Method for manufacturing substrate with antireflection film, and substrate with antireflection film

Abstract

According to the present invention, it is possible to obtain an antireflection film which has excellent glass cleaner resistance that inhibits the antireflection film from being removed when being wiped with a glass cleaner.　An antireflection film formation material (P) contains component (A). Component (A): A polysiloxane (A) which has a styryl group and a ureido group and / or a urea bond, and in which the molar amount of the styryl group included in the polysiloxane is 0.1-70 mol% with respect to 100 mol% of Si atoms.

Description

Method for manufacturing substrate with anti-reflection film, and substrate with anti-reflection film

[0001] The present invention relates to a plastic substrate having an anti-reflection film having excellent glass cleaner resistance formed on the substrate.

[0002] It has been known that forming a coating that reduces the refractive index on the surface of a substrate reduces the reflectance of light reflected from the surface of the coating. Such refractive index-reducing coatings exhibiting reduced light reflectance are used as antireflection films and are applied to various substrate surfaces. Methods for forming such antireflection films include gas-phase methods such as CVD (Chemical Vapor Deposition), PVD (Physical Vapor Deposition), and sputtering, as well as liquid-phase methods using alkoxide compounds, etc. Gas-phase methods generally require expensive, large-scale equipment such as a vacuum deposition apparatus. Furthermore, there is a problem in that the size and shape of the substrate on which the film can be formed are limited. On the other hand, the so-called sol-gel method is known as a liquid-phase method using alkoxide compounds, etc. This method has advantages such as the ability to apply to large areas and to accommodate patterning when film formation is performed using a film formation method such as flexographic printing. For this reason, anti-reflection films formed by a liquid phase method have been actively studied (see, for example, Patent Document 1).

[0003] Japanese Patent Application Publication No. 02-258646

[0004] In recent years, plastic substrates have been replacing glass substrates in various fields due to their light weight and ease of molding. In order to provide a plastic substrate with an anti-reflection function, it has been considered to form an anti-reflection film on the plastic substrate. However, the inventors' investigations have revealed that an anti-reflection film obtained using a conventional anti-reflection film-forming material peels off when a glass cleaner is applied and then wiped off.

[0005] In view of the above, an object of the present invention is to provide an anti-reflective film-forming material capable of obtaining an anti-reflective film that is inhibited from peeling off when wiped with a glass cleaner and has excellent glass cleaner resistance, an anti-reflective film obtained from the anti-reflective film-forming material, and a plastic substrate with an anti-reflective film.

[0006] The present inventors conducted extensive research to achieve the above-mentioned object, and as a result, discovered that using an anti-reflective coating material containing a specific component is extremely effective in achieving the above-mentioned object, and thus completed the present invention. One embodiment of the present invention includes the following: An anti-reflective coating material (P) containing the following component (A): Component (A): a polysiloxane (A) having styryl groups and ureido groups and / or urea bonds, wherein the molar amount of styryl groups contained in the polysiloxane is 0.1 mol % or more and 70 mol % or less relative to 100 mol % of Si atoms.

[0007] One embodiment of the present invention includes the following: A method for producing an antireflective coated substrate, comprising: step (1) of applying the following antireflective coating material (P) to a substrate having a heat resistance temperature of 150°C or less to form a coating film; step (2) of drying the coating film; and step (3) of exposing the dried coating film to light. Antireflective coating material (P): An antireflective coating material containing the following component (A). Component (A): Polysiloxane (A) having styryl groups and ureido groups and / or urea bonds, wherein the molar amount of styryl groups contained in the polysiloxane is 0.1 mol % or more and 70 mol % or less relative to 100 mol % of Si atoms. In this specification, * represents a bond in all cases.

[0008] According to the present invention, it is possible to obtain an anti-reflection film-forming material that can provide an anti-reflection film that is inhibited from peeling off when wiped with a glass cleaner and has excellent glass cleaner resistance, as well as an anti-reflection film obtained from the anti-reflection film-forming material and a plastic substrate with an anti-reflection film.

[0009] <Anti-Reflection Film-Forming Material (P)> The anti-reflection film-forming material (P) of the present invention is an anti-reflection film-forming material containing the following component (A). The polysiloxane (A) may be composed of one or more types of polysiloxane. Component (A): A polysiloxane (A) having a styryl group and a ureido group and / or a urea bond, wherein the molar amount of the styryl groups contained in the polysiloxane is 0.1 mol % or more and 70 mol % or less relative to 100 mol % of Si atoms. The polysiloxane (A) is a polysiloxane containing styryl groups, wherein the molar amount of the styryl groups contained in the polysiloxane is 0.1 mol % or more and 70 mol % or less, and more preferably 1 mol % or more and 30 mol % or less, relative to 100 mol % of Si atoms. The polysiloxane (A) can be obtained, for example, by polycondensation of an alkoxysilane compound component containing an alkoxysilane having at least one styryl group in the molecule, which optionally has one or more substituents, or a hydrolyzate thereof (hereinafter, these are also collectively referred to as compound (St)). A preferred specific example of compound (St) is a compound represented by the following formula (0):

[0010]

[0011] In formula (0), R １ is a hydrogen atom or an alkyl group, and a plurality of R １ may be the same or different. L is a divalent linking group, and when a plurality of L's are present, the L's may be the same or different. n is an integer of 1 to 5. n is preferably an integer of 1 to 4, more preferably 1 or 2, and most preferably 1. m is an integer of 1 to 3. R ２ represents a hydrogen atom or an arbitrary substituent, R ２ If there are multiple ２may be the same or different from each other, and may bond to each other to form a ring structure together with the carbon atoms of the benzene ring. R represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkynyl group having 2 to 5 carbon atoms, and any hydrogen atom possessed by R may be substituted with a halogen atom, an aromatic ring, or an aliphatic ring. When there are multiple R, the R may be the same or different from each other. R in formula (0) １ The alkyl group represented by is preferably an alkyl group having 1 to 6 carbon atoms, and more preferably a methyl group, an ethyl group, or a propyl group. The divalent linking group represented by L in formula (0) is a single bond or *-L １ -L ２ -L ３ -*. １ , L ２ , L ３ are independently a single bond, -(CH ２ ) ｎ R represents a group selected from the group consisting of - (n is an integer of 1 to 5), -NH-, -S-, -O-, -C(=O)-, and a phenylene group which may be substituted with any substituent. Preferred examples of L include a single bond, an alkylene group having 1 to 4 carbon atoms, and an arylene group having 5 to 12 carbon atoms, and most preferably a single bond. ２ is preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 6 to 12 carbon atoms, an acyl group having 1 to 10 carbon atoms, an acyloxy group having 1 to 10 carbon atoms, an arylcarbonyl group having 6 to 12 carbon atoms, or an arylcarbonyloxy group having 6 to 12 carbon atoms. ２ Examples of the ring structure formed by bonding with the carbon atom of the benzene ring include cycloalkyl rings such as a cyclopentane ring and a cyclohexane ring, and aromatic rings such as a benzene ring. ２is more preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkynyl group having 2 to 10 carbon atoms, and most preferably a hydrogen atom. Preferred examples of the compound represented by formula (0) include the following compounds (a0-1) to (a0-23).

