Article and method for producing article

Abstract

An article according to the present invention comprises a crystallized glass substrate, an underlayer that is disposed on the crystallized glass substrate, and a surface layer that is disposed on the underlayer, wherein: the underlayer includes a first underlayer which is disposed on the crystallized glass substrate and a second underlayer which is disposed on the first underlayer; the first underlayer contains at least one substance selected from the group consisting of aluminum oxide, silicon nitride, and zirconium oxide, provided that the first underlayer does not contain silicon oxide when containing aluminum oxide; the second underlayer contains silicon oxide; and the surface layer is formed using a compound having a reactive silyl group.

Description

Articles and methods for manufacturing articles

[0001] This disclosure relates to articles and methods for manufacturing articles.

[0002] Crystallized glass exhibits remarkably high surface hardness and excellent impact resistance. When crystallized glass is applied to components that make up surfaces that come into contact with fingers, a surface layer is required that does not easily deteriorate in performance (e.g., water and oil repellency, fingerprint stain removal, and lubricity (smoothness when touched with a finger)) even after repeated friction. To form a surface layer with friction resistance on a specific type of crystallized glass, it is known to form an intermediate layer containing a first layer of aluminum oxide and silicon oxide and a second layer of silicon oxide located on the first layer (Patent Document 1).

[0003] International Publication No. 2023 / 106293

[0004] However, because crystallized glass has a rougher surface than ordinary glass, simply coating the surface using conventional methods does not allow the coating agent to adhere properly to the crystallized glass, resulting in insufficient performance. When the inventors evaluated a specific crystallized glass with an intermediate layer and a surface layer formed as described in Patent Document 1, they found room for improvement in the frictional durability of the surface layer.

[0005] Therefore, this disclosure relates to the provision of an article having a surface layer with excellent friction resistance and a method for manufacturing the article.

[0006] This disclosure includes the following embodiments: <1> An article comprising a crystallized glass substrate, a base layer disposed on the crystallized glass substrate, and a surface layer disposed on the base layer, wherein the base layer comprises a first base layer disposed on the crystallized glass substrate and a second base layer disposed on the first base layer, the first base layer comprises at least one selected from the group consisting of aluminum oxide, silicon nitride, and zirconium oxide, provided that if aluminum oxide is included, silicon oxide is not included, the second base layer comprises silicon oxide, and the surface layer is formed using a compound having a reactive silyl group. <2> The article according to <1>, wherein the compound having a reactive silyl group is a compound having a perfluoropolyether chain and a reactive silyl group. <3> The article according to <1> or <2>, wherein the thickness of the base layer is 40 to 120 nm. <4> An article according to any one of <1> to <3>, wherein the ratio of the thickness of the first substrate to the thickness of the second substrate is 0.3 to 4.0. <5> An article according to any one of <1> to <4>, wherein the thickness of the first substrate is 20 nm or more. <6> An article according to any one of <1> to <5>, which is an optical component. <7> An article according to any one of <1> to <6>, which is a display or touch panel. <8> An article according to any one of <1> to <7>, which is an antifouling article. <9> A method for manufacturing an article, comprising forming a first underlayer, a second underlayer, and a surface layer in this order on a crystallized glass substrate, wherein the formation of the first underlayer involves coating with a composition for the first underlayer, which includes at least one selected from the group consisting of aluminum oxide, silicon nitride, and zirconium oxide, provided that if aluminum oxide is included, silicon oxide is not included; the formation of the second underlayer involves coating with a composition for the second underlayer, which includes silicon oxide; and the formation of the surface layer involves coating with a composition for the surface layer, which includes a compound having a reactive silyl group.<10> The method for manufacturing an article according to <9>, wherein the formation of the first underlayer comprises wet coating the composition for the first underlayer, the formation of the second underlayer comprises wet coating the composition for the second underlayer, and the formation of the surface layer comprises wet coating the composition for the surface layer. <11> The method for manufacturing an article according to <9>, wherein the formation of the first underlayer comprises dry coating the composition for the first underlayer, the formation of the second underlayer comprises dry coating the composition for the second underlayer, and the formation of the surface layer comprises dry coating the composition for the surface layer.

[0007] According to this disclosure, an article having a surface layer with excellent friction resistance and a method for manufacturing the article are provided.

[0008] In this disclosure, compounds, units, or groups represented by formula (X) are denoted as compound (X), unit (X), or group (X). Compounds, units, and groups represented by other formulas are denoted similarly. Fluoroalkyl groups are a general term encompassing perfluoroalkyl groups and partial fluoroalkyl groups. A perfluoroalkyl group means a group in which all hydrogen atoms of the alkyl group are replaced with fluorine atoms. A partial fluoroalkyl group is an alkyl group in which one or more hydrogen atoms are replaced with fluorine atoms and which has one or more hydrogen atoms. In other words, a fluoroalkyl group is an alkyl group having one or more fluorine atoms. An "organic group" means a hydrocarbon group which may have substituents and which may have heteroatoms or other bonds in its carbon chain. A "hydrocarbon group" is a group consisting of carbon atoms and hydrogen atoms, and includes aliphatic hydrocarbon groups (for example, divalent aliphatic hydrocarbon groups such as linear alkylene groups, branched alkylene groups, and cycloalkylene groups), aromatic hydrocarbon groups (for example, divalent aromatic hydrocarbon groups such as phenylene groups), and combinations thereof. The term "surface layer" refers to the layer formed on the outermost surface of the substrate. In this disclosure, "Me" may refer to a methyl group, and "Et" may refer to an ethyl group. The partial structures of fluoroether chains and fluoropolyether chains, as well as the "molecular weight" of fluorine-containing compounds, are as follows: １H-NMR and １９ This is the number-average molecular weight calculated by determining the number (average value) of oxyfluoroalkylene units based on the terminal groups using F-NMR. The molecular weights of other fluorine-containing compounds other than fluoroether chains and fluoropolyether chains, as well as the molecular weights of other compounds, are as follows: １ H-NMR and １９ The compound's structure can be analyzed and calculated using F-NMR. The "~" indicating a numerical range includes the values ​​before and after it as the lower and upper limits, respectively.

[0009] [Article] The article of this disclosure (hereinafter also referred to as "the Article") comprises a crystallized glass substrate, a base layer disposed on the crystallized glass substrate, and a surface layer disposed on the base layer, wherein the base layer includes a first base layer disposed on the crystallized glass substrate and a second base layer disposed on the first base layer, the first base layer includes at least one selected from the group consisting of aluminum oxide, silicon nitride, and zirconium oxide, provided that if aluminum oxide is included, silicon oxide is not included, the second base layer includes silicon oxide, and the surface layer is formed using a compound having a reactive silyl group.

[0010] The first underlayer, placed on a crystallized glass substrate, contains at least one selected from the group consisting of aluminum oxide, silicon nitride, and zirconium oxide. Since aluminum oxide, silicon nitride, and zirconium oxide are all compounds with higher hardness than silicon oxide, the first underlayer mitigates the surface roughness characteristic of crystallized glass while maintaining the desired surface hardness. Furthermore, a second underlayer containing silicon oxide is placed on the first underlayer. The first and second underlayers have good interaction and adhesion. Furthermore, a surface layer using a compound having a reactive silyl group (hereinafter also referred to as "this compound") is placed on the second underlayer. This compound can impart water-repellent and oil-repellent properties, as well as fingerprint stain removal properties. As a result, when this compound undergoes dehydration condensation, a Si-O-Si bond is formed between the second underlayer and the surface layer, so even when friction is applied to the article, the surface layer is less likely to peel off, resulting in excellent friction resistance, and maintaining water-repellent and oil-repellent properties, as well as fingerprint stain removal properties. Therefore, this article has a surface layer with excellent friction resistance.

[0011] <Crystallized Glass Substrate> This article has a crystallized glass substrate. The crystallized glass substrate contains crystallized glass, and preferably consists of crystallized glass. In this disclosure, "crystallized glass" is glass obtained by heat-treating amorphous glass to precipitate crystals, and contains crystals. Amorphous glass refers to glass in which, when measured using CuKα rays by X-ray diffraction in the range of 2θ from 10 to 80°, no diffraction peaks indicating crystals are observed.

[0012] The crystallized glass is preferably one that contains one or more crystals selected from the group consisting of lithium silicate crystals, lithium aluminosilicate crystals, and lithium phosphate crystals. Preferred lithium silicate crystals include lithium metasilicate crystals or lithium disilicate crystals. Preferred lithium aluminosilicate crystals include β-spodumene crystals or petalite crystals. Preferred lithium phosphate crystals include lithium orthophosphate crystals.

[0013] From the viewpoint of increasing mechanical strength, the crystallinity of crystallized glass is preferably 10% or more, more preferably 15% or more, even more preferably 20% or more, and particularly preferably 25% or more. From the viewpoint of increasing transparency, the crystallinity is preferably 70% or less, more preferably 60% or less, and even more preferably 50% or less. A lower crystallinity makes it easier to heat and bend or shape. The crystallinity of crystallized glass is, for example, 10 to 70%. The crystallinity can be calculated from the X-ray diffraction intensity using the Rietveld method. The Rietveld method is described in "Crystal Analysis Handbook" (Kyōritsu Shuppan, 1999, pp. 492-499), edited by the editorial committee of the Crystallographic Society of Japan.

[0014] From the viewpoint of high transparency, the average particle size of the precipitated crystals in crystallized glass is preferably 300 nm or less, more preferably 200 nm or less, even more preferably 150 nm or less, and particularly preferably 100 nm or less. From the viewpoint of surface smoothness, the average particle size is preferably greater than 0 nm, more preferably 5 nm or more, and even more preferably 10 nm or more. For example, the average particle size of the precipitated crystals in crystallized glass is greater than 0 nm and 300 nm or less. The average particle size can be measured from a transmission electron microscope (TEM) image or estimated from a scanning electron microscope (SEM) image.

[0015] When the crystallized glass substrate is in plate form, the thickness is preferably 3,000 μm or less from the viewpoint of cost-effectiveness, and more preferably, in stages, 2,000 μm or less, 1,600 μm or less, 1,500 μm or less, 1,100 μm or less, 900 μm or less, 800 μm or less, and 700 μm or less. From the viewpoint of obtaining sufficient strength, the thickness is preferably 200 μm or more, more preferably 400 μm or more, and even more preferably 500 μm or more. When the crystallized glass substrate is in plate form, the thickness is, for example, 200 to 3,000 μm. The thickness can be measured using a constant-pressure thickness measuring instrument.

[0016] Crystallized glass substrates are preferably for optical components, and more preferably for touch panels or displays. Crystallized glass substrates are preferably light-transmitting. "Light-transmitting" means a normal incidence visible light transmittance of 25% or more, in accordance with JIS R3106:1998 (ISO 9050:1990).

[0017] The composition of the crystallized glass substrate preferably contains SiO ２ , Li ２ O, and Al ２ O ３ . More specifically, in terms of mass% based on oxides, it is preferable to contain 40 to 80% of SiO ２ , 1 to 35% of Li ２ O, and 1 to 20% of Al ２ O ３ . More preferably, it contains 50 to 63% of SiO ２ , 3 to 21% of Li ２ O, and 5 to 19% of Al ２ O ３ .

[0018] One or both surfaces of the crystallized glass substrate may be a substrate subjected to a surface treatment such as corona discharge treatment, plasma treatment, or plasma graft polymerization treatment. When the surface treatment is performed, the adhesion between the crystallized glass substrate and the underlayer is more excellent, and the friction durability of the surface layer is more excellent. Therefore, it is preferable to perform a surface treatment on the surface of the crystallized glass substrate on the side in contact with the underlayer.

[0019] <Underlayer> This article has an underlayer disposed on the crystallized glass substrate of the present disclosure. The underlayer includes a first underlayer disposed on the crystallized glass substrate and a second underlayer disposed on the first underlayer. In the present disclosure, "Y disposed on X" may have other layers between X and Y, and from the viewpoint of the friction durability of the surface layer, it is preferable that X and Y are in contact with each other. From the viewpoint of excellent friction durability of the surface layer, the underlayer preferably consists of a first underlayer disposed on the crystallized glass substrate and a second underlayer disposed on the first underlayer.

[0020] The first and second substrate layers may both be layers in which the contained components are uniformly distributed (i.e., homogeneous layers) or layers in which the contained components are unevenly distributed (i.e., heterogeneous layers), and homogeneous layers are preferred from the viewpoint of having better frictional durability of the surface layer. Examples of heterogeneous layers include structures in which a concentration gradient of components occurs within the layer (gradation structure), and structures in which other components exist discontinuously within continuously existing components (sea-island structure). The surfaces (or interfaces) of the first and second substrate layers may have irregularities.

[0021] From the viewpoint of increasing the surface hardness of the article, mitigating the surface roughness of the crystallized glass substrate, and ensuring better adhesion of the surface layer to the substrate, the thickness of the substrate is preferably 10 nm or more, more preferably 15 nm or more, particularly preferably 20 nm or more, and most preferably 40 nm or more. From the viewpoint of maintaining the surface hardness of the article, the thickness is preferably 120 nm or less, more preferably 110 nm or less, and particularly preferably 100 nm or less. The thickness of the substrate is, for example, 40 to 120 nm. Methods for measuring the thickness of the substrate include cross-sectional observation of the substrate using an electron microscope (SEM, TEM, etc.), and methods using an optical interferometer, spectroscopic ellipsometer, or step meter.

[0022] The method for forming the first and second sublayers is as described in the manufacturing method of this article, which will be described later.

[0023] (First Substrate) The first substrate comprises at least one selected from the group consisting of aluminum oxide, silicon nitride, and zirconium oxide, provided that if aluminum oxide is included, silicon oxide is not included. From the viewpoint of increasing the surface hardness of the article, the first substrate comprises at least one selected from the group consisting of aluminum oxide and zirconium oxide, provided that if aluminum oxide is included, silicon oxide is preferably not included, and it is more preferable that aluminum oxide is included but silicon oxide is not included. Note that if the first substrate comprises aluminum oxide, silicon oxide is not included, meaning that in this article, aluminum oxide and silicon oxide do not coexist in the first substrate.

[0024] The above aluminum oxide is Al ｙ１ Oｚ１ (y1 and z1 are any integers of 1 or more), and typically Al ２ O ３ However, it may also contain aluminum oxide with different stoichiometric ratios. The silicon nitride mentioned above is Si ｙ２ N ｚ２ (y² and z² are any integers of 1 or more), and typically Si ３ N ４ However, it may also contain silicon nitride with different stoichiometric ratios. The above zirconium oxide is Zr ｙ３ O ｚ３ (where y3 and z3 are any integers of 1 or more), and typically ZrO ２ However, it may also contain zirconium oxide with different stoichiometric ratios. The silicon oxide mentioned above is Si ｙ４ O ｚ４ (where y4 and z4 are any integers of 1 or more) and typically SiO ２ However, it may also contain silicon dioxide with different stoichiometric ratios.

[0025] From the viewpoint of increasing surface hardness, the total content of aluminum oxide, silicon nitride, and zirconium oxide is preferably 30% by mass or more, more preferably 40% by mass or more, and particularly preferably 50% by mass or more, relative to the total amount of the first substrate. This total content may be 100% by mass or less, or less than 100% by mass. The total content of aluminum oxide, silicon nitride, and zirconium oxide is, for example, 30 to 100% by mass, relative to the total amount of the first substrate. The total content of aluminum oxide, silicon nitride, and zirconium oxide can be measured by XPS analysis (X-ray photoelectron spectroscopy).

[0026] The first underlayer may contain compounds other than aluminum oxide, silicon nitride, and zirconium oxide. Examples of compounds other than aluminum oxide, silicon nitride, and zirconium oxide include diamond-like carbon, quartz, and silicon carbide. From the viewpoint of increasing the surface hardness of the article, the surface hardness of the compounds contained in the first underlayer is preferably 2,200 MPa or higher, more preferably 2,350 MPa or higher, and particularly preferably 2,500 MPa or higher. From the viewpoint of excellent scratch resistance, the surface hardness is preferably 10,000 MPa or lower, more preferably 8,000 MPa or lower, and particularly preferably 5,000 MPa or lower. The surface hardness of the compounds contained in the first underlayer is, for example, 2,200 to 10,000 MPa. The surface hardness is measured using an indentation test device.

[0027] The thickness of the first underlayer is preferably 5 nm or more, more preferably 7 nm or more, particularly preferably 10 nm or more, and most preferably 20 nm or more, from the viewpoint of increasing the surface hardness of the article and mitigating the surface roughness of the crystallized glass substrate. From the viewpoint of optical properties, the thickness is preferably 100 nm or less, more preferably 90 nm or less, and particularly preferably 80 nm or less. The thickness of the first underlayer is, for example, 5 to 100 nm. The method for measuring the thickness of the first underlayer is the same as the method for measuring the thickness of the underlayer.

[0028] The ratio of the thickness of the first substrate to the thickness of the second substrate, as described later, is preferably 0.3 or higher, more preferably 0.4 or higher, and particularly preferably 0.5 or higher, from the viewpoint of increasing the surface hardness of the article and mitigating the surface roughness of the crystallized glass substrate. From the viewpoint of increasing the frictional durability of the surface layer, this ratio is preferably 4.0 or lower, more preferably 3.5 or lower, and particularly preferably 3.0 or lower. The ratio of the thickness of the first substrate to the thickness of the second substrate is, for example, 0.3 to 4.0. The ratio of the thickness of the first substrate to the thickness of the second substrate can be calculated from "(thickness of the first substrate) / (thickness of the second substrate)". The method for measuring the thickness of the first and second substrates is the same as the method for measuring the thickness of the substrates.

[0029] (Second Substrate) The second substrate contains silicon oxide. Silicon dioxide is preferred. Because the second substrate contains silicon oxide, when the compound coated on the second substrate undergoes dehydration condensation, Si-O-Si bonds are formed between the second substrate and the surface layer, forming a surface layer with excellent friction resistance.

[0030] The silicon dioxide mentioned above is Si ｙ５ O ｚ５ (y5 and z5 are any integers of 1 or more), and typically SiO ２ However, it may also contain silicon dioxide with different stoichiometric ratios.

[0031] The silicon dioxide content in the second sublayer is preferably 65% ​​by mass or more, more preferably 80% by mass or more, even more preferably 85% by mass or more, and particularly preferably 90% by mass or more, from the viewpoint of sufficient Si-O-Si bonding being formed between the second sublayer and the surface layer and the surface layer having excellent frictional durability. The content may be 100% by mass or less, or less than 100% by mass. For example, the silicon dioxide content in the second sublayer is 65 to 100% by mass. The silicon dioxide content is the remainder obtained by subtracting the total content of other elements (or the amount converted to oxides in the case of oxides) from the mass of the second sublayer.

[0032] From the viewpoint of improving the frictional durability of the surface layer, the second underlayer preferably further contains an oxide of at least one element selected from the group consisting of alkali metal elements, alkaline earth metal elements, platinum group elements, boron, aluminum, phosphorus, titanium, zirconium, iron, nickel, chromium, molybdenum, and tungsten. The presence of this element strengthens the bond between the second underlayer and the compound, thereby improving the frictional durability of the surface layer.

[0033] The thickness of the second underlayer is preferably 5 nm or more, more preferably 7 nm or more, and particularly preferably 10 nm or more, from the viewpoint of improving the frictional durability of the surface layer. From the viewpoint of maintaining the surface hardness of the article, the thickness is preferably 100 nm or less, more preferably 90 nm or less, and particularly preferably 80 nm or less. The thickness of the second underlayer is, for example, 5 to 100 nm. The method for measuring the thickness of the second underlayer is the same as the method for measuring the thickness of the underlayer.

[0034] <Surface Layer> The article has a surface layer disposed on a substrate of the disclosure. The surface layer is formed using the compound. The surface layer preferably contains condensates of the compound, more preferably contains condensates obtained by hydrolysis and dehydration condensation of some or all of the reactive silyl groups, and even more preferably consists of condensates obtained by hydrolysis and dehydration condensation of some or all of the reactive silyl groups.

[0035] The surface layer, like the underlayer, may be a homogeneous or heterogeneous layer, with a homogeneous layer being preferred from the viewpoint of superior frictional durability of the surface layer. Specific examples of heterogeneous layers include a gradient structure and a sea-island structure. The surface of the surface layer may have irregularities.

[0036] From the viewpoint of obtaining sufficient water-repellent and oil-repellent properties, fingerprint stain removal properties, and friction resistance, the thickness of the surface layer is preferably 1 nm or more, and more preferably 5 nm or more. From the viewpoint of improving utilization efficiency, the thickness is preferably 100 nm or less, more preferably 50 nm or less, and even more preferably 20 nm or less. The thickness of the surface layer is, for example, 1 to 100 nm. The thickness of the surface layer can be calculated from the vibration period of the interference pattern obtained by the X-ray reflectivity method using an X-ray diffractometer for thin film analysis.

