Surface treatment agent composition, pellets, and articles

Abstract

The present invention provides a non-fluorine-based surface treatment agent composition that contains an organosilane compound having a high biobased content and is capable of forming a cured coating film that is excellent in water repellency and abrasion resistance, pellets containing the composition, and articles that have been surface-treated with the composition. The present invention relates to a method for producing an organosilane composition comprising: an organosilane compound (α) and / or a partially reacted condensate thereof; and a solvent. the organosilane compound (α) is a non-fluorine-based compound having one or more linear, branched or cyclic monovalent hydrocarbon groups having 3 to 60 carbon atoms, which may contain one or more selected from O, S, N and Si, and a reactive silyl group, and has a biobased content of 50% or more as measured by radiocarbon dating in accordance with ASTM D6866; the solvent is selected from alcohol-based, ether-based, ketone-based, ester-based, carbonate-based, siloxane-based, and hydrocarbon-based solvents; A surface treatment composition comprising a material that does not contain fluorine atoms.

Description

[Technical Field]

[0001] The present invention relates to a surface treatment agent composition, and more particularly to a non-fluorinated surface treatment agent composition capable of forming a cured coating film that has a high biobased content and excellent water repellency and abrasion resistance, a pellet containing the surface treatment agent composition, and an article that has been surface-treated with the surface treatment agent composition. [Background technology]

[0002] Touch panel displays, such as those used in smartphones and in-vehicle displays, and lenses for eyeglasses, are often in direct contact with fingers or cheeks, creating the problem of easy staining with sebum and other contaminants. To improve appearance and visibility, there is an increasing demand for technologies that make the display surface less susceptible to fingerprints and easier to clean. The development of materials that can meet these demands is highly desirable. A common solution is to provide an anti-fouling layer.

[0003] In general, surface treatment agent compositions containing fluoropolyether group-containing compounds have very low surface free energy and can therefore impart water and oil repellency, chemical resistance, lubricity, release properties, stain resistance, and other properties to articles. Taking advantage of these properties, they are widely used industrially as water, oil, and stain repellents for paper and textiles, lubricants for magnetic recording media, oil repellents for precision instruments, release agents, cosmetics, protective films, and more. However, these properties also mean that they are non-sticky and non-adhesive to other substrates, and even if they can be applied to the surface of a substrate, it has been difficult to achieve adhesion of the coating.

[0004] Silane coupling agents are well known for bonding organic compounds to the surfaces of substrates such as glass and cloth, and are widely used as coating agents for various substrate surfaces. Silane coupling agents contain an organic functional group and a reactive silyl group (generally a hydrolyzable silyl group such as an alkoxysilyl group) in each molecule. The hydrolyzable silyl group undergoes a self-condensation reaction in the presence of moisture in the air to form a hardened coating. This coating is durable and strong because the hydrolyzable silyl group chemically and physically bonds with the surface of glass, metal, etc.

[0005] Therefore, compositions have been disclosed that use fluoropolyether group-containing polymers in which hydrolyzable silyl groups have been introduced into fluoropolyether group-containing compounds, which can form coatings that easily adhere to substrate surfaces and have water and oil repellency, chemical resistance, lubricity, releasability, antifouling properties, etc. on the substrate surfaces (Patent Documents 1 to 6: JP-A Nos. 2008-534696, 2008-537557, JP-A Nos. 2012-072272, 2012-157856, 2013-136833, and 2015-199906).

[0006] Furthermore, fluorine-containing compounds, such as perfluorooctanoic acid (PFOA), tend to be highly persistent and accumulate in nature. In recent years, a wide range of fluorine-containing compounds have been categorized as per- or polyfluoroalkyl compounds (PFAS), and PFAS regulations are expected to restrict the use, sale, and discharge of fluorine-containing compounds. Conventional fluoropolyether group-containing compounds and fluoropolyether group-containing polymers also fall under the category of per- or polyfluoroalkyl compounds (PFAS). Therefore, there is a demand for the development of non-fluorine-based surface treatment compositions made from materials that do not contain fluorine atoms.

[0007] Furthermore, as part of efforts to achieve the Sustainable Development Goals (SDGs), there is a growing need for bio-based materials that are not only fluorine-free but also made from biological raw materials rather than fossil fuel-derived materials.

[0008] However, the inventors have found through their investigations that conventional surface treatment agent compositions containing non-fluorinated compounds containing reactive silyl groups such as hydrolyzable silyl groups have a low biobased content, and furthermore, the water repellency and abrasion resistance of the cured coatings formed are sometimes insufficient. [Prior art documents] [Patent documents]

[0009] [Patent Document 1] Special Publication No. 2008-534696 [Patent Document 2] Special Publication No. 2008-537557 [Patent Document 3] Japanese Patent Application Laid-Open No. 2012-072272 [Patent Document 4] Japanese Patent Application Laid-Open No. 2012-157856 [Patent Document 5] Japanese Patent Application Laid-Open No. 2013-136833 [Patent Document 6] Japanese Patent Application Laid-Open No. 2015-199906 Summary of the Invention [Problem to be solved by the invention]

[0010] The present invention has been made in view of the above circumstances, and has an object to provide a non-fluorine-based (i.e., the material (compound) contained in the composition does not contain fluorine atoms) surface treatment agent composition that has a high biobased content and contains a non-fluorine-based (i.e., does not contain fluorine atoms in the molecule) organosilane compound having a reactive silyl group such as a hydrolyzable silyl group, and that is capable of forming a cured coating that is excellent in water repellency and abrasion resistance; pellets containing the surface treatment agent composition; and articles that have been surface-treated with the surface treatment agent composition. [Means for solving the problem]

[0011] As a result of extensive research to achieve the above object, the present inventors have found that An organosilane compound (α) and / or a partially reacted condensate thereof, and a solvent, the organosilane compound (α) is a non-fluorine-based compound having at least one linear, branched or cyclic monovalent hydrocarbon group having 3 to 60 carbon atoms, which may contain at least one atom selected from the group consisting of oxygen, sulfur, nitrogen and silicon atoms, and a reactive silyl group, and having a biobased content of 50% or more as measured by radiocarbon dating in accordance with ASTM D6866; the solvent is selected from an alcohol-based solvent, an ether-based solvent, a ketone-based solvent, an ester-based solvent, a carbonate-based solvent, a siloxane-based solvent, and a hydrocarbon-based solvent; The present inventors have found that a surface treatment agent composition made of a material that does not contain fluorine atoms has a high biobased content, which reduces the burden on the environment, and is capable of forming a cured coating that is excellent in water repellency and abrasion resistance, i.e., it can solve the problems of the prior art described above, and have thus completed the present invention.

[0012] Accordingly, the present invention provides the following surface treatment agent composition, pellets containing the surface treatment agent composition, and articles surface-treated with the surface treatment agent composition. [1] An organosilane compound (α) and / or a partially reacted condensate thereof, and a solvent, the organosilane compound (α) is a non-fluorine-based compound having at least one linear, branched or cyclic monovalent hydrocarbon group having 3 to 60 carbon atoms, which may contain at least one atom selected from the group consisting of oxygen, sulfur, nitrogen and silicon atoms, and a reactive silyl group, and having a biobased content of 50% or more as measured by radiocarbon dating in accordance with ASTM D6866; the solvent is selected from an alcohol-based solvent, an ether-based solvent, a ketone-based solvent, an ester-based solvent, a carbonate-based solvent, a siloxane-based solvent, and a hydrocarbon-based solvent; A surface treatment composition comprising a material that does not contain fluorine atoms. [2] The surface treatment agent composition according to [1], wherein in the organosilane compound (α), the monovalent hydrocarbon group is linear or branched. [3] The surface treatment agent composition according to [1] or [2], wherein the organosilane compound (α) has two or more of the monovalent hydrocarbon groups. [4] The surface treatment agent composition according to [3], wherein in the organosilane compound (α), two or more of the monovalent hydrocarbon groups are bonded to the same atom. [5] The surface treatment agent composition according to [4], wherein in the organosilane compound (α), the same atom to which two or more of the monovalent hydrocarbon groups are bonded is a carbon atom, a nitrogen atom, or a silicon atom. [6] The surface treatment agent composition according to any one of [3] to [5], wherein the organosilane compound (α) has two or more of the monovalent hydrocarbon groups that are the same. [7] The surface treatment agent composition according to any one of [1] to [6], wherein in the organosilane compound (α), the monovalent hydrocarbon group has 8 to 40 carbon atoms. [8] The organosilane compound (α) is represented by the following general formula (1): [ka] (In the formula, R 1 are monovalent hydrocarbon groups having 3 to 32 carbon atoms, which may independently contain at least one atom selected from oxygen, sulfur, nitrogen, and silicon atoms, and which may be linear, branched, or cyclic, or a combination thereof; R 2represents a hydrogen atom, a halogen atom, a hydroxyl group, a siloxy group, an amino group, a thiol group, or a monovalent hydrocarbon group having 1 or 2 carbon atoms; U represents a carbon atom, a silicon atom, a nitrogen atom, or a trivalent or tetravalent organic group; V independently represents a single bond or a divalent hydrocarbon group which may contain at least one atom selected from an oxygen atom, a nitrogen atom, and a sulfur atom; Z independently represents a single bond, a carbon atom, a silicon atom, a nitrogen atom, a sulfur atom, or a trivalent to octavalent organic group; Y independently represents a divalent hydrocarbon group which may contain at least one atom selected from an oxygen atom, a nitrogen atom, a sulfur atom, and a silicon atom; A independently represents a monovalent reactive silyl group; k1 is 2 or 3, k2 is 0 or 1, k3 is 1 or 2, k1 + k2 + k3 is 3 or 4, and m is an integer from 1 to 7. The surface treatment agent composition according to any one of [1] to [7], which is represented by the following formula: [9] In the above formula (1), R 1 But the following formula [ka] (In the formula, R Aare independently a monovalent hydrocarbon group having 3 to 32 carbon atoms which may be linear, branched, or cyclic, or a combination thereof; Q are independently an oxygen atom, a sulfur atom, a divalent cyclic hydrocarbon group having 6 to 8 carbon atoms, a diorganosilylene group, a silalkylene structure, a silarylene structure, a linear organopolysiloxane residue having 2 to 10 silicon atoms or a branched or cyclic organopolysiloxane residue having 3 to 10 silicon atoms, a carbonyl (ketone) group, an ester group, a carbonate group, a sulfinyl group, a sulfonyl group, a thioester group, a thiocarbonate group, a thiocarbamate group, an amino group, an amide group, a carbamate group, a urea group, a methyl ... Q' is independently a trivalent group selected from the group consisting of a nitrogen atom, a trivalent cyclic hydrocarbon group having 6 to 8 carbon atoms, a linear trivalent organopolysiloxane residue having 2 to 10 silicon atoms or a branched or cyclic trivalent organopolysiloxane residue having 3 to 10 silicon atoms, a trivalent amide group, and a trivalent nitrogen-containing heterocyclic group; Q" is independently a tetravalent group selected from the group consisting of a silicon atom, a tetravalent cyclic hydrocarbon group having 6 to 8 carbon atoms, and a linear trivalent organopolysiloxane residue having 2 to 10 silicon atoms or a branched or cyclic trivalent organopolysiloxane residue having 3 to 10 silicon atoms; R B are independently a single bond or a divalent hydrocarbon group having 1 to 32 carbon atoms, which may be linear, branched, or cyclic; R C are independently R A or a hydrogen atom, and p is an integer of 0 to 10. However, the total number of carbon atoms in each structure is 32 or less. [8] The surface treatment agent composition according to [8], wherein the group is any one of the groups represented by the following formula:

[10] In the above formula (1), A is represented by the following general formula (2) or (3): [ka] (In the formula, R is independently an alkyl group having 1 to 4 carbon atoms or a phenyl group, X is independently a hydroxyl group or a hydrolyzable group, and n is an integer of 1 to 3.) [ka] (In the formula, n' is a number from 0 to 3, and n' is (3-n') / 2.) The surface treatment agent composition according to [8] or [9], wherein the group is represented by the following formula:

[11] The surface treatment agent composition according to

[10] , wherein in the above formula (2), X is selected from the group consisting of a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an alkoxyalkoxy group having 2 to 10 carbon atoms, an acyloxy group having 1 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, a halogen group, and a dialkylamino group having 2 to 10 carbon atoms.

[12] The surface treatment agent composition according to any one of [8] to

[11] , wherein in the above formula (1), Y is a group selected from the group consisting of an alkylene group having 1 to 20 carbon atoms which may contain at least one atom selected from oxygen atoms, nitrogen atoms, and sulfur atoms, an alkylene group having 1 to 10 carbon atoms which contains an arylene group having 6 to 8 carbon atoms, a divalent group in which alkylene groups having 1 to 8 carbon atoms are bonded to each other via a diorganosilylene group, a silalkylene structure, a silarylene structure, or a nitrogen-containing heterocyclic group, and a divalent group in which an alkylene group having 1 to 10 carbon atoms is bonded to a bond of a linear organopolysiloxane residue having 2 to 10 silicon atoms or a branched or cyclic organopolysiloxane residue having 3 to 10 silicon atoms.

[13] In the above formula (1), Z is a single bond, a carbon atom, a silicon atom, a nitrogen atom, a trivalent or tetravalent cyclic hydrocarbon group having 6 to 8 carbon atoms, -SiR 3 =(R 3 is a hydroxyl group, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms), -CR 4 =(R 4

[13] The surface treatment agent composition according to any one of [8] to

[12] , wherein ⁢ ⁢ represents a trivalent group represented by the formula (I) (wherein ⁢ ⁢ represents a hydrogen atom, a hydroxyl group, or an alkyl group having 1 to 3 carbon atoms), a trivalent to octavalent group selected from the group consisting of a linear organopolysiloxane residue having 2 to 10 silicon atoms or a branched or cyclic organopolysiloxane residue having 3 to 10 silicon atoms, a trivalent amide group, a trivalent carbamate group, a trivalent or tetravalent urea group, and a trivalent to octavalent nitrogen-containing heterocycle-containing group.