[0012]

[0013]

[0014] (In the formula, Me represents a methyl group, Et represents an ethyl group, ｉ Pr represents an isopropyl group.) The proportion of the alkoxysilane compound represented by formula (0) or its hydrolyzate in the total alkoxysilanes used to obtain polysiloxane (A) is preferably 0.5 mol% or more, and even more preferably 1 mol% or more, from the viewpoint of favorably obtaining the effects of the present invention. Furthermore, from the viewpoint of favorably obtaining the effects of the present invention, it is preferably 65 mol% or less, and more preferably 30 mol% or less. The polysiloxane (A) is a polysiloxane having a ureido group and / or a urea bond. By having such a configuration, an effect is exhibited, such as obtaining a coating film with high hardness even when calcined at a relatively low temperature. The polysiloxane having a ureido group and / or a urea bond can be obtained, for example, by polycondensing an alkoxysilane compound component containing an alkoxysilane compound represented by the following formula (1) (hereinafter also referred to as compound (U)):

[0015] R １ {Si(OR １’ ) ３} ｐ (1) In formula (1), p represents an integer of 1 or 2. １ is a p-valent organic group having 2 to 13 carbon atoms and a ureido group and / or a urea bond, and more preferably a p-valent organic group having 2 to 7 carbon atoms. When p is 1, R １ is preferably a monovalent organic group in which any hydrogen atom of a hydrocarbon group having 1 to 12 carbon atoms has been substituted with a ureido group, and more preferably a monovalent organic group in which any hydrogen atom of a hydrocarbon group having 1 to 6 carbon atoms has been substituted with a ureido group. １is preferably a divalent organic group in which a urea bond is inserted between any carbon-carbon bond of a hydrocarbon group having 2 to 12 carbon atoms, and more preferably a divalent organic group in which a urea bond is inserted between any carbon-carbon bond of a hydrocarbon group having 2 to 6 carbon atoms. １’ is an alkyl group having 1 to 5 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group or an ethyl group. １’ may be the same or different. １ , R １’ may have a linear or branched structure.

[0016] In the alkoxysilane compound represented by formula (1), when p is 1, it is an alkoxysilane compound represented by formula (1-1).

[0017] R １ Si(OR １’ ) ３ (1-1) When p is 2, the alkoxysilane compound is represented by formula (1-2).

[0018] (R １’ O) ３ Si-R １ -Si(OR １’ ) ３ (1-2) Specific examples of the alkoxysilane compound represented by formula (1-1) include, but are not limited to, γ-ureidopropyltriethoxysilane, γ-ureidopropyltrimethoxysilane, γ-ureidopropyltripropoxysilane, (R)-N-1-phenylethyl-N'-triethoxysilylpropylurea, (R)-N-1-phenylethyl-N'-trimethoxysilylpropylurea, and the like.

[0019] Among these, γ-ureidopropyltriethoxysilane or γ-ureidopropyltrimethoxysilane is particularly preferred because it is readily available as a commercial product.

[0020] Specific examples of the alkoxysilane compound represented by formula (1-2) include, but are not limited to, the following. Examples include 1,3-bis[3-(triethoxysilyl)propyl]urea, 1,3-bis[2-(triethoxysilyl)ethyl]urea, 1,3-bis[3-(trimethoxysilyl)propyl]urea, and 1,3-bis[3-(tripropoxysilyl)propyl]urea. Of these, 1,3-bis[3-(triethoxysilyl)propyl]urea is particularly preferred because it is readily available as a commercially available product. The proportion of the alkoxysilane compound represented by formula (1) in the total alkoxysilanes used to obtain polysiloxane (A) is preferably 0.5 mol % or more, more preferably 1.0 mol % or more, and even more preferably 2.0 mol % or more, from the viewpoint of optimally achieving the effects of the present invention. Furthermore, from the viewpoint of optimally achieving the effects of the present invention, it is preferably 99.9 mol% or less, more preferably 99.8 mol% or less, and even more preferably 99.5 mol% or less. From the viewpoint of obtaining a low refractive index coating, the polysiloxane (A) may be a polysiloxane having a fluorine-containing organic group. Such a fluorine-containing organic group is an organic group in which some or all of the hydrogen atoms of an aliphatic group or aromatic group are substituted with fluorine atoms. Specific examples of these include a trifluoropropyl group, a tridecafluorooctyl group, a heptadecafluorodecyl group, a pentafluorophenyl group, a perfluoroalkyl group, and the like. Among these, a perfluoroalkyl group is preferred because it is easy to obtain a highly transparent coating. More preferably, the fluorine-containing organic group is a perfluoroalkyl group having 3 to 15 carbon atoms. Specific examples include a perfluoropropyl group, a perfluorooctyl group, a perfluorodecyl group, and the like.

[0021] In the present invention, multiple types of polysiloxanes having a fluorine-containing organic group on the side chain may be used in combination. The method for obtaining the polysiloxane having the above-mentioned fluorine-containing organic group on the side chain is not particularly limited. In general, it is obtained by polycondensing an alkoxysilane having the above-mentioned organic group on the side chain. Among them, polysiloxanes obtained by polycondensing an alkoxysilane component containing an alkoxysilane compound represented by formula (2a) are preferred. R ２ Si(OR２’ ) ３ (2a) The alkoxysilane compound represented by formula (2a) is an alkoxysilane having the above-mentioned fluorine-containing organic group in the side chain. ２ represents the above-mentioned fluorine-containing organic group, but the number of fluorine atoms contained in this organic group is not particularly limited. ２’ may be the same or different. ２’ represents a hydrocarbon group having 1 to 5 carbon atoms, preferably a saturated hydrocarbon group having 1 to 5 carbon atoms, more preferably a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a t-butyl group, or an s-butyl group, where n- means normal, i- means iso, s- means secondary, and t- means tertiary.