[0037] The surface layer may contain compounds other than condensates obtained by hydrolysis and dehydration condensation reactions in some or all of the reactive silyl groups. Examples of compounds other than condensates obtained by hydrolysis and dehydration condensation reactions in some or all of the reactive silyl groups include fluorine-containing oils, silicone oils, and condensation curing catalysts.

[0038] The method for forming the surface layer is as described in the manufacturing method of this article, which is described later.

[0039] (Compound having a reactive silyl group) The surface layer is formed using a compound having a reactive silyl group (this compound). Since the reactive silyl group forms a Si-O-Si bond with the second substrate layer, the surface layer has excellent friction resistance. The total content of this compound and compounds derived from this compound (e.g., condensates) in the surface layer is preferably 65% ​​by mass or more, more preferably 80% by mass or more, even more preferably 85% by mass or more, and particularly preferably 90% by mass or more, from the viewpoint of better water and oil repellency, friction resistance, fingerprint stain removal, lubricity, and appearance of the surface layer. The content may be 100% by mass or less, or less than 100% by mass. The total content of this compound and compounds derived from this compound in the surface layer is, for example, 65 to 100% by mass. The total content of this compound and compounds derived from this compound can be measured by XPS analysis (X-ray photoelectron spectroscopy).

[0040] -Reactive Silyl Groups- The number of reactive silyl groups contained in this compound is one or more, and from the viewpoint of further improving the friction durability of the surface layer, it is preferably 1 to 18, more preferably 1 to 12, even more preferably 1 to 8, and particularly preferably 1 to 6. In one embodiment, the number of reactive silyl groups contained in this compound is preferably 2 to 18, more preferably 2 to 12, even more preferably 2 to 8, particularly preferably 2 to 6, and very preferably 1 to 4. The number of reactive silyl groups may be 1 or 2.

[0041] A reactive silyl group refers to a group in which a reactive group is bonded to a Si atom. Preferred reactive groups are hydrolyzable groups, groups having hydrolyzable groups, or hydroxyl groups.

[0042] A hydrolyzable group is a group that becomes a hydroxyl group through hydrolysis. That is, Si-L ０ (L ０ A hydrolyzable silyl group (represented by ∫) undergoes a hydrolysis reaction to become a silanol group represented by Si-OH. The silanol groups further react with each other to form Si-O-Si bonds. Additionally, silanol groups can undergo a dehydration condensation reaction with silanol groups derived from oxides present on the surface of the second subsoil to form Si-O-Si bonds.

[0043] Examples of hydrolyzable groups include alkoxy groups, aryloxy groups, halogen atoms, acyl groups, acyloxy groups, amino groups, and -O-N=CR groups. ｒ ２ and isocyanate groups (-NCO) are examples. For alkoxy groups, C1 to C4 alkoxy groups are preferred. For aryloxy groups, C3 to C10 aryloxy groups are preferred. However, the aryl group of the aryloxy group includes heteroaryl groups. For halogen atoms, chlorine atoms are preferred. For acyl groups, C1 to C6 acyl groups are preferred. For acyloxy groups, C1 to C6 acyloxy groups are preferred. R ｒ Each of these is independently an alkyl group having 1 to 10 carbon atoms.

[0044] Examples of groups having hydrolyzable groups include the hydrolyzable groups exemplified above. The hydrolyzable groups are -O-L Ａ -L Ｂ This is preferable. L Ａ L is an alkylene group, Ｂ This is a hydrolyzable group. The number of carbon atoms in the alkylene group is preferably 1 to 10. Ｂ The hydrolyzable group represented by is synonymous with the hydrolyzable group described above, and the preferred embodiment is also the same.

[0045] The reactive silyl group is preferably a group represented by the following formula (S1): -Si(R ２ ) ｎ L ３－ｎ ... (S1)

[0046] In formula (S1), R ２ Each of the following is independently a monovalent hydrocarbon group, each of the following is independently a hydrolyzable group, a group having a hydrolyzable group, or a hydroxyl group, and n is an integer from 0 to 2.

[0047] When there are multiple reactive silyl groups in a single molecule, the multiple reactive silyl groups may be the same or different from one another. From the viewpoint of the availability of raw materials and the ease of manufacturing the compound, it is preferable that the multiple reactive silyl groups are the same.

[0048] R ２Each of these is independently a monovalent hydrocarbon group, and a monovalent saturated hydrocarbon group is preferred. ２ The number of carbon atoms is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 to 2.

[0049] Each L is independently a hydrolyzable group, a group having a hydrolyzable group, or a hydroxyl group. Details of hydrolyzable groups and groups having a hydrolyzable group are as described above.

[0050] In particular, L is preferably an alkoxy group or halogen atom having 1 to 4 carbon atoms from the viewpoint of ease of compound production. From the viewpoint of less outgassing during coating and better storage stability of the compound, L is preferably an alkoxy group having 1 to 4 carbon atoms, and more preferably an ethoxy group or a methoxy group.

[0051] n is an integer between 0 and 2, preferably 0 or 1, and more preferably 0. The presence of multiple Ls strengthens the adhesion of the surface layer to the substrate.

[0052] When n is 1 or less, the multiple Ls present in one molecule may be the same or different from one another. From the viewpoint of the availability of raw materials and the ease of manufacturing the compound, it is preferable that the multiple Ls are the same. When n is 2, the multiple Rs present in one molecule ２ They may be the same or they may be different from one another. From the viewpoint of the availability of raw materials and the ease of manufacturing the compound, multiple R ２ It is preferable that they are the same.

[0053] From the viewpoint of excellent uniformity and durability of the surface layer, the reactive silyl group is preferably an alkoxysilyl group or a trichlorosilyl group. From the viewpoint of ease of handling of by-products generated in the reaction with the substrate, the reactive silyl group is more preferably an alkoxysilyl group. As the alkoxysilyl group, the dialkoxysilyl group or the trialkoxysilyl group is preferred, and the trialkoxysilyl group is more preferred.

[0054] Furthermore, the reactive silyl group may also be a group represented by the following formula (S2): >SiL ２ …(S2) L is the same as L in equation (S1).

[0055] The reactive silyl group is also preferably the group represented by the following formula (S3): -[Si(L ２ ) ２ -P] ｒ１ -Si(L ２ ) ３ ... (S3)

[0056] In formula (S3), L ２ Each of the following is independently a hydrolyzable group, a group having a hydrolyzable group, or a hydroxyl group; each of the following is independently an organic group having an oxygen atom or one carbon atom bonded to two adjacent Si atoms; and r1 is an integer from 1 to 3.

[0057] When there are multiple groups (S3) in one molecule, the multiple groups (S3) may be the same or different from each other. From the viewpoint of the availability of raw materials and the ease of manufacturing the compound, it is preferable that the multiple groups (S3) are the same.

[0058] L ２ These are, independently, a hydrolyzable group, a group having a hydrolyzable group, a hydroxyl group, or a hydrocarbon group. Details of the hydrolyzable group and the group having a hydrolyzable group are as described above. Among them, L ２ In this compound, the hydrolyzable group or group having a hydrolyzable group is preferably a carbon-1 to carbon-4 alkoxy group, an alkylene oxide-modified alkoxy group, or a halogen atom, from the viewpoint of ease of compound production. ２ From the viewpoint of reducing outgassing during application and providing superior storage stability of the compound, an alkoxy group having 1 to 4 carbon atoms is preferred, and an ethoxy group or a methoxy group is more preferred. ２ Examples of hydrocarbon groups represented by include alkyl groups, cycloalkyl groups, alkenyl groups, and allyl groups. From the viewpoint of ease of synthesis, saturated hydrocarbon groups are preferred, and alkyl groups are more preferred. The number of carbon atoms in the hydrocarbon group is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 to 2.

[0059] r1 is an integer between 1 and 3, and from the viewpoint of ease of composition, 1 to 2 is preferred, and 1 is more preferred.

[0060] Multiple L units possessed by one group (S3) ２Of these, at least four are preferably hydrolyzable groups, groups having hydrolyzable groups, or hydroxyl groups. This allows the group (S3) and the substrate to bond more strongly, resulting in a surface layer with excellent durability. From this viewpoint, the number of hydrolyzable groups, groups having hydrolyzable groups, and hydroxyl groups in the group (S3) is preferably 4 to 9, more preferably 4 to 7, and even more preferably 4 or 5. Note that there are multiple L groups present in one molecule. ２ They may be the same or they may be different from one another. For example, multiple L ２ These may be the same hydrolyzable group.

[0061] P is an organic group that independently has an oxygen atom or one carbon atom bonded to two adjacent Si atoms. Here, "an organic group that has one carbon atom bonded to two adjacent Si atoms" means that the Si atoms are linked together via one carbon atom. Examples of P include hydrocarbon groups, for example, -CH ２ -, -C(CH ３ ) ２ - Other options are also acceptable. From the viewpoint of surface layer durability, P can be an oxygen atom, -CH ２ -, or -C (CH ３ ) ２ - is preferred, and an oxygen atom or -CH ２ - is more preferable, and an oxygen atom is even more preferable.

[0062] The base (S3) is -[Si(OR １２ ) ２ -O] ｒ１ -Si(OR １２ ) ３ Preferably, -Si(OR) r1=1 １２ ) ２ -O-Si(OR １２ ) ３ This is particularly preferable. Here, R １２ Each of these is independently a hydrocarbon group. Examples of hydrocarbon groups include alkyl groups, cycloalkyl groups, alkenyl groups, and allyl groups. From the viewpoint of ease of synthesis, saturated hydrocarbon groups are preferred, and alkyl groups are more preferred. １２ The number of carbon atoms is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 or 2.

[0063] Specific examples of the group (S3) include -Si(OCH ３ ) ２ -O-Si(OCH ３ ) ３ ,-Si(OCH ３ ) ２ -CH ２ -Si(OCH ３ ) ３ ,-Si(OCH ３ ) ２ -C(CH ３ ) ２ -Si(OCH ３ ) ３ ,-Si(OCH ２ CH ３ ) ２ -O-Si(OCH ３ ) ３ ,-Si(OCH ３ ) ２ -O-Si(OCH ２ CH ３ ) ３ ,-Si(OCH ２ CH ３ ) ２ -O-Si(OCH ２ CH ３ ) ３ ,-Si(OCH ２ CH ３ ) ２ -CH ２ -Si(OCH ３ ) ３ ,-Si(OCH ３ ) ２ -CH ２ -Si(OCH ２ CH ３ ) ３ ,-Si(OCH<00001​​​​​​​​​​​​​​​​​​​​​​​​​​​３ ) ２ -C(CH ３ ) ２ -Si(OCH) ２ CH ３ ) ３ , -Si(OCH ２ CH ３ ) ２ -C(CH ３ ) ２ -Si(OCH) ２ CH ３ ) ３ -Si(OH) ２ -O-Si(OH) ３ -Si(OH) ２ -O-Si(OCH) ３ ) ３ , -Si(OCH ３ ) ２ -O-Si(OH) ３ -Si(OH) ２ -CH ２ -Si(OH) ３ -Si(OH) ２ -CH ２ -Si(OCH) ３ ) ３ , -Si(OCH ３ ) ２ -CH ２ -Si(OH) ３ -Si(OH) ２ -C(CH ３ ) ２ -Si(OH) ３ -Si(OH) ２ -C(CH ３ ) ２ -Si(OCH) ３ ) ３ , -Si(OCH ３ ) ２ -C(CH ３ ) ２ -Si(OH) ３ , are some examples.

[0064] This compound may be a fluorine-containing compound or a non-fluorine compound.

[0065] -Fluorine-containing compounds- From the viewpoint of improving water-repellent and oil-repellent properties and fingerprint stain removal properties, fluorine-containing compounds having a reactive silyl group are preferred, compounds having a fluoropolyether chain and a reactive silyl group are more preferred, compounds having a perfluoropolyether chain and a reactive silyl group are even more preferred, and fluorine-containing ether compounds having a perfluoropolyether chain and a reactive silyl group are particularly preferred.

[0066] The fluoropolyether chain is preferably group (f1). (OR ｆ１ ) ｙ …(f1)

[0067] R ｆ１ This is a fluoroalkylene group having 1 to 6 carbon atoms, and there are multiple R ｆ１ These two values ​​may be the same or different from each other. y is an integer greater than or equal to 2, preferably between 2 and 200.

[0068] As fluorine-containing compounds, compounds represented by the following formulas (A1), (A2), or (A3) are preferred. [R ｆ２ - ( OR ｆ１ ) ｙ -O-R １ ] ｊ -L １ - (R １１ -T ａ ) ｘ１ …(A1) (T ３１ -R ２ｄ ) ｘ３ -L ３ -R ２ｂ - ( OR ｆ１ ) ｙ -O-R ２ａ -L ４ - (R ２ｃ -T ２１ ) ｘ２ ... (A2) Q １ [-( OR ｆ１ ) ｙ -O-R ３ａ -L ５ - (R ４１ -T ４１ ) ｘ４ ] ｒ２ …(A3) (OR ｆ１ ) ｙThis is, in other words, the above group (f1), R ｆ２ R is a fluoroalkyl group having 1 to 20 carbon atoms. ｆ２ If there are multiple R ｆ２ They may be the same or different from each other, R １ R is an alkylene group or a fluoroalkylene group, １ If there are multiple R １ L may be the same or different from each other. １ R is an organic group with a single bond or which may have N, O, S, Si, and which may have a branch point (j+x1) valence, １ and R １１ The atoms bonded are, independently, N, O, S, Si, carbon atoms constituting the branching point, or carbon atoms having an oxo group (=O), R １１ is, L １ The atom bonded to it may be an etheric oxygen atom, and the alkylene group may have an etheric oxygen atom between the carbon atoms, T ａ This is the above group (S1), that is, -Si(R ２ ) ｎ L ３－ｎ And j is an integer greater than or equal to 1, x1 is an integer greater than or equal to 1, and R ２ａ and R ２ｂ Each of these is independently an alkylene group or a fluoroalkylene group, L ４ R is a (1+x2) valence organic group which may have a single bond or N, O, S, Si, and may have a branch point, ２ａ and R ２ｃ The atoms bonded are, independently, N, O, S, Si, carbon atoms constituting the branching point, or carbon atoms having an oxo group (=O), R ２ｃ is, L ４ The atom adjacent to it may be an etheric oxygen atom, and the alkylene group may have an etheric oxygen atom between the carbon atoms, L ３ R is a (1+x3) valent organic group which may have a single bond or N, O, S, Si, and may have a branch point, ２ｂ and R ２ｄThe atoms bonded are, independently, N, O, S, Si, carbon atoms constituting the branching point, or carbon atoms having an oxo group (=O), R ２ｄ is, L ３ The atom adjacent to it may be an etheric oxygen atom, and the alkylene group may have an etheric oxygen atom between the carbon and carbon atoms, T ２１ and T ３１ Each of these independently consists of the above group (S1), i.e., -Si(R ２ ) ｎ L ３－ｎ And x2 and x3 are each independent integers greater than or equal to 1, Q １ R is a r-valent group with a branching point, ３ａ Each of these is independently an alkylene group or a fluoroalkylene group, L ５ R is a (1+x4) valent organic group which may have a single bond or N, O, S, Si, and may have a branch point, ３ａ and R ４１ The atoms bonded are, independently, N, O, S, Si, carbon atoms constituting the branching point, or carbon atoms having an oxo group (=O), R ４１ is, L ５ The atom adjacent to it may be an etheric oxygen atom, and the alkylene group may have an etheric oxygen atom between the carbon and carbon atoms, T ４１ This is the above group (S1), that is, -Si(R ２ ) ｎ L ３－ｎ Herein, x4 is an integer greater than or equal to 1, and r2 is 3 or 4. The composition of each compound will be described below, but signs indicating similar structures will be indicated so that they can be interpreted and referenced as appropriate.

[0069] Compound (A1) Compound (A1) has the structure represented by the following formula (A1). [R ｆ２ - ( OR ｆ１ ) ｙ -O-R １ ] ｊ -L １ - (R １１ -T ａ ) ｘ１ …(A1) The symbols in equation (A1) are as described above.

[0070] R ｆ２ This is a fluoroalkyl group having 1 to 20 carbon atoms. The fluoroalkyl group may be linear, branched, and / or have a cyclic structure. From the viewpoint of frictional resistance, linear fluoroalkyl groups are preferred, and from the viewpoint of ease of synthesis, the number of carbon atoms in the fluoroalkyl group is preferably 1 to 6, and more preferably 1 to 3.

[0071] (OR ｆ１ ) ｙ R ｆ１ y and y are R in the above equation (f1), respectively. ｆ１ The same applies to y, and the preferred embodiment is also the same.

[0072] R １ R is an alkylene group or a fluoroalkylene group. １ The alkylene group and fluoroalkylene group in this compound may be linear, branched, and / or have a cyclic structure. From the viewpoint of ease of synthesis, linear or branched alkylene or fluoroalkylene groups are preferred, and alkylene or fluoroalkylene groups having a methyl group or fluoromethyl group as linear or branched are more preferred. １ The number of carbon atoms is preferably 1 to 6, and more preferably 1 to 3. １ is, L １ If it is a single bond, R １１ It is joined to R. １ R inside １１ The carbon atom bonded to it is bonded to at least one fluorine atom or fluoroalkyl group.

[0073] j is [R] in one molecule ｆ２ - ( OR ｆ１ ) ｙ -O-R １ This represents the number of [ ], and is an integer of 1 or more, preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 4.

[0074] R １１ is, L １ The atom bonded to it may be an etheric oxygen atom, and the alkylene group may have an etheric oxygen atom between the carbon and carbon atoms. １１The alkylene group in may be linear, branched, and / or cyclic. A linear or branched alkylene group having a methyl group is preferred, and a linear alkylene group is more preferred, as it is easier for compound (A1) to be densely arranged when forming the surface layer. １１ This is expressed by the following equation (g2). *-(O) ａ１ - (R ｇ２ O) ａ２ -R ｇ２ -**...(g2) R ｇ２ R is an alkylene group having one or more carbon atoms, and there are multiple R ｇ２ They may be the same or different from each other, a1 is 0 or 1, a2 is a non-negative integer, and * is L １ It is a bonding term that connects to T ａ It is a bonding hand that connects to [something].

[0075] If a1 is 0, the atom with the bonding bond* is a carbon atom, and if a1 is 1, the atom with the bonding bond* is an oxygen atom. In compound (A1), a1 may be either 0 or 1, and can be appropriately selected from the viewpoint of synthesis, etc. a2 is R ｇ２ This is the number of O repeats, and from the viewpoint of durability as a surface layer, 0 to 6 is preferred, 0 to 3 is more preferred, and 0 to 1 is even more preferred.

[0076] R １１ From the viewpoint of superior water and oil repellency, fingerprint stain removal, and durability such as friction resistance, a group represented by the following formula (g3) is even more preferable as a surface layer. *-(O) ａ１ -R ｇ３ -**...(g3) R ｇ３ is an alkylene group, and a1, * and ** are the same as in formula (g2).

[0077] R ｇ３ The alkylene group in may be linear, branched and / or have a cyclic structure. A linear alkylene group is preferred because it is easily arranged densely when compound (A1) forms a surface layer. ｇ３ The carbon number is 1 or more, preferably 1 to 18, more preferably 1 to 12, and even more preferably 1 to 6.

[0078] T ａ This is the above group (S1), i.e., -Si(R ２ ) ｎ L ３－ｎ And R ２ L and n are R, which constitutes the above group (S1). ２ The same applies to L and n, and the preferred embodiment is also the same.

[0079] x1 is the amount of R in one molecule １１ -T ａ This represents a number, which is an integer greater than or equal to 1, preferably between 1 and 32, more preferably between 1 and 18, and even more preferably between 2 and 12.

[0080] L １ This is a (j+x1) valence group which may have a single bond or N, O, S, Si, and may have a branch point, R １ and R １１ The atoms bonded are, independently, N, O, S, Si, a carbon atom constituting a branching point, or a carbon atom having an oxo group (=O). １ and R １１ The atoms bonded may be the same atom or different atoms.

[0081] L １ If it is a single bond, then R in equation (A1) １ and R １１ They bond directly, and compound (A1) is represented by the following formula (A1'). ｆ２ - ( OR ｆ１ ) ｙ -O-R １ -R １１ -T ａ …(A1') The signs in equation (A1') are the same as those in equation (A1).

[0082] L １ If it is a trivalent or higher group, L １ This is at least one branching point selected from the group consisting of C, N, Si, ring structures, and (j+x1) valent organopolysiloxane residues (hereinafter referred to as "branching point P"). １ It is also called ". ) has.

[0083] N is the branching point P. １ In this case, branch point P １For example, *-N(-**) ２ or (*-) ２ It is represented as N - **, where * is R １ It is a side joint, and ** is R １１ This is a side joint. C is the branching point P. １ In this case, branch point P １ For example, *-C(-**) ３ , (*-) ２ C (-**) ２ , (*-) ３ C-**, *-CR ２４ (-**) ２ , or (*-) ２ CR ２４ It is represented by -**, where * is R １ It is a side joint, and ** is R １１ It is a side joint, R ２４ It is a monovalent group, and examples include a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, etc. Si is at the branching point P. １ In this case, branch point P １ For example, *-Si(-**) ３ , (*-) ２ Si (-**) ２ , (*-) ３ Si-**, *-SiR ２４ (-**) ２ , or (*-) ２ SiR ２４ It is represented by -**, where * is R １ It is a side joint, and ** is R １１ It is a side joint, R ２４ This is a monovalent group, and examples include a hydrogen atom, a hydroxyl group, an alkyl group, and an alkoxy group.

