Thin film

Abstract

Provided is a thin film of a long-chain alkyl group-containing compound having a surface layer which shows excellent water-repellency and wear durability, particularly a thin film that can be formed on a surface of an article by vacuum deposition.　The thin film is formed of a cured product of a long-chain alkyl group-containing compound that has at least one alkyl group at one terminal in a molecule, wherein the total number of carbon atoms in the alkyl group is 19 or more, and that has a group having adhesiveness to a substrate at another terminal. The thin film has a film thickness of 2-5 nm.

Description

Thin film

[0001] The present invention relates to a thin film of a long-chain alkyl group-containing compound formed on the surface of an article by vacuum deposition, characterized in that the surface layer of the thin film of the long-chain alkyl group-containing compound obtained by vacuum deposition exhibits excellent water repellency and abrasion resistance.

[0002] In general, the surfaces of semiconductor manufacturing process components, mold components, precision instrument components, medical device parts, automotive parts, building materials, home appliances, office automation equipment, and household goods are treated with a water-repellent coating to protect them.

[0003] For water-repellent treatment, alkyl group-containing silane compounds (Patent Documents 1 and 2: Japanese Patent Publication No. 2002-038092 and Japanese Patent Publication No. 2021-123678) and fluoropolyether group-containing silane compounds (Patent Documents 3 to 8: Japanese Patent Publication No. 6260579, Japanese Patent Publication No. 6828744, Japanese Patent Publication No. 5761305, Japanese Patent Publication No. 6451279, Japanese Patent Publication No. 6741074 and Japanese Patent Publication No. 6617853) are used. When these silane compounds are applied to and cured on the surface of a substrate such as metal, porcelain, glass, or plastic, a water-repellent layer is formed on the surface of the substrate, adding the ability to prevent dust, fingerprints, and other stains to the substrate.

[0004] The silane compounds described above have 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 undergoes a self-condensation reaction with moisture in the air to form a film. This film becomes a strong and durable coating due to the chemical and physical bonding of the hydrolyzable silyl group to the substrate surface.

[0005] Furthermore, it has been disclosed that friction and wear resistance can be improved by providing a silicon oxide layer between the silane compound and the substrate. (Patent Documents 9-17: International Publication No. 2014 / 097388, Japanese Patent Publication No. 2020-132498, Japanese Patent 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] Japanese Patent Publication No. 2002-038092, Japanese Patent Publication No. 2021-123678, Japanese Patent No. 6260579, Japanese Patent No. 6828744, Japanese Patent No. 5761305, Japanese Patent No. 6451279, Japanese Patent No. 6741074, Japanese Patent No. 6617853, International Publication No. 2014 / 097388, Japanese Patent Publication No. 2020-132498, Japanese Patent 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

[0007] It was found that when alkyl group-containing compounds are vacuum-deposited to form a thin film on the surface of an object, alkyl group-containing compounds that evaporate significantly at relatively low temperatures of around 100°C in a reduced-pressure atmosphere may not provide the desired water repellency and abrasion resistance.

[0008] This invention has been made in view of these circumstances, and aims to provide a thin film of a long-chain alkyl group-containing compound that can be formed on the surface of an article by vacuum deposition and has a surface layer exhibiting excellent water repellency and abrasion resistance.

[0009] The specific means for achieving the above objectives are as follows: [1] A thin film formed using a long-chain alkyl group-containing compound having at least one alkyl group with a total number of carbon atoms of 19 or more at one end of the molecule and a substrate adhesion group at the other end, wherein the film thickness is 2 nm to 5 nm. [2] The thin film according to [1], wherein the long-chain alkyl group-containing compound has a total number of carbon atoms of 22 or more. [3] The thin film according to [1] or [2], wherein when the long-chain alkyl group-containing compound is heated at a heating rate of 10°C / min under a reduced pressure atmosphere of 1 Pa or less, the evaporation rate (weight loss rate) at 100°C is 20% or less. [4] The thin film according to any one of [1] to [3], wherein when the long-chain alkyl group-containing compound is heated at a heating rate of 10°C / min under a reduced pressure atmosphere of 1 Pa or less, the evaporation rate (weight loss rate) at 400°C is 85% or more. [5] The thin film according to any one of [1] to [4], wherein the substrate adhesion group in the long-chain alkyl group-containing compound is a silanol group, a hydrolyzable silyl group, a silazane group, a thiol group, or a phosphonic acid group. [6] The thin film according to any one of [1] to [5], wherein the water contact angle is 95° or more. [7] A long-chain alkyl group-containing compound for vacuum deposition having at least one alkyl group with a total number of carbon atoms of 19 or more at one end of the molecule, and a substrate adhesion group at the other end. [8] The long-chain alkyl group-containing compound for vacuum deposition according to [7], wherein the total number of carbon atoms of the alkyl group is 22 or more. [9] The long-chain alkyl group-containing compound for vacuum deposition according to [7] or [8], wherein when the long-chain alkyl group-containing compound is heated at a heating rate of 10°C / min under a reduced pressure atmosphere of 1 Pa or less, the evaporation rate (weight loss rate) at 100°C is 20% or less.

[10] The long-chain alkyl group-containing compound for vacuum deposition according to any one of [7] to [9], wherein when the long-chain alkyl group-containing compound is heated at a heating rate of 10°C / min under a reduced pressure atmosphere of 1 Pa or less, the evaporation rate (weight loss rate) at 400°C is 85% or more.

[11] The long-chain alkyl group-containing compound for vacuum deposition according to any one of [7] to

[10] , wherein the substrate adhesion group is a silanol group, a hydrolyzable silyl group, a silazane group, a thiol group, or a phosphonic acid group.

