl groups, and are silicone compounds (manufactured by Shin-Etsu Chemical Co., Ltd., KF-9701). B4: Kinematic viscosity at 25℃ is 35 mm² 2 / s, and R in equation (10) 4 ~R 9 Each of these is a methyl group, X 1 and X 2 These are silicone compounds having carbinol groups represented by -CH2CH2CH2OCH2CH2OH (manufactured by Shin-Etsu Chemical Co., Ltd., X-22-160AS). B5: Kinematic viscosity at 25℃ is 40 mm² 2 / s, and R in equation (10) 4 ~R 9 Each of these is a methyl group, X 1 and X 2Either one of them is a carbinol group represented by -CH2CH2CH2OCH2CH2OH, and X 1 and X 2 Of these, the remaining group is a methyl group (i.e., one end is a carbinol group represented by -CH2CH2CH2OCH2CH2OH, and the other end is a methyl group), a silicone compound (manufactured by Shin-Etsu Chemical Co., Ltd., X-22-170BX). B6: Kinematic viscosity at 25℃ is 130 mmHg 2 / s, and R in equation (10) 4 ~R 9 Each of these is a methyl group, X 1 and X 2 Either one of them is a carbinol group represented by formula (11), and X 1 and X 2 Of these, the remainder is a methyl group (where R in formula (11) 10 This is -CH2CH2CH2OCH2-, and R 11 and R 12 Both are CH2, and R 13 (represented by -CH2CH3), a silicone compound (manufactured by Shin-Etsu Chemical Co., Ltd., X-22-176DX) B7: Kinematic viscosity at 25℃ is 8 mm 2 / s, and R in equation (10) 4 ~R 9 Each of these is a methyl group, X 1 and X 2 These are silicone compounds (Momentive Performance Materials, XC96-C7123) that each contain a hydroxyl group. B'1: Kinematic viscosity at 25℃ is 55 mm 2 / s, and R in equation (10) 4 ~R 9 Each of these is a methyl group, X 1 and X 2 These are silicone compounds (manufactured by Shin-Etsu Chemical Co., Ltd., X-22-161B) that each contain an amino group. <(C) component> C1: Organotitanium compound (manufactured by Shin-Etsu Chemical Co., Ltd., D-25) C2: Aluminum chelate compound (manufactured by Shin-Etsu Chemical Co., Ltd., DX-9740) <(D) component> D1: Isoparaffinic solvent containing isododecane (Marukazol®, manufactured by Maruzen Petrochemical Co., Ltd.) D2: Isoparaffinic solvent (Idemitsu Kosan Co., Ltd., IP Solvent 1620).

[0151] Each characteristic was evaluated under the following conditions.

[0152] <Preparation of test specimens> Each curable composition was thoroughly soaked into a nonwoven fabric and thinly spread by hand onto the surface of a black painted board (material: SPCC-SD, dimensions: 0.8mm x 70mm x 150mm, product of Asahi B-Techno Co., Ltd.). Next, the excess curable composition was wiped off with a dry microfiber cloth, and three types of test specimens were prepared by curing them in a 25°C, 55%RH environment for 30 minutes, 24 hours, or 168 hours, respectively.

[0153] <Evaluation of water contact angle> One drop (0.005 mL) of deionized water was dropped onto the surface of each test specimen prepared in the <Preparation of Test Specimens> section above, after being allowed to stand for 24 hours. The contact angle of the water with respect to the substrate (test specimen) surface was measured using a contact angle meter (DM-500, manufactured by Kyowa Interface Science Co., Ltd.) and the water contact angle was evaluated. The results are shown in Table 1. The water contact angle of the curable composition of the present invention is preferably 97 degrees or higher, and more preferably 99 degrees or higher. On the other hand, there is no particular upper limit, but it should be 150 degrees or lower.

[0154] <Evaluation of coating stability in the initial stages of application> One drop (0.005 mL) of deionized water was dropped onto the surface of each test specimen prepared in the <Preparation of Test Specimens> section above, after being allowed to stand for 30 minutes or 24 hours to cure. The contact angle of the water with respect to the substrate (test specimen) surface was measured using a contact angle meter (DM-500, manufactured by Kyowa Interface Science Co., Ltd.) and the water contact angle was evaluated. The initial film stability was then calculated using the following formula, and the results are shown in Table 1. The initial film stability (%) is preferably 97% or higher from the viewpoint of initial curing stability. On the other hand, there is no particular upper limit, but it should be 120% or lower.

[0155]

number

[0156] <Method for evaluating the angle of descent> One drop (approximately 0.05 mL) of deionized water was dropped onto the surface of each test specimen prepared in the <Preparation of Test Specimens> section above, after being allowed to stand for 168 hours. From this state, the test specimen was gradually tilted, and the angle at which the water droplet began to flow (sliding angle) was measured. This sliding angle was evaluated as an indicator of sliding properties (water sliding properties). The results are shown in Table 1. A desirable sliding angle for the sliding properties of the curable composition of the present invention is 20 degrees or less, more preferably 18 degrees or less. On the other hand, there is no particular lower limit, but it should be 5 degrees or more.

