Surface layer

Abstract

Provided is a surface water-repellent layer having excellent wear durability. And a surface layer which is formed on the substrate using a surface treatment agent containing an alkyl group-containing compound having at least one alkyl group and having a substrate adhesion group at the other end, the surface layer has a 287.5 eV peak intensity that decreases as the X-ray incidence angle (where the incidence angle parallel to the sample surface is 0 DEG and the incidence angle in the normal direction of the sample surface is 90 DEG) decreases, and a 292.5 eV peak intensity that increases as the X-ray incidence angle decreases, as measured by a C-K-end X-ray absorption near edge structure (XANES) measurement of the surface layer. [Mathematical formula 1] The ratio of the peak intensity at 292.5 eV when incident at 90 DEG to the peak intensity at 292.5 eV when incident at 15 DEG is 0.90 or less.

Description

Technical Field

[0001] This invention relates to a surface layer applied to a substrate surface, utilizing an oriented film in which alkyl chains are erected on the substrate surface to obtain water repellency and abrasion resistance. Background Technology

[0002] For components used in semiconductor manufacturing processes, mold components, components for precision equipment, parts for medical equipment, automotive parts, building materials, home appliances, OA equipment, and household goods, generally, water-repellent treatment is applied to the surface of these items to protect them.

[0003] In water-repellent treatments, silane compounds containing alkyl groups (Patent Documents 1 & 2: Japanese Patent Application Publication No. 2002-038092, Japanese Patent Application Publication No. 2021-123678) and silane compounds containing fluorinated polyether groups (Patent Documents 3-8: Japanese Patent No. 6260579, Japanese Patent No. 6828744, Japanese Patent No. 5761305, Japanese Patent No. 6451279, Japanese Patent No. 6741074, Japanese Patent No. 6617853) are used. When these silane compounds are coated and cured on the surface of substrates such as metals, magnets, glass, and plastics, a water-repellent layer is formed on the surface of the substrate, imparting the substrate with properties that prevent dust, fingerprints, and other contaminants.

[0004] The aforementioned silane compounds contain an organic functional group and a reactive silyl group (generally a hydrolyzable silyl group such as an alkoxysilyl group) in one molecule. The hydrolyzable silyl group utilizes moisture in the air to initiate a self-condensation reaction, forming a coating. This coating is chemically and physically bonded to the substrate surface through the hydrolyzable silyl group, thus becoming a durable and robust coating.

[0005] Furthermore, it has been disclosed that by providing a silicon oxide layer between the aforementioned silane compound and the substrate, the friction and wear durability can be improved (Patent Documents 9-17: International Publication No. 2014 / 097388, Japanese Patent Application Publication No. 2020-132498, Japanese Patent Application Publication No. 2020-090652, Japanese Patent No. 5655215, Japanese Patent No. 6601492, Japanese Patent No. 5494656, International Publication No. 2019 / 035271, International Publication No. 2023 / 013476, International Publication No. 2023 / 013477).

[0006] Existing technical documents

[0007] Patent documents

[0008] Patent Document 1: Japanese Patent Application Publication No. 2002-038092

[0009] Patent Document 2: Japanese Patent Application Publication No. 2021-123678

[0010] Patent Document 3: Japanese Patent No. 6260579

[0011] Patent Document 4: Japanese Patent No. 6828744

[0012] Patent Document 5: Japanese Patent No. 5761305

[0013] Patent Document 6: Japanese Patent No. 6451279

[0014] Patent Document 7: Japanese Patent No. 6741074

[0015] Patent Document 8: Japanese Patent No. 6617853

[0016] Patent Document 9: International Publication No. 2014 / 097388

[0017] Patent Document 10: Japanese Patent Application Publication No. 2020-132498

[0018] Patent Document 11: Japanese Patent Application Publication No. 2020-090652

[0019] Patent Document 12: Japanese Patent No. 5655215

[0020] Patent Document 13: Japanese Patent No. 6601492

[0021] Patent Document 14: Japanese Patent No. 5494656

[0022] Patent Document 15: International Publication No. 2019 / 035271

[0023] Patent Document 16: International Publication No. 2023 / 013476

[0024] Patent Document 17: International Publication No. 2023 / 013477 Summary of the Invention

[0025] The problem that the invention aims to solve

[0026] It is known that when coating a substrate surface with an alkyl-containing compound, wear durability is sometimes not achieved depending on the orientation of the alkyl chains on the outermost surface of the substrate.

[0027] The present invention was made in view of such actual conditions, and its purpose is to provide a surface water-repellent layer with excellent wear resistance.

[0028] Methods for solving problems

[0029] In order to achieve the above objectives, the inventors conducted in-depth research and found that: in the CK end X-ray absorption near-edge structure (XANES) measurement described later, when the surface layer formed on the substrate by the surface treatment agent containing alkyl compounds is within a specific range, it is estimated that the alkyl links at the outermost surface orientation are in a state of being nearly upright relative to the substrate, thus obtaining excellent water repellency and wear resistance, and thus completing the present invention.

[0030] The specific means for achieving the objectives of this invention are described below.

[0031] [1] A surface layer is a surface layer formed on a substrate using a surface treatment agent, said surface treatment agent comprising an alkyl-containing compound having at least one alkyl group and having a substrate-adhesive group.

[0032] The peak intensity of 287.5 eV obtained by CK-end X-ray absorption near-edge structure (XANES) measurement of the surface layer decreases as the X-ray incident angle (0° for incident angle parallel to the sample surface and 90° for incident angle normal to the sample surface) decreases, while the peak intensity of 292.5 eV increases as the X-ray incident angle decreases.

[0033]

Mathematical Formula 1

[0034] Peak intensity of 292.5 eV at 90° incident angle Peak intensity of 292.5 eV relative to incident at 15° ratio It is below 0.90.

[0035] [2] According to the surface layer of [1], wherein in the compound containing alkyl groups, there are two alkyl groups.

[0036] [3] The surface layer according to [1] or [2], wherein the total number of carbon atoms of the alkyl group is 19 or more.