[14] The surface treatment agent composition according to any one of [8] to

[13] , wherein in the above formula (1), U is a trivalent or tetravalent group selected from the group consisting of a carbon atom, a silicon atom, a nitrogen atom, a trivalent or tetravalent cyclic hydrocarbon group having 6 to 8 carbon atoms, a linear trivalent or tetravalent organopolysiloxane residue having 2 to 10 silicon atoms or a branched or cyclic trivalent or tetravalent organopolysiloxane residue having 3 to 10 silicon atoms, a trivalent amide group, a trivalent carbamate group, a trivalent or tetravalent urea group, and a trivalent or tetravalent nitrogen-containing heterocycle-containing group.

[15] The surface treatment agent composition according to any one of [1] to

[14] , wherein the solvent is selected from the group consisting of ether-based solvents, ketone-based solvents, ester-based solvents, siloxane-based solvents, and hydrocarbon-based solvents.

[16] The surface treatment agent composition according to any one of [1] to

[15] , wherein the biobased content of the solvent is 50% or more as measured by radiocarbon dating in accordance with ASTM D6866.

[17] The surface treatment agent composition according to any one of [1] to

[16] , wherein the proportion of the organosilane compound (α) and / or the partially reacted condensate thereof is 0.05 to 70 mass% in the total of the organosilane compound (α) and / or the partially reacted condensate thereof and the solvent.

[18] The surface treatment agent composition according to any one of [1] to

[17] , further comprising at least one non-fluorine-based material selected from the group consisting of paraffin oil, polyol ester oil, silicone oil, catalyst, transition metal, halide ion, silane coupling agent, and compound containing an atom having an unshared electron pair in the molecular structure.

[19] The surface treatment agent composition according to any one of [1] to

[18] , which is used as an antifouling coating agent or a waterproof coating agent.

[20] The surface treatment agent composition according to any one of [1] to

[19] , which is for vacuum deposition. 〔twenty one〕 The surface treatment agent composition according to any one of [1] to

[19] , which is for spray coating, dip coating, spin coating, wipe coating, squeegee coating, die coating, inkjet coating, flow coating, roll coating, cast coating, Langmuir-Blodgett coating, or gravure coating. 〔twenty two〕 A pellet containing the surface treatment agent composition according to any one of [1] to

[20] . 〔twenty three〕 An article comprising a substrate and a layer formed on the surface of the substrate from the surface treatment agent composition according to any one of [1] to

[21] . 〔twenty four〕 The article according to

[23] , wherein the article is an optical element. 〔twenty five〕 The article according to

[23] , wherein the article is a lens.

[26] The article according to

[23] , wherein the article is a display. [Effects of the Invention]

[0013] The surface treatment composition of the present invention can form a cured coating film having excellent water repellency and abrasion resistance, and therefore an article having a surface treatment layer formed using the surface treatment composition has excellent water repellency and abrasion resistance. Furthermore, the surface treatment composition of the present invention has a low environmental impact because it contains a silane compound having a high biobased content. DETAILED DESCRIPTION OF THE INVENTION

[0014] The surface treatment agent composition of the present invention contains, as essential components, an organosilane compound (α) of a specific structure having a biobased degree of at least a specific level and / or a partial reaction condensate thereof, and a specific solvent, and is made of a material that does not contain fluorine atoms.

[0015] The first essential component of the surface treatment agent composition of the present invention is an organosilane compound (α) and / or a partially reacted condensate thereof. The organosilane compound (α) is a non-fluorine-containing compound having at least one linear, branched, or cyclic monovalent hydrocarbon group having 3 to 60 carbon atoms, which may contain at least one atom selected from oxygen, sulfur, nitrogen, and silicon, and a reactive silyl group, and further has a biobased content of 50% or more as measured by radiocarbon dating in accordance with ASTM D6866. The organosilane compound (α) may be a mixture of one or more of these compounds.

[0016] The organosilane compound (α) has a linear, branched, or cyclic monovalent hydrocarbon group having 3 to 60 carbon atoms that exhibits water repellency and a reactive silyl group that exhibits reactivity with a substrate, and therefore a cured coating film formed on the surface of a substrate using the surface treatment agent composition exhibits excellent water repellency and abrasion resistance.

[0017] The organosilane compound (α) has a biobased content of 50% or more as measured by radiocarbon dating in accordance with ASTM D 6866. When the biobased content is in the above range or higher, the organosilane compound (α) is superior in that it imposes a smaller burden on the environment than surface treatment agent compositions produced using raw materials derived from fossil fuels. The biobased content of the organosilane compound (α) is more preferably 60% or more, and particularly preferably 70% or more. When the biobased content is in the above range or more, the burden on the environment is further reduced.

[0018] Bio-based content is a value that expresses the proportion of biologically derived carbon in the total carbon in a material. 14 Amount reflecting C concentration 14 On the other hand, materials derived from fossil fuels contain carbon dioxide over a long period of time. 14 C has completely decayed, 14 The concentration of C is zero. Therefore, 14 The biobased content can be calculated by measuring the C concentration (radiocarbon dating method).

[0019] In this specification, the bio-based content was measured under the following conditions. Measurement: Compliant with ASTM D6866 Analysis: Compliant with ASTM D6866-22 (METHOD B) Measurement method: The sample was sealed in a tin cup, gasified with CO2 using an elemental analyzer (elementar vario MICRO CUBE), purified in a glass gas purification line (Koshin Chemical Manufacturing Co., Ltd.), and graphite was produced by hydrogen reduction in a graphite reduction ring furnace (Koshin Chemical Manufacturing Co., Ltd.). After preparation, the sample was analyzed using an accelerator mass spectrometer (NEC 1.5SDH). 14 The C concentration was measured. 14 After correcting for isotope fractionation effects on C concentrations, the biobased content was calculated.

[0020] In the present invention, in order to achieve a biobased content of the organosilane compound (α) within the above range, it is desirable to use, as much as possible, biologically derived raw materials as the raw materials for the organosilane compound (α), rather than raw materials derived from fossil fuels. In particular, it is desirable to use biologically derived raw materials as raw materials that can be incorporated into the skeleton of the organosilane compound (α) (excluding components such as reaction solvents that may be separated during the production process). The biologically derived raw materials can be used as pure products by purifying compounds extracted from plants or animals, or as mixtures of compounds without purification.

[0021] In the organosilane compound (α), the monovalent hydrocarbon group is preferably linear or branched, as this provides high molecular mobility and the resulting cured coating exhibits superior slip properties.

[0022] The organosilane compound (α) has at least one, preferably two or more, and more preferably two or three, monovalent hydrocarbon groups.

[0023] When the organosilane compound (α) has two or more monovalent hydrocarbon groups, these monovalent hydrocarbon groups are preferably bonded to the same atom. When two or more monovalent hydrocarbon groups are bonded to the same atom, the organosilane compound (α) has high packing properties, and the cured coating formed by the surface treatment agent composition containing the organosilane compound (α) forms a harder film. As a result, the resulting cured coating exhibits superior water repellency and abrasion resistance. In the present invention, "packing properties" refers to the ease with which multiple hydrocarbon chains are oriented densely in one direction on the surface of the cured coating. Here, the same atom to which two or more of the above monovalent hydrocarbon groups are bonded is preferably a carbon atom, a nitrogen atom, or a silicon atom.

[0024] In the organosilane compound (α), the monovalent hydrocarbon group has a carbon number of 3 to 60, preferably a carbon number of 3 to 40, more preferably a carbon number of 8 to 40, and even more preferably a carbon number of 10 to 40. When the carbon number is 3 to 60, the compound can maintain high solubility in solvents, and a cured coating film made from the surface treatment agent composition can have high water repellency. When two or more of the monovalent hydrocarbon groups are bonded to the same atom, it is preferable that all of the monovalent hydrocarbon groups have the same number of carbon atoms, and in particular that the monovalent hydrocarbon groups are the same, as this further improves packing properties.

[0025] The organosilane compound (α) is more preferably one represented by the following general formula (1). [ka] (In the formula, R 1 are monovalent hydrocarbon groups having 3 to 32 carbon atoms, which may independently contain at least one atom selected from oxygen, sulfur, nitrogen, and silicon atoms, and which may be linear, branched, or cyclic, or a combination thereof; R 2represents a hydrogen atom, a halogen atom, a hydroxyl group, a siloxy group, an amino group, a thiol group, or a monovalent hydrocarbon group having 1 or 2 carbon atoms; U represents a carbon atom, a silicon atom, a nitrogen atom, or a trivalent or tetravalent organic group; V independently represents a single bond or a divalent hydrocarbon group which may contain at least one atom selected from an oxygen atom, a nitrogen atom, and a sulfur atom; Z independently represents a single bond, a carbon atom, a silicon atom, a nitrogen atom, a sulfur atom, or a trivalent to octavalent organic group; Y independently represents a divalent hydrocarbon group which may contain at least one atom selected from an oxygen atom, a nitrogen atom, a sulfur atom, and a silicon atom; A independently represents a monovalent reactive silyl group; k1 is 2 or 3, k2 is 0 or 1, k3 is 1 or 2, k1 + k2 + k3 is 3 or 4, and m is an integer from 1 to 7.

[0026] In the above formula (1), R 1 are monovalent hydrocarbon groups having 3 to 32 carbon atoms, preferably 6 to 28 carbon atoms, and more preferably 8 to 28 carbon atoms, which may independently contain at least one atom selected from oxygen atoms, sulfur atoms, nitrogen atoms, and silicon atoms, and which may be linear, branched, or cyclic, or a combination thereof. When at least one selected from oxygen atoms, sulfur atoms, nitrogen atoms, and silicon atoms is contained, it is preferable that the at least one selected from the group consisting of an ether group, a carbonyl (ketone) group, an ester group, a carbonate group, a thioether group, a sulfinyl group, a sulfonyl group, a thioester group, a thiocarbonate group, a thiocarbamate group, an amino group, an amide group, a carbamate group, a urea group, an oxazole group, an imidazole group, a triazole group, a cyanurate group, an isocyanurate group, a diorganosilylene group, an organopolysiloxane residue, a silalkylene group, a silarylene group, or the like.

[0027] R 1 is preferably a group represented by the following formula: [ka] (In the formula, R Aare independently a monovalent hydrocarbon group having 3 to 32 carbon atoms which may be linear, branched, or cyclic, or a combination thereof; Q are independently an oxygen atom, a sulfur atom, a divalent cyclic hydrocarbon group having 6 to 8 carbon atoms, a diorganosilylene group, a silalkylene structure, a silarylene structure, a linear organopolysiloxane residue having 2 to 10 silicon atoms or a branched or cyclic organopolysiloxane residue having 3 to 10 silicon atoms, a carbonyl (ketone) group, an ester group, a carbonate group, a sulfinyl group, a sulfonyl group, a thioester group, a thiocarbonate group, a thiocarbamate group, an amino group, an amide group, a carbamate group, a urea group, and a divalent nitrogen-containing heterocyclic group (a divalent oxazole group, a divalent imidazole group, Q' is independently a trivalent group selected from the group consisting of a nitrogen atom, a trivalent cyclic hydrocarbon group having 6 to 8 carbon atoms, a linear trivalent organopolysiloxane residue having 2 to 10 silicon atoms or a branched or cyclic trivalent organopolysiloxane residue having 3 to 10 silicon atoms, a trivalent amide group, and a trivalent nitrogen-containing heterocyclic group (a trivalent cyanurate group, a trivalent isocyanurate group, a trivalent triazole group, and the like); Q' is independently a tetravalent group selected from the group consisting of a silicon atom, a tetravalent cyclic hydrocarbon group having 6 to 8 carbon atoms, and a linear trivalent organopolysiloxane residue having 2 to 10 silicon atoms or a branched or cyclic trivalent organopolysiloxane residue having 3 to 10 silicon atoms; R B are independently a single bond or a divalent hydrocarbon group having 1 to 32 carbon atoms, which may be linear, branched, or cyclic; R C are independently R A or a hydrogen atom, and p is an integer of 0 to 10. However, the total number of carbon atoms in each structure is 32 or less.

[0028] In the above formula, R A R is independently a monovalent hydrocarbon group having 3 to 32 carbon atoms, preferably 6 to 28 carbon atoms, and more preferably 8 to 28 carbon atoms, which may be linear, branched, or cyclic, or a combination thereof. A Examples of such materials include the following: [ka] [ka] (In the formula, x is an integer of 2 to 31, preferably 5 to 27, and more preferably 7 to 27, and y and y' are each an integer of 1 or more such that the total number of carbon atoms in each structure is 32 or less.)

[0029] In the above formula, Q independently represents a divalent group selected from the group consisting of an oxygen atom, a sulfur atom, a divalent cyclic hydrocarbon group having 6 to 8 carbon atoms, a diorganosilylene group, a silalkylene structure, a silarylene structure, a linear divalent organopolysiloxane residue having 2 to 10 silicon atoms, particularly 2 to 8 silicon atoms, or a branched or cyclic divalent organopolysiloxane residue having 3 to 10 silicon atoms, particularly 3 to 8 silicon atoms, a carbonyl (ketone) group, an ester group, a carbonate group, a sulfinyl group, a sulfonyl group, a thioester group, a thiocarbonate group, a thiocarbamate group, an amino group, an amide group, a carbamate group, a urea group, and a divalent nitrogen-containing heterocyclic group (such as a divalent oxazole group, a divalent imidazole group, or a divalent triazole group).