[0084] Branch point P １As for the ring structure constituting the ring, from the viewpoint of ease of producing fluorine-containing compounds and further superior friction resistance, light resistance, and chemical resistance of the surface layer, one selected from the group consisting of a 3- to 8-membered aliphatic ring, a 3- to 8-membered aromatic ring, a 3- to 8-membered heteroring, and a fused ring consisting of two or more of these rings is preferred, and the ring structure shown in the following formula is more preferred. The ring structure may have substituents such as halogen atoms, alkyl groups (which may contain etheric oxygen atoms between carbon atoms), cycloalkyl groups, alkenyl groups, allyl groups, alkoxy groups, and oxo groups (=O).

[0085]

[0086] Branch point P １ Examples of organopolysiloxane residues that make up the compound include the following groups. In the formula below, R ２５ R is a hydrogen atom, an alkyl group, an alkoxy group, or a phenyl group. ２５ The number of carbon atoms in the alkyl and alkoxy groups is preferably 1 to 10, and more preferably 1.

[0087]

[0088] L with a valentity of 2 or higher １ is -C(O)N(R ２６ )-,-N(R ２６ )C(O)-, -C(O)O-, -OC(O)-, -C(O)-, -O-, -N(R ２６ )-, -S-, -OC(O)O-, -NHC(O)O-, -OC(O)NH-, -NHC(O)N(R ２６ ) -, -SO ２ N(R) ２６ )-,-N(R ２６ ) SO ２ -, -Si(R ２６ ) ２ -, -OSi(R ２６ ) ２ -, -Si(CH ３ ) ２ -Ph-Si(CH ３ ) ２ - and at least one binding selected from the group consisting of divalent organopolysiloxane residues (hereinafter referred to as "binding B") １It may also have ). ２６ R is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, and Ph is a phenylene group. ２６ The number of carbon atoms in the alkyl group is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 to 2, from the standpoint of facilitating the production of fluorine-containing compounds.

[0089] Examples of divalent organopolysiloxane residues include the group shown in the following formula. ２７ R is a hydrogen atom, an alkyl group, an alkoxy group, or a phenyl group. ２７ The number of carbon atoms in the alkyl and alkoxy groups is preferably 1 to 10, and more preferably 1.

[0090]

[0091] Join B １ As for the ease with which fluorine-containing compounds can be produced, -C(O)NR ２６ -, -N(R ２６ ) C(O)-, -C(O)-, and -NR ２６ - At least one bond selected from the group consisting of - is preferred, and from the viewpoint of further superior light resistance and chemical resistance of the surface layer, -C(O)NR ２６ -, -N(R ２６ )C(O)- or -C(O)- is more preferred.

[0092] divalent L １ For example, R １ and R １１ The atoms bonded to it are, independently, N, O, S, Si, or carbon atoms having an oxo group (=O). That is, R １ and R １１ Each adjacent atom is bonded to B １ It is a constituent element of [the plant]. Divalent L １ Specific examples include a single bond and one or more bonds B. １ (For example, *-B １ -**, *-B １ -R ２８ -B １ Examples include -**). ２８ * is a single bond or a divalent organic group, and * is R １ It is a side joint, and ** is R１１ It is a side joint.

[0093] L with a valent or higher chromosome １ R １ and R １１ The atoms bonded to it are, independently, N, O, S, Si, a carbon atom constituting a branching point, or a carbon atom having an oxo group (=O). That is, R １ and R １１ Each adjacent atom is bonded to B １ Or branching point P １ It is a constituent element of L with a valency of 3 or higher. １ A concrete example of this is one or more branching points P. １ (for example{(*-) ｊ P １ (-**) ｘ１}, {(*-) ｊ P １ -R ２８ -P １ (-**) ｘ１} etc.), one or more branching points P １ and one or more bonds B １ A combination with (for example, {*-B １ -R ２８ -P １ (-**) ｘ１}, {*-B １ -R ２８ -P １ (-R ２８ -B １ -**) ｘ１ Examples include:} etc. ２８ * is a single bond or a divalent organic group, and * is R １ It is a side joint, and ** is R １１ It is a side joint.

[0094] The above R ２８ Examples of divalent organic groups in this context include divalent aliphatic hydrocarbon groups (alkylene groups, cycloalkylene groups, etc.) and divalent aromatic hydrocarbon groups (phenylene groups, etc.), with a bond B between the carbon atoms of the hydrocarbon group. １ It may have a divalent organic group. The number of carbon atoms in the divalent organic group is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 4.

[0095] The above L １As such, a group represented by any of the following formulas (L1) to (L7) is preferred because it facilitates the production of fluorine-containing compounds.

[0096]

[0097] (-A １ -) ｄ５ C(R ｅ２ ) ４－ｄ５―ｄ６ (-Q ２２ -) ｄ６ …(L2) (-A ２ -) ｄ７ N(-Q) ２３ -) ３－ｄ７ …(L3) (-A ３ -) ｄ８ Z １ (-Q ２４ -) ｄ９ …(L4) (-A ２ -) ｄ１０ Si(R ｅ３ ) ４－ｄ１０－ｄ１１ (-Q ２５ -) ｄ１１ …(L5) -A １ - Q ２６ - ... (L6) - A １ -CH(-Q) ２２ -)-Si(R ｅ３ ) ３－ｄ１２ (-Q ２５ -) ｄ１２ ... (L7)

[0098] In equations (L1) to (L7), A １ A ２ Or A ３ The side is R in equation (A1) １ Connect to Q ２２ Q ２３ Q ２４ Q ２５ Or Q ２６ The side is R １１ Connect to A. １ is a single bond, -B ３ -, -B ３ -R ３０ - or -B ３ -R ３０ -B ２ - and R ３０This refers to an alkylene group, or an alkylene group having 2 or more carbon atoms with -C(O)NR between carbon atoms. ｅ６ -, -C(O)-, -NR ｅ６ A group having - or -O-, B ２ is -C(O)NR ｅ６ -, -C(O)-, -NR ｅ６ - or -O-, B ３ Ha-C(O)NR ｅ６ -, -C(O)-, or -NR ｅ６ - and A ２ is a single bond or -B ３ -R ３０ - and A ３ is, A ３ Z that joins １ If the atom in is a carbon atom, then A １ A ３ Z that joins １ If the atom in is a nitrogen atom, then A ２ Q １１ This refers to a single bond, -O-, an alkylene group, or an alkylene group with two or more carbon atoms with -C(O)NR between carbon atoms. ｅ６ -, -C(O)-, -NR ｅ６ A group having - or -O-, Q ２２ is a single bond, -B ３ -, -R ３０ -B ３ - or -B ２ -R ３０ -B ３ - and Q ２３ is a single bond or -R ３０ -B ３ - and Q ２４ Q ２４ Z that joins １ If the atom in Q is a carbon atom, ２２ Q ２４ Z that joins １ If the atom in Q is a nitrogen atom, ２３ Q ２５ is a single bond or -R ３０ -B ３ - and Q ２６ is a single bond or -R ３０ -B ３- and Z １ is, A ３ It has a carbon or nitrogen atom that is directly bonded to it and Q ２４ R is a group having a (d8 + d9) valence ring structure with a carbon or nitrogen atom to which it is directly bonded. ｅ１ R is a hydrogen atom or an alkyl group. ｅ２ R is a hydrogen atom, a hydroxyl group, an alkyl group, or an acyloxy group. ｅ３ R is an alkyl group. ｅ６ d1 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group. d1 is an integer from 0 to 3, d2 is an integer from 0 to 3, (d1 + d2) is an integer from 1 to 3, d3 is an integer from 0 to 3, d4 is an integer from 0 to 3, (d3 + d4) is an integer from 1 to 3, (d1 + d3) is an integer from 1 to 5, (d2 + d4) is an integer from 1 to 5, d5 is an integer from 1 to 3, d6 is an integer from 1 to 3, (d5 + d6) is an integer from 2 to 4, d7 is 1 or 2, d8 is an integer greater than or equal to 1, d9 is an integer greater than or equal to 1, d10 is an integer from 1 to 3, d11 is an integer from 1 to 3, (d10 + d11) is an integer from 2 to 4, and d12 is an integer from 1 to 3. １ If there are multiple A １ They may be the same or different from each other. A ２ A ３ Q ２２ Q ２３ Q ２４ Q ２５ , R ｅ１ , R ｅ２ , R ｅ３ The same applies to . Also, (d1+d3), d5, d7, d8, d10 are j, and (d2+d4), d6, (3-d7), d9, d11, (1+d12) are x1.

[0099] R ３０The number of carbon atoms in the alkylene group is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 4, from the viewpoint of facilitating the production of fluorine-containing compounds and further improving the friction resistance, light resistance, and chemical resistance of the surface layer. The lower limit of the number of carbon atoms in the alkylene group when there is a specific bond between carbon atoms is 2. １ The ring structure in this context is the ring structure described above, and the preferred form is also the same.

[0100] R ｅ１ , R ｅ２ or R ｅ３ The number of carbon atoms in the alkyl group is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 to 2, from the standpoint of facilitating the production of fluorine-containing compounds. ｅ２ The number of carbon atoms in the alkyl group portion of the acyloxy group is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 to 2, from the viewpoint of facilitating the production of compounds. d9 is preferably 2 to 6, more preferably 2 to 4, and even more preferably 2 or 3, from the viewpoint of facilitating the production of fluorine-containing compounds and further improving the friction durability and fingerprint stain removal properties of the surface layer.

[0101] The above L １ Other forms include groups represented by any of the following formulas (L11) to (L17).

[0102]

[0103] (-A １ -) ｄ５ C(R ｅ２ ) ４－ｄ５―ｄ６ (-Q ２２ -G) ｄ６ …(L12) (-A ２ -) ｄ７ N(-Q) ２３ -G) ３－ｄ７ …(L13) (-A ３ -) ｄ８ Z １ (-Q ２４ -G) ｄ９ …(L14) (-A ２ -) ｄ１０ Si(R ｅ３ ) ４－ｄ１０－ｄ１１ (-Q ２５ -G) ｄ１１…(L15) -A １ - Q ２６ -G...(L16) -A １ -CH(-Q) ２２ -)-Si(R ｅ３ ) ３－ｄ１２ (-Q ２５ -G) ｄ１２ ... (L17)

[0104] In equations (L11) to (L17), A １ A ２ Or A ３ The side is R in equation (A1) １ Connect to Q ２２ Q ２３ Q ２４ Q ２５ Or Q ２６ The side is R １１ Connect to the following base (G21), L １ The two or more Gs present may be the same or different. The signs other than G are the same as the signs in equations (L1) to (L7). -Si(R ２１ ) ３－ｋ２ (-Q ２ -) ｋ２ …(G21) In equation (G21), the Si side is Q ２２ Q ２３ Q ２４ Q ２５ Or Q ２６ Connect to Q ２ The side is R １１ Connect to R. ２１ It is an alkyl group. Q ２ This is a single bond, or -R ３ｅ -B ３ - and R ３ｅ This refers to an alkylene group, or an alkylene group having 2 or more carbon atoms with -C(O)NR between carbon atoms. ３４ -, -C(O)-, -NR ３４ A group having - or -O-, or -(OSi(R １４ ) ２ ) ｐ１１ -O- and Q is 2 or greater. ２ They may be the same or different. k2 is 2 or 3. R ３４R is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group. １４ is an alkyl group, a phenyl group, or an alkoxy group, and has two R １４ They may be the same or different. p11 is an integer from 0 to 5, and if p11 is 2 or greater, then 2 or greater (OSi(R １４ ) ２ ) may be the same or different.

[0105] Q ２ The number of carbon atoms in the alkylene group is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 4, from the viewpoint of facilitating the production of fluorine-containing compounds and further improving the friction resistance, light resistance, and chemical resistance of the surface layer. However, the lower limit of the number of carbon atoms in the alkylene group when there is a specific bond between carbon atoms is 2. ２１ The number of carbon atoms in the alkyl group is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 to 2, from the standpoint of facilitating the production of fluorine-containing compounds. １４ The number of carbon atoms in the alkyl group is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 to 2, from the standpoint of facilitating the production of fluorine-containing compounds. １４ The number of carbon atoms in the alkoxy group is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 to 2, from the viewpoint of excellent storage stability of the fluorine-containing compound. p11 is preferably 0 or 1.

[0106] Examples of compound (A1) include the following compounds. ｆ is [R ｆ２ - ( OR ｆ１ ) ｙ -O-R １ ]

[0107]

[0108]

[0109]

[0110]

[0111]

[0112]

[0113]

[0114]

[0115]

[0116]

[0117]

[0118]

[0119]

[0120] Compound (A2) Compound (A2) has the structure represented by the following formula (A2). (T ３１ -R ２ｄ ) ｘ３ -L ３ -R ２ｂ - ( OR ｆ１ ) ｙ -O-R ２ａ -L ４ - (R ２ｃ -T ２１ ) ｘ２ …(A2) The symbols in equation (A2) are as described above.

[0121] (OR ｆ１ ) ｙ R ｆ１ y and y are R in the above equation (f1), respectively. ｆ１ , is the same as y, and the preferred embodiment is also the same. R ２ａ and R ２ｂ Each of the above R independently １ The same applies to the preferred embodiment.

[0122] R ２ｃ and R ２ｄ The above R １１ The same applies to the preferred embodiment. However, "L １ "to join" is R ２ｃ In the case of "L ４ Replace "combine" with "R" ２ｄ In the case of "L ３ This can be reinterpreted as "to join together". Also, "T ａ "to join" is R２ｃ In the case of "T ２１ Replace "combine" with "R" ２ｄ In the case of "T ３１ This should be reinterpreted as "to join to". ４ If it is a single bond, R ２ｃ is R ２ａ It directly binds to L. ３ If it is a single bond, R ２ｄ is R ２ｂ It connects directly to it.

[0123] T ２１ and T ３１ Each of these independently forms the above group (S1), i.e., -Si(R ２ ) ｎ L ３－ｎ And R ２ L and n are R, which constitutes the above group (S1). ２ The same applies to L and n, and the preferred embodiment is also the same.

[0124] x2 and x3 are each independently the same as x1, and the preferred embodiment is also the same.

[0125] L ４ and L ３ Each of the above L １ This is the same as when j is 1. For example, L ４ and L ３ When it is a single bond, compound (A2) is represented by the following formula (A2'). ３１ -R ２ｄ -R ２ｂ - ( OR ｆ１ ) ｙ -O-R ２ａ -R ２ｃ -T ２１ …(A2') The signs in equation (A2') are the same as in equation (A2).

[0126] L ４ or L ３ If the group is trivalent or higher, then L ４ or L ３ This is at least one branching point selected from the group consisting of C, N, Si, ring structures and (1+x2)-valent or (1+x3)-valent organopolysiloxane residues (hereinafter referred to as "branching point P"). ２ It is also called ". ) has.

[0127] N is the branching point P. ２ In this case, branch point P ２ For example, *-N(-**) ２ It is represented as follows: where * is R ２ａ or R ２ｂ It is a side joint, and ** is R ２ｃ or R ２ｄ This is a side joint. C is the branching point P. ２ In this case, branch point P ２ For example, *-C(-**) ３ , or *-CR ２４ (-**) ２ It is represented as follows: where * is R ２ａ or R ２ｂ It is a side joint, and ** is R ２ｃ or R ２ｄ It is a side joint, R ２４ It is a monovalent group, and examples include a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, etc. Si is at the branching point P. ２ In this case, branch point P ２ For example, *-Si(-**) ３ , or *-SiR ２４ (-**) ２ It is represented as follows: where * is R ２ａ or R ２ｂ It is a side joint, and ** is R ２ｃ or R ２ｄ It is a side joint, R ２４ This is a monovalent group, and examples include a hydrogen atom, a hydroxyl group, an alkyl group, and an alkoxy group.

[0128] Branch point P ２ The ring structure and organopolysiloxane residues that make up the structure are located at the above branch point P １ The same applies to the preferred embodiment. Also, L with two or more valent values. ４ or L ３ Each of these independently forms the above combination B １ It may have. Bond B １ The embodiments are as described above, and the preferred embodiments are also as described above.

[0129] divalent L ４ or L ３ R ２ａ and R ２ｃ, or R ２ｂ and R ２ｄ The atoms bonded to it are, independently, N, O, S, Si, or carbon atoms having an oxo group (=O). That is, R ２ａ and R ２ｃ , or R ２ｂ and R ２ｄ Each adjacent atom is bonded to B １ It is a constituent element of [the plant]. Divalent L ４ or L ３ Specific examples include a single bond and one or more bonds B. １ (For example, *-B １ -**, *-B １ -R ２８ -B １ -**) are examples. However, R ２８ * is a single bond or a divalent organic group, and * is R ２ａ or R ２ｂ It is a side joint, and ** is R ２ｃ or R ２ｄ It is a side joint.

[0130] L with a valent or higher chromosome ４ or L ３ R ２ａ and R ２ｃ , or R ２ｂ and R ２ｄ The atoms bonded to it are, independently, N, O, S, Si, a carbon atom constituting a branching point, or a carbon atom having an oxo group (=O). That is, R ２ａ and R ２ｃ , or R ２ｂ and R ２ｄ Each adjacent atom is bonded to B １ Or branching point P ２ It is a constituent element of L with a valency of 3 or higher. ４ or L ３ A concrete example of this is one or more branching points P. ２ (For example {*-P ２ (-**) ｘ}, {*-P ２ -R ２８ -P ２ (-**) ｘ} etc.), one or more branching points P ２ and one or more bonds B １A combination with (for example, {*-B １ -R ２８ -P ２ (-**) ｘ}, {*-B １ -R ２８ -P ２ (-R ２８ -B １ -**) ｘ Examples include} etc. x is L ４ In this case, it is x2, L ３ In this case, it is x3. ２８ * is a single bond or a divalent organic group, and * is R ２ａ or R ２ｂ It is a side joint, and ** is R ２ｃ or R ２ｄ This is a side joint. (See above R) ２８ The embodiments are as described above, and the preferred embodiments are also as described above.

[0131] The above L ４ or L ３ As such, groups that can easily produce fluorine-containing compounds are preferred, as they are each independently represented by any of the following formulas (L21) to (L27).

[0132]

[0133] -A １ -C(R ｅ２ ) ４－ｄ６ (-Q ２２ -) ｄ６ …(L22) -A ２ -N(-Q) ２３ -) ２ …(L23) -A ３ -Z １ (-Q ２４ -) ｄ９ …(L24) -A ２ -Si(R ｅ３ ) ４－ｄ１１ (-Q ２５ -) ｄ１１ …(L25) -A １ - Q ２６ -...(L26) -A １ -CH(-Q) ２２ -)-Si(R ｅ３ ) ３－ｄ１２ (-Q ２５-) ｄ１２ ... (L27)

[0134] In equations (L21) to (L27), A １ A ２ Or A ３ The side is R in formula (A2) ２ａ or R ２ｂ Connect to Q ２２ Q ２３ Q ２４ Q ２５ Or Q ２６ The side is R ２ｃ or R ２ｄ Connect to A. １ A ２ A ３ Q １１ Q ２２ Q ２３ Q ２４ Q ２５ Q ２６ , R ｅ１ , R ｅ２ , R ｅ３ , R ｅ６ L is above １ This is the same as described above, and the preferred embodiment is also the same. Z １ is, A ３ It has a carbon or nitrogen atom that is directly bonded to it and Q ２４ The group is a ring structure having a (1+d9) valency with a carbon or nitrogen atom directly bonded to it, where d2 is an integer from 0 to 3, d4 is an integer from 0 to 3, (d2+d4) is an integer from 1 to 5, d6 is an integer from 1 to 3, d9 is an integer of 1 or more, d11 is an integer from 1 to 3, and d12 is an integer from 1 to 3. (d2+d4), d6, d9, d11, and (1+d12) are x2 or x3. d9 is preferably 2 to 6, more preferably 2 to 4, and even more preferably 2 or 3, from the viewpoint of ease of producing fluorine-containing compounds and further superior friction durability and fingerprint stain removal of the surface layer.

[0135] The above L ４ or L ３ Other forms of this include groups represented by any of the following formulas (L31) to (L37).