[0037] [4] The surface layer according to any one of [1] to [3], wherein, in the alkyl-containing compound, the substrate binding group is silanol, hydrolyzable silyl, silazane, thiol, or phosphonic acid.

[0038] [5] The surface layer according to any one of [1] to [4], wherein the alkyl-containing compound is represented by any one of the following general formulas (11), (12), or (13),

[0039]

Chemistry 1

[0040]

[0041] (In the formula, A is an alkyl group with 10 to 50 carbon atoms, B) 1 E is a hydrogen atom or a hydroxyl group. 1 It is an alkyl group with 9 to 50 carbon atoms, A and E. 1 The total number of carbon atoms contained in Y is 19 or more. 1 It is a single bond, an alkylene group, or contains one or more divalent hydrocarbon groups selected from silicon atoms and siloxane bonds, where R is an alkyl or phenyl group having 1 to 4 carbon atoms, and X 1 (Independently a hydrolyzable group, z is 2 or 3, a is 1 or 2.)

[0042]

Chemistry 2

[0043]

[0044] (where A and B are in the formula) 1 E 1 Y 1 Similar to the above, y is a number from 0 to 3, and x is (3-y) / 2. When y = 3, equation (12) represents the molecular formula of the monomer; when y < 3, equation (12) represents the compositional formula of the polymer.

[0045]

Transformation 3

[0046]

[0047] (where G is in the formula) 1 J is an independent monovalent hydrocarbon group with 10 to 30 carbon atoms. 1 (Independently a hydrogen atom, hydroxyl group, or methyl group.)

[0048] [6] The surface layer according to any one of [1] to [5], wherein the film thickness is 2 nm to 5 nm.

[0049] [7] The surface layer according to any one of [1] to [6], wherein the wear durability test under the following conditions is 1000 cycles or more,

[0050] [Evaluation of Wear Durability]

[0051] For the surface layer formed on the glass, a reciprocating abrasion tester is used to conduct abrasion tests under the following conditions. The number of abrasion cycles in which the water contact angle of the surface remains above 90° after the test is defined as the number of abrasion durability cycles.

[0052] Friction material: Steel wool #0000 (Bonstar)

[0053] Load: 1 kgf

[0054] Reciprocating distance: 40mm

[0055] Reciprocating speed: 60 reciprocations per minute.

[0056] The effects of the invention

[0057] The surface layer of the present invention is characterized by excellent water repellency and durability. Attached Figure Description

[0058] Figure 1 The X-ray absorption near-edge structure (XANES) spectrum of the surface layer in Example 1 is shown.

[0059] Figure 2 The X-ray absorption near-edge structure (XANES) spectrum of the surface layer of Comparative Example 1 is shown. Detailed Implementation

[0060] In this invention, the term "partial (hydrolyzed) condensate" refers to a partial condensate or a partial (hydrolyzed) condensate.

[0061] In this invention, "alkyl" refers to a saturated hydrocarbon group with one or more carbon atoms, either in a straight-chain or branched-chain form.

[0062] In this invention, the term "hydrocarbon group" refers to the remaining atomic group after removing one or more hydrogen atoms from a hydrocarbon composed of carbon and hydrogen atoms. It can be any of the following: straight-chain, branched-chain, or cyclic (including aromatic groups). Furthermore, in this invention, the hydrocarbon group may have substituents; that is, some or all of the hydrogen atoms in the hydrocarbon group may be replaced by a group containing atoms other than carbon and hydrogen atoms, and there may be a group containing atoms other than carbon and hydrogen atoms between carbon atoms.

[0063] The present invention will now be described in more detail.

[0064] [Substrate]

[0065] Examples of substrates that can be used to form the surface layer of this invention include glass, metal, and plastic.

[0066] Examples of glass include, but are not limited to, soda-lime glass, crown glass, lead glass, borosilicate glass, crystallized glass, quartz glass, aluminosilicate glass, Tempax, Pyrex (registered trademark), and Neoceram. Furthermore, glass can be glass that has undergone chemical strengthening or physical strengthening treatments.

[0067] The glass substrate can be in the form of a plate, a film, or other shapes.

[0068] Examples of the aforementioned metals include, but are not limited to, pure metals such as aluminum, titanium, chromium, iron, cobalt, zinc, nickel, and copper, stainless steel (e.g., SUS304 with mirror finish), brass, cobalt, Inconel, and other alloys, as well as metals that have undergone zinc, nickel, or chromium plating.

[0069] The shape of the metal substrate can be plate-shaped, rod-shaped, spherical, or other forms.

[0070] Examples of the aforementioned plastics include, but are not limited to, cellulose resins such as polyethylene, polypropylene, and triacetyl cellulose; polyester resins such as polyethylene terephthalate; polycarbonate, polyimide, polyolefin resins; polyvinyl chloride; polyvinyl alcohol; acrylonitrile-butadiene-styrene copolymer (ABS) resin; acrylic resins; nylon; and polyetheretherketone.

[0071] The plastic substrate can be in the form of a plate, rod, sphere, film, or other shapes.

[0072] The substrate can be a pretreated substrate.

[0073] Pretreatment is not particularly limited as long as it removes contaminants from the substrate surface and hydrophilizes the substrate surface. Examples include alcohol cleaning with ethanol, 2-propanol, etc., alkaline cleaning with alkaline cleaning agents, and plasma cleaning with oxygen or argon plasma. These methods can be combined. Alkaline cleaning with alkaline cleaning agents followed by plasma cleaning is preferred, and alkaline cleaning with alkaline cleaning agents followed by plasma cleaning is even more preferred.

[0074] The effectiveness of the substrate pretreatment is determined based on the degree of hydrophilicity of the substrate surface. Hydrophilicity can be evaluated by the water contact angle on the substrate, preferably 40° or less, more preferably 20° or less, and even more preferably 10° or less. Furthermore, the water contact angle is measured according to JIS R 3257:1999.

[0075] In this invention, a functional layer can be formed between the substrate and the surface layer. Examples of functional layers include, for instance, an anti-reflective coating. Additionally, a primer layer can be formed between the substrate and the surface layer, or between the functional layer and the surface layer.