[12] The long-chain alkyl group-containing compound is a compound represented by the following general formula (11), (12), or (13), which is the long-chain alkyl group-containing compound for vacuum evaporation described in any one of [7] to

[11] . (In the formula, A is an alkyl group having 10 to 50 carbon atoms, B 1 is a hydrogen atom or a hydroxyl group, and E 1 is a hydrogen atom or an alkyl group having 9 to 50 carbon atoms. The total number of carbon atoms contained in A and E 1 is 19 or more. Y 1 is a divalent hydrocarbon group containing one or more selected from the group consisting of a single bond, an alkylene group, or a silicon atom and a siloxane bond. R is an alkyl group having 1 to 4 carbon atoms or a phenyl group. X 1 is independently a hydrolyzable group. z is 2 or 3, and a is 1 or 2.) (In the formula, A, B 1 , E 1 , Y 1 are the same as above. y is a number from 0 to 3, and x is (3 - y) / 2. When y = 3, formula (12) represents the molecular formula of a monomer. When y < 3, formula (12) represents the compositional formula of a polymer.) (In the formula, G 1 is independently a monovalent hydrocarbon group having 10 to 30 carbon atoms, and J 1 is independently a hydrogen atom, a hydroxyl group, or a methyl group.)

[0010] According to the present invention, the surface layer of the thin film formed by the long-chain alkyl group-containing compound is excellent in water repellency and durability.

[0011] It is a graph showing the evaporation rate curves of the compounds in the examples and comparative examples.

[0012] In the present invention, the "partial (hydrolyzed) condensate" means a partial condensate or a partial (hydrolyzed) condensate.

[0013] In the present invention, the "alkyl group" means a linear or branched saturated hydrocarbon group having 1 or more carbon atoms.

[0014] In the present invention, a "hydrocarbon group" refers to the remaining atomic group obtained by removing one or more hydrogen atoms from a hydrocarbon composed of carbon atoms and hydrogen atoms, and may be linear, branched, or cyclic (including aromatic). Furthermore, in the present invention, the hydrocarbon group may have substituents; that is, some or all of the hydrogen atoms in the hydrocarbon group may be substituted with a group containing atoms other than carbon atoms and hydrogen atoms, or it may have a group containing atoms other than carbon atoms and hydrogen atoms between carbon atoms.

[0015] The present invention will be described in more detail below. [Substrate] The thin film of the present invention is preferably formed on a substrate, and examples of substrates include glass, metal, and plastic. 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), Neoceram, etc. The glass may be chemically strengthened or physically strengthened. The shape of the glass substrate may be plate-like, film-like, or other forms.

[0016] Examples of the above-mentioned metals include, but are not limited to, pure metals such as aluminum, titanium, chromium, iron, cobalt, zinc, nickel, and copper, as well as alloys such as stainless steel (e.g., SUS304 mirror finish), brass, Kovar, and Inconel, and metals that have been plated with zinc, nickel, chromium, etc. The shape of the metal substrate may be plate-shaped, rod-shaped, spherical, or other forms.

[0017] Examples of the above-mentioned plastics include, but are not limited to, polyethylene, polypropylene, cellulosic resins such as triacetylcellulose, polyester resins such as polyethylene terephthalate, polycarbonate, polyimide, polyolefin resins, polyvinyl chloride, polyvinyl alcohol, acrylonitrile-butadiene-styrene copolymer (ABS) resin, acrylic resin, nylon, and polyetheretherketone. The shape of the plastic substrate may be plate-like, rod-like, spherical, film-like, or other forms.

[0018] The substrate may be pre-treated. The pre-treatment is not particularly limited as long as it removes contaminants from the substrate surface and makes the substrate surface hydrophilic. Examples include alcohol cleaning with alcohol such as ethanol or 2-propanol, alkaline cleaning with an alkaline cleaning agent, and plasma cleaning with oxygen or argon plasma. These methods may be used in combination. Alkaline cleaning with an alkaline cleaning agent and plasma cleaning with plasma are preferred, and it is even more preferable to perform plasma cleaning with plasma following alkaline cleaning with an alkaline cleaning agent.

[0019] The effect of the substrate pretreatment is confirmed by the degree of hydrophilicity of the substrate surface. Hydrophilicity can be evaluated by the water contact angle on the substrate, which is preferably 40° or less, more preferably 20° or less, and even more preferably 10° or less. The water contact angle is measured in accordance with JIS R 3257:1999.

[0020] In the present invention, a functional layer may be formed between the substrate and the thin film. An example of the functional layer is an anti-reflective coating layer. Alternatively, a primer layer may be formed between the substrate and the thin film, or between the functional layer and the thin film.

[0021] [Primer layer] The primer layer is a thin film containing 30% by mass or more of silicon dioxide, preferably 50% by mass or more, and more preferably 80% by mass or more.

[0022] The primer layer can be formed by applying an aqueous dispersion of silica nanoparticles to the substrate surface using wet coating methods, particularly immersion, brush coating, spin coating, spray coating, or pour coating, and then drying the solvent. To increase the density of the primer layer, it is advisable to heat it at 50 to 500°C for 10 minutes to 24 hours within a temperature range that does not affect the substrate. Alternatively, the primer layer can also be formed using dry coating methods such as physical vapor deposition or chemical vapor deposition. Examples of dry coating methods include electron beam deposition, ion-assisted deposition, sputter deposition, and resistance heating deposition.

[0023] The thickness of the primer layer is appropriately selected depending on the type of substrate, but is usually 1 to 50 nm, preferably 1 to 20 nm, and particularly preferably 1 to 10 nm. If the thickness is thinner than this range, the surface coating may be insufficient and the adhesion of the thin film may be inadequate. If the thickness is thicker than this range, appearance defects such as haze and color changes may occur. In this invention, the thickness can be measured by X-ray reflectance measurement, spectroscopic ellipsometry, etc.

[0024] [Thin Film] The thin film of the present invention has a film thickness of 2 to 5 nm formed on the outer surface of a substrate or on the outer surface of a substrate on which a primer layer is formed, and the surface layer of the thin film is formed of a cured product of a surface treatment agent containing a long-chain alkyl group having substrate adhesion groups that exhibit surface water repellency, and preferably it is formed of a cured product of a surface treatment agent containing a long-chain alkyl group that does not contain fluorine atoms and / or a partial (hydrolysis) condensate thereof.