[0030] Here, the group bonded to a silicon atom in a diorganosilylene group, a silalkylene structure, a silarylene structure, or an organopolysiloxane residue is preferably an alkyl group having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms, such as a methyl group, an ethyl group, a propyl group, or a butyl group, or a phenyl group. Furthermore, the alkylene group in the silalkylene structure is preferably an ethylene group, a propylene group (trimethylene group, methylethylene group), a butylene group (tetramethylene group, methylpropylene group), or the like, having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms. Furthermore, the organopolysiloxane residue may contain a silalkylene structure in which two silicon atoms are bonded via an alkylene group, such as an ethylene group or a propylene group.

[0031] Examples of such Q include the following: In the following structure, the bond on the left is R A or R B and the bond on the right is R B and combine. [ka] [ka] [ka] [ka] (In the formula, f is an integer of 2 to 4, and e is an integer of 1 to 9.)

[0032] In the above formula, Q' independently represents a trivalent group selected from the group consisting of a nitrogen atom, a trivalent cyclic hydrocarbon group having 6 to 8 carbon atoms, a linear trivalent organopolysiloxane residue having 2 to 10 silicon atoms, particularly 2 to 8 silicon atoms, or a branched or cyclic trivalent organopolysiloxane residue having 3 to 10 silicon atoms, particularly 3 to 8 silicon atoms, a trivalent amide group, and a trivalent nitrogen-containing heterocyclic group (such as a trivalent cyanurate group, a trivalent isocyanurate group, or a trivalent triazole group).

[0033] The organopolysiloxane residue may have a phenyl group or an alkyl group such as a methyl group, ethyl group, propyl group, or butyl group having 1 to 8 carbon atoms, preferably 1 to 4. The organopolysiloxane residue may also contain a silalkylene structure in which two silicon atoms are bonded via an alkylene group such as an ethylene group or a propylene group.

[0034] Examples of such Q' include the following: In the following structure, the bond on the left is R A or R B and the bond on the right is R B and the other bonds are R C and combine. [ka] [ka] (In the formula, f is an integer of 2 to 4.)

[0035] In the above formula, Q" is independently a tetravalent group selected from the group consisting of a silicon atom, a tetravalent cyclic hydrocarbon group having 6 to 8 carbon atoms, and a linear tetravalent organopolysiloxane residue having 2 to 10 silicon atoms, particularly 2 to 8 silicon atoms, or a branched or cyclic tetravalent organopolysiloxane residue having 3 to 10 silicon atoms, particularly 3 to 8 silicon atoms.

[0036] The organopolysiloxane residue may have a phenyl group or an alkyl group such as a methyl group, ethyl group, propyl group, or butyl group having 1 to 8 carbon atoms, preferably 1 to 4. The organopolysiloxane residue may also contain a silalkylene structure in which two silicon atoms are bonded via an alkylene group such as an ethylene group or a propylene group.

[0037] Examples of such Q" include the following: In the following structure, the bond on the left is R A or R B and the bond on the right is R B and the other bonds are R C and combine. [ka] [ka]

[0038] In the above formula, R B are independently a single bond or a divalent hydrocarbon group having 1 to 32 carbon atoms which may be linear, branched or cyclic, and examples thereof include the following: [ka] (In the formula, z is an integer of 1 to 10.)

[0039] In the above formula, R C are independently R A or a hydrogen atom. C R A If RA may be the same as or different from.

[0040] In the above formula, p is an integer of 0 to 10, and is preferably 0, 1, or 2. However, R 1 The total number of carbon atoms in each structure is 32 or less.

[0041] Such an R 1 As the solvent, the following are preferably used. [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] (In the formula, x, y, y', and z are the same as above, with the proviso that the total number of carbon atoms in each structure is 3 to 32.)

[0042] In the above formula (1), R 2 is a hydrogen atom, a halogen atom, a hydroxyl group, a siloxy group, an amino group, a thiol group, or a monovalent hydrocarbon group having 1 or 2 carbon atoms (a methyl group, an ethyl group). R 2is preferably a hydrogen atom, a chlorine atom, a hydroxyl group, a methyl group, or an ethyl group.

[0043] In the above formula (1), U represents a carbon atom, a silicon atom, a nitrogen atom, or a trivalent or tetravalent organic group. The trivalent or tetravalent organic group is preferably a trivalent or tetravalent group selected from a trivalent or tetravalent cyclic hydrocarbon group having 6 to 8 carbon atoms, a linear trivalent or tetravalent organopolysiloxane residue having 2 to 10 silicon atoms, particularly 2 to 8 silicon atoms, or a branched or cyclic trivalent or tetravalent organopolysiloxane residue having 3 to 10 silicon atoms, particularly 3 to 8 silicon atoms, a trivalent amide group, a trivalent carbamate group, a trivalent or tetravalent urea group, and a trivalent or tetravalent nitrogen-containing heterocyclic group (such as a trivalent cyanurate group, a trivalent isocyanurate group, or a trivalent triazine ring-containing group).

[0044] The organopolysiloxane residue may have a phenyl group or an alkyl group such as a methyl group, ethyl group, propyl group, or butyl group having 1 to 8 carbon atoms, preferably 1 to 4. The organopolysiloxane residue may also contain a silalkylene structure in which two silicon atoms are bonded via an alkylene group such as an ethylene group or a propylene group.

[0045] Examples of such U include the following: In the following structure, it is preferable that the bond on the right side is bonded to V. [ka] [ka] [ka] [ka]

[0046] In the above formula (1), V is independently a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms which may contain at least one atom selected from oxygen, nitrogen and sulfur atoms, and is a linking group connecting the U group and the Z group. When Z is a single bond, V is preferably a single bond. Specific examples of the divalent hydrocarbon group include alkylene groups having 1 to 10 carbon atoms, which may contain at least one atom selected from oxygen atoms, nitrogen atoms, and sulfur atoms, and alkylene groups having 1 to 10 carbon atoms including arylene groups having 6 to 8 carbon atoms (for example, alkylene-arylene groups having 7 to 18 carbon atoms).

[0047] Specific examples of such V include the following, in addition to a single bond: In the following structure, the left bond is bonded to U, and the right bond is bonded to Z. [ka] [ka] [ka] (In the formula, q is an integer of 1 to 10, r, s, and t are each an integer of 1 to 8, the sum of r and s is an integer of 2 to 10, and the sum of r, s, and t is an integer of 3 to 10.)

[0048] In the above formula (1), Z independently represents a single bond, a carbon atom, a silicon atom, a nitrogen atom, a sulfur atom, or a trivalent to octavalent organic group. The trivalent to octavalent organic group is a trivalent or tetravalent cyclic hydrocarbon group having 6 to 8 carbon atoms, -SiR 3 =(R 3 is a hydroxyl group, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms), -CR 4 =(R 4represents a hydrogen atom, a hydroxyl group, or an alkyl group having 1 to 3 carbon atoms), a linear organopolysiloxane residue having 2 to 10 silicon atoms, particularly 2 to 8 silicon atoms, or a branched or cyclic organopolysiloxane residue having 3 to 10 silicon atoms, particularly 3 to 8 silicon atoms, a trivalent amide group, a trivalent carbamate group, a trivalent or tetravalent urea group, and a trivalent to octavalent nitrogen-containing heterocycle-containing group (e.g., a trivalent cyanurate group, a trivalent isocyanurate group, or a trivalent or tetravalent triazine ring-containing group).

[0049] The organopolysiloxane residue may have a phenyl group or an alkyl group such as a methyl group, ethyl group, propyl group, or butyl group having 1 to 8 carbon atoms, preferably 1 to 4. The organopolysiloxane residue may also contain a silalkylene structure in which two silicon atoms are bonded via an alkylene group such as an ethylene group or a propylene group.

[0050] Examples of such Z include the following, in addition to a single bond: In the following structure, the bond on the left side is bonded to V, and the other bond is bonded to Y. [ka] [ka] [ka] (In the formula, f is an integer of 2 to 4.)

[0051] In the above formula (1), Y may independently contain at least one atom selected from oxygen atoms, nitrogen atoms, sulfur atoms, and silicon atoms, and is preferably a divalent hydrocarbon group having 1 to 20 carbon atoms, and is a linking group connecting the Z group and the A group. Specific examples of the divalent hydrocarbon group include alkylene groups having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, which may contain at least one atom selected from oxygen, nitrogen, and sulfur atoms; alkylene groups having 1 to 10 carbon atoms including an arylene group having 6 to 8 carbon atoms (for example, an alkylene-arylene group having 7 to 18 carbon atoms); divalent groups in which alkylene groups having 1 to 8 carbon atoms are bonded to each other via a diorganosilylene group, a silalkylene structure, a silarylene structure, or a nitrogen-containing heterocyclic group; and divalent groups in which an alkylene group having 1 to 10 carbon atoms is bonded to a bond of a linear organopolysiloxane residue having 2 to 10 silicon atoms, preferably 2 to 8 silicon atoms, or a branched or cyclic organopolysiloxane residue having 3 to 10 silicon atoms, preferably 3 to 8 silicon atoms.

[0052] Here, the group bonded to a silicon atom in a diorganosilylene group, a silalkylene structure, a silarylene structure, or an organopolysiloxane residue is preferably an alkyl group having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms, such as a methyl group, an ethyl group, a propyl group, or a butyl group, or a phenyl group. Furthermore, the alkylene group in the silalkylene structure is preferably an ethylene group, a propylene group (trimethylene group, methylethylene group), a butylene group (tetramethylene group, methylpropylene group), or the like, having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms. Furthermore, the organopolysiloxane residue may contain a silalkylene structure in which two silicon atoms are bonded via an alkylene group, such as an ethylene group or a propylene group.

[0053] Examples of such Y include the following groups: In the following structure, the left bond is bonded to Z, and the right bond is bonded to A. [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] (In the formula, a is independently an integer of 1 to 10, b, c, and d are each an integer of 1 to 8, the sum of b and c is an integer of 2 to 10, and the sum of b, c, and d is an integer of 3 to 10, e is an integer of 1 to 9, and f is an integer of 2 to 4.)

[0054] In the above formula (1), A is independently a monovalent reactive silyl group, and is preferably a hydroxyl group-containing silyl group (silanol group) or a hydrolyzable silyl group.

[0055] The hydroxyl group-containing silyl group and the hydrolyzable silyl group are those represented by the following general formula (2): [ka] (In the formula, R is independently an alkyl group having 1 to 4 carbon atoms or a phenyl group, X is independently a hydroxyl group or a hydrolyzable group, and n is an integer of 1 to 3.) Or the following general formula (3) [ka] (In the formula, n' is a number from 0 to 3, and n' is (3-n') / 2.) A group represented by the following formula is preferred.

[0056] In the above formula (2), R is independently an alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, a propyl group, or a butyl group, or a phenyl group, with a methyl group being preferred. In the formula (2), X is independently a hydroxyl group or a hydrolyzable group. Examples of X include hydroxyl groups; alkoxy groups having 1 to 10 carbon atoms, such as methoxy, ethoxy, propoxy, isopropoxy, and butoxy; alkoxyalkoxy groups having 2 to 10 carbon atoms, such as methoxymethoxy and methoxyethoxy; acyloxy groups having 1 to 10 carbon atoms, such as acetoxy; alkenyloxy groups having 2 to 10 carbon atoms, such as isopropenoxy and cyclopentenyloxy; halogen groups, such as chlorine, bromine, and iodo; and dialkylamino groups having 2 to 10 carbon atoms, such as dimethylamino and diethylamino. Among these, methoxy, ethoxy, isopropenoxy, and chlorine groups are preferred. X may be the same or different.

[0057] In the above formula (3), n" is a number from 0 to 3 (0 or a positive number of 3 or less), preferably n"<3, and more preferably n"=0. When n"=3 in the above formula (3), the above general formula (1) represents the molecular formula (structural formula) of a hydrocarbon terminal group-containing compound (monomer), and when n"<3 in the above formula (3), the above general formula (1) represents the composition formula of a polymer of a hydrocarbon terminal group-containing compound (polysilazane compound). In the above formula (3), n' is (3-n'') / 2, and is preferably 1.5.

[0058] In the above formula (1), k1 is 2 or 3, k2 is 0 or 1, k3 is 1 or 2, k1+k2+k3 is 3 or 4, when U is trivalent, k1+k2+k3 is 3, and when U is tetravalent, k1+k2+k3 is 4. Furthermore, m is an integer of 1 to 7, preferably an integer of 1 to 3.

[0059] The structure of the compound represented by the above formula (1) includes the following structure: R 1 , R 2By changing the combination of U, V, Z, Y, A, k1, k2, k3, and m, several hydrocarbon end group-containing compounds can be obtained.

[0060] [ka] [ka] [ka] [ka] [ka]

[0061] [ka] [ka] [ka] [ka] [ka]

[0062] [ka] [ka] [ka] [ka] [ka]

[0063]

change

change

change

change

change

change

[0064]

change

change

change

change

change

change

[0065]

change

change

change

change

change

[0066]

change

change

change

change

change

change

change

[0067]

change

change

change

change

change

change

change

change

[0068] [ka] [ka] [ka] [ka] [ka]

[0069] [ka] [ka] [ka] [ka] [ka] [ka]

[0070] [ka] [ka] [ka] [ka] (In the formula, x, y, y', z, q, r, s, a, b, c, d, e, and f are each independently the same as above.)