[0076] [Primer coat]

[0077] The primer layer is a thin film containing more than 30% by mass of silicon dioxide, preferably more than 50% by mass, and more preferably more than 80% by mass.

[0078] A primer layer can be formed by applying an aqueous dispersion of silica nanoparticles to the surface of a substrate using wet coating methods, particularly dipping, brush coating, spin coating, spraying, and flow coating, followed by solvent drying. To increase the density of the primer layer, heating at 50–500°C for 10 minutes to 24 hours can be performed without affecting the substrate.

[0079] Furthermore, a primer layer can be formed even when using dry coating methods such as physical vapor deposition and chemical vapor deposition (dry coating). Examples of dry coating methods include electron beam deposition, ion-assisted deposition, sputtering, and resistance heating deposition.

[0080] The thickness of the primer layer is appropriately selected according to the type of substrate, but is typically 1–50 nm, preferably 1–20 nm, and particularly preferably 1–10 nm. If the film thickness is thinner than this range, the surface coverage may be insufficient, and the adhesion of the surface layer may become inadequate. If the film thickness is thicker than this range, appearance defects such as haze and color variations may occur. It should be noted that in this invention, the film thickness can be measured using methods such as X-ray reflectance measurement and spectrophotometry.

[0081] [Surface layer]

[0082] The surface layer of the present invention is a surface layer formed on the outer surface of a substrate or on the outer surface of a substrate having a primer layer. The surface layer is formed by a cured product of a surface treatment agent containing an alkyl compound having substrate-adhesive groups that exhibits surface water repellency, preferably by a cured product of a surface treatment agent containing an alkyl compound and / or a portion thereof (hydrolysis) condensate of a fluorine-free compound.

[0083] <Surface treatment agents containing alkyl-containing compounds and / or portions thereof (hydrolyzed) condensates with substrate-adhesive groups>

[0084] The surface treatment agent forming the surface layer of the present invention comprises an alkyl-containing compound having at least one alkyl group and a substrate-adhesive group. Preferably, the alkyl-containing compound having the substrate-adhesive group is a compound having two alkyl groups in one molecule, and more preferably, a compound having a total carbon number of 19 or more for the alkyl group.

[0085] In compounds containing alkyl groups, the total number of carbon atoms in one or more alkyl groups is preferably 19 or more, more preferably 20 or more, further preferably 22 or more, and particularly preferably 25 or more. If it is within the above range, it is expected that the alkyl groups that are predominantly present on the outermost surface of the substrate in the surface layer formed using a surface treatment agent containing alkyl groups will exhibit high orientation relative to the substrate (becoming a state in which the alkyl groups stand upright relative to the substrate), and the resulting surface layer will be obtained as a surface layer exhibiting high water repellency and durability.

[0086] Furthermore, when there are two or more alkyl groups, each alkyl group is preferably a straight-chain alkyl group, and the number of carbon atoms in each alkyl group is preferably 10 or more, more preferably 13 or more, and particularly preferably 15 or more. Moreover, it is even more preferable that the two or more alkyl groups are identical.

[0087] In compounds containing alkyl groups, there are no particular limitations on the substrate-adhesive group as long as it adheres to various substrates, but it is preferred to be any one of silanol group, hydrolyzable silanyl group, silazyl group, thiol group, and phosphonic acid group.

[0088] In hydrolyzable silyl groups, examples of hydrolyzable groups include alkoxy groups with 1 to 10 carbon atoms such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, and tert-butoxy; alkoxy-substituted alkoxy groups with 2 to 10 carbon atoms such as methoxymethoxy, methoxyethoxy, ethoxymethoxy, and ethoxyethoxy; acyloxy groups with 2 to 10 carbon atoms such as acetoxy and propionyloxy; alkenyloxy groups with 2 to 10 carbon atoms such as vinyloxy, allyloxy, propenoxy, and isopropenoxy; and halogen groups such as chloro, bromo, and iodo. Among these, methoxy, ethoxy, isopropenoxy, and chloro groups are preferred.

[0089] Furthermore, compounds containing alkyl groups are preferably those represented by the following formulas (11), (12), or (13) (wherein formula (12) represents the molecular formula of the monomer or the compositional formula of the polymer). Compounds represented by the following formula (11) are particularly preferred.

[0090]

Chemistry 4

[0091]

[0092] (In the formula, A is an alkyl group with 10 to 50 carbon atoms, B) 1 E is a hydrogen atom or a hydroxyl group. 1 It is an alkyl group with 9 to 50 carbon atoms, A and E. 1 The total number of carbon atoms contained in Y is 19 or more. 1 It is a single bond, an alkylene group, or contains one or more divalent hydrocarbon groups selected from silicon atoms and siloxane bonds, where R is an alkyl or phenyl group having 1 to 4 carbon atoms, and X1 (Independently a hydrolyzable group, z is 2 or 3, a is 1 or 2.)

[0093]

Transformation 5

[0094]

[0095] (where A and B are in the formula) 1 E 1 Y 1 Similar to the above, y is a number from 0 to 3, and x is (3-y) / 2. When y = 3, equation (12) represents the molecular formula of the monomer; when y < 3, equation (12) represents the compositional formula of the polymer.

[0096]

Transformation 6

[0097]

[0098] (where G is in the formula) 1 J is an independent monovalent hydrocarbon group with 10 to 30 carbon atoms. 1 (Independently a hydrogen atom, hydroxyl group, or methyl group.)

[0099] In formulas (11) and (12) above, A is an alkyl group with 10 to 50 carbon atoms, preferably 17 to 50, more preferably 17 to 40, and B... 1 E is a hydrogen atom or a hydroxyl group. 1 It is an alkyl group having 9 to 50 hydrogen atoms or carbon atoms, preferably 10 to 50. As A and E 1 Alkyl groups, for example, can be listed below.

[0100]

Transformation 7

[0101]

[0102] (In the formula, a1 is an integer from 8 to 49, preferably from 9 to 49, and b1 is an integer of 1 or more, and the total number of carbon atoms in each structure is an integer of 50 or less, preferably from 9 to 43.)