[0022] Among such alkoxysilane compounds represented by formula (2a), R ２ an alkoxysilane compound in which R is a perfluoroalkyl group, or ２ is an organic group represented by the following formula (2F): ３ (CF ２ ) ｋ CH ２ CH ２ -* (2F) In formula (2F), k represents an integer of 0 to 12, and from the viewpoint of suitably achieving the effects of the present invention, k is preferably an integer of 2 to 12. Preferred specific examples of the alkoxysilane compound represented by formula (2a) include 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, (1H,1H,2H,2H-tridecafluorooctyl)trimethoxysilane, (1H,1H,2H,2H-tridecafluorooctyl)triethoxysilane, (1H,1H,2H,2H-heptadecafluorodecyl)trimethoxysilane, and (1H,1H,2H,2H-heptadecafluorodecyl)triethoxysilane.

[0023] In the present invention, at least one of the alkoxysilane compounds represented by formula (2a) may be used, but multiple types may be used if necessary. The total molar amount of the alkoxysilanes represented by formula (2a) is preferably 1 mol% or more, more preferably 2 mol% or more, relative to the total molar amount of silicon atoms contained in the alkoxysilane compound used to synthesize the polysiloxane (A). Furthermore, from the viewpoint of obtaining a homogeneous coating liquid, it is preferably 20 mol% or less, more preferably 15 mol% or less. The polysiloxane (A) may be a polysiloxane having a fluorine-containing organic group in the main chain direction of the polysiloxane. As a monomer component for synthesizing such a polysiloxane, for example, an alkoxysilane compound having two trialkoxysilyl groups bonded to a divalent organic group having a fluorine atom may be used. A specific example of the alkoxysilane compound is an alkoxysilane compound represented by the following formula (2b): (R ２ｂ’ O) ３ Si-R ２ｂ -Si(OR ２ｂ’ ) ３ (2b) where R in formula (2b) ２ｂ represents the above-mentioned fluorine-containing organic group, but the number of fluorine atoms contained in this organic group is not particularly limited. ２ｂ is preferably a divalent perfluoroalkyl chain or *-CH ２ -CH ２ -(CF ２ ) ｐ -CH ２ -CH ２ -* (p is an integer of 1 to 12).

[0024] Furthermore, R in formula (2b) ２ｂ’ each independently represents a hydrocarbon group having 1 to 5 carbon atoms, preferably a saturated hydrocarbon group having 1 to 5 carbon atoms, more preferably a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a t-butyl group, or an s-butyl group. ２ｂ’may be the same or different. Specific examples of formula (2b) include 1,6-bis(2-trimethoxysilylethyl)dodecafluorohexane and 1,6-bis(2-triethoxysilylethyl)dodecafluorohexane. Furthermore, as a monomer component for obtaining polysiloxane (A), other alkoxysilane compounds may be used in addition to the alkoxysilane compounds represented by formula (0), formula (1), and the alkoxysilane compounds represented by formula (2a) or (2b) used as needed. One or more of the above other alkoxysilane compounds may be used. Specific preferred examples of the other alkoxysilane compounds include, but are not limited to, alkoxysilane compounds represented by formula (3) below, alkoxysilane compounds represented by formula (4) below, and alkoxysilane compounds represented by formula (5) below. R ３ ｎ Si(OR ３’ ) ４－ｎ (3) (In formula (3), R ３ represents a monovalent organic group that does not contain a styryl group, a ureido group, a urea bond, or a fluorine atom, and R ３’ represents a hydrocarbon group having 1 to 5 carbon atoms, and n represents an integer of 1 to 3. ４ ) ４ (4) (R in formula (4) ４ represents a hydrocarbon group. ５’ O) ３ Si-R ５ -Si(OR ５’ ) ３ (5) (In formula (5), R ５ represents a divalent organic group having 1 to 20 carbon atoms that does not contain a styryl group, a ureido group, a urea bond, or a fluorine atom, and R ５’ represents a hydrocarbon group having 1 to 5 carbon atoms.

[0025] R in formula (3) ３ The number of carbon atoms in R is preferably 1 to 20, more preferably 1 to 15. When n is 2 or 3, R ３ may be the same or different. ３’ In the formula, when n is 1 or 2, R ３’may be the same or different. Specific examples of the alkoxysilane represented by formula (3) are shown below, but are not limited to these: methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, pentyltrimethoxysilane, pentyltriethoxysilane, heptyltrimethoxysilane, heptyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, hexadecyltrimethoxysilane, hexadecyltriethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxy ... Trialkoxysilanes such as alkoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-isocyanatepropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, and 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, and γ-methacryloxypropyltriethoxysilane. The proportion of the alkoxysilane compound represented by formula (3) in all alkoxysilane compounds used to obtain polysiloxane (A) is preferably 0.5 mol% or more, more preferably 1 mol% or more, and even more preferably 2 mol% or more, from the viewpoint of suitably obtaining the effects of the present invention. Furthermore, from the viewpoint of suitably achieving the effects of the present invention, the content is preferably 25 mol % or less, more preferably 20 mol % or less, and even more preferably 15 mol % or less.

[0026] R in formula (4) ４represents a hydrocarbon group, and from the viewpoint of increasing reactivity, a saturated hydrocarbon group having 1 to 5 carbon atoms is preferred, and a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a t-butyl group, or an s-butyl group is more preferred. ４ may be the same or different. Specific examples of the tetraalkoxysilane compound of formula (4) include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, etc., which are readily available as commercial products. In the present invention, at least one of the alkoxysilane compounds represented by formula (4) may be used, but multiple types may be used as necessary. The amount of the alkoxysilane compound of formula (4) used is preferably 40 mol% or more, and more preferably 50 mol% or more, of the total amount of all alkoxysilane compounds used in the synthesis of polysiloxane (A). Furthermore, it is preferably 99 mol% or less, and more preferably 96 mol% or less.

[0027] In the alkoxysilane compound of formula (5), R ５’ is a hydrocarbon group having 1 to 5 carbon atoms, preferably a saturated hydrocarbon group having 1 to 4 carbon atoms, and more preferably a saturated hydrocarbon group having 1 to 3 carbon atoms. ５’ may be the same or different. ５ is a divalent organic group having 1 to 20 carbon atoms that does not contain a styryl group, a ureido group, a urea bond, or a fluorine atom. The divalent organic group may contain a double bond, a triple bond, or a cyclic or branched structure such as a phenyl group. The divalent organic group may also contain a heteroatom such as a nitrogen atom, an oxygen atom, or a fluorine atom. In the present invention, multiple types of alkoxysilane compounds represented by formula (5) can be used as needed. Preferred examples of alkoxysilane compounds represented by formula (5) include dimethyldimethoxysilane and dimethyldiethoxysilane. The proportion of the alkoxysilane compound represented by formula (5) is preferably 1 mol% or more, more preferably 2 mol% or more, of the total amount of alkoxysilane compounds used in the synthesis of polysiloxane (A). The proportion is preferably 20 mol% or less, more preferably 15 mol% or less.