[0071] The cured coating formed by the surface treatment agent composition containing the hydrocarbon terminal group-containing compound represented by the above formula (1) has chemical resistance. Among them, the compound represented by the following general formula (4) is a compound that has particularly excellent chemical resistance. [ka] (In the formula, R 1´ are independently a monovalent hydrocarbon group having 13 to 32 carbon atoms, which may be linear, branched, or cyclic, or a combination thereof; R 2 represents a hydrogen atom, a halogen atom, a hydroxyl group, a siloxy group, an amino group, a thiol group, or a monovalent hydrocarbon group having 1 or 2 carbon atoms; U represents a carbon atom, a silicon atom, a nitrogen atom, or a trivalent or tetravalent organic group; V independently represents a single bond or a divalent hydrocarbon group which may contain at least one atom selected from an oxygen atom, a nitrogen atom, and a sulfur atom; Z independently represents a single bond, a carbon atom, a silicon atom, a nitrogen atom, a sulfur atom, or a trivalent to octavalent organic group; Y independently represents a divalent hydrocarbon group which may contain at least one atom selected from an oxygen atom, a nitrogen atom, a sulfur atom, and a silicon atom; A independently represents a monovalent reactive group; k1 is 2 or 3, k2 is 0 or 1, k3 is 1 or 2, k1 + k2 + k3 is 3 or 4, and m is an integer from 1 to 7.

[0072] In the above formula (4), R 1′ R are independently a monovalent hydrocarbon group having 13 to 32 carbon atoms, which may be linear, branched, or cyclic, or a combination thereof, and preferably a monovalent hydrocarbon group having 15 to 28 carbon atoms. 1′ By having 13 or more carbon atoms, the effect of preventing chemicals from penetrating into the adhesive portion of the substrate is exhibited, and chemical resistance is improved. 1′ By not having a structure containing one or more of oxygen atoms, sulfur atoms, nitrogen atoms, and silicon atoms (particularly, an ester or urethane structure), the effect of preventing penetration of chemicals is more pronounced, and chemical resistance is improved.

[0073] R in the above formula (4) 1 , R 2, U, V, Z, A, k1, k2, k3, k1+k2+k3, m are R in the above formula (1). 1 , R 2 , U, V, Z, A, k1, k2, k3, k1+k2+k3, m.

[0074] The compound represented by general formula (1) can be prepared, for example, by the following method. [Preparation method 1] The compound represented by formula (1) can be produced by mixing a hydrocarbon terminal group-containing compound having an alkenyl group at the terminal with a compound having an SiH group and a hydrolyzable silyl group, and carrying out a hydrosilylation addition reaction in the presence of a hydrosilylation reaction catalyst. When the compound having an SiH group and a hydrolyzable silyl group is one in which the hydrolyzable group is a halogen group, the compound can be produced by subsequently converting the substituent (halogen atom) on the silyl group to another hydrolyzable group.

[0075] Here, examples of hydrocarbon terminal group-containing compounds having an alkenyl group at the end include compounds represented by the following formula (1A). [ka] (In the formula, R 1 , R 2 , U, V, Z, k1, k2, k3, k1+k2+k3, m are the same as above. Y 1 may independently contain at least one atom selected from oxygen atoms, nitrogen atoms, sulfur atoms, and silicon atoms, and are preferably divalent hydrocarbon groups having 1 to 18 carbon atoms.)

[0076] In the above formula (1A), Y 1 may independently contain at least one atom selected from oxygen, nitrogen, sulfur, and silicon atoms, and is preferably a divalent hydrocarbon group having 1 to 18 carbon atoms, examples of which include those shown below. In the following structure, the bond on the left is bonded to Z, and the bond on the right is bonded to a carbon atom. [ka] [ka] [ka] [ka] [ka] [ka] (In the formula, a' is independently an integer of 0 to 8, b and c are each an integer of 1 to 8, c' and d' are each an integer of 0 to 6, the sum of b and c' is an integer of 2 to 8, and the sum of b, c, and d' is an integer of 3 to 8. e is an integer of 1 to 9, and f is an integer of 2 to 4.)

[0077] Examples of the compound represented by formula (1A) include the compounds shown below. [ka] [ka] [ka] [ka] [ka] (In the formula, x, y, y', z, q, a, a', b, c, and c' are each independently the same as above.)

[0078] Examples of compounds having a SiH group and a hydrolyzable silyl group include trimethoxysilane, triethoxysilane, triacetoxysilane, and trichlorosilane.

[0079] In Preparation Method 1, the amount of the compound having a SiH group and a hydrolyzable silyl group used is preferably 1 to 6 moles, particularly 1.5 to 4 moles, per mole of alkenyl group in the hydrocarbon terminal group-containing compound having an alkenyl group at the terminal.

[0080] In Preparation Method 1, examples of the hydrosilylation reaction catalyst include platinum black, chloroplatinic acid, alcohol-modified chloroplatinic acid, complexes of chloroplatinic acid with olefins, aldehydes, vinylsiloxanes, acetylene alcohols, etc., and platinum group metal catalysts such as tetrakis(triphenylphosphine)palladium and chlorotris(triphenylphosphine)rhodium. Platinum compounds such as vinylsiloxane coordination compounds are preferred. The platinum compounds are preferably used by dissolving them in a solvent such as toluene, a lower alcohol, a higher alcohol, or a silicone-based solvent. The amount of the hydrosilylation reaction catalyst used is preferably 0.001 to 1,000 ppm, more preferably 0.01 to 100 ppm, calculated as transition metal (by mass) relative to the mass of the hydrocarbon terminal group-containing compound having an alkenyl group at the terminal.

[0081] A solvent can be used during the reaction in Preparation Method 1. Examples of the solvent include aromatic hydrocarbons such as toluene and xylene, aliphatic or alicyclic hydrocarbons such as n-pentane, n-hexane and cyclohexane, cyclic ether compounds such as tetrahydrofuran and dioxane, and ketones such as acetone and methyl ethyl ketone. The amount of the solvent used is 0 to 1,000 parts by mass, preferably 50 to 200 parts by mass, per 100 parts by mass of the hydrocarbon terminal group-containing compound having an alkenyl group at the end.

[0082] In Preparation Method 1, the reaction conditions for the hydrocarbon terminal group-containing compound having an alkenyl group at the terminal with the compound having a SiH group and a hydrolyzable silyl group are preferably a temperature of 20 to 120°C, particularly 60 to 100°C, for 0.5 to 72 hours, particularly 1 to 36 hours.

[0083] In Preparation Method 1, when a compound having a SiH group and a hydrolyzable silyl group, such as trichlorosilane, in which the hydrolyzable group is a halogen group (a compound containing a SiH group and a halogenated silyl group) is used, the substituent (halogen atom) on the silyl group is then converted to another hydrolyzable group, for example, an alkoxy group such as a methoxy group. Examples of compounds that can be used to convert the substituent (halogen atom) on the silyl group to another hydrolyzable group include methanol, ethanol, isopropanol, ethylene glycol monomethyl ether, and trimethyl orthoformate. The amount used is preferably 3 to 9 moles, particularly 3 to 5 moles, per mole of halogen atoms in the reaction product of the hydrocarbon terminal group-containing compound having an alkenyl group at the terminal and the SiH group- and halogenated silyl group-containing compound.

[0084] In Preparation Method 1, the reaction conditions for converting a substituent (halogen atom) on a silyl group to another hydrolyzable group are preferably a temperature of 0 to 80°C, particularly 20 to 60°C, for 0.5 to 72 hours, particularly 1 to 36 hours.

[0085] Other methods for preparing the compound of the present invention represented by general formula (1) include the following methods. [Preparation method 2] The compound represented by formula (1) can be produced by mixing a hydrocarbon terminal group-containing compound having a terminal SiH group with a compound having a reactive group such as an alkenyl group and a hydrolyzable silyl group, and then carrying out a hydrosilylation addition reaction in the presence of a hydrosilylation reaction catalyst.

[0086] Here, examples of hydrocarbon terminal group-containing compounds having SiH groups at their terminals include compounds represented by the following formula (1B) or (1C). [ka] (In the formula, R 1 , R 2 , U, V, Z, k1, k2, k3, k1+k2+k3, m are the same as above. Z 1is a linear organopolysiloxane residue having 2 to 10 silicon atoms or a branched or cyclic organopolysiloxane residue having 3 to 10 silicon atoms, and having a valence of 3 to 8; Y 2 are independently a monovalent hydrocarbon group having a silicon atom or a siloxane bond and a terminal SiH group.

[0087] In the above formula (1B), Z 1 is a linear organopolysiloxane residue having 2 to 10 silicon atoms, particularly 2 to 8 silicon atoms, or a branched or cyclic trivalent to octavalent organopolysiloxane residue having 3 to 10 silicon atoms, particularly 3 to 8 silicon atoms, and examples thereof include those shown below. In the following structure, the bond on the left is bonded to V, and the other bonds are bonded to H. [ka] (In the formula, f is an integer of 2 to 4.)

[0088] Examples of the compound represented by formula (1B) include the compounds shown below. [ka] [ka] [ka] (In the formula, x, q, r, and s are each independently the same as above.)

[0089] In the above formula (1C), Y 2 are monovalent hydrocarbon groups each having a silicon atom or a siloxane bond and a terminal SiH group, examples of which include those shown below. [ka] [ka] [ka] (In the formula, a is an integer of 1 to 10, b is an integer of 1 to 8, e is an integer of 1 to 9, and f is an integer of 2 to 4.)

[0090] Examples of the compound represented by formula (1C) include the compounds shown below. [ka] (In the formula, x and b are each independently the same as above.)

[0091] In Preparation Method 2, examples of the compound having an alkenyl group and a hydrolyzable silyl group include vinyltrimethoxysilane, allyltrimethoxysilane, and octenyltrimethoxysilane. Furthermore, examples of compounds having a reactive group other than an alkenyl group and a hydrolyzable silyl group include allyl glycidyl ether.

[0092] In Preparation Method 2, the amount of the compound having a reactive group such as an alkenyl group or a hydrolyzable silyl group used is preferably 1 to 5 moles, particularly 1 to 3 moles, per mole of SiH group in the hydrocarbon terminal group-containing compound having a SiH group at the terminal.

[0093] In Preparation Method 2, examples of the hydrosilylation catalyst include the same as those in Preparation Method 1. Platinum compounds such as vinylsiloxane coordination compounds are preferred. The platinum compounds are preferably used by dissolving them in a solvent such as toluene, a lower alcohol, a higher alcohol, or a silicone solvent. The amount of the hydrosilylation catalyst used is preferably 0.001 to 1,000 ppm, more preferably 0.01 to 100 ppm, calculated as transition metal (by mass) relative to the mass of the hydrocarbon terminal group-containing compound having a terminal SiH group.

[0094] A solvent can be used when carrying out the reaction in Preparation Method 2. Examples of the solvent include the same solvents as those in Preparation Method 1 above. The amount of the solvent used is 0 to 1,000 parts by mass, preferably 50 to 200 parts by mass, per 100 parts by mass of the hydrocarbon terminal group-containing compound having a terminal SiH group.

[0095] In Preparation Method 2, the reaction conditions are preferably a temperature of 20 to 120°C, particularly 60 to 100°C, and a time of 0.5 to 72 hours, particularly 1 to 36 hours.

[0096] Other methods for preparing the compound represented by general formula (1) include the following methods. [Preparation method 3] A compound represented by formula (1) (particularly a compound having an amino-group-containing silyl group at its terminal and / or a polysilazane compound which is a polymer thereof) can be produced by mixing a hydrocarbon terminal group-containing compound having an alkenyl group at its terminal with trichlorosilane and reacting them in the presence of a hydrosilylation reaction catalyst, and then reacting the resulting compound with ammonia gas.

[0097] Here, the reaction product of the hydrocarbon terminal group-containing compound having an alkenyl group at the end and trichlorosilane can be prepared in the same manner as in Preparation Method 1.

[0098] In Preparation Method 3, the amount of ammonia gas used is preferably 1 to 300 cc / min, and particularly preferably 30 to 200 cc / min.

[0099] In Preparation Method 3, the reaction conditions for the reaction of ammonia gas with a reaction product of a hydrocarbon terminal group-containing compound having an alkenyl group at the terminal and trichlorosilane are preferably room temperature (23±15°C), particularly 20 to 30°C, for 2 to 36 hours, particularly 4 to 12 hours.

[0100] Other methods for preparing the compound represented by general formula (1) include the following methods. [Preparation method 4] A compound represented by formula (1) (particularly a compound having a reactive silyl group at the terminal via a urethane bond) can be produced by mixing a hydrocarbon terminal group-containing compound having a hydroxyl group at the terminal with a compound having an isocyanate group and a reactive silyl group and reacting them in the presence of a catalyst.

[0101] Here, examples of hydrocarbon terminal group-containing compounds having a hydroxyl group at the end include compounds represented by the following formula (1D) or (1E). [ka] (In the formula, R 1 , R 2 , U, V, Z, k1, k2, k3, k1+k2+k3, m, b are the same as above. V 1 is a divalent hydrocarbon group having 1 to 10 carbon atoms.

[0102] Examples of the compound represented by formula (1D) include the compounds shown below. [ka] [ka] [ka] (In the formula, x, z, and b are each independently the same as above.)

[0103] In the above formula (1E), V 1 is a divalent hydrocarbon group having 1 to 10 carbon atoms, preferably an alkylene group, and examples thereof include those shown below. [ka] (wherein q is the same as above.)

[0104] Examples of the compound represented by formula (1E) include the compounds shown below. [ka] (In the formula, x, z, and q are each independently the same as above.)

[0105] Examples of compounds having an isocyanate group and a reactive silyl group include (3-isocyanatopropyl)trimethoxysilane and (3-isocyanatopropyl)triethoxysilane.

[0106] In Preparation Method 4, the amount of the compound having an isocyanate group and a reactive silyl group used is preferably 1 to 3 moles, particularly 1 to 1.5 moles, per mole of hydroxyl group in the hydrocarbon terminal group-containing compound having a terminal hydroxyl group.