[0025] <Surface treatment agent containing a long-chain alkyl group having a substrate adhesion group and / or a partial (hydrolysis) condensate thereof> A long-chain alkyl group having a substrate adhesion group is a compound having at least one alkyl group at one end of the molecule, the total number of carbon atoms of the alkyl group being 19 or more, and having a substrate adhesion group at the other end.

[0026] In long-chain alkyl group-containing compounds, the total number of carbon atoms of one or more alkyl groups is 19 or more, preferably 20 or more, more preferably 22 or more, and particularly preferably 25 or more. Within the above range, the long-chain alkyl group-containing compound is suitable for thin film formation (for example, thin film formation by vacuum deposition), and the formed thin film exhibits high water repellency and durability. Furthermore, when there are two or more alkyl groups, each alkyl group is preferably a linear alkyl group, and the number of carbon atoms of each linear 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 the same.

[0027] In long-chain alkyl group-containing compounds, the substrate-adhering group is not particularly limited as long as it adheres to various substrates, but it is preferably one of a silanol group, a hydrolyzable silyl group, a silazane group, a thiol group, or a phosphonic acid group.

[0028] In hydrolyzable silyl groups, examples of hydrolyzable groups include alkoxy groups having 1 to 10 carbon atoms such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, and tert-butoxy; alkoxy-substituted alkoxy groups having 2 to 10 carbon atoms such as methoxymethoxy, methoxyethoxy, ethoxymethoxy, and ethoxyethoxy; acyloxy groups having 2 to 10 carbon atoms such as acetoxy and propionoxy; alkenyloxy groups having 2 to 10 carbon atoms such as vinyloxy, allyloxy, propenoxy, and isopropenoxy; and halogen groups such as chlorine, bromo, and iodine. Among these, methoxy, ethoxy, isopropenoxy, and chlorine are preferred.

[0029] Furthermore, the long-chain alkyl group-containing compound is preferably a long-chain alkyl group-containing compound represented by the following formulas (11), (12), or (13) (where formula (12) represents the molecular formula of the monomer or the compositional formula of the polymer). In particular, the compound represented by the following formula (11) is preferred. (In the formula, A is an alkyl group having 10 to 50 carbon atoms, and B 1is a hydrogen atom or a hydroxyl group, E 1 A and E are hydrogen atoms or alkyl groups having 9 to 50 carbon atoms. 1 The total number of carbon atoms contained in Y is 19 or more. 1 R is a divalent hydrocarbon group containing one or more selected from the group consisting of a single bond, an alkylene group, or a silicon atom and a siloxane bond, and R is an alkyl group or phenyl group having 1 to 4 carbon atoms, X 1 (These are independently hydrolyzable groups, z is 2 or 3, and a is 1 or 2.) (In the formula, A, B 1 , E 1 , Y 1 The same applies as above, where y is a number between 0 and 3, and x is (3-y) / 2. When y=3, equation (12) represents the molecular formula of the monomer, and when y<3, equation (12) represents the empirical formula of the polymer. (In the formula, G 1 These are independently monovalent hydrocarbon groups having 10 to 30 carbon atoms, and J 1 (These are independently a hydrogen atom, a hydroxyl group, or a methyl group.)

[0030] In the above formulas (11) and (12), A is an alkyl group having 10 to 50 carbon atoms, preferably 17 to 50, more preferably 17 to 40 carbon atoms, and B 1 is a hydrogen atom or a hydroxyl group, E 1 A and E are hydrogen atoms or alkyl groups having 9 to 50 carbon atoms, preferably 10 to 50 carbon atoms. 1 Examples of alkyl groups include the following:

[0031] (In the formula, a1 is an integer between 8 and 49, preferably between 9 and 49, and b1 is an integer of 1 or more, where the sum of the number of carbon atoms in each structure is 50 or less, preferably between 9 and 43.) Also, A is preferably a linear alkyl group, and B 1 Preferably, it is a hydroxyl group, E 1 Preferably, it is a linear alkyl group having 10 to 50 carbon atoms. However, in formulas (11) and (12), A and E 1 The total number of carbon atoms contained in is 19 or more, preferably 20 to 60, and more preferably 22 to 60.

[0032] In the above equations (11) and (12), Y 1 The group may have one or more selected from single bonds, alkylene groups, or silicon atoms and siloxane bonds, preferably a divalent hydrocarbon group having 1 to 20 carbon atoms. Examples of such divalent hydrocarbon groups include alkylene groups having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, alkylene groups having 1 to 10 carbon atoms including arylene groups having 6 to 8 carbon atoms (for example, alkylene-arylene groups having 7 to 18 carbon atoms), divalent groups in which alkylene groups having 1 to 8 carbon atoms are bonded to each other via diorganosilylene groups, sylalkylene structures, or sylarylene structures, and divalent groups in which alkylene groups having 1 to 10 carbon atoms are bonded to the bonding sites of linear organopolysiloxane residues having 2 to 10 silicon atoms, particularly 2 to 8 silicon atoms, or branched or cyclic organopolysiloxane residues having 3 to 10 silicon atoms, particularly 3 to 8 silicon atoms.

[0033] Here, the groups that bond to silicon atoms in diorganosilylene groups, sylalkylene structures, sylarylene structures, and organopolysiloxane residues are preferably alkyl groups such as methyl, ethyl, propyl, and butyl groups, or phenyl groups, having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms. Furthermore, the alkylene groups in the sylalkylene structures are preferably ethylene groups, propylene groups (trimethylene group, methylethylene group), butylene groups (tetramethylene group, methylpropylene group), etc., having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms. Moreover, the organopolysiloxane residue may also contain a sylalkylene structure in which two silicon atoms are bonded by alkylene groups such as ethylene and propylene groups.