[0103] As A, a straight-chain alkyl group is preferred; as B, 1 Preferably, hydroxyl groups are used as E. 1 Preferably, it is a straight-chain alkyl group with 10 to 50 carbon atoms.

[0104] In equations (11) and (12), A and E 1 The total number of carbon atoms contained therein is 19 or more, preferably 20 to 60, and more preferably 22 to 60.

[0105] In equations (11) and (12) above, Y 1It is a single bond, or may have one or more divalent hydrocarbon groups selected from silicon atoms and siloxane bonds, preferably having 1 to 20 carbon atoms. Specifically, examples of such divalent hydrocarbon groups include alkylene groups with 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms; alkylene groups with 1 to 10 carbon atoms containing 6 to 8 carbon atoms (e.g., alkylene-arylene groups with 7 to 18 carbon atoms); divalent groups in which alkylene groups with 1 to 8 carbon atoms are interposed by two organosilyl groups, silaneyl groups, or silaneyl groups; and divalent groups in which alkylene groups with 1 to 10 carbon atoms are attached to the binding ends of linear or branched or cyclic organopolysiloxane residues with 2 to 10 silicon atoms, particularly 2 to 8 silicon atoms.

[0106] Among these, the groups bonded to silicon atoms, such as diorganosilyl groups, silanediyl groups, silanearyl groups, and organopolysiloxane residues, are preferably alkyl groups such as methyl, ethyl, propyl, butyl, or phenyl groups with 1 to 8 carbon atoms, preferably 1 to 4. Furthermore, the alkyl group in the silanediyl group is preferably ethylene, propylene (trimethylene, methyl ethylene), butylene (tetramethylene, methyl propyleneene), etc., with 2 to 6 carbon atoms, preferably 2 to 4. In addition, the organopolysiloxane residue may contain a silanediyl group structure in which two silicon atoms are bonded to alkyl groups such as ethylene or propylene.

[0107] As such Y 1 Examples of such groups include the following. Furthermore, in the following structures, it is preferable that the left-hand bonding end is bonded to a carbon atom and the right-hand bonding end is bonded to a silicon atom.

[0108]

Transformation 8

[0109]

[0110]

Chemistry 9

[0111]

[0112] (In the formula, f1 is an integer from 1 to 10 independently, g1 and h1 are each integers from 1 to 8, and the sum of g1 and h1 is an integer from 2 to 10. j1 is an integer from 1 to 9, and k1 is an integer from 2 to 4.)

[0113] In the above equation (11), X 1It is an independently hydrolyzable group. Examples of hydrolyzable groups include alkoxy groups with 1 to 10 carbon atoms, such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, and tert-butoxy; alkoxy-substituted alkoxy groups with 2 to 10 carbon atoms, such as methoxymethoxy, methoxyethoxy, ethoxymethoxy, and ethoxyethoxy; acyloxy groups with 2 to 10 carbon atoms, such as acetoxy and propionyloxy; alkenyloxy groups with 2 to 10 carbon atoms, such as vinyloxy, allyloxy, propenoxy, and isopropenoxy; and halogen groups such as chlorine, bromine, and iodo. Among these, methoxy, ethoxy, isopropenoxy, and chlorine are preferred.

[0114] In the above formula (11), R is an alkyl or phenyl group having 1 to 4 carbon atoms, wherein methyl or ethyl is preferred.

[0115] In the above formula (11), z is 2 or 3, preferably 3.

[0116] In the above formula (12), y is a number from 0 to 3 (a positive number less than 3), preferably a number from 0 to 2, and preferably 0. In addition, x is (3-y) / 2, preferably 1.5. Furthermore, when y = 3, formula (12) represents the molecular formula of the monomer, and when y < 3, formula (12) represents the compositional formula of the polymer.

[0117] In the above equation (13), G 1 It is independently a monovalent hydrocarbon group having 10 to 30 carbon atoms, preferably 10 to 28 carbon atoms, for example, the following groups can be exemplified.

[0118]

Chemistry 10

[0119]

[0120] (In the formula, m1 is an integer from 9 to 29, preferably from 9 to 27, and n1 is an integer of 1 or more, and the total number of carbon atoms in each structure is an integer from 10 to 30, preferably from 10 to 28.)

[0121] In the above equation (13), J 1 It is independently a hydrogen atom, a hydroxyl group or a methyl group, with methyl being preferred.

[0122] Specifically, compounds represented by the above formula (11) include eicosyltrichlorosilane, docosyltriethoxysilane, triacontyltrichlorosilane, and compounds represented by the following.

[0123]

Chemistry 11

[0124]

[0125] Specifically, compounds represented by the above formula (12) can be listed as shown below.

[0126]

Chemistry 12

[0127]

[0128]

Chemistry 13

[0129]

[0130]

Chemistry 14

[0131]

[0132] Specifically, examples of compounds represented by the above formula (13) include 1,3-bis(octadecyl)-1,1,3,3-tetramethyldisilazane, 1,3-bis(dodecyl)-1,1,3,3-tetramethyldisilazane, and 1,3-decyl-1,1,3,3-tetramethyldisilazane.

[0133] In the compound represented by the above formula (11), as E 1 Methods for producing compounds of alkyl groups having 9 to 50 carbon atoms, for example, are listed below.

[0134] Preparation method 1 can be manufactured by mixing a compound containing a hydrocarbon terminal group with an alkenyl group with a compound having a SiH group and a hydrolyzable silyl group, and carrying out a hydrosilylation addition reaction in the presence of a hydrosilylation reaction catalyst.

[0135] Alternatively, it can be manufactured by mixing a compound containing a hydrocarbon terminal group with a SiH group at the end with a compound having an alkenyl group and a hydrolyzable silyl group, and carrying out a hydrosilylation addition reaction in the presence of a hydrosilylation reaction catalyst (Preparation Method 2).

[0136] Here, as a compound containing a hydrocarbon terminal group having an alkenyl group at the end, a compound represented by the following formula (11a) can be exemplified.