[0136]

[0137] -A １ -C(R ｅ２ ) ４－ｄ６ (-Q ２２ -G) ｄ６ …(L32) -A ２ -N(-Q ２３ -G) ２ …(L33) -A ３ -Z １ (-Q ２４ -G) ｄ９ …(L34) -A ２ -Si(R ｅ３ ) ４－ｄ１１ (-Q ２５ -G) ｄ１１ …(L35) -A １ -Q ２６ -G …(L36) -A １ -CH(-Q ２２ -)-Si(R ｅ３ ) ３－ｄ１２ (-Q ２５ -G) ｄ１２ …(L37)

[0138] In formulas (L31) to (L37), the A １ , A ２ or A ３ side is connected to R ２ａ or R ２ｂ of formula (A2), and the Q ２２ , Q ２３ , Q ２４ , Q ２５ or Q ２６ side is connected to R ２ｃ > or R ２ｄ . G is the above group (G21), and the preferred embodiments are the same. The symbols other than G are the same as those in formulas (L21) to (L27), and the preferred embodiments are the same.

[0139] Examples of the compound (A2) include the following compounds. Q ｆ is -R ２ｂ -(OR ｆ１ ) ｙ -O-R ２ａ -.

[0140]

[0141]

[0142]

[0143] - Compound (A3) Compound (A3) has a structure represented by the following formula (A3). Q １ [-(OR ｆ１ ) ｙ -O-R ３ａ -L ５ -(R ４１ -T ４１ ) ｘ４ ｒ２ ...(A3) Each symbol in formula (A3) is as described above.

[0144] (OR ｆ１ ) ｙ 's R ｆ１ , y are the same as R ｆ１ , y in the above formula (f1), and the preferred embodiments are also the same. R ３ａ is the same as the above R １ , and the preferred embodiments are also the same.

[0145] R ４１ is the same as the above R １１ , and the preferred embodiments are also the same. However, "bonded to L １ " is read as "bonded to L ５ ". Also, "bonded to T ａ " is read as "bonded to T ４１ ". When L ５ is a single bond, R ４１ is directly bonded to R ３ａ .

[0146] T ４１ is the above group (S1), that is, -Si(R ２ ) ｎ L ３－ｎ , and R ２ , L, n are the same as R ２ , L, n constituting the above group (S1), respectively, and the preferred embodiments are also the same.

[0147] x4 is the same as x1, and the preferred embodiments are also the same. L ５ is L ４ or L ３It is the same, and the preferred embodiments are also the same.

[0148] Q １ is a divalent group having a branch point, and r2 is 3 or 4.

[0149] Q １ The branch point P that constitutes ３ Examples of P include N, C, Si, or a ring structure. The branch point P ３ may be one, or may have two or more.

[0150] When N is the branch point P ３ the branch point P ３ is, for example, N(−*) ３ , NR ２９ (−*) ２ represented by. When C is the branch point P ３ the branch point P ３ is C(−*) ４ , CR ２９ (−*) ３ , C(R ２９ ) ２ (−*) ２ etc. are included. When Si is the branch point P ３ the branch point P ３ is Si(−*) ４ , SiR ２９ (−*) ３ , Si(R ２９ ) ２ (−*) ２ etc. are included. However, * is a bond on the OR ｆ１ side, and R ２９ is a monovalent group. As R ２９ examples include a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a fluoroalkyl group, a fluoropolyether chain having no R ４１ -T ４１ etc.

[0151] Examples of the ring structure that constitutes the branch point P ３ include the same ones as the branch point P １ In addition to the above substituents, as substituents of the ring structure, a fluorine atom, a fluoroalkyl group, and a fluoropolyether chain having no R ４１ -T ４１ may also be present.

[0152] Q above １ As such, a group represented by any of the following formulas (Q1) to (Q8) is preferred because it facilitates the production of fluorine-containing compounds.

[0153]

[0154] C(-A １０ -) ｄ２３ (R ｅ１２ ) ４－ｄ２３ …(Q2) N(-A １４ -) ３ ... (Q3) Z １ (-A １５ -) ｄ２４ ...(Q4) Si(-A １４ -) ｄ２５ (R ｅ１３ ) ４－ｄ２５ ...(Q5) CH(-A １０ -) ２ -Si(R ｅ１３ ) ３－ｄ２６ (-A １０ -) ｄ２６ ... (Q6)

[0155]

[0156]

[0157] In equations (Q1) to (Q8), A １０ A １４ Or A １５ (OR ｆ１ ) connects to this. Here, A １０ This is a single bond, -R ４２ -, -B １３ -R ４２ - and R ４２ This refers to an alkylene group, a fluoroalkylene group, or an alkylene group having two or more carbon atoms, or a fluoroalkylene group with -C(O)NR between carbon atoms. ｅ１７ -, -C(O)-, -NR ｅ１７ A group having - or -O-, B １３ is -C(O)NR ｅ６ -, -C(O)-, -NR ｅ６ - or -O-, A １４ This is a single bond, or -R４２ - and A １５ is, A １５ Z that joins １ If the atom in is a carbon atom, then A １０ A １５ Z that joins １ If the atom in is a nitrogen atom, then A １４ Z １ is, A １５ Q is a group having an r2 valent ring structure with a carbon or nitrogen atom to which it is directly bonded. ５２ This includes single bonds, -O-, alkylene groups, fluoroalkylene groups, or alkylene groups with two or more carbon atoms, or -C(O)NR between carbon atoms of fluoroalkylene groups. ｅ１７ -, -C(O)-, -NR ｅ１７ A group having - or -O-, R ｅ１１ is a hydrogen atom, a fluorine atom, an alkyl group, a fluoroalkyl group, R ４１ -T ４１ A fluoropolyether chain that does not have -Q in the range where r2 is 3 to 4. ５２ -C(R ｅ１１ ) ３－ｄ２１ (-A １０ -) ｄ２１ It is a group having a repeating structure, R ｅ１２ is a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a fluoroalkyl group, or R ４１ -T ４１ A fluoropolyether chain that does not have R ｅ１３ R is an alkyl group or fluoroalkyl group. ｅ１４ , R ｅ１５ , and R ｅ１６ Each of these is independently a hydrogen atom, a fluorine atom, an alkyl group, or a fluoroalkyl group, and R ｅ１７d21 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a fluoroalkyl group, or a phenyl group which may be fluorine-substituted, d21 is an integer from 0 to 3, d22 is an integer from 0 to 3, (d21 + d22) is an integer from 3 to 4, d23 is 3 or 4, d24 is 3 or 4, d25 is 3 or 4, d26 is 1 or 2, d27 is an integer from 1 to 3, d28 is 1 or 2, d29 is an integer from 1 to 3, d30 is an integer from 1 to 3, d31 is 1 or 2, d32 is 1 or 2, and d33 is an integer from 1 to 3. １０ If there are multiple A １０ They may be the same or different from each other. A １４ A １５ , R ｅ１１ , R ｅ１２ , R ｅ１３ The same applies to this matter.

[0158] R ４２ The number of carbon atoms in the alkylene group or fluoroalkylene group is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 4, from the viewpoint of facilitating the production of fluorine-containing compounds and further improving the friction resistance, light resistance, and chemical resistance of the surface layer. However, the lower limit of the number of carbon atoms in the alkylene group when there is a specific bond between carbon atoms is 2. １ The ring structure in this context is the ring structure described above, and the preferred form is also the same.

[0159] R ｅ１１ , R ｅ１２ , R ｅ１３ , R ｅ１４ , R ｅ１５ and R ｅ１６ In this context, the number of carbon atoms in the alkyl group or fluoroalkyl group is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 to 2, from the standpoint of facilitating the production of fluorine-containing compounds.

[0160] Examples of compound (A3) include the following compounds. ｆ３ is (OR ｆ１ ) ｙ -O-R ３ａ That is the case.

[0161]

[0162]

[0163]

[0164]

[0165] -Non-fluorinated compounds- This compound may be a non-fluorinated compound having a reactive silyl group. Non-fluorinated compounds do not contain fluorine atoms in the compound.

[0166] Examples of nonfluorine compounds include compounds having a linear organo(poly)siloxane residue and a reactive silyl group attached to only one end of the linear organo(poly)siloxane residue (hereinafter also referred to as "the first compound"), compounds having a linear organo(poly)siloxane residue and reactive silyl groups attached to both ends of the linear organo(poly)siloxane residue (hereinafter also referred to as "the second compound"), and compounds having a linear group and a reactive silyl group but lacking a linear organo(poly)siloxane residue (hereinafter also referred to as "the third compound"). The main chain refers to the skeleton consisting of the longest carbon and silicon atoms in the compound.

[0167] The number-average molecular weight (Mn) of the nonfluorine compound is preferably 500 to 20,000, more preferably 600 to 18,000, and particularly preferably 700 to 15,000. In one embodiment, the Mn of the nonfluorine compound may be 500 to 5,000 or 500 to 3,000.

[0168] [First compound] Compound (C) is an example of the first compound.

[0169]

[0170] In formula (C), T １１ B is a monovalent group that does not contain a reactive silyl group, B is independently -O- or -C(=O)-, r is independently 0 or 1, R ３ Each is independently a hydrocarbon group, k1 is independently a number greater than or equal to 1, p1 is an integer greater than or equal to 1, A１１ is a (p1 + q1) valence linking group, where q1 is an integer greater than or equal to 1, and R ２ Each of the following is independently a hydrocarbon group, each of the following is independently a hydrolyzable group, a group having a hydrolyzable group, or a hydroxyl group, and each of the following is independently an integer from 0 to 2.

[0171] In formula (C), R ３ These are each, independently, hydrocarbon groups. ３ Examples of hydrocarbon groups represented include aliphatic hydrocarbon groups and aromatic hydrocarbon groups. Among these, aliphatic hydrocarbon groups are preferred, and alkyl groups are more preferred. The alkyl group may be a linear alkyl group, a branched alkyl group, or a cyclic alkyl group, but a linear alkyl group is preferred, a methyl group, an ethyl group, an n-propyl group, or an n-butyl group is more preferred, and a methyl group is even more preferred. As for the aromatic hydrocarbon group, a phenyl group is preferred.

[0172] In formula (C), k1 is independently a number of 1 or more. k1 is preferably a number between 1 and 600, more preferably a number between 1 and 500, even more preferably a number between 3 and 500, particularly preferably a number between 9 and 50, extremely preferably a number between 11 and 30, and most preferably a number between 11 and 25.

[0173] R ２ , L, and n are R in equation (S1). ２ It is the same as L and n.

[0174] In formula (C), T １１ It is a monovalent group. １１ Examples include alkyl groups and T １ ３ M １ - (Here, M １ is Si, Sn, or Ge, and T １ Each of these is independently a hydrocarbon group or a trialkylsilyloxy group. １ ３ M １ -R ｃ - (Here, M １ is Si, Sn, or Ge, and T １Each of these is independently a hydrocarbon group or a trialkylsilyloxy group, R ｃ Examples include monovalent cyclic polysiloxane residues or monovalent cage-like polysiloxane residues (where is an alkylene group), and combinations of monovalent cyclic polysiloxane residues or monovalent cage-like polysiloxane residues with a divalent hydrocarbon group.

[0175] T １１ The alkyl group represented by may be a linear alkyl group, a branched alkyl group, or a cyclic alkyl group, with linear or branched alkyl groups being preferred. The alkyl group may have one carbon atom or two or more. When the alkyl group has two or more carbon atoms, the number of carbon atoms is preferably 2 to 30, more preferably 3 to 28, and even more preferably 4 to 22.

[0176] T １ ３ M １ - and T １ ３ M １ -R ｃ - M １ Si is preferred as the material.

[0177] T １ ３ M １ - and T １ ３ M １ -R ｃ - T １ Preferably, the group is an alkyl group or a trialkylsilyloxy group, and more preferably a methyl group, a butyldimethylsilyloxy group, a trimethylsilyloxy group, or a triethylsilyloxy group.

[0178] R ｃ Preferably, the alkylene group has 1 to 20 carbon atoms, more preferably an alkylene group has 1 to 10 carbon atoms, even more preferably an alkylene group has 1 to 5 carbon atoms, and particularly preferably an ethylene group.

[0179] In one embodiment, T １１ The alkyl group or trialkylsilyl group is preferred, and the methyl group or trimethylsilyl group is more preferred.

[0180] The monovalent cyclic polysiloxane residue is preferably a group represented by the following formula (T1). In formula (T1), R Ｔ Each of these is independently a hydrocarbon group or a hydrocarbon group having a substituent, and s is an integer from 1 to 4.

[0181]

[0182] R Ｔ Examples of hydrocarbon groups represented by include aliphatic hydrocarbon groups and aromatic hydrocarbon groups. Among these, aliphatic hydrocarbon groups are preferred, and alkyl groups are more preferred.

[0183] R Ｔ Among the hydrocarbon groups represented, the alkyl group may be a linear alkyl group, a branched alkyl group, or a cyclic alkyl group, but a linear alkyl group is preferred. The alkyl group has 1 to 10 carbon atoms, more preferably 1 to 8, and even more preferably 1 to 4. Specifically, the alkyl group is preferably a methyl group, an ethyl group, an n-propyl group, or an n-butyl group, with a methyl group being more preferred.

[0184] R Ｔ Examples of hydrocarbon groups included in a hydrocarbon group having substituents represented by include aliphatic hydrocarbon groups and aromatic hydrocarbon groups. Among these, aliphatic hydrocarbon groups are preferred, and alkyl groups are more preferred. The alkyl group may be a linear alkyl group, a branched alkyl group, or a cyclic alkyl group, but a linear alkyl group is preferred. The number of carbon atoms in the alkyl group included in the substituted alkyl group is preferably 1 to 10, more preferably 1 to 8, and even more preferably 2 to 4.

[0185] R Ｔ Examples of substituents in hydrocarbon groups having substituents represented by include halogen atoms, hydroxyl groups, alkoxy groups, trialkylsilyl ether groups, trialkylsilyl groups, amino groups, nitro groups, cyano groups, sulfonyl groups, and trifluoromethyl groups.

[0186] Multiple R ＴThey may be identical or different from each other, but from the viewpoint of ease of manufacture, it is preferable that they be identical.

[0187] Examples of monovalent cyclic polysiloxane residues include the following groups:

[0188]

[0189] The monovalent cage-like polysiloxane residue is preferably a group represented by the following formula (T2). In formula (T2), R ５ Each of these is independently a hydrocarbon group or a trialkylsilyloxy group.

[0190]

[0191] R ５ Examples of hydrocarbon groups represented by include aliphatic hydrocarbon groups and aromatic hydrocarbon groups. Among these, aliphatic hydrocarbon groups are preferred, and alkyl groups are more preferred. The alkyl group may be a linear alkyl group, a branched alkyl group, or a cyclic alkyl group, but linear alkyl groups or branched alkyl groups are preferred, methyl groups, ethyl groups, n-propyl groups, n-butyl groups, or isobutyl groups are more preferred, and isobutyl groups are even more preferred.

[0192] R ５ The alkyl group contained in the trialkylsilyloxy group represented by may be a linear alkyl group, a branched alkyl group, or a cyclic alkyl group, but a linear alkyl group is preferred, a methyl group, an ethyl group, an n-propyl group, or an n-butyl group is more preferred, and a methyl group is even more preferred. ５ When the group is a trialkylsilyloxy group, the three alkylsilyloxy groups may be the same or different from each other, but from the viewpoint of ease of manufacture, it is preferable that they be the same.

[0193] Examples of monovalent cage-like polysiloxane residues include the following groups:

[0194]

[0195] Examples of divalent hydrocarbon groups in combinations of monovalent cyclic polysiloxane residues or monovalent cage-like polysiloxane residues with divalent hydrocarbon groups include alkylene groups. The alkylene group preferably has 1 to 20 carbon atoms, more preferably 1 to 10, and even more preferably 1 to 5 carbon atoms.

[0196] In formula (C), B is independently either -O- or -C(=O)-, with -O- being preferred.

[0197] In formula (C), p1 is an integer of 1 or more, preferably an integer between 1 and 3, more preferably 1 or 2, and even more preferably 1. When p1 is 2 or 3, multiple T １１ -B ｒ -[Si(R ３ ) ２ -O] ｋ１ -Si(R ３ ) ２ The dashes may be the same or they may be different from each other.

[0198] In formula (C), A １１ A is a linking group with (p1 + q1) valence. １１ Examples include alkylene groups, organo(poly)siloxane residues, polyalkylene oxide groups, and combinations thereof; as well as combinations thereof with (p1+1) valency groups and / or (q1+1) valency groups. Examples of alkylene groups include C1 to C30 alkylene groups, preferably C1 to C20 alkylene groups, which may or may not have an etheric oxygen atom. Examples of organo(poly)siloxane residues include chain-like organo(poly)siloxane residues. Examples of polyalkylene oxide groups include those of formula (XO) ｍ２ A group represented by the following is an example. Here, X is an alkylene group having 1 to 5 carbon atoms, and m2 is an integer of 1 or more. The number of carbon atoms in X is preferably 1 to 4, more preferably 2 or 3. The number of carbon atoms in m2 is preferably 1 to 200, more preferably 1 to 20, and even more preferably 1 to 10. A １１ As for the formula A(Si(R) described later ２ ) ｎ L ３－ｎ ) ｑ１ A is an example of this.

[0199] In formula (C), q1 is an integer of 1 or more, preferably 1 to 18, more preferably 1 to 12, even more preferably 1 to 8, particularly preferably 1 to 6, and very preferably 1 to 4. In one embodiment, q1 is preferably 2 to 18, more preferably 2 to 12, even more preferably 2 to 8, particularly preferably 2 to 6, and very preferably 2 to 4. q1 may also be 1. When q1 is an integer of 2 or more, a plurality of [Si(R ２ ) ｎ L ３－ｎ These may be the same or they may be different from one another.

[0200] In one aspect, T in formula (C) １１ A trialkylsilyl group or alkyl group is preferred, and a trimethylsilyl group or methyl group is more preferred. B is preferably O, and r is 0 or 1. ３ A methyl group is preferred. k1 is preferably 1 to 100. p1 is preferably 1. A １１ This is an alkylene group having 1 to 30 carbon atoms, or a group described below (3-1A) from Si (R ２ ) ｎ L ３－ｎ The group excluding is preferred, and is an alkylene group having 1 to 30 carbon atoms, or Si(R) from the group described below (3-1A-4). ２ ) ｎ L ３－ｎ A base excluding is more preferable. Q1 is preferably an integer from 1 to 4.

[0201] [Second Compound] Compound (D) is an example of the second compound.

[0202]

[0203] In formula (D), R ４ Each of these independently comprises a hydrocarbon group or T １１ -B ｒ - (SiR ３ ２ -O) ｋ１ - and T １１ Each of the following is independently a monovalent group, B is independently -O- or -C(=O)-, r is independently 0 or 1, R３ Each is independently a hydrocarbon group, and each is independently a number of 1 or more, A １２ Each of these is an independent (q1+1) valence linking group, and each of these is an independent integer greater than or equal to 1, R ２ Each of the following is independently a hydrocarbon group, each of the following is independently a hydrolyzable group, a group having a hydrolyzable group, or a hydroxyl group, and each of the following is independently an integer from 0 to 2.

[0204] In formula (D), R ４ Each of these independently comprises a hydrocarbon group or T １１ -B ｒ - (SiR ３ ２ -O) ｋ１ - and a hydrocarbon group is preferred. Details of the hydrocarbon group are as shown in formula (C) R ３ This is similar to the hydrocarbon group represented by . In formula (D), the specific form of k1 is the same as k1 in formula (C). R ２ , L, and n are R in equation (S1). ２ It is the same as L and n.

[0205] A １２ Examples include alkylene groups, organo(poly)siloxane residues, polyalkylene oxide groups, and combinations thereof; as well as combinations thereof with (q1+1) valent groups. Examples of alkylene groups include alkylene groups having 1 to 30 carbon atoms, preferably alkylene groups having 1 to 20 carbon atoms, which may or may not have an etheric oxygen atom. Examples of organo(poly)siloxane residues include chain-like organo(poly)siloxane residues. Examples of polyalkylene oxide groups include those of the formula (XO) ｍ２ A group represented by the formula is shown below. Here, X is an alkylene group having 1 to 5 carbon atoms, and m2 is an integer of 1 or more. The number of carbon atoms in X is preferably 1 to 4, more preferably 2 or 3. The number of carbon atoms in m2 is preferably 1 to 100, more preferably 1 to 10, and even more preferably 1 to 5. A １２ As for the formula A(Si(R) described later ２ ) ｎ L ３－ｎ )ｑ１ Among A in this, the (q1+1) valence base is mentioned.

[0206] Each q1 is an integer of 1 or more, and each is independently preferably 1 to 18, more preferably 1 to 12, even more preferably 1 to 8, particularly preferably 1 to 6, and extremely preferably 1 to 4. In one embodiment, q1 is preferably 2 to 18, more preferably 2 to 12, even more preferably 2 to 8, particularly preferably 2 to 6, and extremely preferably 2 to 4. q1 may also be 1. When q1 is an integer of 2 or more, a plurality of [Si(R ２ ) ｎ L ３－ｎ These may be the same or they may be different from one another.