[0034] This kind of Y 1 Examples of such groups include the following. In the structure below, it is preferable that the bond on the left is bonded to a carbon atom and the bond on the right is bonded to a silicon atom. (In the formula, f1 is an independent integer between 1 and 10, g1 and h1 are each integers between 1 and 8, and the sum of g1 and h1 is an integer between 2 and 10. j1 is an integer between 1 and 9, and k1 is an integer between 2 and 4.)

[0035] In the above formula (11), X 1 These are independently hydrolyzable groups. Examples of hydrolyzable groups include alkoxy groups having 1 to 10 carbon atoms such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, and tert-butoxy; alkoxy-substituted alkoxy groups having 2 to 10 carbon atoms such as methoxymethoxy, methoxyethoxy, ethoxymethoxy, and ethoxyethoxy; acyloxy groups having 2 to 10 carbon atoms such as acetoxy and propionoxy; alkenyloxy groups having 2 to 10 carbon atoms such as vinyloxy, allyloxy, propenoxy, and isopropenoxy; and halogen groups such as chlor, bromo, and iodine. Among these, methoxy, ethoxy, isopropenoxy, and chlor are preferred.

[0036] In the above formula (11), R is an alkyl group having 1 to 4 carbon atoms or a phenyl group, with methyl and ethyl groups being preferred. In the above formula (11), z is 2 or 3, preferably 3.

[0037] In formula (12) above, y is a number from 0 to 3 (a positive number less than or equal to 3), preferably a number from 0 to 2, and preferably 0. Also, x is (3 - y) / 2, preferably 1.5. Note that 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.

[0038] In the above formula (13), G 1 These are independently monovalent hydrocarbon groups having 10 to 30 carbon atoms, preferably 10 to 28 carbon atoms, and the following are examples. (In the formula, m1 is an integer between 9 and 29, preferably between 9 and 27, and n1 is an integer of 1 or more such that the total number of carbon atoms in each structure is between 10 and 30, preferably between 10 and 28.) In the above formula (13), J 1 The group is independently a hydrogen atom, a hydroxyl group, or a methyl group, with the methyl group being preferred.

[0039] Examples of compounds represented by formula (11) above include eicosyltrichlorosilane, docosenyltriethoxysilane, triacontyltrichlorosilane, and those listed below.

[0040] Examples of compounds represented by formula (12) above include those listed below.

[0041] Examples of compounds represented by formula (13) above include 1,3-dioctadecyl-1,1,3,3-tetramethyldisilazane, 1,3-didodecyl-1,1,3,3-tetramethyldisilazane, and 1,3-didecyl-1,1,3,3-tetramethyldisilazane.

[0042] In the compound represented by the above formula (11), E 1 For example, the following methods can be used to produce compounds in which the group is an alkyl group having 9 to 50 carbon atoms. One method is to mix a hydrocarbon terminal group-containing compound having an alkenyl group at the terminal end with a compound having an SiH group and a hydrolyzable silyl group, and carry out a hydrosilylation addition reaction in the presence of a hydrosilylation catalyst (Preparation Method 1). Alternatively, one can produce these compounds by mixing a hydrocarbon terminal group-containing compound having an SiH group at the terminal 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 catalyst (Preparation Method 2).

[0043] Here, examples of hydrocarbon terminal group-containing compounds having an alkenyl group at the terminal include the compound shown in formula (11a) below. (In the formula, A, B 1 This is the same as above. E 1' A and E are alkyl groups having 9 to 50 carbon atoms. 1' The total number of carbon atoms contained in Y is 19 or more. 1' (This may have one or more elements selected from silicon atoms and siloxane bonds, preferably a divalent hydrocarbon group having 1 to 18 carbon atoms.)

[0044] In the above formula (11a), E 1' is an alkyl group having 9 to 50 carbon atoms, and examples similar to the alkyl group having 9 to 50 carbon atoms of E mentioned above can be given. In the above formula (11a), Y 1' The group may have one or more selected from silicon atoms and siloxane bonds, preferably a divalent hydrocarbon group having 1 to 18 carbon atoms, as shown below as examples. In the structure below, the left-hand bonds are A and B. 1 , E 1' It is preferable that the carbon atom bonded to the right-hand side is bonded to a vinyl group. (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.)

[0045] Examples of compounds represented by formula (11a) are listed below. (In the formula, a1 and f1' are independently the same as above.)

[0046] Examples of compounds having an SiH group and a hydrolyzable silyl group include trimethoxysilane, triethoxysilane, triacetoxysilane, and trichlorosilane.

[0047] In preparation method 1, the amount of compound having an SiH group and a hydrolyzable silyl group used is preferably 1 to 6 moles, particularly 1.5 to 4 moles, per mole of alkenyl group in the hydrocarbon terminal group-containing compound having an alkenyl group at the terminal end.

[0048] Furthermore, examples of hydrocarbon terminal group-containing compounds having an SiH group at the terminal include the compound shown in formula (11b) below. (In the formula, A, B 1 , E 1' The above is the same as Y 1" (This refers to a divalent hydrocarbon group having a silicon atom or a siloxane bond.)

[0049] In the above formula (11b), Y 1"This is a divalent hydrocarbon group having a silicon atom or a siloxane bond, and examples are shown below. In the structure below, it is preferable that the bond on the left is bonded to a carbon atom and the bond on the right is bonded to a hydrogen atom. (In the formula, f1 and k1 are the same as above.)

[0050] Examples of compounds represented by formula (11b) are listed below. (In the formula, a1 and f1 are independently the same as above.)

[0051] Examples of compounds having an alkenyl group and a hydrolyzable silyl group include vinyltrimethoxysilane, allyltrimethoxysilane, and octenyltrimethoxysilane.

[0052] In preparation method 2, the amount of compound having an alkenyl group and a hydrolyzable silyl group used is preferably 1 to 5 moles, particularly 1 to 3 moles, per mole of SiH group in the hydrocarbon-terminated compound having an SiH group at the terminal.