[0028] (Polysiloxane (B)) The anti-reflective coating material (P) of the present invention may be an anti-reflective coating material containing the following component (B): Component (B): a polysiloxane (B) different from the polysiloxane (A). The polysiloxane (B) is a polysiloxane different from the polysiloxane (A). More preferred embodiments include, for example, polysiloxanes that do not contain a styryl group and polysiloxanes that do not contain either a ureido group or a urea bond. Examples of monomer components for obtaining the polysiloxane (B) include the alkoxysilane compounds exemplified for the polysiloxane (A) or derivatives thereof. However, the monomer components for obtaining the polysiloxane (B) do not simultaneously contain an alkoxysilane compound or derivative thereof that contains a styryl group and an alkoxysilane compound or derivative thereof that has at least one of a ureido group and a urea bond. From the viewpoint of optimally achieving the effects of the present invention, the monomer component for obtaining polysiloxane (B) preferably contains at least one compound selected from the group consisting of alkoxysilane compounds represented by the above formulas (1) to (5). Polysiloxane (B) may be a polysiloxane containing at least one functional group selected from the group consisting of a ureido group and a urea bond. Polysiloxane (B) may be a polysiloxane having a fluorine-containing organic group. Polysiloxane (B) may be a polysiloxane obtained using the other alkoxysilane compounds described above. From the viewpoint of optimally achieving the effects of the present invention, the other alkoxysilane compound used in the synthesis of polysiloxane (B) may be at least one compound selected from the group consisting of alkoxysilane compounds represented by the above formula (3) and alkoxysilane compounds represented by the above formula (4). Polysiloxane (B) may be composed of one or more types of polysiloxanes. The mass ratio of the content of polysiloxane (A) to the content of polysiloxane (B) (content of polysiloxane (A) / content of polysiloxane (B)) is preferably 1 / 99 to 99 / 1, more preferably 5 / 95 to 95 / 5, and even more preferably 10 / 90 to 90 / 10.

[0029] The method for polycondensing the polysiloxane used in the present invention is not particularly limited, but examples include a method in which an alkoxysilane compound is hydrolyzed and condensed in an organic solvent such as an alcohol or glycol. The hydrolysis and condensation reaction may be either partial or complete hydrolysis. In the case of complete hydrolysis, water may be added in an amount 0.5 times or more by mole relative to the total alkoxy groups in the alkoxysilane compound. In the present invention, the amount of water used in the reaction can be selected as desired, but is typically 0.1 to 2.5 times, and preferably 0.1 to 2.0 times, by mole relative to the total alkoxy groups in the alkoxysilane compound. Furthermore, an acid or alkali may be added as a catalyst to accelerate the hydrolysis and condensation reaction. Examples of acid catalysts include inorganic acids such as hydrochloric acid, sulfuric acid, and nitric acid; and organic acids such as acetic acid, oxalic acid, and formic acid. Examples of alkali catalysts include inorganic salts such as sodium and potassium; and various amines (e.g., methylamine, ethylamine, ethanolamine, triethylamine, ammonia, etc.). In this case, the amount of catalyst used in the reaction is preferably 0.001 to 0.05 times by mole, more preferably 0.01 to 0.03 times by mole, the total alkoxy groups in the alkoxysilane compound. Furthermore, the hydrolysis and condensation reaction may be accelerated by heating a solution in which the alkoxysilane compound is dissolved. The heating temperature can be appropriately selected as desired, and the reaction system is preferably 50°C or higher, and preferably 180°C or lower. The heating time can also be appropriately selected as desired, and is preferably 10 minutes or longer, and more preferably within 24 hours. More preferred reaction conditions include, for example, a method in which the mixture is heated and stirred at 50°C for 24 hours, or a method in which the mixture is heated and stirred under reflux for 2 to 10 hours.

[0030] Another example of an alternative method is to heat a mixture of an alkoxysilane compound, a solvent, and an acid. Specifically, an acid is first added to an alcoholic solvent to prepare an alcoholic solution of the acid, and then the solution is mixed with an alkoxysilane and heated. The amount of acid is preferably 0.2 to 2 moles, more preferably 0.5 to 2 moles, per mole of all alkoxy groups in the alkoxysilane compound. The heating temperature in this method is preferably 50°C or higher, and more preferably 180°C or lower, in terms of liquid temperature. The reaction time is preferably 10 minutes or longer, and preferably within 24 hours. In each of the above methods, when multiple alkoxysilane compounds are used, the multiple alkoxysilane compounds may be mixed in advance, or the multiple alkoxysilane compounds may be added sequentially. When polycondensing an alkoxysilane compound using the above method, the total number of silicon atoms in the alkoxysilane compounds used in the reaction may be adjusted to SiO ２ (hereinafter referred to as SiO ２ The concentration (referred to as the equivalent concentration) is preferably 20% by mass or less, and more preferably 15% by mass or less. Selecting any concentration within this concentration range is preferable from the viewpoint of suppressing gel formation and obtaining a homogeneous polysiloxane solution. The solvent used in polycondensing the alkoxysilane compound is not particularly limited, as long as it dissolves the alkoxysilane compound represented by formula (1) and, added as needed, the alkoxysilane compound represented by formula (2a), the alkoxysilane compound represented by formula (2b), and the alkoxysilane compounds represented by formulas (3) to (5). Preferably, alcohols or organic solvents with good compatibility with alcohols are used. Specific examples of organic solvents used in polycondensing the alkoxysilane compound include alcohols such as methanol, ethanol, propanol, and butanol; glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, and diethylene glycol monoethyl ether; and ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone. In the present invention, a mixture of multiple types of the above organic solvents may be used.

[0031] <Molecular Weight of Polysiloxane> The polysiloxane used in the present invention preferably has a weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) of 500 to 500,000, more preferably 1,000 to 300,000. Furthermore, the polysiloxane used in the present invention preferably has a molecular weight distribution (Mw / Mn) expressed as the ratio of Mw to the number average molecular weight (Mn) in terms of polystyrene measured by GPC of 15 or less, more preferably 10 or less. A molecular weight within this range is preferred from the viewpoint of optimally achieving the effects of the present invention.