[0207] In one embodiment, R ４ A methyl group is preferred. k1 is preferably a number from 1 to 100. １２ This is an alkylene group having 1 to 30 carbon atoms, or a group described below (3-1A) from Si (R ２ ) ｎ L ３－ｎ The group excluding is preferred, and is an alkylene group having 1 to 30 carbon atoms, or Si(R) from the group described below (3-1A-4). ２ ) ｎ L ３－ｎ A base excluding is more preferable. Q1 is preferably an integer from 1 to 4.

[0208] [Third Compound] Compound (E) is an example of a third compound.

[0209]

[0210] In formula (E), R ２０ A is a monovalent group comprising at least one selected from the group consisting of Si, Ge, and Sn, which does not have a hydroxyl group or hydrolyzable group directly bonded to it; or a monovalent group comprising a branched alkyl group, A １３ is a (q1+1) valence linking group, where q1 is an integer greater than or equal to 1, and R ２ Each of the following is independently a hydrocarbon group, each of the following is independently a hydrolyzable group, a group having a hydrolyzable group, or a hydroxyl group, and each of the following is independently an integer from 0 to 2.

[0211] In formula (E), R ２ , L, and n are R in equation (S1). ２ The same applies to L and n. Q1 is the same as Q1 in equation (C).

[0212] R ２０ This is a monovalent group comprising at least one selected from the group consisting of Si, Ge, and Sn, which does not have a hydroxyl group or hydrolyzable group directly bonded to it. The monovalent group comprising at least one selected from the group consisting of Si, Ge, and Sn, which does not have a hydroxyl group or hydrolyzable group directly bonded to it, may or may not contain Si, Ge, or Sn to which a hydroxyl group or hydrolyzable group is directly bonded.

[0213] In one embodiment, R ２０ The group may be a group having group (a) or group (b).

[0214]

[0215]

[0216] In formula (a), R ５１ is, -(R ６１ -SiR ５３ ２ ) ｍａ -R ５３ It is a group represented by R, where R ６１ Each is independently an oxygen atom or an alkylene group having 1 to 6 carbon atoms, R ５３ Each of these independently comprises a hydrocarbon group or R ５１’ And R ５１’ R ５１ This is synonymous, where ma is an integer from 1 to 5, however R ５１ Medium, R ５１’ The number is 20 or less, R ５２ is a hydrocarbon group, na is an integer from 1 to 3, z is 0 or 1, and * represents a bonding site with an adjacent atom.

[0217] In formula (b), R ５４Each of these is independently a hydrocarbon group, nb is an integer from 1 to 5, z is 0 or 1, and * represents a bonding site with an adjacent atom.

[0218] R ６１ The alkylene group having 1 to 6 carbon atoms may be a straight chain or a branched chain. Of the alkylene groups having 1 to 6 carbon atoms, an alkylene group having 1 to 4 carbon atoms is preferred, and an alkylene group having 2 to 4 carbon atoms is more preferred.

[0219] R ５３ The hydrocarbon group represented is preferably an alkyl group or an aryl group. The alkyl group may be linear or branched. C1-C6 alkyl groups are preferred, C1-C4 alkyl groups are more preferred, and methyl, ethyl, n-propyl, isopropyl, or tert-butyl groups are even more preferred.

[0220] R ５２ The hydrocarbon group represented is preferably an alkyl group or an aryl group. The alkyl group may be linear or branched. C1-C6 alkyl groups are preferred, C1-C4 alkyl groups are more preferred, and methyl, ethyl, n-propyl, isopropyl, or tert-butyl groups are even more preferred.

[0221] Groups having group (a) or group (b) include group (a) or group (b) alone, and groups in which a chain-like group is linked to group (a) or group (b). Chain-like groups include chain-like hydrocarbon groups; and groups with -O-, -S-, -C(=O)NH-, -NHC(=O)-, -C(=O)O-, -OC(=O)-, -C(=O)S-, -SC(=O)-, -S(=O)- at the ends of the chain-like hydrocarbon group or between carbon atoms. ２ NH-, -NHS (=O) ２ -, -S (=O) ２ O-, -OS (=O) ２ Examples include groups having at least one selected from the group consisting of - and phenylene groups; and combinations thereof.

[0222] Examples of linear hydrocarbon groups include linear or branched linear hydrocarbon groups having 2 to 100 carbon atoms, preferably 5 to 90, and more preferably 10 to 80 carbon atoms. Alkylene groups are preferred as linear hydrocarbon groups, and from the viewpoint of forming a surface layer with excellent acid resistance, hot water resistance, and abrasion resistance, alkylene groups with 13 or more carbon atoms are preferred. The terminal or carbon-carbon spaces of the linear hydrocarbon group may be -O-, -S-, -C(=O)NH-, -NHC(=O)-, -C(=O)O-, -OC(=O)-, -C(=O)S-, -SC(=O)-, -S(=O) ２ NH-, -NHS (=O) ２ -, -S (=O) ２ O-, -OS (=O) ２ The number of carbon atoms in the group having at least one selected from the group consisting of - and a phenylene group is the same as described above.

[0223] In one embodiment, R ２０ The group may have a group (c). -M ３１ (R ２３ ) ２ -...(c) In formula (c), M ３１ is Sn or Ge, and R ２３ Each of these is independently a hydrocarbon group or a trialkylsilyloxy group.

[0224] M ３１ This is either Sn or Ge. Ge has a larger atomic size than Sn, which allows for a greater reduction in surface free energy and the formation of a surface layer with superior fingerprint removal properties. ３１ Ge is preferred.

[0225] R ２３ R is a hydrocarbon group or a trialkylsilyloxy group. Examples of hydrocarbon groups include alkyl groups, cycloalkyl groups, alkenyl groups, and allyl groups. From the viewpoint of ease of synthesis, saturated hydrocarbon groups are preferred, and alkyl groups are more preferred. ２３ The number of carbon atoms is preferably 1 to 6, more preferably 1 to 3, and among them -CH ３ or -CH ２ CH ３ This is preferable. The trialkylsilyloxy group is -O-SiR４０ ３ A group represented by is preferred. However, R ４０ Each of these is independently a hydrocarbon group. ４０ The hydrocarbon group in is preferably an alkyl group or an aryl group, with alkyl groups being more preferred. ４０ The number of carbon atoms is preferably 1 to 6, more preferably 1 to 4, and even more preferably 1 to 2. ４０ Specific examples of hydrocarbon groups in this context include -CH ３ ien-CH ２ CH ３ , -C(CH ３ ) ３ These are some examples.

[0226] Groups containing group (c) include group (c) alone, and group (c) in M ３１ Examples include groups in which organic groups are linked to one or both sides. Examples of organic groups include monovalent organic groups, divalent organic groups, and combinations thereof. However, monovalent organic groups are not linked to both sides. Examples of monovalent organic groups include hydrocarbon groups, trialkylsilyloxy groups, or organopolysiloxane groups. Examples of divalent organic groups include chain-like hydrocarbon groups; and groups with -O-, -S-, -C(=O)NH-, -NHC(=O)-, -C(=O)O-, -OC(=O)-, -C(=O)S-, -SC(=O)-, and -S(=O) at the ends of the chain-like hydrocarbon group or between carbon atoms. ２ NH-, -NHS (=O) ２ -, -S (=O) ２ O-, -OS (=O) ２ Examples include groups having at least one selected from the group consisting of - and phenylene groups; and combinations thereof.

[0227] Examples of linear hydrocarbon groups include linear or branched linear hydrocarbon groups having 2 to 100 carbon atoms, preferably 5 to 90, and more preferably 10 to 80 carbon atoms. Examples of linear hydrocarbon groups include alkyl groups or alkylene groups. From the viewpoint of forming a surface layer with excellent acid resistance, hot water resistance, and abrasion resistance, alkylene groups with 13 or more carbon atoms are preferred for the linear hydrocarbon group. The terminal or carbon-carbon intercostal groups of the linear hydrocarbon group include -O-, -S-, -C(=O)NH-, -NHC(=O)-, -C(=O)O-, -OC(=O)-, -C(=O)S-, -SC(=O)-, and -S(=O). ２ NH-, -NHS (=O) ２ -, -S (=O) ２ O-, -OS (=O) ２ The number of carbon atoms in the group having at least one selected from the group consisting of - and a phenylene group is the same as described above.

[0228] In one embodiment, R ２０ The group may be a monovalent group containing a branched alkyl group. The branched alkyl group is preferably unsubstituted. The branched alkyl group is preferably a tert-butyl group or contains a tert-butyl group. The branched alkyl group may contain one branch or multiple branches. The number of branches in the branched alkyl group may be 1 to 30, 1 to 20, 1 to 10, or 1 to 5.

[0229] Examples of branched alkyl groups include the group represented by the following formula: [(CH ３ ) ３ CR-R ２２ -] ｍ２２ C (CH ３ ) ３－ｍ２２ - In the formula, R ２２ Each of these is an alkylene group having 1 to 6 carbon atoms, and m22 is an integer from 0 to 3.

[0230] Examples of monovalent groups containing branched alkyl groups include groups in which a chain-like group is linked to the carbon atom at the branching point of the branched alkyl group. Examples of chain-like groups include chain-like hydrocarbon groups; and groups with -O-, -S-, -C(=O)NH-, -NHC(=O)-, -C(=O)O-, -OC(=O)-, -C(=O)S-, -SC(=O)-, and -S(=O) at the end of the chain-like hydrocarbon group or between carbon atoms. ２ NH-, -NHS (=O) ２ -, -S (=O) ２ O-, -OS (=O) ２ Examples include groups having at least one selected from the group consisting of - and phenylene groups; and combinations thereof.

[0231] Examples of linear hydrocarbon groups include linear or branched linear hydrocarbon groups having 2 to 100 carbon atoms, preferably 5 to 90, and more preferably 10 to 80 carbon atoms. Alkylene groups are preferred as linear hydrocarbon groups, and from the viewpoint of forming a surface layer with excellent acid resistance, hot water resistance, and abrasion resistance, alkylene groups with 13 or more carbon atoms are preferred. The terminal or carbon-carbon spaces of the linear hydrocarbon group may be -O-, -S-, -C(=O)NH-, -NHC(=O)-, -C(=O)O-, -OC(=O)-, -C(=O)S-, -SC(=O)-, -S(=O) ２ NH-, -NHS (=O) ２ -, -S (=O) ２ O-, -OS (=O) ２ The number of carbon atoms in the group having at least one selected from the group consisting of - and a phenylene group is the same as described above.

[0232] In formula (E), A １３ A is a linking group with (q1+1) valence. １３ As for A in equation (C), １１ A specific example of the case where p1 = 1 can be given.

[0233] Specific examples of compound (E) include the following compounds. In the formula below, sa is preferably 1 to 30, more preferably 4 to 20, and even more preferably 5 to 15.

[0234]

[0235] [Partial structures of the first compound, the second compound, and the third compound] Hereinafter, A in formula (C) １１ (Si(R ２ ) ｎ L ３－ｎ ) ｑ１ A in equation (D) １２ (Si(R ２ ) ｎ L ３－ｎ ) ｑ１ , and A in formula (E) １３ (Si(R ２ ) ｎ L ３－ｎ ) ｑ１ Preferred embodiments of will be described in detail below. １１ (Si(R ２ ) ｎ L ３－ｎ ) ｑ１ A in equation (D) １２ (Si(R ２ ) ｎ L ３－ｎ ) ｑ１ , and A in formula (E) １３ (Si(R ２ ) ｎ L ３－ｎ ) ｑ１ Including A(Si(R ２ ) ｎ L ３－ｎ ) ｑ１ This is shown. However, in the case of formula (C), A is a (p1 + q1) valence base, and in the cases of formulas (D) and (E), A is a (q1 + 1) valence base.

[0236] Furthermore, the descriptions of the chain-like organo(poly)siloxane residues in this section [substructures of the first compound, the second compound, and the third compound] refer to the substructures of formula (C) and formula (D).

[0237] A(Si(R ２ ) ｎ L ３－ｎ ) ｑ１ The group represented is preferably group (3-1A) or group (3-1B), with group (3-1A) being more preferred.

[0238] - Q ａ -X ３１ (-Q ｂ-Si(R ２ ) ｎ L ３－ｎ ) ｈ (-R ３１ ) ｉ …(3-1A) -Q ｃ - [CH ２ C(R ３２ ) (-Q ｄ -Si(R ２ ) ｎ L ３－ｎ )] ｗ -R ３３ …(3-1B) Note that in equations (3-1A) and (3-1B), R ２ The definitions of L and n are as described above.

[0239] In equation (3-1A), Q ａ These are single or divalent linking groups. Examples of divalent linking groups include divalent hydrocarbon groups, divalent heterocyclic groups, -O-, -S-, and -SO ２ -, -N(R ｄ )-, -C(O)-, -Si(R ａ ) ２ - and groups formed by combining two or more of these. The above-mentioned divalent hydrocarbon group may be a divalent saturated hydrocarbon group, a divalent aromatic hydrocarbon group, an alkenylene group, or an alkylylene group. The divalent saturated hydrocarbon group may be linear, branched, or cyclic, for example, an alkylene group. The number of carbon atoms in the alkylene group is preferably 1 to 30, more preferably 1 to 20, even more preferably 4 to 20, and particularly preferably 5 to 15. In addition, the divalent aromatic hydrocarbon group is preferably one with 5 to 20 carbon atoms, for example, a phenylene group. Other options include an alkenylene group with 2 to 20 carbon atoms and an alkylylene group with 2 to 20 carbon atoms. The above R ａ R is an alkyl group (preferably having 1 to 10 carbon atoms) or a phenyl group. ｄ This is a hydrogen atom or an alkyl group (preferably having 1 to 10 carbon atoms). Examples of groups formed by combining two or more of these include -OC(O)-, -C(O)O-, -C(O)S-, and -C(O)N(R). ｄ )-,-N(R ｄ )C(O)-,-N(Rｄ ) C(O)N(R ｄ )-,-N(R ｄ )C(O)O-, -OC(O)N(R ｄ ) -, -SO ２ N(R) ｄ )-,-N(R ｄ ) SO ２ -, -C(O)N(R ｄ )- an alkylene group having -N(R ｄ ) an alkylene group having C(O)-, -OC(O)N(R ｄ Alkylene group having -, alkylene group having an etheric oxygen atom, alkylene group having -S-, alkylene group having -OC(O)-, alkylene group having -C(O)O-, alkylene group having -C(O)S-, -N(R ｄ )- an alkylene group having -N(R ｄ ) C(O)N(R ｄ ) an alkylene group having -SO ２ N(R) ｄ Alkylene group having )- and alkylene group-Si(R ａ ) ２ - Phenylene group - Si (R ａ ) ２ - is one example.

[0240] In formula (3-1A), X ３１ This group is a single bond, an alkylene group, a carbon atom, a nitrogen atom, a silicon atom, a divalent to octavalent organo(poly)siloxane residue, or a group having an (h+i+1) valent ring. The alkylene group may also have -O-, a sylphenylene skeleton, a divalent organo(poly)siloxane residue, or a dialkylsilylene group. The alkylene group may have multiple groups selected from the group consisting of -O-, a sylphenylene skeleton, a divalent organo(poly)siloxane residue, and a dialkylsilylene group. ３１ The number of carbon atoms in the alkylene group represented by is preferably 1 to 20, and more preferably 1 to 10.

[0241] In formula (3-1A), X ３１ If is a group having a (h+i+1) valent ring, Q ａ , (-Q ｂ -Si(R２ ) ｎ L ３－ｎ ) and R ３１ It is directly bonded to the atoms constituting the ring. However, the ring is a ring other than an organopolysiloxane ring. ３１ The ring in the compound may be a monoring, a fused polyring, a bridging ring, a spiroring, or an aggregated polyring. The atoms constituting the ring may be a carbon ring consisting only of carbon atoms, or a heteroring consisting of a heteroatom with a valence of 2 or more and a carbon atom. The bonds between the atoms constituting the ring may be single bonds or multiple bonds. Furthermore, the ring may be aromatic or a non-aromatic ring. As monorings, 4-membered to 8-membered rings are preferred, and 5-membered and 6-membered rings are more preferred. As fused polyrings, fused polyrings formed by the fusion of two or more 4-membered to 8-membered rings are preferred, fused polyrings formed by the bonding of two or three rings selected from 5-membered and 6-membered rings, and fused polyrings formed by the bonding of one or two rings selected from 5-membered and 6-membered rings and one 4-membered ring are more preferred. As the bridging ring, a bridging ring with a 5-membered or 6-membered ring as the largest ring is preferred, and as the spiro ring, a spiro ring consisting of two 4-membered to 6-membered rings is preferred. As the aggregated polyring, an aggregated polyring in which two or three rings selected from the 5-membered and 6-membered rings are bonded via single bonds, one to three carbon atoms, or one heteroatom with a valency of 2 or 3 is preferred. In the aggregated polyring, each ring has Q ａ , (-Q ｂ -Si(R ２ ) ｎ L ３－ｎ ) and R ３１ It is preferable that any of the (if i = 1 or greater) atoms are bonded. The heteroatoms constituting the ring are preferably nitrogen atoms, oxygen atoms, and sulfur atoms, and more preferably nitrogen atoms and oxygen atoms. It is preferable that the number of heteroatoms constituting the ring is three or less. If the number of heteroatoms constituting the ring is two or more, those heteroatoms may be different.

[0242] X ３１The preferred ring in the compound is one selected from the group consisting of a 3- to 8-membered aliphatic ring, a benzene ring, a 3- to 8-membered heteroring, a fused ring formed by the fusion of two or three of these rings, a bridging ring with a 5- or 6-membered ring as the largest ring, and a polycyclic aggregate having two or more of these rings, where the linking group is a single bond, an alkylene group with 3 or fewer carbon atoms, an oxygen atom, or a sulfur atom. Preferred rings are a benzene ring, a 5- or 6-membered aliphatic ring, a 5- or 6-membered heteroring having a nitrogen atom or an oxygen atom, and a fused ring of a 5- or 6-membered carbon ring and a 4- to 6-membered heteroring. Specific examples of rings include the following, as well as 1,3-cyclohexadiene rings, 1,4-cyclohexadiene rings, anthracene rings, cyclopropane rings, decahydronaphthalene rings, norbornene rings, norbornadiene rings, furan rings, pyrrole rings, thiophene rings, pyrazine rings, morpholine rings, aziridine rings, isoquinoline rings, oxazole rings, isoxazole rings, thiazole rings, imidazole rings, pyrazole rings, pyran rings, pyridazine rings, pyrimidine rings, and indene rings. Rings containing an oxo group (=O) are also shown below.

[0243]

[0244] X ３１ In this case, the bonds between atoms that constitute a ring and that do not constitute a ring are Q ａ , (-Q ｂ -Si(R ２ ) ｎ L ３－ｎ ) or R ３１ This is a bond that connects to Q. If there are any remaining bonds, the remaining bonds are bonded to a hydrogen atom or a substituent. Examples of substituents include halogen atoms, alkyl groups (which may contain an etheric oxygen atom between carbon atoms), cycloalkyl groups, alkenyl groups, allyl groups, alkoxy groups, oxo groups (=O), etc. Also, one of the carbon atoms constituting the ring is Q. ａ , (-Q ｂ -Si(R ２ ) ｎ L ３－ｎ ) or R ３１If it has two bonding bonds, one of the carbon atoms is Q ａ and (-Q ｂ -Si(R ２ ) ｎ L ３－ｎ ) and may be joined together, and two (-Q ｂ -Si(R ２ ) ｎ L ３－ｎ ) may be joined together. Q ａ And, (-Q ｂ -Si(R ２ ) ｎ L ３－ｎ ) or R ３１ It is preferable that it is bonded to a different ring-constituting atom. h (-Q ｂ -Si(R ２ ) ｎ L ３－ｎ Each of these may be bonded to a separate ring-forming atom, two of which may be bonded to one ring-forming carbon atom, and two of these may be bonded to two (-Q ｂ -Si(R ２ ) ｎ L ３－ｎ There may be two or more ring-forming carbon atoms to which ) are bonded. i R ３１ Each of these may be bonded to a separate ring-forming atom, two of which may be bonded to one ring-forming carbon atom, and two R ３１ There may be two or more ring-forming carbon atoms to which the compound is bonded.

[0245] Among them, X ３１ From the viewpoint of improving the frictional durability of the surface layer, carbon atoms, nitrogen atoms, silicon atoms, 4-8 valent organo(poly)siloxane residues, or groups having a (h+i+1) valent ring are preferred, with carbon atoms being more preferred.

[0246] In equation (3-1A), Q ｂ It is a single bond or a divalent linking group. The definition of a divalent linking group is given in Q above. ａ This is synonymous with the definition explained earlier.

[0247] Among them, Q ｂThe alkylene group may have an etheric oxygen atom. The number of carbon atoms in the alkylene group is preferably 1 to 30, more preferably 1 to 20, even more preferably 2 to 20, and may be 2 to 10, 2 to 6, or 2 to 5. Examples include 2, 3, 8, 9, and 11. The number of carbon atoms may also be 1 to 10.

[0248] In formula (3-1A), R ３１ This is a hydrogen atom, a hydroxyl group, or an alkyl group. The number of carbon atoms in the alkyl group is preferably 1 to 5, more preferably 1 to 3, and even more preferably 1.