[0107] In Preparation Method 4, examples of the catalyst include titanium compounds such as titanium tetra-2-ethylhexoxide, tetra n-butyl titanate, and tetra n-propyl titanate; zirconium compounds such as tetra n-butyl zirconate and tetra n-propyl zirconate; tin compounds such as dibutyltin dimethoxide and dibutyltin dilaurate; bismuth compounds such as bismuth tris(2-ethylhexanoate); and amine catalysts such as diazabicycloundecene. The amount of the catalyst used is 0.01 to 100 parts by mass, preferably 0.1 to 20 parts by mass, per 100 parts by mass of the compound containing a hydrocarbon terminal group having a terminal hydroxyl group.

[0108] A solvent can be used when carrying out the reaction in Preparation Method 4. Examples of the solvent include the same solvents as those in Preparation Method 1 above. The amount of the solvent used is 0 to 1,000 parts by mass, preferably 50 to 200 parts by mass, per 100 parts by mass of the hydrocarbon terminal group-containing compound having a terminal hydroxyl group.

[0109] In Preparation Method 4, the reaction conditions are preferably a temperature of 20 to 100°C, particularly 30 to 60°C, and a time of 0.5 to 72 hours, particularly 1 to 36 hours.

[0110] Other methods for preparing the compound represented by general formula (1) include the following methods. [Preparation method 5] A compound represented by formula (1) (particularly a compound having a reactive silyl group at its terminal via a urea bond) can be produced by mixing and reacting a hydrocarbon terminal group-containing compound having an NH group at its terminal with a compound having an isocyanate group and a reactive silyl group.

[0111] Here, examples of hydrocarbon terminal group-containing compounds having an NH group at the end include compounds represented by the following formula (1F). [ka] (In the formula, R 1 is the same as above.)

[0112] Examples of the compound represented by formula (1F) include the compounds shown below. [ka] (wherein x is independently the same as above).

[0113] Examples of compounds having an isocyanate group and a reactive silyl group include (3-isocyanatopropyl)trimethoxysilane and (3-isocyanatopropyl)triethoxysilane.

[0114] In Preparation Method 5, the amount of the compound having an isocyanate group and a reactive silyl group used is preferably 1 to 3 moles, particularly 1 to 1.5 moles, per mole of the hydrocarbon terminal group-containing compound having an NH group at the terminal.

[0115] A solvent can be used when carrying out the reaction in Preparation Method 5. Examples of the solvent include the same solvents as those in Preparation Method 1 above. The amount of the solvent used is 0 to 1,000 parts by mass, preferably 50 to 200 parts by mass, per 100 parts by mass of the hydrocarbon terminal group-containing compound having an NH group at the end.

[0116] In Preparation Method 5, the reaction conditions are preferably a temperature of 0 to 100°C, particularly 20 to 60°C, and a time of 0.5 to 72 hours, particularly 1 to 36 hours.

[0117] The compound represented by general formula (1) obtained by the above reaction is preferably subjected to purification and isolation procedures such as concentration, column purification, distillation, extraction, etc. When the reaction solution satisfies the conditions of the solvent, which is the second essential component described below, the reaction solution can be used as it is as a mixture containing the compound represented by general formula (1).

[0118] Furthermore, the surface treatment agent composition of the present invention may contain a partial reaction condensate obtained by partial reaction condensation of the reactive silyl groups of the organosilane compound (α) (for example, a partial (hydrolysis) condensate obtained by condensing the hydroxyl groups of the compound represented by the above formula (1) or the hydroxyl groups obtained by partially hydrolyzing the hydrolyzable groups of the compound represented by the above formula (1) in advance by a known method). In the present invention, the term "partial (hydrolyzed) condensate" refers to a partial condensate or a partial hydrolyzed condensate.

[0119] The solvent, which is the second essential component of the surface treatment agent composition of the present invention, is selected from alcohol-based solvents, ether-based solvents, ketone-based solvents, ester-based solvents, carbonate-based solvents, siloxane-based solvents, and hydrocarbon-based solvents. When the solvent is selected from these, it is easy to handle, has good solubility for the organosilane compound (α) and / or its partial reaction condensate, and is less likely to precipitate, so that the surface treatment agent composition can maintain its performance even after long-term storage.

[0120] Examples of such solvents include alcohol-based solvents (propylene glycol monomethyl ether, butanol, isopropanol, etc.), ether-based solvents (tetrahydrofuran (THF), dipropyl ether, dibutyl ether, methyl cyclopentyl ether, methyl t-butyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, propylene glycol dimethyl ether, etc.), ketone-based solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, etc.), ester-based solvents (ethyl acetate, propyl acetate, butyl acetate, pentyl acetate, propylene glycol monomethyl ether acetone ... Examples of suitable solvents include methyl methyl carbonate, methyl methyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, etc.), carbonate solvents (dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, etc.), siloxane solvents (hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, etc.), hydrocarbon solvents (petroleum benzine, toluene, xylene, hexane, cyclohexane, methylcyclohexane, ethylcyclohexane, heptane, octane (n-octane, isooctane, etc.), nonane (n-nonane, isononane, etc.), etc.).

[0121] Here, the solvent is more preferably selected from ether-based solvents, ketone-based solvents, ester-based solvents, siloxane-based solvents, and hydrocarbon-based solvents. When the solvent is selected from these preferred solvents, the solubility of the organosilane compound (α) and / or its partial reaction condensate is further improved, and the surface treatment agent composition can maintain its performance even after long-term storage under severe conditions such as a high-temperature and high-humidity environment.

[0122] It is also preferable to select and use the above solvents with a biobased content of 50% or more as measured by radiocarbon dating in accordance with ASTM D 6866. Solvents with a biobased content of at least the above range are superior in that they pose a smaller environmental burden than solvents produced using raw materials derived from fossil fuels. It is more preferable to use a solvent with a bio-based content of 60% or more, and particularly preferably 70% or more. When the bio-based content of the solvent is in the above range or higher, the burden on the environment is further reduced.

[0123] In the surface treatment agent composition of the present invention, the proportion of the organosilane compound (α) and / or its partial reaction condensate in the total amount of the organosilane compound (α) and / or its partial reaction condensate and the solvent is preferably 0.05 to 70 mass%, more preferably 0.06 to 60 mass%, and even more preferably 0.07 to 50 mass%. This proportion ensures a good balance between the shelf life and ease of handling of the surface treatment agent composition. If the proportion of the organosilane compound (α) and / or its partial reaction condensate in the total amount of the organosilane compound (α) and / or its partial reaction condensate and the solvent is less than the lower limit of the above range, the surface treatment agent composition will be a dilute solution, and trace amounts of water may cause hydrolysis and polycondensation of the organosilane compound (α), resulting in a risk of performance degradation after long-term storage, although this tendency will vary depending on the type of organosilane compound (α) and the solvent. If the proportion of the organosilane compound (α) and / or its partial reaction condensate in the total of the organosilane compound (α) and / or its partial reaction condensate and the solvent exceeds the upper limit of the above range, the surface treatment agent composition will become a concentrated solution, which may increase the dynamic viscosity and reduce handleability, although the tendency will differ depending on the types of organosilane compound (α) and solvent.

[0124] The surface treatment agent composition of the present invention is made of a material that does not contain fluorine atoms, which makes it less likely to decompose and less likely to accumulate in nature compared to conventional fluorine-based surface treatment agent compositions.

[0125] The surface treatment agent composition of the present invention further comprises a compound represented by the following general formula (5): SiR 5 n-4 X 1 n (5) (In the formula, R 5 are independently a hydrogen atom or a monovalent hydrocarbon group having 1 or 2 carbon atoms, and X 1 are independently a hydroxyl group or a hydrolyzable group, and n is an integer of 1 to 4. It is more preferable that the silane compound contains at least one of the following compounds:

[0126] When the surface treatment agent composition of the present invention contains a silane compound represented by general formula (5), the silane compound represented by general formula (5) acts as a dehydrating agent that captures moisture in the surface treatment agent composition, and the surface treatment agent composition can maintain its performance even after long-term storage.

[0127] In the above formula (5), R 5 are independently a hydrogen atom or a monovalent hydrocarbon group having 1 or 2 carbon atoms. Examples of the monovalent hydrocarbon group having 1 or 2 carbon atoms include alkyl groups such as methyl and ethyl groups, and alkenyl groups such as vinyl groups. R 5 Among these, a methyl group and a vinyl group are preferred.

[0128] In the above formula (5), X 1 are independently a hydroxyl group or a hydrolyzable group. 1 Examples of X include hydroxyl groups; alkoxy groups having 1 to 10 carbon atoms such as methoxy, ethoxy, propoxy, isopropoxy, and butoxy; alkoxyalkoxy groups having 2 to 10 carbon atoms such as methoxymethoxy and methoxyethoxy; acyloxy groups having 1 to 10 carbon atoms such as acetoxy; alkenyloxy groups having 2 to 10 carbon atoms such as isopropenoxy and cyclopentenyloxy; halogen groups such as chlorine, bromine, and iodo; and dialkylamino groups having 2 to 10 carbon atoms such as dimethylamino and diethylamino. Of these, methoxy, ethoxy, isopropenoxy, and chlorine groups are preferred. 1may be the same or different.

[0129] In the above formula (5), n is an integer of 1 to 4, and preferably 3 or 4.

[0130] Particularly preferred examples of the silane compound represented by the general formula (5) include the following compounds. Si(OCH3)4, Si(OC2H5)4, Si(OC3H7)4, Si(OC4H9)4, CH2=CHSi(OCH3)3, CH2=CHSi(OC2H5)3, CH2=CHSi(OC3H7)3, CH2=CHSi(OC4H9)3, CH2=CHSi(OCOCH3)3, CH3Si(OCH3)3, CH3Si(OC2H5)3, CH3Si(OC3H7)3, CH3Si(OC4H9)3, CH3Si(OCOCH3)3

[0131] In the surface treatment agent composition of the present invention, the content of the silane compound represented by formula (5) is preferably 0.001 to 10 parts by mass, more preferably 0.005 to 9 parts by mass, and even more preferably 0.01 to 8 parts by mass, per 100 parts by mass of the total amount of the organosilane compound (α) and / or its partial reaction condensate and the solvent. If the content of the silane compound represented by formula (5) is below the lower limit of the above range, the amount of water that the silane compound represented by formula (5) can capture in the surface treatment agent composition is limited to a small amount, and the silane compound cannot fully function as a dehydrating agent, which may result in a decrease in performance after long-term storage. If the content of the silane compound represented by formula (5) exceeds the upper limit of the above range, the water repellency and abrasion resistance of the cured coating obtained from the surface treatment agent composition may be reduced.

[0132] The surface treatment agent composition of the present invention may further contain one or more non-fluorine-based materials selected from a paraffin compound (hereinafter referred to as paraffin oil) that is non-reactive with the organosilane compound (α), a polyol ester compound (hereinafter referred to as polyol ester oil) that is non-reactive with the organosilane compound (α), a silicone compound (hereinafter referred to as silicone oil) that is non-reactive with the organosilane compound (α), a catalyst, a transition metal, a halide ion, a silane coupling agent, and a compound containing an atom having an unshared electron pair in its molecular structure, within an extent that does not impair the present invention.

[0133] The paraffin oil may be linear, branched, or cyclic paraffin oil having a carbon number of 2,000 or less. Specific examples of paraffin oil include liquid paraffin, paraffin wax, polyethylene, polypropylene, and PAO (polyalphaolefin). While paraffin oil that is liquid at room temperature (25°C) is preferred, solid paraffin oils can also be used.

[0134] When paraffin oil is blended into the surface treatment agent composition of the present invention, the content is preferably 0.001 to 80 parts by mass per 100 parts by mass of the total amount of the organosilane compound (α) and / or its partial reaction condensate and the solvent.

[0135] The polyol ester oils include polyol ester compounds formed from condensates of dihydric to hexahydric alcohols and fatty acids having 3 to 22 carbon atoms. Specific examples of polyol ester compounds include neopentyl glycol di(2-ethylhexanoate), neopentyl glycol di(oleate), neopentyl glycol di(stearate), trimethylolethane tri(2-ethylhexanoate), trimethylolethane tri(oleate), trimethylolethane tri(stearate), trimethylolpropane tri(2-ethylhexanoate), trimethylolpropane tri(oleate), and trimethylolethane tri(stearate). Examples of suitable polyol ester oils include glycerol tri(2-ethylhexanoate) ester, glycerol tri(oleate) ester, glycerol tri(stearate) ester, pentaerythritol tetra(2-ethylhexanoate) ester, pentaerythritol tetra(oleate) ester, pentaerythritol tetra(stearate) ester, dipentaerythritol hexa(2-ethylhexanoate) ester, dipentaerythritol hexa(oleate) ester, and dipentaerythritol hexa(stearate) ester. Polyol ester oils that are liquid at room temperature (25°C) are preferred, but solid polyol esters can also be used.

[0136] When polyol ester oil is blended into the surface treatment agent composition of the present invention, the content is preferably 0.001 to 80 parts by mass per 100 parts by mass of the total amount of the organosilane compound (α) and / or its partial reaction condensate and the solvent.

[0137] Examples of the silicone oil include linear, branched, and cyclic silicone oils having 2,000 or less siloxane bonds. The linear silicone oil may be a so-called straight silicone oil or a modified silicone oil. Examples of straight silicone oils include dimethyl silicone oil, methylphenyl silicone oil, and methylhydrogen silicone oil. Examples of modified silicone oils include straight silicone oils modified with alkyl, aralkyl, polyether, higher fatty acid ester, fluoroalkyl, amino, epoxy, carboxyl, alcohol, or the like. Examples of cyclic silicone oils include cyclic dimethylsiloxane oil. Silicone oils that are liquid at room temperature (25°C) are preferred, but solid silicone oils can also be used.