[0053] In preparation methods 1 and 2, examples of hydrosilylation reaction catalysts include platinum black, chloroplatinic acid, alcohol-modified chloroplatinic acid, complexes of chloroplatinic acid with olefins, aldehydes, vinylsiloxanes, acetylene alcohols, etc., and platinum group metal catalysts such as tetrakis(triphenylphosphine)palladium and chlorotris(triphenylphosphine)rhodium. Preferably, it is a platinum-based compound such as a vinylsiloxane coordination compound. It is preferable to dissolve the platinum-based compound in a solvent such as toluene, lower alcohol, higher alcohol, or silicone-based solvent before use. The amount of hydrosilylation reaction catalyst used is preferably 0.001 to 1000 ppm, more preferably 0.01 to 100 ppm, in terms of transition metal (mass), relative to the mass of the hydrocarbon-terminal group-containing compound having an alkenyl group or SiH group at the terminal end.

[0054] In preparation methods 1 and 2, a solvent can be used when carrying out 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. The amount of solvent used is preferably 0 to 1000 parts by mass, more preferably 50 to 200 parts by mass, per 100 parts by mass of the hydrocarbon terminal group-containing compound having an alkenyl group or SiH group at the terminal end.

[0055] In preparation methods 1 and 2, the reaction conditions for the hydrocarbon terminal group-containing compound having an alkenyl group at the terminal and the compound having an SiH group and a hydrolyzable silyl group, and the reaction conditions for the hydrocarbon terminal group-containing compound having an SiH group at the terminal and the compound having an alkenyl group and a hydrolyzable silyl group, are preferably a temperature of 20 to 120°C, particularly 60 to 100°C, for 0.5 to 72 hours, and especially 1 to 36 hours, respectively.

[0056] In the compound represented by the above formula (12), E 1 For example, a method for producing a compound in which the group has 9 to 50 C1 alkyl groups can be described as follows: A hydrocarbon terminal group-containing compound having an alkenyl group at the terminal end is mixed with trichlorosilane and reacted in the presence of a hydrosilylation catalyst, and then the resulting compound is reacted with ammonia gas to produce it.

[0057] Here, the reaction product of a hydrocarbon terminal group-containing compound having an alkenyl group at its terminus and trichlorosilane can be prepared in the same manner as in preparation method 1 described above.

[0058] In the method for preparing the compound shown in formula (12), the amount of ammonia gas used is preferably 1 to 300 cc / min, and more preferably 30 to 200 cc / min.

[0059] In the method for preparing the compound represented by formula (12), the reaction conditions for the reaction product of the hydrocarbon terminal group-containing compound having an alkenyl group at the terminal and trichlorosilane with ammonia gas are preferably at room temperature (23 ± 15°C, the same applies hereinafter), particularly 20 to 30°C, for 2 to 36 hours, and especially 4 to 12 hours.

[0060] Surface treatment agents containing long-chain alkyl group-containing compounds and / or partial (hydrolysis) condensates thereof having substrate adhesion groups may optionally contain hydrolysis condensation catalysts, such as organotin compounds (e.g., dibutyltin dimethoxide, dibutyltin dilaurate), organotitanium compounds (e.g., tetra-n-butyl titanate), organic acids (e.g., acetic acid, methanesulfonic acid, fluorine-modified carboxylic acid), or inorganic acids (e.g., hydrochloric acid, sulfuric acid). Among these, acetic acid, tetra-n-butyl titanate, and dibutyltin dilaurate are particularly preferred. The amount added is a catalytic amount, usually 0.01 to 5 parts by mass, particularly 0.1 to 1 part by mass, per 100 parts by mass of the long-chain alkyl group-containing compound and / or partial (hydrolysis) condensate thereof.

[0061] Furthermore, surface treatment agents containing long-chain alkyl group-containing compounds having substrate adhesion groups and / or partial (hydrolysis) condensates thereof may contain a solvent. The solvent is preferably a hydrocarbon solvent (such as petroleum benzine, mineral spirits, toluene, xylene, etc.), a ketone solvent (such as acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), an alcohol solvent (such as ethanol, 1-propanol, 2-propanol, butanol, etc.), or an ether solvent (such as tetrahydrofuran (THF), monoethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, dioxane, etc.).

[0062] The above solvents may be mixed in two or more forms, and it is preferable that they uniformly dissolve the long-chain alkyl group-containing compound and / or its partial (hydrolysis) condensate. The optimal concentration of the long-chain alkyl group-containing compound and / or its partial (hydrolysis) condensate to be dissolved in the solvent can be appropriately selected depending on the method of use of the surface treatment agent and is not limited. The concentration of the long-chain alkyl group-containing compound 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.

[0063] The thin film is preferably formed by wet or dry application of a surface treatment agent containing a long-chain alkyl group having substrate adhesion groups exhibiting surface water repellency and / or a partial (hydrolyzed) condensate thereof onto the outer surface of the primer layer formed as described above, followed by drying and removing the solvent from the surface treatment agent, and curing the long-chain alkyl group having substrate adhesion groups and / or a partial (hydrolyzed) condensate thereof.

[0064] Methods for forming thin films using surface treatment agents are preferably carried out in a reduced pressure atmosphere rather than atmospheric pressure. Examples include physical vapor deposition (PVD), chemical vapor deposition (CVD), and spray coating under reduced pressure.

[0065] The evaporation rate (weight loss rate) under a reduced pressure atmosphere of 1 Pa or less can be measured using a thermogravimetric analyzer equipped with a vacuum evacuation device. In this disclosure, a thermogravimetric analyzer (NETZSCH STA 2500 Regulus) connected to a vacuum evacuation device (Phifer Vacuum Hi Cube classic) is used to measure the evaporation rate under a reduced pressure atmosphere. Evaporation rate (W V ) refers to the difference between the initial weight (W0) at room temperature (approximately 30°C) and the sample weight (W) at the measurement temperature. T The value obtained by subtracting ) and dividing it by the initial weight (W0) to express it as a percentage is expressed by the following formula: W V = {(W0 - W T ) / W0} × 100 [%] The pressure during measurement is preferably 1 Pa or less. The heating rate during measurement is preferably 2°C per minute or more and 50°C per minute or less, and more preferably 5°C per minute or more and 20°C per minute or less.