[0032] <Anti-reflection coating-forming material (P)> The anti-reflection coating-forming material (P) of the present invention is preferably a coating liquid containing a polymer component and a solvent, and contains, as the polymer component, polysiloxane (A) and, if necessary, polysiloxane (B). Specific examples of solvents that can be used in the anti-reflection coating-forming material (P) include the following solvents. Alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, and diacetone alcohol; cyclic alcohols such as cyclopropanol, cyclobutanol, cyclopentanol, cyclohexanol, 2-methylcyclohexanol, cycloheptanol, cyclooctanol, cyclononanol, and cyclodecanol; glycols such as ethylene glycol, propanediol, diethylene glycol, dipropylene glycol, butanediol (1,3-butanediol, 2,3-butanediol, etc.), 2-methyl-2,4-pentanediol (also known as hexylene glycol), pentanediol, hexanediol, and heptanediol;Glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene glycol dibutyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether, propylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether (ethyl carbitol), diethylene glycol monopropyl ether, diethylene glycol monobutyl ether (butyl carbitol), diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether; ethers such as tetrahydrofuran and 1,4-dioxane; Examples of suitable ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; esters include methyl acetate, ethyl acetate, and ethyl lactate; lactams such as N-methyl-2-pyrrolidone; amides such as N,N-dimethylformamide, N,N-dimethylacetamide, tetramethylurea, and hexamethylphosphotriamide; lactones such as γ-butyrolactone; and dimethyl sulfoxide.

[0033] Among the solvents that can be used in the anti-reflective coating-forming material (P), it is preferable to include one or more solvents selected from the group consisting of cyclic alcohols having 3 to 10 carbon atoms and glycols having 3 to 10 carbon atoms (e.g., ethylene glycol, propanediol, 2-methyl-2,4-pentanediol, etc.). Among the solvents that can be used in the anti-reflective coating-forming material (P), it is preferable to include one or more glycol ethers having 4 to 8 carbon atoms (e.g., the above-mentioned glycol ethers having 4 to 8 carbon atoms are preferred, such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, and propylene glycol monobutyl ether). The method for preparing the anti-reflective coating-forming material (P) is not particularly limited. For example, a simple method is to use a polymerization solution containing polysiloxane (A) and / or polysiloxane (B) as is and mix it with a solvent to dilute it. If necessary, the polymerization solution may be concentrated and diluted by adding a solvent, or may be substituted with another solvent and then diluted by mixing with a solvent.

[0034] The content of polysiloxane (A) in the anti-reflection film forming material (P) is determined by dividing the total amount of silicon atoms contained in polysiloxane (A) by the total amount of silicon atoms contained in SiO ２ Concentration converted to SiO ２ The total content of the polysiloxane (A) and the polysiloxane (B) is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, in terms of the total concentration (converted into SiO 2 ). From the viewpoint of enhancing the storage stability of the solution, the total content is preferably 15% by mass or less, more preferably 8% by mass or less. When the anti-reflection film-forming material (P) contains polysiloxane (B), the total content of the polysiloxane (A) and the polysiloxane (B) is determined by multiplying the total amount of silicon atoms contained in the polysiloxane (A) and the polysiloxane (B) by the ratio of SiO 2 to SiO 2 . ２ Concentration converted to SiO ２The polysiloxane (A) content in the anti-reflective coating-forming material (P) is preferably 0.1% by mass or more, and more preferably 0.3% by mass or more (equivalent concentration). From the viewpoint of improving the storage stability of the solution, it is preferably 15% by mass or less, and more preferably 8% by mass or less. From the viewpoint of suitably obtaining the effects of the present disclosure, the content of polysiloxane (A) in the anti-reflective coating-forming material (P) is preferably 10% by mass or more, and more preferably 20% by mass or more, based on the total mass of the solids contained in the anti-reflective coating-forming material (P). When the anti-reflective coating-forming material (P) contains other components described below, the content of polysiloxane (A) is preferably 99.9% by mass or less, and more preferably 99% by mass or less, based on the total mass of the solids contained in the anti-reflective coating-forming material (P). Furthermore, when the anti-reflection film-forming material (P) contains polysiloxane (B), the total content of polysiloxane (A) and polysiloxane (B) in the anti-reflection film-forming material (P) is, from the viewpoint of suitably obtaining the effects of the present disclosure, preferably 10 mass % or more, and more preferably 20 mass % or more, based on the total mass of the solid content contained in the anti-reflection film-forming material (P).

[0035] In addition to the above cases, when the anti-reflective coating-forming material (P) contains other components described below, the sum of the polysiloxane (A) and the polysiloxane (B) is preferably 99.9 mass % or less, and more preferably 99 mass % or less, based on the total mass of the solids contained in the anti-reflective coating-forming material (P). In this specification, the term "total mass of the solids of the anti-reflective coating-forming material (P)" means the total mass of the anti-reflective coating-forming material (P) when the anti-reflective coating-forming material (P) does not contain a solvent, and means the mass obtained by subtracting the mass of the solvent from the total mass of the anti-reflective coating-forming material (P) when the anti-reflective coating-forming material (P) contains a solvent.

[0036] <Other Components> In the present invention, other components may be contained in addition to the polysiloxane (A), the polysiloxane (B), and the solvent. Specific examples of other components include inorganic fine particles, fillers, leveling agents, surface modifiers, surfactants, etc. Examples of inorganic fine particles include metal oxide fine particles, metal double oxide fine particles, and magnesium fluoride fine particles. Examples of metal oxide fine particles include fine particles of silica, alumina, titanium oxide, zirconium oxide, tin oxide, zinc oxide, etc. These may also be in a beaded shape. Examples of metal double oxide fine particles include fine particles of ITO (indium tin oxide), ATO (antimony trioxide), AZO (aluminum zinc oxide), zinc antimonate, etc. Other examples include hollow silica fine particles and porous silica fine particles. The hollow silica fine particles may also be in a beaded shape. The inorganic fine particles may be in the form of either a powder or a colloidal solution, with colloidal solutions being preferred due to their ease of handling. This colloidal solution may be a dispersion of inorganic fine particle powder in a dispersion medium, or a commercially available colloidal solution. Commercially available inorganic fine particles include organosilica sols manufactured by Nissan Chemical Industries, Ltd. (e.g., methanol silica sol, MA-ST-S, MA-ST-M, MA-ST-L, MEK-ST-40, TOL-ST, MA-ST-UP, IPA-ST, IPA-ST-UP, MEK-ST-UP, EG-ST, and NPC-ST-30). One type of inorganic fine particle may be used alone, or two or more types may be used in combination. In the present invention, the inclusion of inorganic fine particles can impart various functions to the surface shape of the cured coating film. The inorganic fine particles preferably have an average particle diameter of 0.001 to 0.2 μm, more preferably 0.001 to 0.1 μm. If the average particle size of the inorganic fine particles exceeds 0.2 μm, the transparency of the cured coating formed from the prepared anti-reflective coating material may decrease.Here, the "average particle size" can be determined by converting the average primary particle size of inorganic fine particles into a particle size equivalent from the specific surface area by nitrogen gas adsorption (BET method) or by measuring the particle size by transmission electron microscope observation. In the present invention, however, the "average particle size" is determined by converting the particle size into a particle size equivalent from the specific surface area by nitrogen gas adsorption (BET method). Examples of dispersion media for inorganic fine particles include water and organic solvents. From the viewpoint of the stability of the anti-reflection coating material, the pH or pKa of the colloidal solution is preferably adjusted to 2 to 10, more preferably 3 to 7. Examples of organic solvents used as dispersion media for colloidal solutions include alcohols such as methanol, ethanol, propanol, and butanol; glycols such as ethylene glycol; ketones such as methyl ethyl ketone and methyl isobutyl ketone; aromatic hydrocarbons such as toluene and xylene; amides such as dimethylformamide and dimethylacetamide; lactams such as N-methylpyrrolidone; esters such as ethyl acetate and butyl acetate; lactones such as γ-butyrolactone; glycol ethers such as ethylene glycol monopropyl ether; and ethers such as tetrahydrofuran and 1,4-dioxane. Among these, alcohols and ketones are preferred. These organic solvents can be used alone or in combination as a dispersion medium. Known fillers, leveling agents, surface modifiers, surfactants, and the like can be used, with commercially available products being particularly preferred due to their ease of availability.