[0137]

Chemistry 15

[0138]

[0139] (where A and B are in the formula) 1 Same as above. E 1’ Alkyl groups with 9 to 50 carbon atoms, A and E 1’ The total number of carbon atoms contained in Y is 19 or more. 1’ It may have one or more divalent hydrocarbon groups selected from silicon atoms and siloxane bonds, preferably having 1 to 18 carbon atoms.

[0140] In the above equation (11a), E 1’ It is an alkyl group with 9 to 50 carbon atoms, and examples can be given of the same alkyl group with 9 to 50 carbon atoms as E above.

[0141] In the above equation (11a), Y 1’ The group can have one or more divalent hydrocarbon groups selected from silicon atoms and siloxane bonds, preferably having 1 to 18 carbon atoms, and can be exemplified by the groups shown below. It should be noted that in the following structures, the left-hand bonding end is preferably connected to A and B. 1 E 1’ The carbon atoms are bonded together, and the bonding end on the right is bonded to the vinyl group.

[0142]

Chemistry 16

[0143]

[0144]

Chemistry 17

[0145]

[0146] (In the formula, g1, j1, and k1 are the same as above, f1' is an integer from 0 to 8, h1' is an integer from 0 to 6, and the sum of g1 and h1' is an integer from 2 to 8.)

[0147] As a compound represented by formula (11a), the compounds shown below can be exemplified.

[0148] [Chemistry 18]

[0149]

[0150] (In the formula, a1 and f1' are each independently the same as above.)

[0151] Examples of compounds containing a SiH group and a hydrolyzable silyl group include trimethoxysilane, triethoxysilane, triacetoxysilane, and trichlorosilane.

[0152] In preparation method 1, the amount of the compound having the SiH group and the hydrolyzable silyl group used is preferably 1 to 6 moles, particularly 1.5 to 4 moles, relative to 1 mole of the alkenyl group in the compound containing the hydrocarbon terminal group having an alkenyl group at the end.

[0153] In addition, as a compound containing a hydrocarbon terminal group having a SiH group at the end, a compound represented by the following formula (11b) can be exemplified.

[0154]

Chemistry 19

[0155]

[0156] (where A and B are in the formula) 1 E 1’ Similar to the above, Y 1” It is a divalent hydrocarbon group containing a silicon atom or a siloxane bond.

[0157] In the above equation (11b), Y 1” It is a divalent hydrocarbon group having a silicon atom or a siloxane bond, and examples of the groups shown below can be given. Furthermore, in the structures described below, it is preferable that the left-hand bonding end is bonded to a carbon atom and the right-hand bonding end is bonded to a hydrogen atom.

[0158]

Chemistry 20

[0159]

[0160] (In the formula, f1 and k1 are the same as above.)

[0161] As a compound represented by formula (11b), the compounds shown below can be exemplified.

[0162]

Chemistry 21

[0163]

[0164] (In the formula, a1 and f1 are each independently the same as above.)

[0165] Examples of compounds having an alkenyl group and a hydrolyzable silyl group include vinyltrimethoxysilane, allyltrimethoxysilane, and octenyltrimethoxysilane.

[0166] In preparation method 2, the amount of the compound having an alkenyl group and a hydrolyzable silyl group used is preferably 1 to 5 moles, particularly 1 to 3 moles, relative to 1 mole of the SiH group in the compound containing a hydrocarbon terminal group having a SiH group at the end.

[0167] In preparation methods 1 and 2, examples of platinum group metal catalysts used as catalysts for the hydrosilylation reaction include platinum black, chloroplatinic acid, alcohol-modified chloroplatinic acid, complexes of chloroplatinic acid with olefins, aldehydes, vinylsiloxanes, alkynyl alcohols, tetra(triphenylphosphine)palladium, and trichloro(triphenylphosphine)rhodium. Platinum group compounds, such as vinylsiloxane coordination compounds, are preferred. Furthermore, the platinum group compounds are preferably used in solvents such as toluene, lower alcohols, higher alcohols, and organosilicon compounds.

[0168] The amount of catalyst used in the hydrosilylation reaction, relative to the mass of the compound containing a hydrocarbon terminal group having an alkenyl or SiH group at the end, is preferably 0.001 to 1000 ppm, more preferably 0.01 to 100 ppm, in transition metal conversion (mass).

[0169] In preparation methods 1 and 2, solvents can be used during the reaction. Examples of solvents include aromatic hydrocarbons such as toluene and xylene, aliphatic or alicyclic hydrocarbons such as n-pentane, n-hexane, and cyclohexane, cyclic ether compounds such as tetrahydrofuran and dioxane, and ketones such as acetone and methyl ethyl ketone.

[0170] The amount of solvent used is preferably 0 to 1000 parts by mass relative to 100 parts by mass of the compound containing a hydrocarbon terminal group having an alkenyl or SiH group at the end, more preferably 50 to 200 parts by mass.

[0171] In preparation methods 1 and 2, the reaction conditions for the compound containing a hydrocarbon terminal group having an alkenyl group at the end and the compound having a SiH group and a hydrolyzable silyl group, and the reaction conditions for the compound containing a hydrocarbon terminal group having a SiH group at the end and the compound having an alkenyl group and a hydrolyzable silyl group, are preferably carried out at a temperature of 20 to 120°C, particularly 60 to 100°C, for 0.5 to 72 hours, particularly 1 to 36 hours.

[0172] In the compound represented by the above formula (12), as E 1 Methods for producing compounds of alkyl groups having 9 to 50 carbon atoms, for example, are listed below.

[0173] It can be manufactured by mixing a compound containing a hydrocarbon terminal group with an alkenyl group at the end with trichlorosilane, reacting it in the presence of a hydrosilylation catalyst, and then reacting the resulting compound with ammonia.

[0174] Here, the reaction product of a compound containing a hydrocarbon terminal group with an alkenyl group at the end and trichlorosilane can be prepared in the same manner as preparation method 1 described above.

[0175] In the method for preparing the compound represented by formula (12), the amount of ammonia used is preferably 1 to 300 cc / min, and particularly preferably 30 to 200 cc / min.