[0066] When heated at a heating rate of 10°C / min under a reduced pressure atmosphere of 1 Pa or less, it is preferable that the evaporation rate at 100°C be 20% or less. If the evaporation rate at 100°C is greater than 20%, the material evaporates easily, and it may be difficult to control the deposition rate and film thickness in vacuum deposition. In addition, the material deposited by vacuum deposition may re-evaporate from the substrate even at room temperature. For these reasons, if it is greater than 20%, the water repellency and durability of the film surface may not be sufficiently obtained. To make the evaporation rate at 100°C under the above conditions 20% or less, it is preferable that the total number of carbon atoms in the alkyl group of the long-chain alkyl group-containing compound be 19 or more.

[0067] When heated at a heating rate of 10°C / min under a reduced pressure atmosphere of 1 Pa or less, it is preferable that the evaporation rate at 400°C be 85% or more. If the evaporation rate at 400°C is less than 85%, the material will not evaporate easily, and in film formation by vacuum deposition, deterioration or decomposition of the material due to heating may occur, which may result in insufficient water repellency and durability of the film surface. To achieve an evaporation rate of 85% or more at 400°C under the above conditions, it is preferable that the total number of carbon atoms in the alkyl group of the long-chain alkyl group-containing compound be 40 or less.

[0068] After applying the surface treatment agent, the solvent is dried and removed, and a curing treatment is performed. In the case of the wet coating method, the curing time can be 30 minutes to 24 hours, preferably 30 minutes to 2 hours, at 60 to 150°C, preferably 60 to 120°C, and a relative humidity of 95% or less. In the case of the dry coating method, the curing time can be 30 minutes to 48 hours, preferably 30 minutes to 24 hours, at 25°C to 150°C, preferably 25°C to 140°C, more preferably 25°C to 80°C, and a relative humidity of 95% or less. This allows for the formation of a thin film on the substrate, functional layer, or primer layer, which is formed from a cured product of a long-chain alkyl group compound. In particular, a temperature below 150°C is preferable because it prevents the re-evaporation of the thin film during the curing treatment, and it can be applied to substrates with low heat resistance.

[0069] The film thickness is 2 to 5 nm, preferably 2 to 4 nm, and particularly preferably 2 to 3 nm. If the film thickness is less than 2 nm, the mechanical strength of the film may be low and durability may not be obtained, and if it exceeds 5 nm, the adhesion to the substrate and primer layer may decrease, resulting in reduced water repellency and durability. In this invention, the film thickness can be measured by X-ray reflectivity measurement, spectroscopic ellipsometry, etc.

[0070] Articles having the thin film of the present invention can be used as water-repellent articles in a variety of applications, such as casings, frames, floors, touch panels, windows, lenses, display covers, protective films, etc., for mobile electronic devices, household electrical appliances, automobiles, outdoor equipment, building materials, housing equipment, eyeglasses, etc.

[0071] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples. In the following examples, the mol amount of the compound is, with respect to the measured mass of the target compound, 1 This value was calculated by dividing by the molecular weight of the polymer identified by 1H-NMR analysis. The test environment conditions were 23°C and 50% relative humidity.

[0072] [Example 1] [Alkaline cleaning of the substrate] The soda-lime glass substrate was immersed in an alkaline cleaning solution (an aqueous solution of Yokohama Oils & Fat Co., Ltd. Semiclean L.G.L. diluted to 5% by mass) and ultrasonically cleaned for 5 minutes. After that, it was immersed in deionized water and ultrasonically cleaned for 6 minutes. The moisture from the substrate was blown off with compressed air and dried.

[0073] [Formation of Primer Layer] A 10 nm thick SiO2 film was deposited on the surface of the alkaline-cleaned glass substrate using a sputtering deposition apparatus under the following conditions. Oxygen plasma irradiation was performed before SiO2 deposition. The SiO2 deposition rate was 0.3 nm / second, and the film thickness was controlled by the deposition time.

[0074] [SiO2 Deposition Conditions] Deposition apparatus: RAS-1100B (Synchron) Oxygen plasma irradiation conditions during substrate pretreatment Oxygen gas flow rate: 70 sccm (Standard Cubic Centimeters) Argon gas flow rate: 100 sccm Deposition chamber pressure: 0.1 Pa RF power supply: 3000 W Processing time: 50 seconds SiO2 Deposition Conditions Target material: Silicon Argon gas flow rate: 100 sccm Deposition chamber pressure: 0.1 Pa RF power supply: 8000 W Deposition rate: 0.3 nm / s Oxygen plasma irradiation conditions during SiO2 deposition Oxygen gas flow rate: 70 sccm RF power supply: 3000 W

[0075] [Preparation of surface layer forming agent 1] In the reaction vessel, prepare the following formula (a) 1.00 g (3.24 × 10) of the compound represented by -3 mol), toluene 1.00 g, trimethoxysilane 0.792 g (6.48 x 10 -3 mol), and toluene solution of chloroplatinate / vinylsiloxane complex 1.23 × 10 -2 g (3.83 × 10 as Pt alone) -8 The mixture (containing mol) was aged at 80°C for 24 hours. Then, the solvent and unreacted materials were removed by reduced pressure distillation to obtain the product. The resulting compound was: 1 ¹H-NMR confirmed that the structure is represented by the following formula (A).