[0037] <Substrate with Antireflection Film> The substrate with antireflection film of the present invention includes an antireflection film. The antireflection film of the present invention is obtained using the antireflection film-forming material (P). One embodiment of the antireflection film of the present invention is a substrate with antireflection film obtained by a production method including: a step (1) of applying the antireflection film-forming material (P) to a substrate (also referred to as substrate (A)) having a heat-resistant temperature of 150°C or less to form a coating film; a step (2) of drying the coating film; and a step (3) of exposing the coating film dried in step (2) to light.

[0038] <Substrate (A)> The substrate (A) is a substrate with a heat resistance temperature of 150°C or less. Here, the heat resistance temperature refers to a temperature at which the substrate does not suffer from problems such as deformation even when exposed to a processing process such as forming a resin film on the substrate. For resin substrates, the heat resistance temperature varies depending on the degree of stretching treatment, but it is necessary that the heat resistance temperature does not exceed at least the glass transition temperature (Tg). Examples of materials for the substrate (A) include polycarbonate (PC), poly(meth)acrylate, polyurethane, polyolefin, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polystyrene, polyethylene naphthalate, nylon 6, tetrafluoroethylene, (meth)acrylonitrile, diacetyl cellulose, triacetyl cellulose (TAC), and acetate butyrate cellulose. Heat resistance temperatures are disclosed, for example, in JP-A-09-100363. Among these, from the viewpoints of substrate availability, processability, and environmental resistance, polycarbonate, poly(meth)acrylate, polyethylene terephthalate, and triacetyl cellulose are preferred, and polycarbonate and poly(meth)acrylate are more preferred. The anti-reflective coating material (P) can be used to form a coating film by a commonly used coating method. Examples of the coating method include dip coating, spin coating, spray coating, slit coating, brush coating, roll transfer, screen printing, inkjet printing, and flexographic printing. When forming a film by flexographic printing, in order to obtain in-plane uniformity when the film is formed, the viscosity of the anti-reflective coating material (P) is preferably 8 mPa·s or more, more preferably 9 mPa·s or more. Furthermore, the viscosity of the anti-reflective coating material (P) is preferably 80 mPa·s or less, more preferably 70 mPa·s or less, and even more preferably 60 mPa·s or less. When forming a film by spray coating, in order to obtain in-plane uniformity when the film is formed, the viscosity of the anti-reflection film-forming material (P) is more preferably 0.5 mPa·s or more, and even more preferably 0.8 mPa·s or more. The viscosity of the anti-reflection film-forming material (P) is more preferably 80 mPa·s or less, and even more preferably 50 mPa·s or less. The thickness of the coating formed on the substrate can be adjusted by the above-mentioned parameters during application. ２It can also be easily adjusted by the converted concentration.

[0039] The above-mentioned step (2) is a drying step for drying the solvent, and is suitable when the time from coating to baking or exposure is not constant for each substrate, or when baking or exposure is not performed immediately after coating. This drying step is not particularly limited as long as the solvent is removed to an extent that the coating film shape does not deform during transportation of the substrate, etc. For example, a drying method can be used in which the coating is dried on a hot plate at a drying temperature of 30 to 150°C (set so as not to exceed the heat resistance temperature of the substrate), preferably 40 to 100°C, for 0.5 to 30 minutes, preferably 1 to 5 minutes. The method for producing an anti-reflective coated substrate of the present invention may include the following step (2') after the above-mentioned step (2). Note that step (2') may be performed after the above-mentioned step (3).

[0040] "Step (2'): Step of curing the dried coating film by baking." The baking temperature can be any temperature between 70 and 150°C, preferably between 80 and 120°C. Heating can be performed by a conventional method, such as using a hot plate, a hot air circulation oven, a far-infrared heating furnace (IR oven), or a belt furnace. The coating thus obtained is characterized by good film-forming properties and high transmittance. In step (3), the light to be irradiated can be, for example, ultraviolet light and visible light having a wavelength of 150 to 800 nm, but ultraviolet light having a wavelength of 300 to 400 nm is preferred. Examples of light sources that can be used for the irradiation light include low-pressure mercury lamps, high-pressure mercury lamps, deep UV lamps, deuterium lamps, metal halide lamps, argon resonance lamps, xenon lamps, mercury-xenon lamps, excimer lasers (e.g., KrF excimer lasers), fluorescent lamps, LED lamps, halogen lamps (e.g., sodium lamps), and microwave-excited electrodeless lamps. The light irradiation dose is preferably 1,000 to 200,000 J / m ２ and more preferably 1,000 to 100,000 J / m ２ is.

[0041] When the coating obtained according to the method of the present invention is used as an antireflection film, the coating can be formed on the surface of a substrate having a higher refractive index than that of the coating, such as ordinary glass or film, by forming the coating according to the method of the present invention, thereby converting the substrate into one having antireflection properties. In this case, the coating can be effectively used as a single coating on the substrate surface, but it can also be effectively used as an antireflection laminate in which the coating is formed on an underlayer coating having a high refractive index. The antireflection film of the present invention preferably has an average luminous reflectance of 3.0% or less, more preferably 2.0% or less, for visible light having a wavelength of 380 nm to 800 nm. The average luminous reflectance can be determined from a spectral reflectance curve. The spectral reflectance curve is obtained after matting the surface of the antireflection substrate opposite the low refractive index layer with a black paint or by attaching a black film. The curve is obtained under conditions of a 2-degree visual field, with an incident angle of 5 degrees from the normal to the low refractive index layer surface, using a C light source as the light source. The average luminous reflectance is the reflectance value obtained by averaging the reflectance of each wavelength of visible light calibrated by relative luminous efficiency. In this case, the relative luminous efficiency is the standard relative luminous efficiency for photopic vision.