[0138] When silicone oil is blended into the surface treatment agent composition of the present invention, the content is preferably 0.001 to 80 parts by mass per 100 parts by mass of the total amount of the organosilane compound (α) and / or its partial reaction condensate and the solvent.

[0139] Examples of the catalyst include organic acids (acetic acid, methanesulfonic acid, etc.), inorganic acids (hydrochloric acid, sulfuric acid, phosphoric acid, etc.), organic bases (ammonia, triethylamine, diethylamine, etc.), inorganic bases (sodium hydroxide, potassium hydroxide, calcium hydroxide, etc.), organotin compounds (dibutyltin dimethoxide, dibutyltin dilaurate, etc.), organotitanium compounds (tetra-n-butyl titanate, etc.), etc. The catalyst can promote the hydrolysis polycondensation reaction of the organosilane compound (α) and promote the formation of a cured coating.

[0140] The surface treatment composition of the present invention can form a cured coating film having excellent water repellency and abrasion resistance, and is therefore suitable for imparting these properties to a substrate. Specifically, the surface treatment composition of the present invention can be used as an antifouling coating agent or a waterproof coating agent.

[0141] The substrate to be treated with the surface treatment composition of the present invention is not particularly limited, and may be made of various materials such as paper, cloth, metal and its oxides, glass, plastic, ceramic, quartz, etc. In particular, SiO2-treated glass and film are preferred.

[0142] The surface treatment agent composition of the present invention can be applied to a substrate by a known method such as dry coating (vacuum deposition, etc.) or wet coating (spray coating, dip coating, spin coating, wipe coating, squeegee coating, die coating, inkjet coating, flow coating, roll coating, cast coating, Langmuir-Blodgett coating, or gravure coating). The heating method used during dry coating, particularly vacuum deposition, is not particularly limited and may be either a resistance heating method or an electron beam heating method.

[0143] In general, in vacuum deposition, the surface treatment agent composition is handled in a state where it is impregnated into a porous base material and placed on a resistance heating boat or an electron beam heating boat. The porous base material impregnated with the surface treatment agent composition is called a pellet (or tablet). Since the pellet is heated together with the surface treatment agent composition, it is desirable that the material be a substance with a high boiling point or melting point that is not easily volatilized or melted by heating, and for example, metal or ceramic is preferably used. The surface treatment agent composition of the present invention can be impregnated into a porous base material, such as a porous ceramic material or a porous metal material (such as a sintered body of metal fiber, a sintered body of metal powder, a mass of metal fiber (such as a mass of metal wool), or a metal sponge), to form a pellet. The pellet can be used for vacuum deposition. When the surface treatment agent composition is formed into a pellet, handling is easy, productivity in the coating process can be improved, and variability in the vacuum deposition completion time can be reduced.

[0144] The pellets are handled while being contained in a container made of metal or ceramic. The container may be circular or polygonal, such as triangular or rectangular. Furthermore, since the container is heated together with the pellets and the surface treatment agent composition, it is desirable that the container be made of a substance with a high boiling point or melting point that is unlikely to volatilize or melt upon heating, such as metal or ceramic.

[0145] The curing conditions for the surface treatment agent composition of the present invention vary depending on the curing method, but are preferably, for example, 25 to 200°C, particularly 25 to 150°C, for 15 minutes to 36 hours, particularly 30 minutes to 24 hours. Curing may also be carried out under humid conditions.

[0146] The thickness of the cured coating is determined depending on the type of substrate, but is usually 0.1 to 100 nm, particularly 1 to 20 nm. The thickness can be measured by, for example, spectral reflectance measurement, X-ray reflectance measurement, spectroscopic ellipsometry measurement, X-ray fluorescence measurement, etc.

[0147] Examples of articles that can be treated with the surface treatment agent composition of the present invention include car navigation systems, mobile phones, smartphones, digital cameras, digital video cameras, PDAs, portable audio players, car audio equipment, game machines, eyeglass lenses, camera lenses, lens filters, sunglasses, medical devices such as gastroscopes, copiers, PCs, liquid crystal displays, organic EL displays, plasma displays, touch panel displays, protective films, anti-reflection films, and other optical components.

[0148] The surface treatment agent composition of the present invention is also useful as an anti-fouling coating for sanitary products such as bathtubs and washbasins; an anti-fouling coating for window glass or tempered glass for automobiles, trains, aircraft, etc., and headlamp covers, etc.; a water-repellent coating for exterior wall building materials; a stain-resistant coating for kitchen building materials; an anti-fouling and anti-poster / anti-graffiti coating for telephone booths; a coating that provides stain resistance for artworks, etc.; a stain-resistant coating for compact discs, DVDs, etc.; a release agent for molds; a flowability modifier or dispersibility modifier for inorganic fillers; and a lubricity improver for tapes, films, etc.

[0149] The surface treatment composition of the present invention is capable of forming a cured coating film having excellent water repellency and abrasion resistance, and is therefore useful as a surface treatment agent, particularly for optical members, lenses, and displays. [Example]

[0150] The present invention will be described in more detail below with reference to synthesis examples, examples, and comparative examples. However, the present invention is not limited to the following examples. In the following examples, the film thickness is a value measured by spectroscopic ellipsometry using a spectroscopic ellipsometer. The room temperature was 25°C.

[0151] [Synthesis Example 1] In a reaction vessel, the following formula (A) [ka] 1.00 g (2.96 × 10 -3 mol), toluene 1.00 g, trimethoxysilane 1.08 g (8.87 × 10 -3 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 1.13 × 10 -2 g (3.49 × 10 as Pt alone) -8 mol) were mixed and aged for 24 hours at 80° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure to obtain 1.30 g of a product.

[0152] The resulting compound is 1H-NMR confirmed that the compound had the structure represented by the following formula (B): Furthermore, the biobased content of the compound, as measured by radiocarbon dating in accordance with ASTM D6866, was 77%. [ka]

[0153] [Synthesis Example 2] In a reaction vessel, the following formula (C) [ka] 1.00 g (3.10 × 10 -3 mol), toluene 1.00 g, trimethoxysilane 1.14 g (9.31 × 10 -3 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 1.18 × 10 -2 g (3.66 x 10 as Pt alone) -8 mol) were mixed and aged for 24 hours at 80° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure to obtain 1.25 g of a product.

[0154] The resulting compound is 1 H-NMR confirmed that the compound had a structure represented by the following formula (D): Furthermore, the biobased content of the compound was determined to be 88% by radiocarbon dating in accordance with ASTM D6866. [ka]

[0155] [Synthesis Example 3] In a reaction vessel, the following formula (E) [ka] 1.00 g (1.73 × 10 -3 mol), toluene 1.00 g, trimethoxysilane 0.636 g (5.20 × 10 -3 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 6.62 × 10-3 g (2.05 × 10 as Pt alone) -8 mol) were mixed and aged for 24 hours at 80° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure to obtain 1.13 g of a product.

[0156] The resulting compound is 1 H-NMR confirmed that the compound had a structure represented by the following formula (F): Furthermore, the biobased content of the compound, as measured by radiocarbon dating in accordance with ASTM D6866, was 92%. [ka]

[0157] [Synthesis Example 4] In a reaction vessel, the following formula (G) [ka] 1.00 g (1.25 × 10 -3 mol), toluene 1.00 g, trimethoxysilane 0.458 g (3.75 × 10 -3 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 4.77 × 10 -3 g (1.47 × 10 as Pt alone) -8 mol) were mixed and aged for 24 hours at 80° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure to obtain 1.10 g of a product.

[0158] The resulting compound is 1 H-NMR confirmed that the compound had a structure represented by the following formula (H): Furthermore, the compound was found to be 75% biobased, as determined by radiocarbon dating in accordance with ASTM D6866. [ka]

[0159] [Synthesis Example 5] In a reaction vessel, the following formula (I) [ka] 1.00 g (1.34 × 10 -3 mol), toluene 1.00 g, trimethoxysilane 0.490 g (4.01 × 10 -3 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 5.10 × 10 -3 g (1.58×10 as Pt alone) -8 mol) were mixed and aged for 24 hours at 80° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure to obtain 1.11 g of a product.

[0160] The resulting compound is 1 H-NMR confirmed that the compound had a structure represented by the following formula (J): Furthermore, the biobased content of the compound, as measured by radiocarbon dating in accordance with ASTM D6866, was 68%. [ka]

[0161] [Synthesis Example 6] In a reaction vessel, the following formula (M) [ka] 1.00 g (1.37 × 10 -3 mol), toluene 1.00 g, trimethoxysilane 0.502 g (4.11 × 10 -3 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 5.23 × 10 -3 g (1.62 × 10 as Pt alone) -8 mol) were mixed and aged for 24 hours at 80° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure to obtain 1.09 g of a product.

[0162] The resulting compound is 1 H-NMR confirmed that the compound had the structure represented by the following formula (N): Furthermore, the biobased content of the compound, as measured by radiocarbon dating in accordance with ASTM D6866, was 94%. [ka]

[0163] [Synthesis Example 7] In a reaction vessel, the following formula (O) [ka] 1.00 g (1.29 × 10 -3 mol), toluene 2.00 g, allyltrimethoxysilane 1.25 g (7.73 × 10 -3 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 4.92 × 10 -3 g (1.52 × 10 as Pt alone) -8 mol) were mixed and aged for 24 hours at 80° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure to obtain 1.58 g of a product.

[0164] The resulting compound is 1 H-NMR confirmed that the compound had the structure represented by the following formula (P): Furthermore, the biobased content of the compound, as measured by radiocarbon dating in accordance with ASTM D6866, was 57%. [ka]

[0165] [Synthesis Example 8] In a reaction vessel, the following formula (Q) [ka] 1.00 g (2.59 × 10 -3 mol), toluene 1.00 g, trimethoxysilane 0.949 g (7.77 × 10 -3 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 9.89 × 10 -3 g (3.06 × 10 as Pt alone) -8 mol) were mixed and aged for 24 hours at 80° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure to obtain 1.30 g of a product.

[0166] The resulting compound is 1 H-NMR confirmed that the compound had a structure represented by the following formula (R): Furthermore, the compound was found to be 60% biobased, as determined by radiocarbon dating in accordance with ASTM D6866. [ka]

[0167] [Synthesis Example 9] In a reaction vessel, the following formula (S) [ka] 1.00 g (1.29 × 10 -3 mol), toluene 1.00 g, trimethoxysilane 0.474 g (3.88 × 10 -3 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 4.94 × 10 -3 g (1.53 × 10 as Pt alone) -8 mol) were mixed and aged for 24 hours at 80° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure to obtain 1.14 g of a product.

[0168] The resulting compound is 1 H-NMR confirmed that the compound had a structure represented by the following formula (T): Furthermore, the biobased content of the compound was determined to be 85% by radiocarbon dating in accordance with ASTM D6866. [ka]

[0169] [Synthesis Example 10] In a reaction vessel, the following formula (U) [ka] 1.00 g (1.48 × 10 -3mol), toluene 1.00 g, trimethoxysilane 0.544 g (4.45 × 10 -3 mol), and chloroplatinic acid / vinylsiloxane complex in toluene solution 5.67 × 10 -3 g (1.75 x 10 as Pt alone) -8 mol) were mixed and aged for 24 hours at 80° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure to obtain 1.12 g of a product.

[0170] The resulting compound is 1 H-NMR confirmed that the compound had a structure represented by the following formula (V): Furthermore, the compound was found to be 80% biobased, as determined by radiocarbon dating in accordance with ASTM D6866. [ka]

[0171] [Synthesis Example 11] In a reaction vessel, the following formula (W) [ka] 1.00 g (1.79 × 10 -3 mol), toluene 1.00 g, trimethoxysilane 1.31 g (1.07 × 10 -2 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 6.83 × 10 -3 g (2.11 x 10 as Pt alone) -8 mol) were mixed and aged for 24 hours at 80° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure to obtain 1.36 g of a product.

[0172] The resulting compound is 1 H-NMR confirmed that the compound had a structure represented by the following formula (X): Furthermore, the compound was found to have a biobased content of 73% as determined by radiocarbon dating in accordance with ASTM D6866. [ka]

[0173] [Synthesis Example 12] In a reaction vessel, the following formula (AG) [ka] 1.00 g (1.69 × 10 -3 mol), toluene 1.00 g, trimethoxysilane 0.621 g (5.08 × 10 -3 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 6.47 × 10 -3 g (2.00 x 10 as Pt alone) -8 mol) were mixed and aged for 24 hours at 80° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure to obtain 1.18 g of a product.

[0174] The resulting compound is 1 H-NMR confirmed that the compound had the structure represented by the following formula (AH): Furthermore, radiocarbon dating according to ASTM D6866 determined that the compound had a biobased content of 70%. [ka]

[0175] [Synthesis Example 13] In a reaction vessel, the following formula (AM) [ka] 1.00 g (1.35 × 10 -3 mol), toluene 1.00 g, trimethoxysilane 1.49 g (1.22 × 10 -2 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 5.17 × 10 -3 g (1.60×10 as Pt alone) -8 mol) were mixed and aged for 24 hours at 80° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure to obtain 1.47 g of a product.

[0176] The resulting compound is 1H-NMR confirmed that the compound had the structure represented by the following formula (AN): Furthermore, the biobased content of the compound, as measured by radiocarbon dating in accordance with ASTM D6866, was 56%. [ka]

[0177] [Synthesis Example 14] In a reaction vessel, the following formula (AO) [ka] 1.00 g (1.73 × 10 -3 mol), toluene 1.00 g, trimethoxysilane 0.636 g (5.20 × 10 -3 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 6.62 × 10 -3 g (2.05 × 10 as Pt alone) -8 mol) were mixed and aged for 24 hours at 80° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure to obtain 1.20 g of a product.