[0076] Thermogravimetric analysis was performed on the compound represented by the above formula (A) under reduced pressure. The measurement procedure involved placing the sample compound in a sample container, setting it in the analyzer, evacuating the analyzer, and heating the sample from room temperature (approximately 30°C) to 500°C at a heating rate of 10°C / min, at which point the weight was measured. The analytical conditions are shown below. Table 1 shows the evaporation rate at 100°C (a percentage of the weight loss when reaching 100°C, based on the sample weight at 30°C (initial weight)) and the evaporation rate at 400°C (a percentage of the weight loss when reaching 400°C, based on the sample weight at 30°C (initial weight)). Figure 1 shows the evaporation rate curve, with the evaporation rate on the vertical axis and the measurement temperature on the horizontal axis. Analytical instrument: STA 2500 Regulus (manufactured by Netsch) Sample container: Deep aluminum pan Sample volume: Approximately 10 mg Measurement pressure: 0.01 to 1.0 Pa Heating rate: 10°C / min Measurement temperature range: Approximately 30 to 500°C

[0077] The compound represented by formula (A) above was dissolved in propylene glycol monomethyl ether (PGME) to a concentration of 10% by mass to obtain surface layer forming agent 1.

[0078] [Method for forming a thin film] The above SiO2-coated glass substrate was set in a resistance-heating type vacuum deposition apparatus (VTR-350M, manufactured by ULVAC KIKO), and 10 μL of the following surface layer forming agent was dropped into the resistance heating section, and the pressure was reduced. The internal pressure of the container was 6 × 10⁻⁶. -3 Once the pressure was reduced to below Pa, resistance heating was started. The power supplied to the resistance heating was adjusted so that the maximum evaporation rate measured by a quartz crystal film thickness gauge, located approximately 20 cm away from the resistance heating section, was 1.0 nm / second or higher, and the resistance heating was continued for 300 seconds. After waiting for 5 minutes for the apparatus to cool, the system was opened to the atmosphere, and a glass substrate with a surface layer coated was obtained. The substrate temperature during the deposition process was 40°C or lower. The above substrate was left for 4 hours in an environment of 80°C and 80% relative humidity to fix the surface layer, and a glass substrate having a surface layer made of a cured compound (A) was obtained.

[0079] [Surface Layer Thickness Measurement] The surface layer thickness was obtained by X-ray reflectance measurement. Specifically, the measured profile was subjected to simulation fitting to determine the thickness. The results are shown in Table 1. The measurement conditions are as follows: Measurement device: SmartLab (manufactured by Rigaku) ​​X-ray source: Rotating pair cathode (Cu), output 45kV, 200mA Incident optical system: Ge(111) asymmetric beam compressed crystal Receiver side solar slit: 5.0° Slit: Incident side IS = 0.05 mm Receiver side RS1 = 0.1 mm, RS2 = 0.1 mm Scanning conditions: Scanning axis 2θ / ω Scanning speed 0.2° / min Step width: 0.002°

[0080] [Measurement of Water Contact Angle on the Surface Layer] The water contact angle of the thin film was measured using a Drop Master contact angle meter (Kyowa Interface Science Co., Ltd., DMo-701SA) (droplet: 2 μl, temperature: 25°C, relative humidity: 40%). The measurement involved capturing a photograph of the droplet 1 second after dropping using a CCD camera connected to the contact angle meter. The droplet image was then analyzed using FAMAS, the contact angle analysis software included with the contact angle meter, to measure the contact angle between the glass substrate and the droplet. The contact angle was calculated using the θ / 2 method. The analysis conditions are as follows. The results are shown in Table 1. [Analysis Conditions] Method: Droplet method (θ / 2 method) Droplet recognition: Automatic Droplet recognition line (distance from needle tip): 50 dots Algorithm: Automatic Image mode: Frame threshold level: Automatic

[0081] [Abrasion Resistance Test] The surface layer of the glass substrate was tested using a reciprocating abrasion tester (Type 40, manufactured by Shinto Kagaku Co., Ltd.) under the following conditions: Abrasive material: Steel wool #0000 (Bonstar) Load: 1 kgf Reciprocating distance: 40 mm Reciprocating speed: 60 reciprocations per minute The water contact angle of the frictional abrasion area was measured every 500 friction reciprocations using the same method as above. The number of friction reciprocations in which the water contact angle remained at 90° or higher was defined as the abrasion resistance count. A count of 3000 or more was rated as excellent (◎), 2000 to less than 3000 was rated as good (〇), 1000 to less than 2000 was rated as acceptable (△), and less than 1000 was rated as unacceptable (×). The results are shown in Table 1.

[0082] [Example 2] In the reaction vessel, the following formula (b) 1.00 g (1.98 × 10) of the compound represented by -3 mol), toluene 1.00 g, trimethoxysilane 1.45 g (1.19 x 10 -2 mol), and 7.57 × 10¹³ toluene solution of chloroplatinic acid / vinylsiloxane complex -3 g (Pt alone is 2.34 × 10) -8 The mixture (containing mol) was aged at 80°C for 24 hours. Then, the solvent and unreacted materials were removed by reduced pressure distillation to obtain the product. The resulting compound was: 1 ¹H-NMR confirmed that the structure is represented by the following formula (B). The compound represented by formula (B) above was dissolved in propylene glycol monomethyl ether (PGME) to a concentration of 10% by mass to obtain surface layer forming agent 2.

[0083] Thermogravimetric analysis of the compound under reduced pressure was performed in the same manner as in Example 1. The evaporation rate at 100°C and the evaporation rate and evaporation rate curve at 400°C are shown in Table 1 and Figure 1, respectively. Furthermore, glass substrates with a surface layer were prepared, and film thickness measurement, water contact angle measurement, and abrasion resistance test were performed. The results are shown in Table 1.

[0084] [Example 3] In the reaction vessel, the following formula (c) 1.00 g (1.82 × 10) of the compound represented by -3 mol), toluene 1.00 g, trimethoxysilane 0.667 g (5.46 x 10 -3 mol), and toluene solution of chloroplatinate / vinylsiloxane complex 6.62 × 10 -3 g (Pt alone: ​​2.05 × 10) -8 The mixture (containing mol) was aged at 80°C for 24 hours. Then, the solvent and unreacted materials were removed by reduced pressure distillation to obtain the product. The resulting compound was: 1 ¹H-NMR confirmed that the structure is represented by the following formula (C). The compound represented by formula (C) above was dissolved in propylene glycol monomethyl ether (PGME) to a concentration of 10% by mass to obtain surface layer forming agent 3.