[0176] In the method for preparing the compound represented by formula (12), the reaction conditions of the compound containing a hydrocarbon terminal group having an alkenyl group at the end and the reactant trichlorosilane with ammonia are preferably carried out at room temperature (23±15°C, the same below), especially at 20 to 30°C for 2 to 36 hours, especially 4 to 12 hours.

[0177] In surface treatment agents containing alkyl-containing compounds and / or their partial (hydrolyzed) condensates having substrate-adhesive groups, hydrolysis condensation catalysts may be added as needed, such as organotin compounds (dimethoxydibutyltin, dibutyltin dilaurate, etc.), organotitanium compounds (tetrabutyl titanate, etc.), organic acids (acetic acid, methanesulfonic acid, fluorinated carboxylic acids, etc.), and inorganic acids (hydrochloric acid, sulfuric acid, etc.). Among these, acetic acid, tetrabutyl titanate, and dibutyltin dilaurate are particularly preferred. The amount added is a catalytic amount, typically 0.01 to 5 parts by mass, particularly 0.1 to 1 part by mass, relative to 100 parts by mass of the alkyl-containing compound and / or its partial (hydrolyzed) condensate.

[0178] Additionally, surface treatment agents comprising alkyl-containing compounds and / or their partial (hydrolyzed) condensates having substrate-adhesive groups may contain a solvent. The solvent is preferably a hydrocarbon solvent (petroleum ether, mineral ether, toluene, xylene, etc.), a ketone solvent (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), an alcohol solvent (ethanol, 1-propanol, 2-propanol, butanol, etc.), or an ether solvent (tetrahydrofuran (THF), monoethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, dioxane, etc.).

[0179] Two or more of the aforementioned solvents can be mixed, preferably to uniformly dissolve the alkyl-containing compound having a substrate-adhesive group and / or its partial (hydrolyzed) condensate. Furthermore, the optimal concentration of the alkyl-containing compound having a substrate-adhesive group and / or its partial (hydrolyzed) condensate dissolved in the solvent can be appropriately selected according to the method of use of the surface treatment agent and is not limited thereto. The concentration of the alkyl-containing compound having a substrate-adhesive group in the surface treatment agent is preferably 0.01 to 30% by mass, more preferably 0.02 to 25% by mass, and even more preferably 0.05 to 20% by mass to dissolve it.

[0180] The surface layer is preferably formed by wet or dry application of a surface treatment agent containing an alkyl-containing compound having substrate-adhesive groups that will exhibit surface water repellency to the outer surface of the primer layer formed above, followed by drying and removal of the solvent from the surface treatment agent, while simultaneously curing the alkyl-containing compound having substrate-adhesive groups and / or a portion thereof (hydrolysis) condensate.

[0181] The surface layer formed using surface treatment agents can be achieved using wet coating methods such as brush coating, dip coating, and spray coating, or dry coating methods such as vapor deposition (physical vapor deposition (PVD) and chemical vapor deposition (CVD)).

[0182] After applying the surface treatment agent, the solvent is dried and removed, and a curing process is performed simultaneously. In the case of a wet coating method, curing can be carried out at 60–150°C, preferably 60–120°C, and a relative humidity of 95% or less for 30 minutes to 24 hours, preferably 30 minutes to 2 hours. In the case of a dry coating method, curing can be carried out at 25°C to 150°C, preferably 25°C to 80°C, and a relative humidity of 95% or less for 30 minutes to 48 hours, preferably 30 minutes to 24 hours.

[0183] The thickness of the surface layer is 2–5 nm. If the surface layer thickness is less than 2 nm, the mechanical strength of the surface layer is sometimes low, resulting in poor durability. If it exceeds 5 nm, the adhesion to the substrate and primer layer decreases, and sometimes the water repellency and durability decrease. It should be noted that in this invention, the film thickness can be measured using methods such as X-ray reflectance measurement and spectroscopic ellipsometry.

[0184] The surface layer of the present invention, when used as a test sample and subjected to CK-end X-ray absorption near-edge structure (XANES) measurements, is attributed to 287.5 eV for 1s→Rydberg / σ. ＊ The intensity of the (CH) peak decreases as the X-ray incident angle decreases (0° for incident angle parallel to the sample surface and 90° for incident angle normal to the sample surface) and is attributed to the 1s→σ peak at 292.5 eV. ＊ The intensity of the (CC) peak increases as the X-ray incident angle decreases. This indicates the alkyl chain orientation of the alkyl compounds constituting the surface layer.

[0185] In addition, preferred

[0186]

Mathematical Formula 2

[0187] Peak intensity of 292.5 eV at 90° incident angle Peak intensity of 292.5 eV relative to incident at 15° ratio The value is 0.90 or less. That is, the alkyl chain is preferably oriented upright relative to the substrate surface.

[0188] The water-repellent articles of the present invention can be used in various applications, such as frames, flooring, touch panels, windows, lenses, display covers, and protective films for mobile electronic devices, household electrical products, automobiles, door and window products, building materials, residential equipment, and eyeglasses.

[0189] Example

[0190] The following examples and comparative examples illustrate the invention in more detail, but the invention is not limited to the examples described below. It should be noted that in the examples below, the molar amount of the compound is calculated by dividing the mass of the target compound by the amount of the compound measured using...1 The value was calculated based on the molecular weight of the polymer determined by ¹H-NMR analysis. The experimental conditions were 23°C and 50% relative humidity.

[0191] [Example 1]

[0192] [Alkali cleaning of substrate]

[0193] The soda-lime glass substrate was immersed in an alkaline cleaning solution (Yokohama Yushi's SEMICLEAN LGL diluted to a 5% by mass aqueous solution) and ultrasonically cleaned for 5 minutes. Then, it was immersed in ion-exchanged water and ultrasonically cleaned for 6 minutes. The substrate was then dried by blowing away moisture with compressed air.