[0042] The relationship between coating thickness and light wavelength will now be described. It is known that the relationship between the thickness d (nm) of a coating having a refractive index a and the wavelength λ (nm) of light whose reflectance is desired to be reduced by this coating is expressed as d = (2b-1)λ / 4a (where b is an integer of 1 or greater). Therefore, by determining the coating thickness using this formula, reflection of light of the desired wavelength can be easily prevented. Furthermore, the anti-reflection film-coated substrate of the present invention may further include an anti-fouling film laminated on the anti-reflection film. An anti-fouling film is a film that inhibits the adhesion of organic or inorganic substances to the surface, or a film that provides the effect of easily removing organic or inorganic substances from the surface by cleaning, such as wiping. The thickness of the anti-fouling film is not particularly limited, but when the anti-fouling film is a fluorine-containing organosilicon compound coating, the film thickness is preferably 2 to 20 nm, more preferably 2 to 15 nm, and even more preferably 2 to 10 nm. If the film thickness is 2 nm or more, the antifouling layer will be uniformly covered, and will be practically usable in terms of abrasion resistance.

[0043] The antireflection film-forming material (P) of the present invention can be suitably used in fields where antireflection of light is desired, such as displays of televisions, computers, car navigation systems, mobile phones, etc.; mirrors having glass surfaces; solar cells, etc. In particular, it is useful for antireflection films used in cover lenses and front panels of liquid crystal displays, plasma displays, projection displays, EL (electroluminescence) displays, SEDs (surface-conduction electron-emitter displays), FEDs (field emission displays), CRTs (cathode ray tubes), solar cells, etc.

[0044] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. The abbreviations for compounds and solvents are as follows.

[0045] STMS: p-styryltrimethoxysilane (contained in compound (St)) UPS: γ-ureidopropyltriethoxysilane (contained in compound (U)) TEOS: tetraethoxysilane F13: (1H,1H,2H,2H-tridecafluorooctyl)trimethoxysilane GPS: γ-glycidoxypropyltrimethoxysilane MPMS: γ-methacryloxypropyltrimethoxysilane MeOH: methanol EtOH: ethanol HG: 2-methyl-2,4-pentanediol PB: propylene glycol monobutyl ether

[0046] Synthesis Example 1: TEOS (18.7 g, 90.0 mmol), STMS (1.12 g, 5.0 mmol), and MeOH (18.6 g) were added to a 200 mL four-neck flask equipped with a reflux condenser, stirred, and cooled in an ice bath at 10° C. After that, MeOH (9.4 g), water (8.8 g), and nitric acid (0.5 g) were added and stirred in an ice bath at 10° C. for 30 minutes. The mixture was then stirred at 65° C. for 2 hours, after which UPS (1.32 g, 5.0 mmol) and MeOH (1.4 g) were added, and the mixture was further reacted at 65° C. for 2 hours. The mixture was then allowed to cool to room temperature, and EtOH (40.0 g) was added thereto. The mixture was stirred at room temperature for 30 minutes to obtain Solution K1.

[0047] Synthesis Example 2: TEOS (17.7 g, 85.0 mmol), STMS (2.24 g, 10.0 mmol), and MeOH (18.6 g) were added to a 200 mL four-neck flask equipped with a reflux condenser, stirred, and cooled in an ice bath at 10 ° C. After that, MeOH (9.2 g), water (8.8 g), and nitric acid (0.5 g) were added and stirred in an ice bath at 10 ° C. for 30 minutes. The mixture was then stirred at 65 ° C. for 2 hours, after which UPS (1.32 g, 5.0 mmol) and MeOH (1.4 g) were added and reacted at 65 ° C. for another 2 hours. The mixture was then allowed to cool to room temperature, and EtOH (40.0 g) was added thereto and stirred at room temperature for 30 minutes to obtain Solution K2.

[0048] Synthesis Example 3: TEOS (13.5 g, 65.0 mmol), STMS (6.73 g, 30.0 mmol), and MeOH (18.4 g) were added to a 200 mL four-neck flask equipped with a reflux condenser, stirred, and cooled in an ice bath at 10 ° C. After that, MeOH (9.2 g), water (8.8 g), and nitric acid (0.5 g) were added and stirred in an ice bath at 10 ° C. for 30 minutes. The mixture was then stirred at 65 ° C. for 2 hours, after which UPS (1.32 g, 5.0 mmol) and MeOH (1.4 g) were added and reacted at 65 ° C. for another 2 hours. The mixture was then allowed to cool to room temperature, and EtOH (40.0 g) was added thereto and stirred at room temperature for 30 minutes to obtain Solution K3.

[0049] Synthesis Example 4: TEOS (19.8 g, 95.0 mmol) and MeOH (19.7 g) were added to a 200 mL four-neck flask equipped with a reflux condenser, stirred, and cooled in an ice bath at 10° C. After that, MeOH (8.4 g), water (8.8 g), and nitric acid (0.5 g) were added and stirred in an ice bath at 10° C. for 30 minutes. The mixture was then stirred at 60° C. for 2 hours, after which UPS (1.32 g, 5.0 mmol) and MeOH (1.4 g) were added and reacted at 60° C. for an additional 1 hour. The mixture was then allowed to cool to room temperature, and EtOH (40.0 g) was added thereto and stirred at room temperature for 30 minutes to obtain Solution K4.

[0050] Synthesis Example 5: TEOS (13.5 g, 65.0 mmol), GPS (7.09 g, 30.0 mmol), and MeOH (18.1 g) were added to a 200 mL four-neck flask equipped with a reflux condenser, stirred, and cooled in an ice bath at 10 ° C. After that, MeOH (9.1 g), water (8.8 g), and nitric acid (0.5 g) were added and stirred in an ice bath at 10 ° C. for 30 minutes. The mixture was then stirred at 65 ° C. for 2 hours, after which UPS (1.32 g, 5.0 mmol) and MeOH (1.4 g) were added and reacted at 65 ° C. for another 2 hours. The mixture was then allowed to cool to room temperature, and EtOH (40.0 g) was added thereto and stirred at room temperature for 30 minutes to obtain Solution K5.

[0051] Synthesis Example 6: TEOS (13.5 g, 65.0 mmol), MPMS (7.45 g, 30.0 mmol), and MeOH (17.9 g) were added to a 200 mL four-neck flask equipped with a reflux condenser, stirred, and cooled in an ice bath at 10 ° C. After that, MeOH (9.0 g), water (8.8 g), and nitric acid (0.5 g) were added and stirred in an ice bath at 10 ° C. for 30 minutes. The mixture was then stirred at 65 ° C. for 2 hours, after which UPS (1.32 g, 5.0 mmol) and MeOH (1.4 g) were added and reacted at 65 ° C. for another 2 hours. The mixture was then allowed to cool to room temperature, and EtOH (40.0 g) was added thereto and stirred at room temperature for 30 minutes to obtain Solution K6.