[0249] X ３１ When it is a single bond or an alkylene group, h is 1 and i is 0, X ３１ If it is a nitrogen atom, then h is an integer from 1 to 2, i is an integer from 0 to 1, and (h + i) = 2, X ３１ If is a carbon atom or a silicon atom, then h is an integer from 1 to 3, i is an integer from 0 to 2, and (h + i) = 3, X ３１ If the organo(poly)siloxane residue is 2-8 valent, then h is an integer from 1 to 7, i is an integer from 0 to 6, and (h+i) = 1-7. ３１ If the group has a ring with (h+i+1) valencies, then h is an integer from 1 to 7, i is an integer from 0 to 6, and (h+i) = 1 to 7. (-Q ｂ -Si(R) ｎ L ３－ｎ If there are two or more (-Q) then ｂ -Si(R) ｎ L ３－ｎ ) may be the same or different. ３１ If there are two or more (-R ３１ These may be the same or different.

[0250] In particular, from the viewpoint of improving the frictional durability of the surface layer, i is preferably 0.

[0251] In formula (3-1B), Q ｃ It is a single bond or a divalent linking group. The definition of a divalent linking group is given in Q above. ａ This is synonymous with the definition explained earlier.

[0252] In formula (3-1B), R ３２ This is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and a hydrogen atom is preferred because it is easier to produce compounds with it. A methyl group is preferred as the alkyl group.

[0253] In formula (3-1B), Q ｄ Q is a single bond or an alkylene group. The number of carbon atoms in the alkylene group is preferably 1 to 10, and more preferably 1 to 6. From the viewpoint of ease of compound production, ｄ This is a single bond or -CH ２ - is preferable.

[0254] In formula (3-1B), R ３３ This atom is either a hydrogen atom or a halogen atom, and a hydrogen atom is preferred because it facilitates the production of compounds.

[0255] w is an integer from 1 to 10, preferably an integer from 1 to 6. Two or more [CH ２ C(R ３２ ) (-Q ｄ -Si(R ２ ) ｎ L ３－ｎ ) ] may be the same or different.

[0256] The preferred group (3-1A) is groups (3-1A-1) to (3-1A-7).

[0257] - (X ３２ ) ｓ１ - Q ｂ１ -Si(R ２ ) ｎ L ３－ｎ ...(3-1A-1) -(X ３３ ) ｓ２ - Q ａ２ -N[-Q ｂ２ -Si(R ２ ) ｎ L ３－ｎ ] ２ ...(3-1A-2) -Q ａ３ -Si(R ｇ ) [-Q ｂ３ -Si(R ２ ) ｎ L ３－ｎ ] ２...(3-1A-3) -[Q ｅ ] ｓ４ - Q ａ４ - (O) ｔ４ -C[-(O) ｕ４ - Q ｂ４ -Si(R ２ ) ｎ L ３－ｎ ] ３－ｗ１ (-R ３１ ) ｗ１ ...(3-1A-4) -Q ａ５ -Si[-Q] ｂ５ -Si(R ２ ) ｎ L ３－ｎ ] ３ ...(3-1A-5) -[Q ｅ ] ｖ - Q ａ６ -Z ａ [-Q] ｂ６ -Si(R ２ ) ｎ L ３－ｎ ] ｗ２ ...(3-1A-6) -[Q ｅ ] ｓ４ - Q ａ４ - (O) ｔ４ -Z ｃ [-(O-Q) ｂ４ ) ｕ４ -Si(R ２ ) ｎ L ３－ｎ ] ｗ３ (-OH) ｗ４ …(3-1A-7) Note that in equations (3-1A-1) to (3-1A-7), R ２ The definitions of L and n are as described above.

[0258] Among these, group (3-1A) is preferably group (3-1A-4).

[0259] In the base (3-1A-1), X ３２ is -O-, -S-, -N(R ｄ )-, -C(O)-, -C(O)O-, -C(O)S-, -SO ２ N(R) ｄ )-,-N(R ｄ ) SO ２ -, -N(R ｄ )C(O)-,-N(Rｄ ) C(O)N(R ｄ )-,-OC(O)N(R ｄ )-, or-C(O)N(R ｄ ) -; or a combination of these with a divalent linking group (wherein N is Q) ｂ１ (to be joined). R ｄ The definition is as described above. s1 is either 0 or 1.

[0260] X ３２ However, -O-, -S-, -N(R ｄ )-, -C(O)-, -C(O)O-, -C(O)S-, -SO ２ N(R) ｄ )-,-N(R ｄ ) SO ２ -, -N(R ｄ )C(O)-,-N(R ｄ ) C(O)N(R ｄ )-,-OC(O)N(R ｄ )-, or-C(O)N(R ｄ )- and a divalent linking group, in the case of a combination of these, the divalent linking group is Si(R) of formula (C) or (D). ３ ) ２ Or Si(R ４ ) ２ , or R of formula (E) ２０ It binds to. Examples of divalent linking groups include alkylene groups, organo(poly)siloxane residues, polyalkylene oxide groups, and combinations thereof.

[0261] Q ｂ１ This is either a single bond or an alkylene group. The alkylene group may have -O-, a sylphenylene skeleton group, or a dialkylsilylene group. The alkylene group may have multiple groups selected from the group consisting of -O-, a sylphenylene skeleton group, a divalent organo(poly)siloxane residue, and a dialkylsilylene group. When the alkylene group has -O-, a sylphenylene skeleton group, a divalent organo(poly)siloxane residue, or a dialkylsilylene group, it is preferable that these groups are located between carbon atoms. Q ｂ１The number of carbon atoms in the alkylene group represented by is preferably 1 to 30, more preferably 1 to 20, even more preferably 2 to 20, and particularly preferably 2 to 6. The number of carbon atoms may also be 1 to 10.

[0262] In the base (3-1A-2), X ３３ is -O-, -S-, -N(R ｄ )-, -C(O)-, -C(O)O-, -C(O)S-, -SO ２ N(R) ｄ )-,-N(R ｄ ) SO ２ -, -N(R ｄ )C(O)-,-N(R ｄ ) C(O)N(R ｄ )-,-OC(O)N(R ｄ )-, or-C(O)N(R ｄ ) -; or a combination of these with a divalent linking group. R ｄ The definition is as described above. s2 is either 0 or 1. s2 is preferably 0 because it facilitates the production of the compound.

[0263] X ３３ However, -O-, -S-, -N(R ｄ )-, -C(O)-, -C(O)O-, -C(O)S-, -SO ２ N(R) ｄ )-,-N(R ｄ ) SO ２ -, -N(R ｄ )C(O)-,-N(R ｄ ) C(O)N(R ｄ )-,-OC(O)N(R ｄ )-, or-C(O)N(R ｄ )- and a divalent linking group, in the case of a combination of these, the divalent linking group is Si(R) of formula (C) or (D). ３ ) ２ Or Si(R ４ ) ２ , or R of formula (E) ２０ It binds to. Examples of divalent linking groups include alkylene groups, organo(poly)siloxane residues, polyalkylene oxide groups, and combinations thereof.

[0264] Q ａ２This includes single bonds, alkylene groups, -C(O)-, or etheric oxygen atoms between carbon atoms of alkylene groups with 2 or more carbon atoms, -C(O)-, -C(O)O-, -OC(O)-, and -C(O)N(R). ｄ )-,-N(R ｄ )C(O)-,-N(R ｄ ) C(O)N(R ｄ )-,-N(R ｄ )C(O)O-, -OC(O)N(R ｄ ) -, -SO ２ N(R) ｄ )-,-N(R ｄ ) SO ２ -, -C(O)N(R ｄ ) - or -NH- is a group having NH-. Q ａ２ The number of carbon atoms in the alkylene group represented by is preferably 1 to 20, more preferably 1 to 10, even more preferably 1 to 6, and particularly preferably 1 to 3. Q ａ２ An alkylene group with 2 or more carbon atoms represented by an etheric oxygen atom between carbon atoms, -C(O)-, -C(O)O-, -OC(O)-, -C(O)N(R) ｄ )-,-N(R ｄ )C(O)-,-N(R ｄ ) C(O)N(R ｄ )-,-N(R ｄ )C(O)O-, -OC(O)N(R ｄ ) -, -SO ２ N(R) ｄ )-,-N(R ｄ ) SO ２ -, -C(O)N(R ｄ The number of carbon atoms in the group having - or -NH- is preferably 2 to 10, and more preferably 2 to 6.

[0265] Q ａ２ Single bonds are preferred because they facilitate the production of compounds.

[0266] Q ｂ２ This refers to an alkylene group, or an alkylene group having two or more carbon atoms with a divalent organo(poly)siloxane residue, an etheric oxygen atom, or -NH- between carbon atoms. Q ｂ２The number of carbon atoms in the alkylene group represented by is preferably 1 to 30, more preferably 1 to 20, even more preferably 2 to 20, and may also be 2 to 10 or 2 to 6. For example, 2, 3, 8, 9, and 11 are given. Also, the number of carbon atoms may be 1 to 10. Q ｂ２ The number of carbon atoms in the alkylene group having two or more carbon atoms represented by the formula, which has a divalent organo(poly)siloxane residue, an etheric oxygen atom, or -NH- between carbon atoms, is preferably 2 to 10, and more preferably 2 to 6.

[0267] Q ｂ２ As for the ease of producing the compound, -CH ２ CH ２ CH ２ -ien-CH ２ CH ２ OCH ２ CH ２ CH ２ - is preferable (provided that the right-hand bond connects to Si).

[0268] Two [-Q ｂ２ -Si(R ２ ) ｎ L ３－ｎ These may be the same or different.

[0269] In the base (3-1A-3), Q ａ３ This is an alkylene group which may have a single bond or an etheric oxygen atom. From the standpoint of ease of compound production, Q ａ３ A single bond is preferred. The number of carbon atoms in the alkylene group, which may have an etheric oxygen atom, is preferably 1 to 10, and particularly preferably 2 to 6.

[0270] R ｇ R is a hydrogen atom, a hydroxyl group, or an alkyl group. ｇ From the viewpoint of ease of compound production, hydrogen atoms or alkyl groups are preferred. The alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms, and even more preferably a methyl group.

[0271] Q ｂ３This refers to an alkylene group, or a group having an etheric oxygen atom or a divalent organo(poly)siloxane residue between carbon atoms of an alkylene group having two or more carbon atoms. Q ｂ３ The number of carbon atoms in the alkylene group represented by is preferably 1 to 30, more preferably 1 to 20, even more preferably 2 to 20, and may also be 2 to 10 or 2 to 6. For example, 2, 3, 8, 9, and 11 are given. Also, the number of carbon atoms may be 1 to 10. Q ｂ３ The number of carbon atoms in the alkylene group having two or more carbon atoms, represented by [the formula], is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6. ｂ３ Because it is easy to manufacture the compound, -CH ２ CH ２ -ien-CH ２ CH ２ CH ２ -, or -CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ - is preferable.

[0272] Two [-Q ｂ３ -Si(R ２ ) ｎ L ３－ｎ These may be the same or different.

[0273] In the base (3-1A-4), Q ｅ is -C(O)O-, -SO ２ N(R) ｄ )-,-N(R ｄ ) SO ２ -, -N(R ｄ )C(O)-, or -C(O)N(R ｄ ) -; or a combination of these with a divalent linking group. Q ｅ is -C(O)O-, -SO ２ N(R) ｄ )-,-N(R ｄ ) SO ２ -, -N(Rｄ )C(O)-, or -C(O)N(R ｄ )- and a divalent linking group, in the case of a combination of these, the divalent linking group is Si(R) of formula (C) or (D). ３ ) ２ Or Si(R ４ ) ２ , or R of formula (E) ２０ It binds to. Examples of divalent linking groups include alkylene groups, organo(poly)siloxane residues, polyalkylene oxide groups, and combinations thereof. ３１ The definition is as described above. If w1 is 1 or 2, R ３１ A hydrogen atom is preferred. s4 is 0 or 1. Q ａ４ This is an alkylene group which may have a single bond or an etheric oxygen atom. The number of carbon atoms in the alkylene group which may have an etheric oxygen atom is preferably 1 to 20, more preferably 1 to 10, even more preferably 1 to 6, and particularly preferably 1 to 3. t4 is 0 or 1 (however, Q ａ４ It is 0 if it is a single bond. ) -Q ａ４ - (O) ｔ４ - As for the ease of compound production, if s4 is 0, it is a single bond, -CH ２ O-, -CH ２ OCH ２ -ien-CH ２ OCH ２ CH ２ O-, -CH ２ OCH ２ CH ２ OCH ２ - or -CH ２ OCH ２ CH ２ CH ２ CH ２ OCH ２ - is preferred, and if s4 is 1, a single bond, -CH ２ - or -CH ２ CH ２ - is preferable.

[0274] Q ｂ４ This is an alkylene group, and the above alkylene group is -O-, -C(O)N(R ｄ) - (R ｄ The definition is as described above. It may have a silphenylene skeleton group, a divalent organo(poly)siloxane residue, or a dialkylsilylene group. When the alkylene group has an -O- or silphenylene skeleton group, it is preferable that the -O- or silphenylene skeleton group is between carbon atoms. Also, the alkylene group may have -C(O)N(R ｄ )-, if it has a dialkylsilylene group or a divalent organo(poly)siloxane residue, carbon-carbon or (O) ｕ４ It is preferable to have these groups at the terminal end that bonds with the other. ｂ４ The number of carbon atoms in the alkylene group represented by is preferably 1 to 30, more preferably 1 to 20, even more preferably 2 to 20, and may also be 2 to 10 or 2 to 6. For example, 2, 3, 8, 9, and 11 are given. The number of carbon atoms may also be 1 to 10.

[0275] u4 is either 0 or 1. - (O) ｕ４ - Q ｂ４ -As for the ease of manufacturing the compound, -CH ２ CH ２ -ien-CH ２ CH ２ CH ２ -ien-CH ２ OCH ２ CH ２ CH ２ -ien-CH ２ OCH ２ CH ２ CH ２ CH ２ CH ２ -, -OCH ２ CH ２ CH ２ -, -OSi(CH ３ ) ２ CH ２ CH ２ CH ２ -, -OSi(CH ３ ) ２ OSi(CH ３ ) ２ CH ２ CH ２ CH ２ - or -CH２ CH ２ CH ２ Si(CH) ３ ) ２ PhSi(CH ３ ) ２ CH ２ CH ２ - is preferable (provided that the right-hand bond connects to Si).

[0276] w1 is an integer between 0 and 2, preferably 0 or 1, and more preferably 0. [-(O) ｕ４ - Q ｂ４ -Si(R ２ ) ｎ L ３－ｎ If there are two or more [-(O)] ｕ４ - Q ｂ４ -Si(R ２ ) ｎ L ３－ｎ ] may be the same or different. ３１ If there are two or more (-R ３１ These may be the same or different.

[0277] In the base (3-1A-5), Q ａ５ This is an alkylene group which may have an etheric oxygen atom. The number of carbon atoms in the alkylene group which may have an etheric oxygen atom is preferably 1 to 10, and particularly preferably 2 to 6. Q ａ５ As for the ease of producing the compound, -OCH ２ CH ２ CH ２ -, -OCH ２ CH ２ OCH ２ CH ２ CH ２ -ien-CH ２ CH ２ - or -CH ２ CH ２ CH ２ - is preferable (provided that the right-hand bond connects to Si).

[0278] Q ｂ５This refers to an alkylene group, or a group having an etheric oxygen atom or a divalent organo(poly)siloxane residue between carbon atoms of an alkylene group having two or more carbon atoms. Q ｂ５ The number of carbon atoms in the alkylene group represented by is preferably 1 to 30, more preferably 1 to 20, even more preferably 2 to 20, and may also be 2 to 10 or 2 to 6. For example, 2, 3, 8, 9, and 11 are given. Also, the number of carbon atoms may be 1 to 10. Q ｂ５ The number of carbon atoms in the alkylene group having two or more carbon atoms, represented by [the formula], is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6. ｂ５ As for the ease of producing the compound, -CH ２ CH ２ CH ２ - or -CH ２ CH ２ OCH ２ CH ２ CH ２ - is preferable (however, the bond on the right side is Si(R ２ ) ｎ L ３－ｎ (Combine.)

[0279] 3 [-Q ｂ５ -Si(R ２ ) ｎ L ３－ｎ These may be the same or different.

[0280] Q in the base (3-1A-6) ｅ The definition of is as defined in the above-mentioned base (3-1A-4). v is either 0 or 1.

[0281] Q ａ６ This is an alkylene group which may have an etheric oxygen atom. The number of carbon atoms in the alkylene group which may have an etheric oxygen atom is preferably 1 to 10, and particularly preferably 2 to 6. Q ａ６ As for the ease of producing the compound, -CH ２ OCH ２ CH ２ CH ２ -ien-CH２ OCH ２ CH ２ OCH ２ CH ２ CH ２ -ien-CH ２ CH ２ - or -CH ２ CH ２ CH ２ - is preferable (however, the right-hand joint is Z ａ (Combine.)

[0282] Z ａ is a (w2+1) valent organo(poly)siloxane residue, or a (w2+1) valent group having an alkylene group between organo(poly)siloxane residues. w2 is an integer from 2 to 7. Examples of (w2+1) valent organo(poly)siloxane residues and (w2+1) valent groups having an alkylene group between organo(poly)siloxane residues are listed below. However, R in the following formula ａ This is as described above. * indicates the binding site.

[0283]

[0284] Q ｂ６ This refers to an alkylene group, or a group having an etheric oxygen atom or a divalent organo(poly)siloxane residue between carbon atoms of an alkylene group having two or more carbon atoms. Q ｂ６ The number of carbon atoms in the alkylene group represented by is preferably 1 to 30, more preferably 1 to 20, even more preferably 2 to 20, and may also be 2 to 10 or 2 to 6. For example, 2, 3, 8, 9, and 11 are given. Also, the number of carbon atoms may be 1 to 10. Q ｂ６ The number of carbon atoms in the alkylene group having two or more carbon atoms, represented by [the formula], is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6. ｂ６ As for the ease of producing the compound, -CH ２ CH ２ - or -CH ２CH ２ CH ２ - is preferable. Two [-Q] ｂ６ -Si(R ２ ) ｎ L ３－ｎ These may be the same or different.

[0285] In base (3-1A-7), Z ｃ w3 is a (w3 + w4 + 1) valent hydrocarbon group. w3 is an integer greater than or equal to 4. w4 is an integer greater than or equal to 0. Q ｅ s4, Q ａ４ t4, Q ｂ４ The definitions and preferred ranges of u4 and u4 are the same as the definitions of each symbol in base (3-1A-4).

[0286] Z ｃ It may consist of a hydrocarbon chain, and may have etheric oxygen atoms between carbon atoms in the hydrocarbon chain; it is preferable that it consists of a hydrocarbon chain. ｃ The valency is preferably 5 to 20, more preferably 5 to 10, even more preferably 5 to 8, and particularly preferably 5 to 6. ｃ The number of carbon atoms in w3 is preferably 3 to 50, more preferably 4 to 40, and even more preferably 5 to 30. The number of carbon atoms in w3 is preferably 4 to 20, more preferably 4 to 16, even more preferably 4 to 8, and particularly preferably 4 to 5. The number of carbon atoms in w4 is preferably 0 to 10, more preferably 0 to 8, even more preferably 0 to 6, particularly preferably 0 to 3, and most preferably 0 to 1. [-(O-Q ｂ４ ) ｕ４ -Si(R ２ ) ｎ L ３－ｎ If there are two or more [-(O-Q], then two or more [-(O-Q) ｂ４ ) ｕ４ -Si(R ２ ) ｎ L ３－ｎ These may be the same or different.

[0287] Formula A (Si(R ２ ) ｎ L ３－ｎ ) ｑ１ In this, A may be the base (g2-1) to (g2-7).