[0194] [Formation of the primer layer]

[0195] On the surface of the glass substrate that had undergone the aforementioned alkaline cleaning, a 10 nm thick SiO2 film was formed using a sputtering film deposition apparatus under the following conditions. Furthermore, oxygen plasma irradiation was performed before SiO2 film deposition. The SiO2 film deposition rate was 0.3 nm / s, and the film thickness was controlled by the film deposition time.

[0196] [SiO2 film formation conditions]

[0197] Film forming device: RAS-1100B (manufactured by SHINCRON CO.,LTD.)

[0198] Oxygen plasma irradiation conditions during substrate pretreatment

[0199] Oxygen flow rate: 70 sccm (Standard Cubic CentiMeters)

[0200] Argon flow rate: 100 sccm

[0201] Film-forming chamber pressure: 0.1 Pa

[0202] RF power supply: 3000W

[0203] Processing time: 50 seconds

[0204] SiO2 film forming conditions

[0205] Target material: silicon

[0206] Argon flow rate: 100 sccm

[0207] Film-forming chamber pressure: 0.1 Pa

[0208] RF power supply: 8000W

[0209] Film deposition rate: 0.3 nm / s

[0210] Oxygen plasma irradiation conditions during SiO2 film formation

[0211] Oxygen flow rate: 70 sccm

[0212] RF power supply: 3000W

[0213] [Preparation of Surface Layer Forming Agent 1]

[0214] In the reaction vessel, the following formula (a) will be used.

[0215]

Chemistry 22

[0216]

[0217] The compound represented is 1.00 g (1.82 × 10⁻⁶ g). -3 mol), toluene 1.00 g, trimethoxysilane 0.667 g (5.46 × 10⁻⁶ mol), -3 A toluene solution of 6.62 × 10⁻⁶ mol) and chloroplatinic acid / vinylsiloxane complex. -3 g (based on elemental Pt, containing 2.05 × 10⁻⁶) -8 The mixture (mol) was aged at 80°C for 24 hours. Then, the solvent and unreacted substances were removed by vacuum distillation to obtain the product.

[0218] use 1 H-NMR confirmed that the obtained compound had the structure represented by the following formula (A).

[0219]

Chemistry 23

[0220]

[0221] The compound represented by the above formula (A) was dissolved in propylene glycol monomethyl ether (PGME) to make a concentration of 10% by mass, thus preparing surface layer forming agent 1.

[0222] [Methods for forming the surface layer]

[0223] In a resistance-heated vacuum evaporation apparatus (VTR-350M, ULVAC machine manufacturing), a soda-lime glass substrate containing SiO2 and a mirror-polished Si wafer substrate are placed. 10 μL of the surface layer forming agent described above is dropped into the resistance heating section, and the pressure is reduced. The pressure is reduced until the pressure inside the container reaches 6 × 10⁻⁶. -3 After the pressure drop below 1 Pa, resistance heating was initiated. The power applied to the resistance heating was adjusted to ensure that the maximum evaporation rate of the crystal oscillator film thickness gauge, positioned approximately 20 cm from the resistance heating element, was 1.0 nm / s or higher, and resistance heating continued for 300 seconds. After a 5-minute standby period to allow the device to cool, atmospheric ventilation was initiated, resulting in a glass substrate coated with a surface layer.

[0224] The above-mentioned substrate was placed in an environment of 80°C and 80% relative humidity for 4 hours to fix the surface layer, thus obtaining a glass substrate with a surface layer formed by the curing of compound (A).

[0225] [XANES Measurement and Analysis]

[0226] X-rays were irradiated onto a glass substrate with the aforementioned surface layer, and its absorption was measured to determine the X-ray absorption near-edge structure (XANES) spectrum. The measurement and resolution conditions are described below. The XANES spectrum of the CK absorption end is shown below. Figure 1 The analysis results are shown in Table 1.

[0227] Detection method: All-electronic output method

[0228] Absorption end: K absorption end of C (carbon)

[0229] Horizontal axis correction: The π* peak of highly oriented thermally decomposed graphite was corrected to 255.5 eV.

[0230] For the XANES spectrum at the K-absorber of C, the angle between the incident X-rays and the longitudinal direction spectrum of the Si wafer substrate with the surface layer is set as θ. The 1s→Rydberg / σ value at 287.5 eV is calculated for θ = 90° and θ = 15°. ＊ The intensity values ​​of the (CH) peaks are shown below.

[0231]

Mathematical Expression 3

[0232] Peak intensity of 287.5 eV at θ = 90° (incidence at 90°)

[0233] Peak intensity of 287.5 eV at θ = 15° (incidence at 15°)

[0234] Similarly, the 1s→σ value attributable to 292.5 eV was calculated for the cases where θ = 90° and θ = 15°. ＊ The intensity values ​​of the (CC) peaks are used to calculate their ratios. The following describes the peak intensities and their ratios.

[0235]

Mathematical Expression 4

[0236] Peak intensity of 292.5 eV at θ = 90° (incidence at 90°)

[0237] Peak intensity of 292.5 eV at θ = 15° (incidence at 15°)

[0238] ratio

[0239] [Surface layer film thickness measurement]

[0240] The thickness of the surface layer was obtained by X-ray reflectance measurement. That is, the film thickness was calculated by simulation fitting for the measured profile. The results are shown in Table 1.

[0241] The measurement conditions are shown below.

[0242] Measurement apparatus: SmartLab (manufactured by Rigaku Corporation)

[0243] X-ray source: Rotating cathode (Cu), output 45kV, 200mA

[0244] Incident optics system: Ge(111) asymmetric beam compression crystal

[0245] Sunlight-receiving side solar slit: 5.0°

[0246] Slit: IS = 0.05 mm on the incident side

[0247] On the light-receiving side, RS1 = 0.1 mm, RS2 = 0.1 mm

[0248] Scanning conditions: Scanning axis 2θ / ω

[0249] Scanning speed: 0.2° / minute

[0250] Step width: 0.002°

[0251] [Measurement of water contact angle on surface layer]

[0252] The water contact angle of the surface layer was measured using a Drop Master contact angle meter (DMo-701SA, manufactured by Kyowa Interface Science Co., Ltd.) (droplet: 2 μl, temperature: 25°C, relative humidity: 40%). Furthermore, for the measurement, after photographing the droplet 1 second after it was dropped using a CCD camera connected to the aforementioned contact angle meter, the droplet image was analyzed using the FAMAS contact angle analysis software attached to the contact angle meter, and the contact angle between the glass substrate and the droplet was measured. The contact angle was calculated using the θ / 2 method. The analysis conditions are described below. The results are shown in Table 1.