[0157] [Table 1]

[0158] According to the results of Examples 1 to 9 in Table 1, the curable composition according to the present invention can form a coating with excellent water repellency and slipperiness, and also exhibits excellent coating stability in the initial stages of application.

[0159] Furthermore, Comparative Example 1 in Table 1 is a curable composition that excludes (does not contain) component (B) of the present invention, and it can be seen that this composition is inferior in terms of film stability in the initial stages of application. Furthermore, Comparative Example 2 is a curable composition that uses an organic polysilazane compound that is not component (A) of the present invention, and it can be seen that this curable composition is inferior in terms of sliding angle. Moreover, Comparative Example 3 is a curable composition that uses a terminally amino-modified reactive silicone compound that is not component (B) of the present invention, and it can be seen that this curable composition is inferior in terms of film stability in the initial stages of application and sliding angle. [Industrial applicability]

[0160] According to the present invention, it is possible to provide a curable composition that can form a coating with excellent water repellency and slipperiness, and furthermore, has excellent coating stability in the initial stages of application. Therefore, the present invention is industrially useful as it can be used as a curable composition in fields such as automobiles.

[0161] This application is based on Japanese Patent Application No. 2021-043634, filed on 17 March 2021, and its disclosures are referenced and incorporated as a whole.

Claims

1. The material comprises a polysiloxane compound (A) having a weight-average molecular weight of 3,000 to 10,000 and a number-average molecular weight of 2,000 to 8,000, and a silicone compound (B) having a hydroxyl group. The mixture contains 0.1 to 500 parts by mass of component (B) per 100 parts by mass of component (A), The aforementioned component (A) includes constituent units a to d represented by formula (1), and the molar ratio a:b:c:d of each constituent unit is 5 to 15:1 to 3:6 to 10:0.5 to 1.

5. A curable composition in which component (B) is a silicone compound represented by formula (10). 【Chemistry 1】 (In formula (1), R １ R represents an unsubstituted monovalent alkyl group having 3 to 10 carbon atoms. ２ and R ３ Each of these independently represents an unsubstituted monovalent alkyl group having 1 to 6 carbon atoms. m is 0 or 1, and n is an integer between 30 and 100. 【Chemistry 2】 (In formula (10), R4 to R9 each independently represent an alkyl group having 1 to 20 carbon atoms, X1 and X2 each independently represent an alkyl group having 1 to 20 carbon atoms, a hydroxyl group, or a carbinol group, and at least one of X1 and X2 is a hydroxyl group or a carbinol group. nB is 5 to 850.)

2. The curable composition according to claim 1, wherein in formula (10), R4 to R9 each independently represent an alkyl group having 1 to 5 carbon atoms.

3. The curable composition according to claim 1 or 2, wherein the carbinol group as X1 or X2 in formula (10) is represented by formula (11) or formula (12). 【Transformation 3】 (In formula (11), R10, R11, and R12 each independently represent an alkylene group having 1 to 20 carbon atoms or an oxyalkylene group having 1 to 20 carbon atoms, and R13 represents an alkyl group having 1 to 20 carbon atoms.) 【Chemistry 4】 (In formula (12), R 14 and R 15 each independently represent an alkylene group having 1 to 10 carbon atoms.)

4. The curable composition according to any one of claims 1 to 3, wherein m of component (A) is 0.

5. The R of component (A) １ The curable composition according to any one of claims 1 to 4, wherein is an unsubstituted monovalent alkyl group having 4 to 8 carbon atoms.

6. The aforementioned component (B) has a kinematic viscosity of 1 to 500 mm at 25°C. ２ A curable composition according to any one of claims 1 to 5, wherein the ratio is / s.

7. The curable composition according to any one of claims 1 to 6, comprising 1 to 300 parts by mass of component (B) with respect to 100 parts by mass of component (A).

8. The curable composition according to any one of claims 1 to 7, further comprising a catalyst as component (C).

9. The curable composition according to claim 8, wherein component (C) comprises one or more compounds selected from the group consisting of organotin compounds, organotitanium compounds, organoaluminum compounds, aluminum salt compounds, organozinc compounds, organozirconium compounds, inorganic acid compounds, organic acid compounds, inorganic base compounds, and organic base compounds.

10. The curable composition according to any one of claims 1 to 9, further comprising an organic solvent as component (D).

11. The curable composition according to claim 10, wherein the component (D) is an aromatic hydrocarbon solvent or an aliphatic hydrocarbon solvent.

12. The curable composition according to claim 10 or 11, comprising 200 to 15,000 parts by mass of component (D) per 100 parts by mass of component (A).

13. A curable composition according to any one of claims 1 to 12, used for forming a coating on the surface of a substrate selected from the group consisting of metals, glass, ceramics, plastics, fibers, steel sheets, and exterior steel sheets.

14. A cured film obtained by curing a curable composition according to any one of claims 1 to 13.

15. An article having a cured coating as described in claim 14, The aforementioned articles are selected from the group consisting of automobiles, motorcycles, bicycles, railway vehicles, solar panels, vending machines, and buildings.

16. A method for forming a coating, comprising applying a curable composition according to any one of claims 1 to 12 to a substrate surface and curing it on the substrate surface.

Images