[0178] The resulting compound is 1 H-NMR confirmed that the compound had the structure represented by the following formula (AP): Furthermore, radiocarbon dating according to ASTM D6866 determined that the compound had a biobased content of 86%. [ka]

[0179] [Synthesis Example 15] In a reaction vessel, the following formula (AY) [ka] 1.00 g (1.52 × 10 -3 mol), toluene 1.00 g, trimethoxysilane 0.557 g (4.55 × 10 -3 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 5.80 × 10-3 g (1.79 × 10 as Pt alone) -8 mol) were mixed and aged for 24 hours at 80° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure to obtain 1.13 g of a product.

[0180] The resulting compound is 1 H-NMR confirmed that the compound had the structure represented by the following formula (AZ): Furthermore, the compound was found to be 79% biobased, as determined by radiocarbon dating in accordance with ASTM D6866. [ka]

[0181] [Synthesis Example 16] In a reaction vessel, the following formula (BC) [ka] 1.00 g (1.97 × 10 -3 mol), toluene 1.00 g, trichlorosilane 0.802 g (5.92 × 10 -3 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 7.54 × 10 -3 g (2.33 × 10 as Pt alone) -8 The resulting mixture (containing 1.00 mol) was mixed and aged at 60°C for 24 hours. The solvent and unreacted materials were then distilled off under reduced pressure. The resulting product was mixed with 3.00 g of toluene and aged for 6 hours at room temperature while bubbling ammonia gas (ammonia gas used at a rate of 40 cc / min). The mixture was then filtered, and the solvent and unreacted materials were distilled off under reduced pressure to obtain 1.01 g of product.

[0182] The resulting compound is 1 H-NMR confirmed that the compound had the structure represented by the following formula (BD): Furthermore, the biobased content of the compound, as measured by radiocarbon dating in accordance with ASTM D6866, was 91%. [ka]

[0183] [Synthesis Example 17] In a reaction vessel, the following formula (BI) [ka] 1.00 g (1.92 × 10 -3 mol), toluene 1.00 g, (3-isocyanatopropyl)triethoxysilane 0.521 g (2.11 × 10 -3 mol) were mixed and aged for 24 hours at 50° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure to obtain 1.45 g of a product.

[0184] The resulting compound is 1 H-NMR confirmed that the compound had the structure represented by the following formula (BJ): Furthermore, the biobased content of the compound, as measured by radiocarbon dating in accordance with ASTM D6866, was 78%. [ka]

[0185] [Synthesis Example 18] In a reaction vessel, the following formula (BK) [ka] 1.00 g (3.33 × 10 -3 mol), toluene 1.00 g, (3-isocyanatopropyl)trimethoxysilane 1.43 g (6.99 × 10 -3 mol), and titanium tetra-2-ethylhexoxide 9.40 × 10 -2 g (1.67 × 10 -4 mol) were mixed and aged for 24 hours at 50° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure to obtain 2.34 g of a product.

[0186] The resulting compound is 1H-NMR confirmed that the compound had the structure represented by the following formula (BL): Furthermore, the biobased content of the compound, as measured by radiocarbon dating in accordance with ASTM D6866, was 58%. [ka]

[0187] [Synthesis Example 19] In a reaction vessel, the following formula (XA) [ka] 1.00 g (1.82 × 10 -3 mol), toluene 1.00 g, trimethoxysilane 0.668 g (5.47 × 10 -3 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 6.96 × 10 -3 g (2.15 × 10 as Pt alone) -8 mol) were mixed and aged for 24 hours at 80° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure to obtain 1.21 g of a product.

[0188] The resulting compound is 1 H-NMR confirmed that the compound had the structure represented by the following formula (XB): Furthermore, the biobased content of the compound, as measured by radiocarbon dating in accordance with ASTM D6866, was 52%. [ka]

[0189] [Synthesis Example 20] In a reaction vessel, the following formula (XC) [ka] 1.00 g (1.59 × 10 -3 mol), toluene 1.00 g, trimethoxysilane 1.16 g (9.51 × 10 -3 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 6.06 × 10-3 g (1.87 × 10 as Pt alone) -8 mol) were mixed and aged for 24 hours at 80° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure to obtain 1.35 g of a product.

[0190] The resulting compound is 1 H-NMR confirmed that the compound had the structure represented by the following formula (XD): Furthermore, the compound was found to be 76% biobased, as determined by radiocarbon dating in accordance with ASTM D6866. [ka]

[0191] The compounds obtained in the synthesis examples were dissolved in a solvent to prepare surface treatment agent compositions.

[0192] [Example 1] A surface treatment agent composition was prepared by dissolving the compound obtained in Synthesis Example 1 in toluene to a concentration of 20 mass %. The biobased content of the toluene used was measured by radiocarbon dating in accordance with ASTM D6866 and was found to be 100%.

[0193] [Example 2] A surface treatment agent composition was prepared by dissolving the compound obtained in Synthesis Example 2 in isooctane to a concentration of 20 mass %. The biobased content of the isooctane used was measured by radiocarbon dating in accordance with ASTM D6866 and was found to be 0%.

[0194] [Example 3] A surface treatment agent composition was prepared by dissolving the compound obtained in Synthesis Example 3 in dibutyl ether to a concentration of 20 mass %. The biobased content of the dibutyl ether used was measured by radiocarbon dating in accordance with ASTM D6866 and was found to be 0%.

[0195] [Example 4] The compound obtained in Synthesis Example 4 was dissolved in dibutyl ether to a concentration of 20% by mass to prepare a surface treatment agent composition.

[0196] [Example 5] The compound obtained in Synthesis Example 5 was dissolved in toluene to a concentration of 10% by mass to prepare a surface treatment agent composition.

[0197] [Example 6] A surface treatment agent composition was prepared by dissolving the compound obtained in Synthesis Example 6 in isononane to a concentration of 20 mass %. The biobased content of the isononane used was measured by radiocarbon dating in accordance with ASTM D6866 and was found to be 0%.

[0198] [Example 7] The compound obtained in Synthesis Example 7 was dissolved in dibutyl ether to a concentration of 5 mass % to prepare a surface treatment agent composition.

[0199] [Example 8] A surface treatment agent composition was prepared by dissolving the compound obtained in Synthesis Example 8 in propylene glycol monomethyl ether acetate to a concentration of 30 mass %. The biobased content of the propylene glycol monomethyl ether acetate used was measured by radiocarbon dating in accordance with ASTM D6866 and was found to be 0%.

[0200] [Example 9] The compound obtained in Synthesis Example 9 was dissolved in toluene to a concentration of 20% by mass to prepare a surface treatment agent composition.

[0201] [Example 10] The compound obtained in Synthesis Example 10 was dissolved in toluene to a concentration of 20% by mass to prepare a surface treatment agent composition.

[0202] [Example 11] The compound obtained in Synthesis Example 11 was dissolved in isooctane to a concentration of 10% by mass to prepare a surface treatment agent composition.

[0203] [Example 12] A surface treatment agent composition was prepared by dissolving the compound obtained in Synthesis Example 12 in a hexane / isooctane (mass ratio 50 / 50) mixed solution to a concentration of 20 mass %. The biobased content of the hexane / isooctane (mass ratio 50 / 50) mixed solution used was measured by radiocarbon dating in accordance with ASTM D6866 and was found to be 0%.

[0204] [Example 13] The compound obtained in Synthesis Example 13 was dissolved in toluene to a concentration of 20% by mass to prepare a surface treatment agent composition.

[0205] [Example 14] The compound obtained in Synthesis Example 14 was dissolved in dibutyl ether to a concentration of 20% by mass to prepare a surface treatment agent composition.

[0206] [Example 15] The compound obtained in Synthesis Example 15 was dissolved in isooctane to a concentration of 20% by mass to prepare a surface treatment agent composition.

[0207] [Example 16] The compound obtained in Synthesis Example 16 was dissolved in isooctane to a concentration of 20% by mass to prepare a surface treatment agent composition.

[0208] [Example 17] The compound obtained in Synthesis Example 17 was dissolved in isooctane to a concentration of 20% by mass to prepare a surface treatment agent composition.

[0209] [Example 18] A surface treatment agent composition was prepared by dissolving the compound obtained in Synthesis Example 18 in butyl acetate to a concentration of 10 mass %. The biobased content of the butyl acetate used was 100% as measured by radiocarbon dating in accordance with ASTM D6866.

[0210] [Example 19] A surface treatment agent composition was prepared by dissolving the compound obtained in Synthesis Example 19 in ethylcyclohexane to a concentration of 10 mass %. The biobased content of the ethylcyclohexane used was measured by radiocarbon dating in accordance with ASTM D6866 and was found to be 0%.

[0211] [Example 20] The compound obtained in Synthesis Example 20 was dissolved in dibutyl ether to a concentration of 10% by mass to prepare a surface treatment agent composition.

[0212] [Example 21] The compound obtained in Synthesis Example 1 was dissolved in toluene to a concentration of 20% by mass. 3 parts by mass of tetramethoxysilane as a dehydrating agent was added to 100 parts by mass of the prepared solution to prepare a surface treatment agent composition.

[0213] [Example 22] The compound obtained in Synthesis Example 19 was dissolved in ethylcyclohexane to a concentration of 10 mass %. 3 parts by mass of methyltrimethoxysilane as a dehydrating agent was added to 100 parts by mass of the prepared solution to prepare a surface treatment agent composition.

[0214] [Comparative Example 1] The following formula [ka] A surface treatment agent composition was prepared by dissolving a compound represented by the formula (I) in ethylcyclohexane to a concentration of 20 mass %. The biobased content of the compound was measured by radiocarbon dating in accordance with ASTM D6866 and was found to be 0%.

[0215] Comparative Example 2 No surface treatment composition.

[0216] Formation of a cured coating of the surface treatment composition Each of the surface treatment agent compositions prepared in the above Examples and Comparative Examples was vacuum-deposited (apparatus: ULVAC Kiko Co., Ltd., product number: VTR-350M) onto glass (Corning Gorilla Glass (product number: Gorilla III, size: 100 mm × 50 mm × 0.7 mm)) whose outermost surface was coated with SiO2 to a thickness of 10 nm (treatment conditions: pressure: 2.0 × 10 -2 The coating was cured at 80°C and 80% relative humidity for 1 hour (Pa, heating temperature: 700°C), and then at 25°C and 50% relative humidity for 12 hours to form a cured coating with a thickness of 3 to 5 nm.

[0217] The glass on which the cured coating was formed was evaluated for water repellency, slipperiness, ease of wiping, and abrasion resistance using the methods described below. Note that the same evaluation was carried out on glass (Corning Gorilla Glass (product number: Gorilla III, size: 100 mm × 50 mm × 0.7 mm)) that had not undergone any surface treatment and had been coated on its outermost surface with SiO2 to a thickness of 10 nm, which was used as is as Comparative Example 2.

[0218] Water repellency evaluation The contact angle (water repellency) of the cured coating on the glass surface prepared as described above was measured with a contact angle meter, Drop Master (Kyowa Interface Science Co., Ltd.) (droplet: 2 μl, temperature: 25° C., relative humidity: 40%). The results are shown in Table 1. In the present invention, a good (water-repellent) water contact angle is defined as 90° or more (the same applies hereinafter).

[0219] Evaluation of slipperiness The coefficient of dynamic friction of the glass having the cured coating formed thereon as prepared above against nonwoven fabric was evaluated using the method described below to assess its slipperiness. The coefficient of dynamic friction of the glass having the cured coating formed against nonwoven fabric was measured in accordance with ASTM D1894 using a surface property tester Type: 14FW (manufactured by Shinto Scientific Co., Ltd.) under conditions of a load of 100 gf and a pulling speed of 500 mm / min. The results (coefficient of dynamic friction) are shown in Table 1. [Slipperiness evaluation conditions] Load: 100gf Stroke: 100mm Contact area: 1 x 3cm 2 Nonwoven fabric: BEMCOT (manufactured by Asahi Kasei Corporation)

[0220] Evaluation of dirt wiping ability A 2 cm straight line was drawn on the glass surface with the cured coating prepared as described above using a Hi-Macchie (manufactured by Zebra), after which the ink dried and the line was wiped off with tissue paper. The number of times the ink was rubbed until it was wiped off was evaluated according to the following criteria. The results are shown in Table 1. [Evaluation criteria for dirt wiping ability] A: Rubbed less than 4 times B: 5 or more rubs C: Ink cannot be wiped off

[0221] Wear resistance evaluation The glass having the cured coating formed thereon was rubbed every 1,000 times using a rubbing tester (manufactured by Shinto Scientific Co., Ltd.) under the following conditions, and the water contact angle (water repellency) of the cured coating was measured in the same manner as above. The number of times the water contact angle became less than 80° was counted and used to evaluate abrasion resistance. The test environment conditions were 25°C and a relative humidity of 40%. The results (the number of times the water contact angle became less than 80°) are shown in Table 1. [Steel wool abrasion resistance test conditions] Steel wool: Bonster #0000 Contact area: 1cm 2 Travel distance (one way): 40 mm Traveling speed: 4,800mm / min Load: 500gf / 1cm 2

[0222] The cured coatings of the surface treatment agent compositions of Examples 1 to 22 exhibited good water repellency, slipperiness, dirt wipeability, and abrasion resistance. Furthermore, the biobased content of the silane compound contained in each surface treatment agent composition was high, resulting in a low environmental impact. The cured coating of the surface treatment agent composition of Comparative Example 1 exhibited good water repellency, slipperiness, and dirt wipeability, but low abrasion resistance. Furthermore, the biobased content of the silane compound contained in the surface treatment agent composition was 0%, resulting in a high environmental impact. Comparative Example 2, which uses a glass substrate without a cured coating of the surface treatment agent composition, exhibits none of these properties, confirming the effects of the Examples. As described above, the surface treatment agent compositions of the Examples were able to obtain cured coatings with high levels of water repellency, slipperiness, dirt wipeability, and abrasion resistance by vapor deposition coating.