[0253] [Analysis Conditions]

[0254] Method: Droplet method (θ / 2 method)

[0255] Droplet detection: Automatic

[0256] Drop detection line (distance from needle tip): 50 dots

[0257] Algorithm: Automatic

[0258] Image mode: Frame

[0259] Threshold level: Automatic

[0260] [Wear Durability Test]

[0261] For the surface layer of soda-lime glass substrate containing SiO2, a reciprocating abrasion tester (Type 40, manufactured by Shin-To Science Co., Ltd.) was used to test under the following conditions.

[0262] Friction material: Steel wool #0000 (Bonstar)

[0263] Load: 1 kgf

[0264] Reciprocating distance: 40mm

[0265] Reciprocating speed: 60 reciprocations per minute

[0266] Every 500 cycles of friction, the water contact angle of the worn portion was measured using the same method as described above. The number of wear cycles in which the water contact angle remained above 90° was defined as the wear durability cycle. The results are shown in Table 1.

[0267] [Comparative Example 1]

[0268] In the reaction vessel, the following formula (b) will be used.

[0269]

Chemistry 24

[0270]

[0271] The compound represented is 1.00 g (3.08 × 10⁻⁶). -3 mol), toluene 1.00 g, trimethoxysilane 1.129 g (9.24 × 10⁻⁶ mol), -3 A toluene solution of 1.01 × 10⁻⁶ mol) and chloroplatinic acid / vinylsiloxane complex. -2 g (based on elemental Pt, containing 3.08 × 10⁻⁶) -8 The mixture (mol) was aged at 80°C for 24 hours. Then, the solvent and unreacted substances were removed by vacuum distillation to obtain the product.

[0272] use 1 H-NMR confirmed that the obtained compound had the structure represented by the following formula (B).

[0273]

Chemistry 25

[0274]

[0275] The compound represented by the above formula (B) was dissolved in propylene glycol monomethyl ether (PGME) to make a concentration of 10% by mass, thus preparing surface layer forming agent 2.

[0276] A glass substrate with a surface layer was fabricated in the same manner as in Example 1, and XANES measurements, film thickness measurements, water contact angle measurements, and wear durability tests were performed. The XANES spectrum of the CK absorber is shown in [the diagram / image]. Figure 2 Other results are shown in Table 1.

[0277] Table 1

[0278]

[0279] In the surface layer shown in the embodiment, the peak intensity of 287.5 eV obtained by X-ray absorption near-edge structure (XANES) measurement at the CK end decreased as the X-ray incident angle decreased, while the peak intensity of 292.5 eV increased as the X-ray incident angle decreased. It was confirmed that the peak intensity ratio was below 0.90, indicating that high wear durability was obtained.

Claims

1. A surface layer, formed on a substrate using a surface treatment agent, said surface treatment agent comprising an alkyl-containing compound having at least one alkyl group and a substrate-adhesive group. The surface layer was subjected to CK-end X-ray absorption near-edge structure spectroscopy, i.e., XANES determination, wherein... The incident angle parallel to the sample surface was set as 0°, and the normal direction of the sample surface was set as 90°. The measured peak intensity of 287.5 eV decreased as the X-ray incident angle decreased, while the peak intensity of 292.5 eV increased as the X-ray incident angle decreased. 【Mathematical Formula 1】 Peak intensity of 292.5 eV at 90° incident angle Peak intensity of 292.5 eV relative to incident at 15° ratio It is below 0.

90.

2. The surface layer according to claim 1, wherein, In the alkyl-containing compounds, there are two alkyl groups.

3. The surface layer according to claim 1, wherein, The alkyl group has a total carbon number of 19 or more.

4. The surface layer according to claim 1, wherein, In the alkyl-containing compound, the substrate binding group is silanol, hydrolyzable silyl, silazyl, thiol, or phosphonic acid.

5. The surface layer according to claim 1, wherein, The alkyl-containing compound is represented by any one of the following general formulas (11), (12), or (13). 【Chemistry 1】 In the formula, A is an alkyl group with 10 to 50 carbon atoms, and B... 1 E is a hydrogen atom or a hydroxyl group. 1 It is an alkyl group with 9 to 50 carbon atoms, A and E. 1 The total number of carbon atoms contained in Y is 19 or more. 1 It is a single bond, an alkylene group, or contains one or more divalent hydrocarbon groups selected from silicon atoms and siloxane bonds, where R is an alkyl or phenyl group having 1 to 4 carbon atoms, and X 1 Independently a hydrolyzable group, z is 2 or 3, a is 1 or 2. 【Chemistry 2】 In the formula, A and B 1 E 1 Y 1 Similar to the above, y is a number from 0 to 3, x is (3-y) / 2, when y = 3, equation (12) represents the molecular formula of the monomer, when y < 3, equation (12) represents the compositional formula of the polymer. 【Transformation 3】 In the formula, G 1 J is an independent monovalent hydrocarbon group with 10 to 30 carbon atoms. 1 It can be a hydrogen atom, hydroxyl group, or methyl group independently.

6. The surface layer according to claim 1, wherein, The film thickness is 2nm to 5nm.

7. The surface layer according to claim 1, wherein, The wear durability test under the following conditions exceeded 1000 cycles. Evaluation of wear durability: For the surface layer formed on glass, a reciprocating abrasion tester is used to conduct abrasion tests under the following conditions. The number of abrasion cycles in which the water contact angle of the surface remains above 90° after the test is defined as the wear durability cycle. Friction material: steel wool #0000, Bonstar load: 1 kgf Reciprocating distance: 40mm Reciprocating speed: 60 reciprocations per minute.

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