[0288]

[0289] (-A ４ - Q １２ -) ｅ１ C(R ｅ８ ) ４－ｅ１－ｅ２ (-Q ３２ -) ｅ２ …(g2-2) -A ４ - Q １３ -N(-Q) ３３ -) ２ ...(g2-3) (-A ４ - Q １４ -) ｈ１ Z ４ (-Q ３４ -) ｈ２ ...(g2-4) (-A ４ - Q １５ -) ｉ１ Si(R ｅ９ ) ４－ｉ１－ｉ２ (-Q ３５ -) ｉ２ …(g2-5) -A ４ - Q ３６ -...(g2-6) -A ４ - Q １２ -CH(-Q) ３２ -)-Si(R ｅ９ ) ３－ｉ３ (-Q ３５ -) ｉ３ ... (g2-7)

[0290] However, in equations (g2-1) to (g2-7), A ４ The side is Si(R ３ ) ２ or Si(R ４ ) ２ Combined with Q ３２ Q ３３ Q ３４ Q ３５ Or Q ３６ The side is [-Si(R ２ ) ｎ L ３－ｎ It combines with ]. A ４ This is a single bond, -C(O)NR ６ -, -C(O)-, -OC(O)O-, -NHC(O)O-, -NHC(O)NR ６ -, -O-, or SO２ NR ６ - is the case. Q １０ This refers to a single bond, -O-, an alkylene group, or an alkylene group with two or more carbon atoms with -C(O)NR between carbon atoms. ６ -, -C(O)-, -NR ６ It is a group having - or -O-. Q １２ This refers to a single bond, an alkylene group, or an alkylene group having two or more carbon atoms with -C(O)NR between carbon atoms. ６ -, -C(O)-, -NR ６ A group having - or -O-, where A is Q １２ If you have two or more Q １２ They may be the same or different. Q １３ is a single bond (however, A ４ is -C(O)-. ), alkylene group, -C(O)NR between carbon atoms of alkylene groups with 2 or more carbon atoms ６ -, -C(O)-, -NR ６ It is a group having - or -O-, or a group having -C(O)- at the N-side terminal of an alkylene group. Q １４ Q １４ Z that joins ４ If the atom in Q is a carbon atom, １２ Q １４ Z that joins ４ If the atom in Q is a nitrogen atom, １３ And A is Q １４ If you have two or more Q １４ They may be the same or different. Q １５ This refers to an alkylene group, or an alkylene group having 2 or more carbon atoms with -C(O)NR between carbon atoms. ６ -, -C(O)-, -NR ６ A group having - or -O-, where A is Q １５ If you have two or more Q １５ They may be the same or different. Q ３２ This refers to an alkylene group, an alkylene group having 2 or more carbon atoms, with -C(O)NR between the carbon atoms. ６ -, -C(O)-, -NR ６A group having - or -O-, or -C(O)NR at the end of the alkylene group that is not connected to Si. ６ -, -C(O)-, -NR ６ A group having - or -O-, or an alkylene group having 2 or more carbon atoms with -C(O)NR between carbon atoms. ６ -, -C(O)-, -NR ６ - or -O- and -C(O)NR at the end not connected to Si ６ -, -C(O)-, -NR ６ A group having - or -O-, where A is Q ３２ If you have two or more Q ３２ They may be the same or different. Q ３３ This refers to an alkylene group, or an alkylene group having 2 or more carbon atoms with -C(O)NR between carbon atoms. ６ -, -C(O)-, -NR ６ A group having - or -O-, and two Q ３３ They may be the same or different. Q ３４ Q ３４ Z that joins ４ If the atom in Q is a carbon atom, ３２ Q ３４ Z that joins ４ If the atom in Q is a nitrogen atom, ３３ And A is Q ３４ If you have two or more Q ３４ They may be the same or different. Q ３５ This refers to an alkylene group, or an alkylene group having 2 or more carbon atoms with -C(O)NR between carbon atoms. ６ -, -C(O)-, -NR ６ A group having - or -O-, where A is Q ３５ If you have two or more Q ３５ They may be the same or different. Q ３６ This refers to an alkylene group, or an alkylene group having 2 or more carbon atoms with -C(O)NR between carbon atoms. ６ -, -C(O)-, -NR ６ It is a group having - or -O-. Q ３２ Q ３３ Q ３４ Q３５ Q ３６ If the group is an alkylene group, the number of carbon atoms is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 6. ４ Q １４ It has a carbon or nitrogen atom that is directly bonded to it and Q ３４ It is a group having a (h1 + h2) valence ring structure with a carbon or nitrogen atom directly bonded to it. ｅ７ is a hydrogen atom or an alkyl group, and A is R ｅ７ If there are two or more, then there are two or more R ｅ７ They may be the same or different. ｅ８ R is a hydrogen atom, a hydroxyl group, an alkyl group, or an acyloxy group. ｅ９ R is an alkyl group. ６ These are a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group.

[0291] d13 is an integer between 0 and 3, preferably 1 or 2. d14 is an integer between 0 and 3, preferably 1 or 2. (d13 + d14) is an integer between 1 and 3. d15 is an integer between 0 and 3, preferably 0 or 1. d16 is an integer between 0 and 3, preferably 2 or 3. (d15 + d16) is an integer between 1 and 3. (d13 + d15) is an integer between 1 and 5, preferably 1 or 2. (d14 + d16) is an integer between 1 and 5, preferably 4 or 5. (e1 + e2) is 3 or 4. e1 is an integer between 1 and 3, preferably 1 or 2. e2 is an integer between 1 and 3, preferably 2 or 3. h1 is an integer of 1 or more, preferably 1 or 2. h2 is an integer of 1 or more, preferably 2 or 3. (i1 + i2) is 3 or 4. i1 is an integer between 1 and 3, preferably 1 or 2. i2 is an integer between 1 and 3, preferably 2 or 3. i3 is 2 or 3.

[0292] Q １０ Q １２ Q １３ Q １４ Q １５ Q ３２ Q ３３ Q ３４ Q３５ and Q ３６ The number of carbon atoms in the alkylene group is preferably 1 to 30, more preferably 1 to 20, even more preferably 2 to 20, and may also be 2 to 10 or 2 to 6, from the viewpoint of ease of compound production and further improvement in the frictional durability of the surface layer. Examples include 2, 3, 8, 9, and 11. Furthermore, the number of carbon atoms may also be 1 to 10, 1 to 6, or 1 to 4. However, the lower limit of the number of carbon atoms in the alkylene group when there is a specific bond between carbon atoms is 2.

[0293] Z ４ The ring structure in is the ring structure described above, and the preferred form is also the same. ４ The ring structure in Q １４ Ya Q ３４ Because they bond directly, for example, an alkylene group is linked to the ring structure, and Q is attached to that alkylene group. １４ Ya Q ３４ They will not be connected.

[0294] R ｅ７ , R ｅ８ or R ｅ９ The number of carbon atoms in the alkyl group is preferably 1 to 6, more preferably 1 to 3, and particularly preferably 1 to 2, from the standpoint of facilitating compound production. ｅ８ The number of carbon atoms in the alkyl group portion of the acyloxy group is preferably 1 to 6, more preferably 1 to 3, and particularly preferably 1 to 2, from the viewpoint of ease of compound production and even better frictional durability of the surface layer. For h1, it is preferably 1 to 6, more preferably 1 to 4, even more preferably 1 or 2, and particularly preferably 1, from the viewpoint of ease of compound production and even better frictional durability of the surface layer. For h2, it is preferably 2 to 6, more preferably 2 to 4, and particularly preferably 2 or 3, from the viewpoint of ease of compound production and even better frictional durability of the surface layer.

[0295] Formula A (Si(R ２ ) ｎ L ３－ｎ ) ｑ１ Other forms of A in this context include groups (g2-8) to (g2-14).

[0296]

[0297] (-A ４ - Q １２ -) ｅ１ C(R ｅ８ ) ４－ｅ１－ｅ２ (-Q ３２ -G １ ) ｅ２ …(g2-9) -A ４ - Q １３ -N(-Q) ３３ -G １ ) ２ ...(g2-10) (-A ４ - Q １４ -) ｈ１ Z ４ (-Q ３４ -G １ ) ｈ２ ...(g2-11) (-A ４ - Q １５ -) ｉ１ Si(R ｅ９ ) ４－ｉ１－ｉ２ (-Q ３５ -G １ ) ｉ２ ...(g2-12) -A ４ - Q ３６ -G １ ...(g2-13) -A ４ - Q １２ -CH(-Q) ３２ -G １ )-Si(R ｅ９ ) ３－ｉ３ (-Q ３５ -G １ ) ｉ３ …(g2-14)

[0298] However, in equations (g2-8) to (g2-14), A ４ The side is Si(R ３ ) ２ or Si(R ４ ) ２ Combined with G １ The side is [-Si(R ２ ) ｎ L ３－ｎ It combines with ].

[0299] G １ The group is (g3) described below, and A has two or more G １ They may be the same or different. G１ The signs other than are the same as the signs in equations (g2-1) to (g2-7). -Si(R １３ ) ３－ｋ３ (-Q ３ -) ｋ３ …(g3) However, in the base (g3), the Si side is Q ３２ Q ３３ Q ３４ Q ３５ and Q ３６ Connect to Q ３ The side is [-Si(R ２ ) ｎ L ３－ｎ Connect to ]. R １３ It is an alkyl group. Q ３ This refers to an alkylene group, an alkylene group having 2 or more carbon atoms, with -C(O)NR between the carbon atoms. ６ -, -C(O)-, -NR ６ A group having - or -O-, or (OSi(R ９ ) ２ ) ｐ -O- and Q is 2 or greater. ３ They may be the same or different. k3 is 2 or 3. R ６ R is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group. ９ is an alkyl group, a phenyl group, or an alkoxy group, and has two R ９ They may be the same or different. p is an integer from 0 to 5, and if p is 2 or greater, then 2 or greater (OSi(R ９ ) ２ ) may be the same or different.

[0300] Q ３ The number of carbon atoms in the alkylene group is preferably 1 to 30, more preferably 1 to 20, even more preferably 2 to 20, and may also be 2 to 10 or 2 to 6, from the viewpoint of ease of compound production and further improvement in surface layer friction durability. Examples include 2, 3, 8, 9, and 11. Furthermore, the number of carbon atoms may be 1 to 10, 1 to 6, or 1 to 4. However, the lower limit of the number of carbon atoms in the alkylene group when it has a specific bond between carbon atoms is 2. １３The number of carbon atoms in the alkyl group is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 to 2, from the standpoint of facilitating compound production. ９ The number of carbon atoms in the alkyl group is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 to 2, from the standpoint of facilitating compound production. ９ The number of carbon atoms in the alkoxy group is preferably 1 to 6, more preferably 1 to 3, and particularly preferably 1 to 2, from the viewpoint of excellent storage stability of the compound. p is preferably 0 or 1.

[0301] Specific examples of non-fluorinated compounds include the following compounds:

[0302] In the following formula, n10 is a number greater than or equal to 1, and n10 is preferably a number between 1 and 60, but may also be a number between 3 and 50, a number between 5 and 30, or a number between 7 and 25.

[0303]

[0304] In the following formula, k is preferably 1 to 80, more preferably 3 to 50, and even more preferably 3 to 30. m is preferably 1 to 30, more preferably 3 to 20, and even more preferably 3 to 10. t is preferably 1 to 30, more preferably 3 to 20, and even more preferably 3 to 10. In the following formula, n10 is a number of 1 or more, and n10 is preferably a number from 1 to 60, may be a number from 3 to 50, may be a number from 5 to 30, or may be a number from 7 to 25.

[0305]

[0306] In the following formula, n10 is a number greater than or equal to 1, and n10 is preferably a number between 1 and 60, but may also be a number between 3 and 50, a number between 5 and 30, or a number between 7 and 25.

[0307]

[0308] In the following formula, n10 is a number greater than or equal to 1, and n10 is preferably a number between 1 and 60, but may also be a number between 3 and 50, a number between 5 and 30, or a number between 7 and 25.

[0309]

[0310]

[0311]

[0312]

[0313] In the following formula, n10 is a number greater than or equal to 1, and n10 is preferably a number between 1 and 60, but may also be a number between 3 and 50, a number between 5 and 30, or a number between 7 and 25.

[0314]

[0315] In the following formula, n10 is a number greater than or equal to 1, and n10 is preferably a number between 1 and 60, but may also be a number between 3 and 50, a number between 5 and 30, or a number between 7 and 25.

[0316]

[0317] <Applications> This article is used as a display component, input component, exterior component, lens component, and protective component in electrical machinery, transportation machinery, precision machinery, and housing equipment. Examples of electrical machinery include generators, consumer electrical equipment, communication equipment (e.g., smartphones), electronic application devices, and electrical measuring instruments. Examples of transportation machinery include automobiles, railway vehicles, ships, and aircraft. Examples of precision machinery include optical instruments, watches, and precision measuring instruments. Examples of housing equipment include water supply and drainage equipment (e.g., bathrooms, toilets, washbasins, and kitchens). Examples of display components and input components include displays and touch panels. Examples of protective components include components that protect parts requiring stain resistance, water repellency, oil repellency, moisture resistance, water-sliding properties, or low surface friction.

[0318] The article may be an optical material having a surface layer as its outermost layer. Preferred optical materials include optical materials related to displays and a wide variety of other optical materials. Examples of optical materials include displays such as cathode ray tubes (CRTs; for example, personal computer monitors), liquid crystal displays, plasma displays, organic EL displays, inorganic thin-film EL dot matrix displays, rear projection displays, fluorescent display tubes (VFDs), and field emission displays (FEDs), or protective plates for such displays, or materials with an anti-reflective coating applied to their surfaces.

[0319] The article is preferably an optical component. Examples of optical components include car navigation systems, mobile phones, smartphones, digital cameras, digital video cameras, PDAs, portable audio players, car audio systems, game consoles, eyeglass lenses, camera lenses, lens filters, sunglasses, medical equipment such as endoscopes, photocopiers, PCs, displays (e.g., liquid crystal displays, organic EL displays, plasma displays, touch panel displays), touch panels, protective films, and anti-reflective films. Examples of optical components include front protective plates, anti-reflective plates, polarizing plates, and anti-glare plates for displays such as PDPs and LCDs; disc surfaces for optical discs such as Blu-ray (registered trademark) discs, DVD discs, CD-Rs, and MOs; optical fibers; and display surfaces for watches.

[0320] The article is more preferably a display or touch panel. The article is even more preferably a stain-resistant article, and particularly preferably a fingerprint-resistant article.

[0321] [Method for Manufacturing Articles] The method for manufacturing articles of the present disclosure (hereinafter also referred to as "the manufacturing method") is a method for manufacturing articles comprising forming a first underlayer, a second underlayer, and a surface layer on a crystallized glass substrate in this order, wherein the formation of the first underlayer includes coating with a first underlayer composition comprising at least one selected from the group consisting of aluminum oxide, silicon nitride, and zirconium oxide, provided that if aluminum oxide is included, silicon oxide is not included; the formation of the second underlayer includes coating with a second underlayer composition comprising silicon oxide; and the formation of the surface layer includes coating with a surface layer composition comprising the compound.

[0322] The preferred embodiment of the article produced by this manufacturing method is the same as the preferred embodiment of the article described above.

[0323] <Formation of the First Substrate> This manufacturing method includes forming a first substrate on a crystallized glass substrate. The crystallized glass substrate is described above. The formation of the first substrate includes coating with a first substrate composition which includes at least one selected from the group consisting of aluminum oxide, silicon nitride, and zirconium oxide, provided that if aluminum oxide is included, silicon oxide is not included.

[0324] (Composition for the first underlayer) The composition for the first underlayer comprises at least one selected from the group consisting of aluminum oxide, silicon nitride, and zirconium oxide, provided that if aluminum oxide is included, silicon oxide is not included. From the viewpoint of increasing the surface hardness of the article, it is preferable that the composition for the first underlayer comprises at least one selected from the group consisting of aluminum oxide and zirconium oxide, provided that if aluminum oxide is included, silicon oxide is not included, and it is more preferable that it contains aluminum oxide but does not contain silicon oxide. Note that if the composition for the first underlayer comprises aluminum oxide, silicon oxide is not included, meaning that in this manufacturing method, aluminum oxide and silicon oxide do not coexist in the first underlayer and the composition for the first underlayer.

[0325] The above aluminum oxide is Al ｙ１O ｚ１ (y1 and z1 are any integers of 1 or more), and typically Al ２ O ３ However, it may also contain aluminum oxide with different stoichiometric ratios. The silicon nitride mentioned above is Si ｙ２ N ｚ２ (y² and z² are any integers of 1 or more), and typically Si ３ N ４ However, it may also contain silicon nitride with different stoichiometric ratios. The above zirconium oxide is typically Zr ｙ３ O ｚ３ (where y3 and z3 are any integers of 1 or more), and typically ZrO ２ However, it may also contain zirconium oxide with different stoichiometric ratios. The silicon oxide mentioned above is Si ｙ４ O ｚ４ (where y4 and z4 are any integers of 1 or more) and typically SiO ２ However, it may also contain silicon dioxide with different stoichiometric ratios.

[0326] The first base layer composition may or may not contain a liquid medium. If the first base layer composition does not contain a liquid medium, the first base layer composition consists of solids. If the first base layer composition contains a liquid medium, the first base layer composition consists of solids and a liquid medium. The liquid medium may be a solution or a dispersion. Details of the liquid medium are as follows. From the viewpoint of increasing the surface hardness of the article, the total content of aluminum oxide, silicon nitride, and zirconium oxide is preferably 30% by mass or more, more preferably 40% by mass or more, and particularly preferably 50% by mass or more, relative to the total solid content of the first base layer composition. This total content may be 100% by mass or less, or less than 100% by mass. The total content of aluminum oxide, silicon nitride, and zirconium oxide in the total solid content of the first base layer composition is, for example, 30 to 100% by mass. The method for measuring the total content of aluminum oxide, silicon nitride, and zirconium oxide is as described above.

[0327] The first base layer composition may contain compounds other than aluminum oxide, silicon nitride, and zirconium oxide. Examples of compounds other than aluminum oxide, silicon nitride, and zirconium oxide include diamond-like carbon, quartz, and silicon carbide. From the viewpoint of increasing the surface hardness of the article, the surface hardness of the compounds contained in the first base layer composition is preferably 2,200 MPa or higher, more preferably 2,350 MPa or higher, and particularly preferably 2,500 MPa or higher. From the viewpoint of excellent scratch resistance, the surface hardness is preferably 10,000 MPa or lower, more preferably 8,000 MPa or lower, and particularly preferably 5,000 MPa or lower. The surface hardness of the compounds contained in the first base layer composition is, for example, 2,200 to 10,000 MPa. The method for measuring surface hardness is as described above.

[0328] When the first base layer composition is used by a wet coating method, the liquid medium content is preferably 70% by mass or more, and more preferably 80% by mass or more, relative to the total amount of the first base layer composition, from the viewpoint of ease of film formation. This content may be 99.99% by mass or less, or 99.9% by mass or less. The liquid medium content is, for example, 70 to 99.99% by mass relative to the total amount of the first base layer composition. When the first base layer composition is used by a dry coating method, the first base layer composition may or may not contain a liquid medium.

[0329] <Formation of the second base layer> This manufacturing method includes forming a second base layer on the first base layer. The formation of the second base layer includes coating with a second base layer composition containing silicon dioxide.

[0330] (Composition for the second base layer) The composition for the second base layer contains silicon oxide. Silicon dioxide is preferred. The composition for the second base layer may or may not contain a liquid medium. If the composition for the second base layer does not contain a liquid medium, the composition for the second base layer consists of solids. If the composition for the second base layer contains a liquid medium, the composition for the second base layer consists of solids and a liquid medium. The liquid medium may be a solution or a dispersion. Details of the liquid medium are as follows. From the viewpoint of ensuring sufficient Si-O-Si bonding between the second base layer and the surface layer and that the surface layer has excellent friction resistance, the silicon oxide content is preferably 65% ​​by mass or more, more preferably 80% by mass or more, even more preferably 85% by mass or more, and particularly preferably 90% by mass or more, based on the total solid content of the composition for the second base layer. The content may be 100% by mass or less, or less than 100% by mass. The silicon dioxide content in the total solid content of the second sublayer composition is, for example, 65 to 100% by mass. The silicon dioxide content in the total solid content is the remainder obtained by subtracting the sum of the total content of other elements (or the amount converted to oxides in the case of oxides) from the mass of the solid content of the second sublayer composition.

[0331] The silicon dioxide mentioned above is Si ｙ５ O ｚ５ (y5 and z5 are any integers of 1 or more), and typically SiO ２ However, it may also contain silicon dioxide with different stoichiometric ratios.

[0332] From the viewpoint of excellent durability of the surface layer, the composition for the second underlayer preferably further contains an oxide of at least one element selected from the group consisting of alkali metal elements, alkaline earth metal elements, platinum group elements, boron, aluminum, phosphorus, titanium, zirconium, iron, nickel, chromium, molybdenum, and tungsten. The presence of this element strengthens the bond between the second underlayer and the compound, improving the frictional durability of the surface layer.

[0333] When the second base layer composition is used by a wet coating method, the liquid medium content is preferably 70% by mass or more, and more preferably 80% by mass or more, relative to the total amount of the second base layer composition, from the viewpoint of ease of film formation. This content may be 99.99% by mass or less, or 99.9% by mass or less. The liquid medium content is, for example, 70 to 99.99% by mass relative to the total amount of the second base layer composition. When the second base layer composition is used by a dry coating method, the second base layer composition may or may not contain a liquid medium.

[0334] <Surface Layer> This manufacturing method includes forming a surface layer on a second substrate layer. The formation of the surface layer includes coating with a surface layer composition containing the compound.