[0223] [Table 1]

[0224] [Example 23] The compound obtained in Synthesis Example 1 was dissolved in dibutyl ether to a concentration of 0.1% by mass to prepare a surface treatment agent composition.

[0225] [Example 24] The compound obtained in Synthesis Example 3 was dissolved in toluene to a concentration of 0.1% by mass to prepare a surface treatment agent composition.

[0226] [Example 25] The compound obtained in Synthesis Example 12 was dissolved in isooctane to a concentration of 0.1% by mass to prepare a surface treatment agent composition.

[0227] Formation of a cured coating of the surface treatment composition Each of the surface treatment agent compositions prepared in the above Examples was spray-coated onto glass (Corning Gorilla Glass (product number: Gorilla III, size: 100 mm × 50 mm × 0.7 mm)), and cured for 1 hour in an atmosphere of 80°C and 80% relative humidity, and then for 12 hours in an atmosphere of 25°C and 50% relative humidity to form a cured coating having a thickness of 3 to 5 nm.

[0228] The glass having the cured coating formed thereon was evaluated for water repellency, slipperiness, dirt wiping ability, and abrasion resistance by the methods described below.

[0229] Water repellency evaluation The contact angle (water repellency) of the cured coating on the glass surface prepared as described above was measured with a contact angle meter, Drop Master (Kyowa Interface Science Co., Ltd.) (droplet: 2 μl, temperature: 25° C., relative humidity: 40%). The results are shown in Table 2.

[0230] Evaluation of slipperiness The coefficient of dynamic friction of the glass coated with the cured coating prepared above against nonwoven fabric was evaluated using the method described below to assess its slipperiness. The coefficient of dynamic friction of the glass coated with the cured coating against nonwoven fabric was measured in accordance with ASTM D1894 using a surface property tester Type: 14FW (manufactured by Shinto Scientific Co., Ltd.) under conditions of a load of 100 gf and a pulling speed of 500 mm / min. The results (coefficient of dynamic friction) are shown in Table 2. [Slipperiness evaluation conditions] Load: 100gf Stroke: 100mm Contact area: 1 x 3cm 2 Nonwoven fabric: BEMCOT (manufactured by Asahi Kasei Corporation)

[0231] Evaluation of dirt wiping ability A 2 cm straight line was drawn on the glass surface with the cured coating prepared as described above using a Hi-Macchie (manufactured by Zebra), after which the ink was dried and the line was wiped off with tissue paper. The number of times the ink was rubbed until it was wiped off was evaluated according to the following criteria. The results are shown in Table 2. [Evaluation criteria for dirt wiping ability] A: Rubbed less than 4 times B: 5 or more rubs C: Ink cannot be wiped off

[0232] Wear resistance evaluation The glass having the cured coating formed thereon was rubbed every 500 times using a rubbing tester (manufactured by Shinto Scientific Co., Ltd.) under the following conditions, and the contact angle (water repellency) of the cured coating with water was measured in the same manner as above. The number of times the water contact angle became less than 80° was counted and used to evaluate abrasion resistance. The test environment conditions were 25°C and a relative humidity of 40%. The results (the number of times the water contact angle became less than 80°) are shown in Table 2. [Steel wool abrasion resistance test conditions] Steel wool: Bonster #0000 Contact area: 1cm 2 Travel distance (one way): 40 mm Traveling speed: 4,800mm / min Load: 500gf / 1cm 2

[0233] The cured coatings of the surface treatment agent compositions of Examples 23 to 25 exhibited good water repellency, slipperiness, dirt wipeability, and abrasion resistance. Furthermore, the biobased content of the silane compounds contained in each surface treatment agent composition was high, resulting in a low environmental impact. As described above, the surface treatment agent compositions of the Examples were able to produce cured coatings with high levels of water repellency, slipperiness, dirt wipeability, and abrasion resistance, even when spray coated, which is an example of wet coating.

[0234] [Table 2]

Claims

1. An organosilane compound (α) and / or a partially reacted condensate thereof, and a solvent, the organosilane compound (α) is a non-fluorine-based compound having at least one linear, branched or cyclic monovalent hydrocarbon group having 3 to 60 carbon atoms, which may contain at least one atom selected from the group consisting of an oxygen atom, a sulfur atom, a nitrogen atom and a silicon atom, and a reactive silyl group, and has a biobased content of 50% or more as measured by radiocarbon dating in accordance with ASTM D6866; the solvent is selected from an alcohol-based solvent, an ether-based solvent, a ketone-based solvent, an ester-based solvent, a carbonate-based solvent, a siloxane-based solvent, and a hydrocarbon-based solvent; A surface treatment composition comprising a material that does not contain fluorine atoms.

2. 2. The surface treatment composition according to claim 1, wherein the monovalent hydrocarbon group in the organosilane compound (α) is linear or branched.

3. 2. The surface treatment composition according to claim 1, wherein the organosilane compound (α) has two or more of the monovalent hydrocarbon groups.

4. 4. The surface treatment composition according to claim 3, wherein in the organosilane compound (α), two or more of the monovalent hydrocarbon groups are bonded to the same atom.

5. 5. The surface treatment composition according to claim 4, wherein in the organosilane compound (α), the same atom to which two or more of the monovalent hydrocarbon groups are bonded is a carbon atom, a nitrogen atom, or a silicon atom.

6. 4. The surface treatment composition according to claim 3, wherein the organosilane compound (α) has two or more of the monovalent hydrocarbon groups that are the same.

7. 2. The surface treatment composition according to claim 1, wherein in the organosilane compound (α), the monovalent hydrocarbon group has 8 to 40 carbon atoms.

8. The organosilane compound (α) is represented by the following general formula (1): 【Chemistry 1】 (In the formula, R 1 are monovalent hydrocarbon groups having 3 to 32 carbon atoms, which may independently contain at least one atom selected from oxygen, sulfur, nitrogen, and silicon atoms, and which may be linear, branched, or cyclic, or a combination thereof; R 2 represents a hydrogen atom, a halogen atom, a hydroxyl group, a siloxy group, an amino group, a thiol group, or a monovalent hydrocarbon group having 1 or 2 carbon atoms; U represents a carbon atom, a silicon atom, a nitrogen atom, or a trivalent or tetravalent organic group; V independently represents a single bond or a divalent hydrocarbon group which may contain at least one atom selected from an oxygen atom, a nitrogen atom, and a sulfur atom; Z independently represents a single bond, a carbon atom, a silicon atom, a nitrogen atom, a sulfur atom, or a tri- to octavalent organic group; Y independently represents a divalent hydrocarbon group which may contain at least one atom selected from an oxygen atom, a nitrogen atom, a sulfur atom, and a silicon atom; A independently represents a monovalent reactive silyl group; k1 is 2 or 3, k2 is 0 or 1, k3 is 1 or 2, k1 + k2 + k3 is 3 or 4, and m is an integer from 1 to 7. The surface treatment composition according to claim 1, wherein the surface treatment composition is represented by the formula:

9. In the above formula (1), R 1 But the following formula 【Chemistry 2】 (In the formula, R A are independently a monovalent hydrocarbon group having 3 to 32 carbon atoms which may be linear, branched, or cyclic, or a combination thereof; Q independently represents an oxygen atom, a sulfur atom, a divalent cyclic hydrocarbon group having 6 to 8 carbon atoms, a diorganosilylene group, a silalkylene structure, a silarylene structure, a linear organopolysiloxane residue having 2 to 10 silicon atoms or a branched or cyclic organopolysiloxane residue having 3 to 10 silicon atoms, a carbonyl (ketone) group, an ester group, a carbonate group, a sulfinyl group, a sulfonyl group, a thioester group, a thiocarbonate group, a thiocarbamate group, an amino group, an amide group, a carbamate group, a urea group, a methyl ... Q' is independently a trivalent group selected from the group consisting of a nitrogen atom, a trivalent cyclic hydrocarbon group having 6 to 8 carbon atoms, a linear trivalent organopolysiloxane residue having 2 to 10 silicon atoms or a branched or cyclic trivalent organopolysiloxane residue having 3 to 10 silicon atoms, a trivalent amide group, and a trivalent nitrogen-containing heterocyclic group; Q" is independently a tetravalent group selected from the group consisting of a silicon atom, a tetravalent cyclic hydrocarbon group having 6 to 8 carbon atoms, and a linear trivalent organopolysiloxane residue having 2 to 10 silicon atoms or a branched or cyclic trivalent organopolysiloxane residue having 3 to 10 silicon atoms; R B are independently a single bond or a divalent hydrocarbon group having 1 to 32 carbon atoms, which may be linear, branched, or cyclic; R C are independently R A or a hydrogen atom, and p is an integer of 0 to 10. However, the total number of carbon atoms in each structure is 32 or less. The surface treatment agent composition according to claim 8, wherein the group is any one of the groups represented by the following formula:

10. In the above formula (1), A is represented by the following general formula (2) or (3): 【Transformation 3】 (In the formula, R is independently an alkyl group having 1 to 4 carbon atoms or a phenyl group, X is independently a hydroxyl group or a hydrolyzable group, and n is an integer of 1 to 3.) 【Chemistry 4】 (In the formula, n" is a number from 0 to 3, and n' is (3-n") / 2.) The surface treatment agent composition according to claim 8, wherein the group is a group represented by the formula:

11. The surface treatment agent composition according to claim 10, wherein in the above formula (2), X is selected from the group consisting of a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an alkoxyalkoxy group having 2 to 10 carbon atoms, an acyloxy group having 1 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, a halogen group, and a dialkylamino group having 2 to 10 carbon atoms.

12. 9. The surface treatment agent composition according to claim 8, wherein in the formula (1), Y is a group selected from the group consisting of alkylene groups having 1 to 20 carbon atoms which may contain at least one atom selected from oxygen atoms, nitrogen atoms, and sulfur atoms; alkylene groups having 1 to 10 carbon atoms which contain an arylene group having 6 to 8 carbon atoms; divalent groups in which alkylene groups having 1 to 8 carbon atoms are bonded to each other via a diorganosilylene group, a silalkylene structure, a silarylene structure, or a nitrogen-containing heterocyclic group; and divalent groups in which an alkylene group having 1 to 10 carbon atoms is bonded to a bond of a linear organopolysiloxane residue having 2 to 10 silicon atoms or a branched or cyclic organopolysiloxane residue having 3 to 10 silicon atoms.

13. In the above formula (1), Z is a single bond, a carbon atom, a silicon atom, a nitrogen atom, a trivalent or tetravalent cyclic hydrocarbon group having 6 to 8 carbon atoms, or —SiR 3 = (R 3 represents a hydroxyl group, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms), 4 = (R 4 and n is a hydrogen atom, a hydroxyl group, or an alkyl group having 1 to 3 carbon atoms), a trivalent to octavalent group selected from the group consisting of a linear organopolysiloxane residue having 2 to 10 silicon atoms or a branched or cyclic organopolysiloxane residue having 3 to 10 silicon atoms and having a valence of 3 to 8, a trivalent amide group, a trivalent carbamate group, a trivalent or tetravalent urea group, and a trivalent to octavalent nitrogen-containing heterocycle-containing group.

14. 9. The surface treatment agent composition according to claim 8, wherein in the above formula (1), U is a trivalent or tetravalent group selected from the group consisting of a carbon atom, a silicon atom, a nitrogen atom, a trivalent or tetravalent cyclic hydrocarbon group having 6 to 8 carbon atoms, a linear trivalent or tetravalent organopolysiloxane residue having 2 to 10 silicon atoms or a branched or cyclic trivalent or tetravalent organopolysiloxane residue having 3 to 10 silicon atoms, a trivalent amide group, a trivalent carbamate group, a trivalent or tetravalent urea group, and a trivalent or tetravalent nitrogen-containing heterocycle-containing group.

15. 2. The surface treatment composition according to claim 1, wherein the solvent is selected from the group consisting of ether-based solvents, ketone-based solvents, ester-based solvents, siloxane-based solvents, and hydrocarbon-based solvents.

16. 2. The surface treatment composition according to claim 1, wherein the biobased content of the solvent is 50% or more as measured by radiocarbon dating in accordance with ASTM D6866.

17. 2. The surface treatment agent composition according to claim 1, wherein the proportion of the organosilane compound (α) and / or the partially reacted condensate thereof is 0.05 to 70 mass% in the total of the organosilane compound (α) and / or the partially reacted condensate thereof and the solvent.

18. 2. The surface treatment agent composition according to claim 1, further comprising at least one non-fluorinated material selected from the group consisting of paraffin oil, polyol ester oil, silicone oil, catalyst, transition metal, halide ion, silane coupling agent, and compound containing an atom having an unshared electron pair in its molecular structure.

19. The surface treatment composition according to claim 1, which is used as an antifouling coating agent or a waterproof coating agent.

20. 2. The surface treatment composition according to claim 1, which is for vacuum deposition.

21. 2. The surface treatment agent composition according to claim 1, which is for spray coating, dip coating, spin coating, wipe coating, squeegee coating, die coating, inkjet coating, flow coating, roll coating, cast coating, Langmuir-Blodgett coating, or gravure coating.

22. A pellet comprising the surface treatment agent composition according to any one of claims 1 to 20.

23. An article comprising a substrate and a layer formed on the surface of the substrate from the surface treatment agent composition according to any one of claims 1 to 21.

24. 24. The article of claim 23, wherein the article is an optical element.

25. 24. The article of claim 23, wherein the article is a lens.

26. 24. The article of claim 23, wherein the article is a display.

Images