[0085] Thermogravimetric analysis of the compound under reduced pressure was performed in the same manner as in Example 1. The evaporation rate at 100°C and the evaporation rate and evaporation rate curve at 400°C are shown in Table 1 and Figure 1, respectively. Furthermore, glass substrates with a surface layer were prepared, and film thickness measurement, water contact angle measurement, and abrasion resistance test were performed. The results are shown in Table 1.

[0086] [Comparative Example 1] Octadecyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in propylene glycol monomethyl ether (PGME) to a concentration of 10% by mass to prepare surface layer forming agent 4.

[0087] Thermogravimetric analysis of the compound under reduced pressure was performed in the same manner as in Example 1. The evaporation rate at 100°C and the evaporation rate and evaporation rate curve at 400°C are shown in Table 1 and Figure 1, respectively. Furthermore, glass substrates with a surface layer were prepared, and film thickness measurement, water contact angle measurement, and abrasion resistance test were performed. The results are shown in Table 1.

[0088] [Comparative Example 2] The reaction vessel is given the following formula (e) 1.00 g (3.08 × 10) of the compound represented by -3 mol), toluene 1.00 g, trimethoxysilane 1.129 g (9.24 x 10 -3 mol), and 1.01 × 10¹⁶ toluene solution of chloroplatinate / vinylsiloxane complex -2 g (3.08 × 10 as Pt alone) -8 The mixture (containing mol) was aged at 80°C for 24 hours. Then, the solvent and unreacted materials were removed by reduced pressure distillation to obtain the product. The resulting compound was: 1 ¹H-NMR confirmed that the structure is represented by the following formula (E). The compound represented by the above formula (E) was dissolved in propylene glycol monomethyl ether (PGME) to a concentration of 10% by mass to obtain surface layer forming agent 5.

[0089] Thermogravimetric analysis of the compound under reduced pressure was performed in the same manner as in Example 1. The evaporation rate at 100°C and the evaporation rate and evaporation rate curve at 400°C are shown in Table 1 and Figure 1, respectively. Furthermore, glass substrates with a surface layer were prepared, and film thickness measurement, water contact angle measurement, and abrasion resistance test were performed. The results are shown in Table 1.

[0090]

[0091] It was found that when the compounds shown in the examples were deposited by vacuum deposition, thin films exhibiting excellent water repellency (water contact angle) and abrasion resistance were obtained.

Claims

1. A thin film formed from a cured product of a long-chain alkyl group-containing compound, wherein the molecule has at least one alkyl group at one end, the total number of carbon atoms of the alkyl group is 19 or more, and the other end has a substrate adhesion group, and the thin film has a thickness of 2 nm to 5 nm.

2. The thin film according to claim 1, wherein the long-chain alkyl group-containing compound has a total number of carbon atoms of 22 or more.

3. The thin film according to claim 1, wherein when the long-chain alkyl group-containing compound is heated at a heating rate of 10°C / min under a reduced pressure atmosphere of 1 Pa or less, the evaporation rate (weight loss rate) at 100°C is 20% or less.

4. The thin film according to claim 1, wherein when the long-chain alkyl group-containing compound is heated at a heating rate of 10°C / min under a reduced pressure atmosphere of 1 Pa or less, the evaporation rate (weight loss rate) at 400°C is 85% or more.

5. The thin film according to claim 1, wherein the long-chain alkyl group-containing compound is a silanol group, a hydrolyzable silyl group, a silazane group, a thiol group, or a phosphonic acid group.

6. The thin film according to claim 1, wherein the water contact angle is 95° or greater.

7. A long-chain alkyl group-containing compound for vacuum deposition, having at least one alkyl group at one end of the molecule, the total number of carbon atoms of the alkyl group being 19 or more, and a substrate adhesion group at the other end.

8. The long-chain alkyl group-containing compound for vacuum deposition according to claim 7, wherein the total number of carbon atoms of the alkyl group is 22 or more.

9. The long-chain alkyl group-containing compound for vacuum deposition according to claim 7, wherein when the long-chain alkyl group-containing compound is heated at a heating rate of 10°C / min under a reduced pressure atmosphere of 1 Pa or less, the evaporation rate (weight loss rate) at 100°C is 20% or less.

10. The long-chain alkyl group-containing compound for vacuum deposition according to claim 7, wherein when the long-chain alkyl group-containing compound is heated at a heating rate of 10°C / min under a reduced pressure atmosphere of 1 Pa or less, the evaporation rate (weight loss rate) at 400°C is 85% or more.

11. The long-chain alkyl group-containing compound for vacuum deposition according to claim 7, wherein the substrate adhesion group is a silanol group, a hydrolyzable silyl group, a silazane group, a thiol group, or a phosphonic acid group.

12. The long-chain alkyl group-containing compound for vacuum deposition according to claim 7, wherein the long-chain alkyl group-containing compound is a compound represented by the following general formula (11), (12), or (13). (In the formula, A is an alkyl group having 10 to 50 carbon atoms, B 1 is a hydrogen atom or a hydroxyl group, E 1 is a hydrogen atom or an alkyl group having 9 to 50 carbon atoms, and the total number of carbon atoms contained in A and E 1 is 19 or more, Y 1 is a divalent hydrocarbon group containing one or more selected from the group consisting of a single bond, an alkylene group, or a silicon atom and a siloxane bond, R is an alkyl group having 1 to 4 carbon atoms or a phenyl group, X 1 is independently a hydrolyzable group, z is 2 or 3, and a is 1 or 2.) (In the formula, A, B 1 , E 1 , Y 1 are the same as above, y is a number from 0 to 3, x is (3 - y) / 2, and when y = 3, formula (12) represents the molecular formula of a monomer, and when y < 3, formula (12) represents the composition formula of a polymer.) (In the formula, G 1 is independently a monovalent hydrocarbon group having 10 to 30 carbon atoms, and J 1 is independently a hydrogen atom, a hydroxyl group, or a methyl group.)

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