[0335] (Surface layer composition) The surface layer composition contains a compound having a reactive silyl group (this compound). The description of this compound is as described above. The surface layer composition may or may not contain a liquid medium. If the surface layer composition does not contain a liquid medium, the surface layer composition consists of solids. If the surface layer composition contains a liquid medium, the surface layer composition consists of solids and the liquid medium. The liquid medium may be a solution or a dispersion. Details of the liquid medium are as follows. From the viewpoint of superior water and oil repellency, friction durability, fingerprint stain removal, lubricity, and appearance of the surface layer, the content of this compound is preferably 70% by mass or more, more preferably 80% by mass or more, and even more preferably 95% by mass or more, based on the total solid content of the surface layer composition. From the viewpoint of excellent storage stability, the content may be 100% by mass or less, or 95% by mass or less. The content of this compound in the total solid content of the surface layer composition is, for example, 70 to 100% by mass. The method for measuring the content of this compound is as described above.

[0336] The surface layer composition may contain compounds other than the present compound (hereinafter also referred to as "other compounds"). Examples of other compounds include by-products generated during the manufacturing process of the present compound, and unavoidable compounds in the manufacturing process such as unreacted raw materials. From the viewpoint of fully exhibiting the properties of the present compound, the content of other compounds is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 1% by mass or less, based on the total solid content of the surface layer composition. This content may be 0% by mass or greater than 0% by mass. The content of other compounds is, for example, 0 to 10% by mass, based on the total solid content of the surface layer composition.

[0337] When the surface layer composition is used by a wet coating method, the liquid medium content is preferably 70% by mass or more, and more preferably 80% by mass or more, based on the total amount of the surface layer composition. This content may be 99.99% by mass or less, or 99.9% by mass or less. The liquid medium content is, for example, 70 to 99.99% by mass, based on the total amount of the surface layer composition. When the surface layer composition is used by a dry coating method, the surface layer composition may or may not contain a liquid medium.

[0338] When the surface layer composition contains a liquid medium, the content of this compound in the surface layer composition is preferably 0.1% by mass or more, and more preferably 0.2% by mass or more, from the viewpoint of superior water-repellent and oil-repellent properties, friction durability, fingerprint stain removal, lubricity, and appearance of the surface layer. From the viewpoint of excellent handling, the content is preferably 30% by mass or less, more preferably 10% by mass or less, and even more preferably 1% by mass or less. When the surface layer composition contains a liquid medium, the content of this compound in the surface layer composition is, for example, 0.1 to 30% by mass.

[0339] The surface layer composition may further contain known additives such as acid catalysts or basic catalysts that promote the hydrolysis and condensation reactions of reactive silyl groups. The additives may be included as solid components or as liquid media. The content of the additives is preferably 10% by mass or less, and more preferably 1% by mass or less, based on the total mass of the surface layer composition.

[0340] <Coating> In this manufacturing method, the coating methods for the first base layer composition, the second base layer composition, and the surface layer composition (hereinafter collectively referred to as "the composition") may be dry coating or wet coating, each independently.

[0341] If the composition is to be used in a wet coating method, it is preferable that the composition contains a liquid medium. If the composition is to be used in a dry coating method, the composition may or may not contain a liquid medium.

[0342] In this manufacturing method, preferably, the formation of the first base layer includes wet coating with the composition for the first base layer, the formation of the second base layer includes wet coating with the composition for the second base layer, and the formation of the surface layer includes wet coating with the composition for the surface layer.

[0343] In this manufacturing method, preferably, the formation of the first base layer includes dry coating with the first base layer composition, the formation of the second base layer includes dry coating with the second base layer composition, and the formation of the surface layer includes dry coating with the surface layer composition.

[0344] In the wet coating method, the composition containing the liquid medium is coated onto the surface and dried to form a layer. Examples of wet coating methods include spin coating, wipe coating, spray coating, squeegee coating, dip coating, die coating, inkjet coating, flow coating, roll coating, casting, Langmuir-Bludget coating, and gravure coating. The drying temperature after wet coating with the composition is preferably 20 to 200°C, and particularly preferably 80 to 160°C.

[0345] In the dry coating method, the composition without a liquid medium, or the composition from which part or all of the liquid medium has been removed, is coated onto the surface to form a layer. Examples of dry coating methods include vacuum deposition, CVD, and sputtering, and vacuum deposition is preferred from the viewpoint of suppressing the decomposition of the compound and the simplicity of the equipment.

[0346] In the case of vacuum deposition, the forms of the deposition material include powder, molten body, sintered body, granulated body, and crushed body, and from the viewpoint of ease of handling, the molten body, sintered body, and granulated body are preferred. A molten body refers to a solid obtained by melting the powder of the deposition material at a high temperature and then cooling and solidifying it. A sintered body refers to a solid obtained by firing the powder of the deposition material, and if necessary, a molded body formed by press-forming the powder may be used instead of the powder of the deposition material. A granulated body refers to a pellet-like substance obtained by impregnating the powder of the deposition material in a liquid medium and drying it. The form of the deposition material may also be a pellet-like substance in which the composition is supported on a porous metal body such as iron or steel.

[0347] The temperature during deposition (for example, the temperature of the boat in which the deposition material is placed when using a vacuum deposition apparatus) is preferably 100 to 3,000°C, and more preferably 500 to 3,000°C. The pressure during deposition (for example, the absolute pressure in the tank in which the deposition material is placed when using a vacuum deposition apparatus) is preferably 1 Pa or less, and more preferably 0.1 Pa or less. Methods for evaporating the deposition material include the resistance heating method, in which the deposition material is melted and evaporated on a resistance heating boat made of a high-melting-point metal, and the electron gun method, in which an electron beam is irradiated onto the deposition material to directly heat the material, melt the surface, and evaporate it. The electron gun method is preferred as an evaporation method for the deposition material because it can be heated locally, allowing for the evaporation of high-melting-point substances, and because areas not hit by the electron beam are at low temperatures, there is no risk of reaction with the container or contamination with impurities. As the deposition material used in the electron gun method, molten granules or sintered bodies are preferred because they are less likely to scatter even if an airflow is generated.

[0348] When forming layers using deposition materials, one deposition material may be used, or two or more deposition materials containing different elements may be used. For the evaporation method in vacuum deposition, multiple boats may be used, or all deposition materials may be placed in a single boat. The deposition method may be co-deposition, alternating deposition, etc. The deposition conditions and order are appropriately selected depending on the composition of the underlayer and surface layer.

[0349] (Liquid medium) Examples of liquid mediums include water and organic solvents. Organic solvents are preferred as the liquid medium, and organic solvents with a boiling point (standard boiling point) of 35 to 250°C are more preferred from the viewpoint of excellent coating properties. Examples of organic solvents include fluorinated organic solvents and non-fluorinated organic solvents, and fluorinated organic solvents are preferred in terms of excellent solubility. Organic solvents may be used alone or in combination of two or more.

[0350] Examples of fluorinated organic solvents include fluorinated alkanes, fluorinated aromatic compounds, fluoroalkyl ethers, fluorinated alkylamines, fluoroalcohols, and hydrofluoroolefins. Among fluorinated alkanes, compounds having 4 to 8 carbon atoms are preferred. Commercially available examples include C ６ F １３ H (AGC Corporation, Asahi Clean® AC-2000), C ６ F １３ C ２ H ５ (Manufactured by AGC Corporation, Asahi Clean® AC-6000), C ２ F ５ CHFCHFCF ３ Examples include (Chemours Bartrell® XF). Examples of fluorinated aromatic compounds include hexafluorobenzene, trifluoromethylbenzene, perfluorotoluene, and bis(trifluoromethyl)benzene. As for fluoroalkyl ethers, compounds having 4 to 12 carbon atoms are preferred. A commercially available product is CF ３ CH ２ OCF ２ CF ２ H (manufactured by AGC Corporation, Asahi Clean® AE-3000), C ４ F ９ OCH３ (Manufactured by 3M, Novec® 7100), C ４ F ９ OC ２ H ５ (Manufactured by 3M, Novec® 7200), C ２ F ５ CF(OCH) ３ ) C ３ F ７ Examples include Novec® 7300 (manufactured by 3M). Examples of fluorinated alkylamines include perfluorotripropylamine and perfluorotributylamine. Examples of fluoroalcohols include 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, and hexafluoroisopropanol. Examples of hydrofluoroolefins include 1-chloro-2,3,3-trifluoro-1-propene (HCFO-1233yd), reaction products of methanol and 1,1,1,2,2,3,4,5,5,6,6,7,7,7-tetradecafluoro-3-heptene, and reaction products of methanol and 1,1,1,2,3,4,4,5,5,6,6,7,7,7-tetradecafluoro-3-heptene. Commercially available products include Amorea® AS-300 from AGC Corporation and Opteon® (SF01, SF05, SF10, SF30, SF33, SF70, SF79, SF80) from Chemours Corporation.

[0351] As non-fluorinated organic solvents, compounds consisting only of hydrogen atoms and carbon atoms, and compounds consisting only of hydrogen atoms, carbon atoms, and oxygen atoms are preferred. Specifically, examples include hydrocarbon organic solvents, ketone organic solvents, ether organic solvents, ester organic solvents, alcohol organic solvents, amide organic solvents, and sulfoxide organic solvents. Hydrocarbon organic solvents are compounds consisting only of hydrogen atoms and carbon atoms, and any of aromatic hydrocarbons, aliphatic hydrocarbons, and unsaturated hydrocarbons can be used. Examples of aromatic hydrocarbons include benzene, toluene, and xylene. Examples of aliphatic hydrocarbons include n-hexane, n-heptane, n-octane, and n-decane. Examples of unsaturated hydrocarbons include cyclopentene, hexene, heptene, and butene. Specific examples of ketone organic solvents include acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-hexanone, cyclohexanone, methylamino ketone, 2-heptanone, diisobutyl ketone, and diacetone alcohol. Specific examples of ether-based organic solvents include diethyl ether, diisopropyl ether, methyl t-butyl ether, dimethoxyethane, 1,4-dioxane, 1,3-dioxolane, tetrahydrofuran, cyclopentyl methyl ether, 4-methyltetrahydrofuran, 2-methyltetrahydrofuran, and glycol-based solvents. Examples of glycol-based solvents include mono- or dialkylene glycols, mono- or dialkyl ethers, and mono- or dialkyl ether acetates. The alkylene group is preferably an ethylene group or a propylene group. The alkyl group is preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group or an ethyl group. More specific examples of glycol-based solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and propylene glycol monobutyl ether.Examples of ester-based organic solvents include ethyl acetate, isopropyl acetate, butyl acetate, amyl acetate, methyl formate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 2-hydroxyisobutyrate, and ethyl 2-hydroxyisobutyrate, as well as ester compounds of the above glycol-based solvents with carboxylic acids such as acetic acid. Examples of alcohol-based organic solvents include methanol, ethanol, propanol, isopropanol, and butanol. Note that the following glycol-based solvents are not included in the alcohol-based solvents.

[0352] Examples of amide-based organic solvents include N,N-dimethylformamide. Examples of sulfoxide-based organic solvents include dimethyl sulfoxide.

[0353] The present disclosure will be described in detail below with reference to examples. Examples 4 to 13 are embodiments, and Examples 1 to 3 and 14 to 16 are comparative examples. Note that Example 16 is an embodiment described in Patent Document 1. However, the present disclosure is not limited to these examples.

[0354] [Composition for Surface Layer] <Synthesis of Compound (1X) Having a Reactive Silyl Group> Compound (1X) having a reactive silyl group was obtained according to the synthesis method of compound A-2 described in International Publication No. 2020 / 071330. In compound (1X), n is 13. The number average molecular weight of compound (1X) is 5,035. Compound (1X) was diluted with a fluorine-based organic solvent (AGC Corporation, Asahi Clean® AC-6000) to a concentration of 0.3% by mass to obtain the composition for the surface layer (1X).

[0355]

[0356] <Synthesis of Compound (2X) Having a Reactive Silyl Group> Compound (2X) having a reactive silyl group was obtained according to the methods described in Synthesis Examples 11 to 15 of Japanese Patent Publication No. 2014-218639. In compound (2X), m is 18 and n is 22. The number-average molecular weight of compound (2X) is 4,600. m (CF ２ O) Chain and n (CF ２ CF ２O) The chains are arranged randomly. The compound (2X) was diluted with a fluorine-based organic solvent (AGC Corporation, Asahi Clean® AC-6000) to a concentration of 0.3% by mass to obtain a surface layer composition (2X).

[0357]

[0358] <Synthesis of Compound (3X) Having a Reactive Silyl Group> Compound (3X) having a reactive silyl group was obtained according to the method described in Example 1 of Japanese Patent Application Publication No. 2015-199906. In compound (3X), m is 20 and n is 23. The number-average molecular weight of compound (3X) is 4,470. m (CF ２ O) Chain and n (CF ２ CF ２ O) The chains are arranged randomly. Compound (3X) was diluted with a fluorine-based organic solvent (AGC Corporation, Asahi Clean® AC-6000) to a concentration of 0.3% by mass to obtain a surface layer composition (3X).

[0359]

[0360] [Manufacturing of Articles] <Examples 4-13> A molybdenum boat inside a vacuum deposition apparatus (SGCS-900i manufactured by Showa Vacuum Co., Ltd.) is filled with the first underlayer composition (2g), the second underlayer composition (2g), and the surface layer composition (0.2g) shown in Table 1 as deposition sources, and the inside of the vacuum deposition apparatus is filled to 1 × 10⁻¹⁶ －３The air was exhausted to below Pa. The boat containing the first underlayer composition (2 g) was heated at a heating rate of 10°C / min or less. When the deposition rate measured by a quartz crystal thickness gauge exceeded 1 nm / second, the shutter was opened to begin film formation on the surface of the crystallized glass substrate (manufactured by Kanou Precision Co., Ltd., crystallized glass). When the first underlayer reached the thickness shown in Table 1, the shutter was closed to end film formation on the surface of the crystallized glass substrate. Next, the boat containing the second underlayer composition (2 g) was heated at a heating rate of 10°C / min or less. When the deposition rate measured by a quartz crystal thickness gauge exceeded 1 nm / second, the shutter was opened to begin film formation on the surface of the first underlayer. When the second underlayer reached the thickness shown in Table 1, the shutter was closed to end film formation. Next, a boat containing the surface layer composition (0.2 g) was heated at a rate of 10°C / min or less. When the deposition rate measured by a quartz crystal thickness gauge exceeded 1 nm / second, the shutter was opened to begin film formation on the surface of the second substrate layer. When the surface layer reached a thickness of 10 nm, the shutter was closed to end the film formation. The crystallized glass substrate, dry-coated in this order with the first substrate composition, the second substrate composition, and the surface layer composition, was heat-treated at 200°C for 30 minutes and washed with dichloropentafluoropropane (AGC, AK-225) to obtain the article.

[0361] <Examples 1-3 and 14-15> In Example 1, the procedure was carried out in the same manner as in Example 4, except that the first and second sublayers were not formed. In Examples 2-3 and 14-15, the procedure was carried out in the same manner as in Examples 4-13, except that the second sublayer was not formed and the thickness of the first sublayer was changed as shown in Table 1.

[0362] <Example 16> The procedure was carried out in the same manner as in Examples 4 to 13, except that a mixture of aluminum oxide and silicon dioxide with a mass ratio of 89:11 was deposited as the composition for the first sub-layer, and the thicknesses of the first and second sub-layers were changed as shown in Table 1.

[0363] [Evaluation] The following evaluation tests were conducted using items 1 to 16.

[0364] <Initial Water Contact Angle> The contact angle of approximately 2 μL of distilled water placed on the surface layer of an object was measured at 20°C using a contact angle measuring device (DM-500, manufactured by Kyowa Interface Science Co., Ltd.). Measurements were taken at five different locations on the surface layer, and the average value was calculated to determine the initial water contact angle. The 2θ method was used to calculate the water contact angle. Based on the obtained initial water contact angle values, water repellency was evaluated according to the following evaluation criteria. An evaluation result of A indicates excellent water repellency. A: Water contact angle of 100 degrees or more B: Water contact angle less than 100 degrees

[0365] <Friction Durability> For the surface layer of the article, a reciprocating surface friction tester (PA-300A, manufactured by Daiei Seiki Co., Ltd.) was used in accordance with JIS L0849:2013 (ISO 105-X12:2001), and steel wool was reciprocated with a load of 9.8 N, a speed of 60 rpm (60 revolutions per minute), and an amplitude of 40 mm. The water contact angle was measured at predetermined intervals using the method described above. Friction durability was evaluated according to the following evaluation criteria. The smaller the change in the water contact angle before and after friction, the smaller the performance degradation due to friction, and the better the friction durability. An evaluation result of C or higher indicates excellent friction durability. A: Water contact angle of 100 degrees or more even after 3,000 friction cycles with steel wool. B: Water contact angle of 100 degrees or more even after 2,000 friction cycles with steel wool, AND water contact angle of less than 100 degrees after 3,000 friction cycles with steel wool. C: Water contact angle of 100 degrees or more even after 1,000 friction cycles with steel wool, AND water contact angle of less than 100 degrees after 2,000 friction cycles with steel wool. D: Water contact angle of less than 100 degrees after 1,000 friction cycles with steel wool.

[0366] <Surface Hardness> Martens hardness (unit: MPa) was measured using an indentation test apparatus (Fischer, Picodenter HM500) with an indentation load of 0.03 mN, a holding time of 5 seconds, and a loading and unloading rate of 0.05 mN / 5 seconds. Measurements were taken at three different locations on the surface of the article, and the average value was calculated to determine the surface hardness. Based on the obtained surface hardness, the surface hardness was evaluated according to the following evaluation criteria. An evaluation result of B or higher indicates excellent surface hardness. A: Surface hardness of 2,500 MPa or higher B: Surface hardness of 2,200 MPa or higher but less than 2,500 MPa C: Surface hardness less than 2,200 MPa

[0367] <Surface Roughness> The surface roughness of the articles was measured by surface observation using AFM under the following conditions. Based on the obtained surface roughness, the surface roughness was evaluated according to the following evaluation criteria. If the evaluation result is B or higher, the surface roughness is reduced and can be said to be excellent. Measurement range: 0.5 μm × 0.5 μm, Equipment: Bruker stylus profiling system (stylus thin film step meter) Dektak XT, Mode: ScanAsys mode, Probe: OPUS (spring constant: 9 N / m), Samples / Line: 256, Lines: 256, Scan Rate: 0.8 Hz, Measurement field of view: 0.5 × 0.5 μm (targeting areas without contamination) A: Sa value less than 1.3 B: Sa value 1.3 or more and less than 1.6 C: Sa value 1.6 or more

[0368] [Results] The results of the above evaluation tests are shown in Table 1.

[0369]

[0370] In Examples 4 to 13, articles having a surface layer with excellent friction resistance were obtained.

[0371] Furthermore, the disclosure of Japanese Patent Application No. 2024-220238, filed on 16 December 2024, is incorporated herein by reference in its entirety. In addition, all documents, patent applications, and technical standards described herein are incorporated herein by reference to the same extent as if each individual document, patent application, and technical standard were specifically and individually noted to be incorporated by reference.

Claims

It comprises a crystallized glass substrate, a base layer disposed on the crystallized glass substrate, and a surface layer disposed on the base layer. The aforementioned underlayer includes a first underlayer disposed on the crystallized glass substrate and a second underlayer disposed on the first underlayer. The first underlayer comprises at least one selected from the group consisting of aluminum oxide, silicon nitride, and zirconium oxide, provided that if aluminum oxide is included, silicon oxide is not included. The second sublayer contains silicon dioxide, The surface layer is formed using a compound having a reactive silyl group in the article. 　 The article according to claim 1, wherein the compound having the reactive silyl group is a compound having a perfluoropolyether chain and a reactive silyl group. 　 The article according to claim 1 or 2, wherein the thickness of the aforementioned underlayer is 40 to 120 nm. 　 The article according to claim 1 or 2, wherein the ratio of the thickness of the first substrate to the thickness of the second substrate is 0.3 to 4.

0. The article according to claim 1 or 2, wherein the thickness of the first underlayer is 20 nm or more. 　 An article according to claim 1 or 2, which is an optical component. 　 The article according to claim 1 or 2, which is a display or touch panel. 　 The article according to claim 1 or 2, which is a stain-resistant article. A method for manufacturing an article, comprising forming a first underlayer, a second underlayer, and a surface layer in that order on a crystallized glass substrate, The formation of the first underlayer involves coating with a composition for the first underlayer, which includes at least one selected from the group consisting of aluminum oxide, silicon nitride, and zirconium oxide, provided that if aluminum oxide is included, silicon oxide is not included. The formation of the second underlayer includes coating it with a composition for the second underlayer containing silicon dioxide. The formation of the surface layer includes coating with a surface layer composition containing a compound having a reactive silyl group. A method for manufacturing articles. 　 The formation of the first underlayer includes wet coating the composition for the first underlayer, The formation of the second underlayer includes wet coating the composition for the second underlayer, The formation of the surface layer includes wet coating the surface layer composition. A method for manufacturing an article according to claim 9. 　 The formation of the first underlayer includes dry coating the composition for the first underlayer, The formation of the second underlayer includes dry coating the composition for the second underlayer, The formation of the surface layer includes dry coating the surface layer composition. A method for manufacturing an article according to claim 9.

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