[0052] Synthesis Example 7: TEOS (18.7 g, 90.0 mmol), F13 (2.34 g, 5.0 mmol), and MeOH (17.9 g) were added to a 200 mL four-neck flask equipped with a reflux condenser, stirred, and cooled in an ice bath at 10 ° C. After that, MeOH (8.9 g), water (8.8 g), and nitric acid (0.5 g) were added and stirred in an ice bath at 10 ° C. for 30 minutes. The mixture was then stirred at 65 ° C. for 2 hours, after which UPS (1.32 g, 5.0 mmol) and MeOH (1.4 g) were added and reacted at 65 ° C. for another 2 hours. The mixture was then allowed to cool to room temperature, and EtOH (40.0 g) was added thereto and stirred at room temperature for 30 minutes to obtain Solution K7.

[0053] Synthesis Example 8: To a 200 mL recovery flask equipped with a reflux condenser, 30.0 g of MA-ST-UP silica particles (manufactured by Nissan Chemical Industries, Ltd.) and 50.0 g of EtOH were added, stirred, and cooled in an ice bath at 10°C. Then, 12.5 g of EtOH, 7.0 g of water, and 0.5 g of nitric acid were added, and the mixture was stirred for 30 minutes in an ice bath at 10°C. The mixture was then stirred under reflux for 1 hour and allowed to cool to room temperature, yielding Solution K8. The types and weighed amounts of the monomer components used in Synthesis Examples 1 to 7 are summarized in Table 1.

[0054]

[0055] Example 1 To a 200 mL recovery flask, K8 (36.2 g) was added and stirred at room temperature, K1 (13.8 g) was added thereto and stirred at room temperature for an additional 30 minutes, and then HG (5.0 g) and PB (45.0 g) were added thereto and stirred at room temperature for an additional 30 minutes, thereby obtaining an anti-reflective coating-forming material KL1.

[0056] Examples 2 to 7, Comparative Examples 1 to 4 As shown in Table 2, anti-reflective coating-forming materials KL2 to KL7 and KM1 to KM4 were obtained by the same procedure as in Example 1, except that the type and amount of polysiloxane solution used were changed. In the table, the values ​​in parentheses represent the blending ratio of each component when the total of the polysiloxane and silica particles contained in the anti-reflective coating-forming material is taken as 100 mass%. For anti-reflective coating-forming material KL7 in Example 7, the blending ratios of the total polysiloxane contained in K3 and K6 to the silica particles contained in K8 were 27.5% and 72.5%, respectively, and the blending ratio of the polysiloxane (A) contained in K3 to the polysiloxane (B) contained in K6 was 1:1.

[0057]

[0058] Example 8: HG (1.0 g) and PB (9.0 g) were added to KL1 solution (10.0 g) and stirred to obtain solution KL1'. Examples 9 to 14, Comparative Examples 5 to 8: Solutions KL2' to KL7' and KM1' to KM4' were obtained by carrying out the same procedure as in Example 8, except that KL2 to 7 solutions and KM1 to KM4 solutions were used instead of KL1 solution.

[0059] <Preparation of substrate with anti-reflective coating> The solutions of Examples 8 to 14 and Comparative Examples 5 to 8 were pressure-filtered onto a 50 mm x 50 mm x 2.0 mm thick PMMA (polymethyl methacrylate) substrate using a membrane filter with a pore size of 0.5 μm, and a film was formed on the substrate by spin coating so that the film thickness after baking would be 100 nm. The substrate was dried on a hot plate at 30°C for 5 minutes. Thereafter, it was baked in a hot air circulating oven at 90°C for 1 hour. Thereafter, the substrate was further irradiated with 50 mW / cm using an ultraviolet irradiation device (manufactured by Eye Graphics, Model UB 011-3A) and a high-pressure mercury lamp (input power 1000 W). ２ (wavelength 365 nm equivalent) for 20 seconds (accumulated 1000 mJ / cm ２ ) to obtain a substrate with an anti-reflection coating.

[0060] <Evaluation of Reflectance> Using the anti-reflection coated substrate obtained by the above method, a black film (Kukkiri Miel, manufactured by Tomoegawa Paper Co., Ltd.) was attached to the back surface (uncoated surface), and the reflectance was measured in the wavelength range of 380 nm to 800 nm at a light incident angle of 5° using a UV-3600 ultraviolet-visible-near-infrared spectrophotometer manufactured by Shimadzu Corporation. From the obtained spectral reflectance curve, the average luminous reflectance of one surface (coated surface) was calculated in accordance with JIS R 3106. The evaluation results are shown in Table 3.

[0061] <Chemical Resistance Test> A glass cleaner (Honda Access Co., Ltd., product number 08CBC-A030L1) was sprayed onto the anti-reflective coated substrate obtained by the above method and left as is for 24 hours. The chemicals adhering to the surface were then wiped off with a dry cloth, the surface was washed with EtOH, and dried by air blowing. The surface was then visually observed, and the evaluation was performed with a score of 0 if the film peeled off from the entire substrate, 1 if only the area where the chemical solution remained peeled off, 2 if only a portion of the area where the chemical solution remained peeled off, and 3 if no peeling at all. The evaluation results are shown in Table 3.

[0062]

[0063] From Table 3, it was found that by using a polysiloxane having a styryl group and a ureido group as substituents, an antireflective coating and a coated substrate having excellent chemical resistance could be obtained.

[0064] Because the present invention has excellent anti-reflection performance and chemical resistance, it is expected to be used in various displays, particularly in vehicle cover lenses for automobiles, motorcycles, and other vehicles that are cleaned with various chemicals during maintenance.

[0065] The entire contents of the specification, claims and abstract of Japanese Patent Application No. 2023-134269 filed on August 21, 2023 are hereby incorporated by reference as the disclosure of the present invention.

Claims

1. An anti-reflective coating material (P) containing the following component (A): Component (A): A polysiloxane (A) having a styryl group and a ureido group and / or a urea bond, in which the molar amount of the styryl group contained in the polysiloxane is 0.1 mol % or more and 70 mol % or less relative to 100 mol % of Si atoms.

2. The anti-reflective coating material according to claim 1, wherein the polysiloxane (A) is obtained by polycondensation of an alkoxysilane compound component containing an alkoxysilane having in the molecule at least one styryl group optionally having one or more substituents, or a hydrolyzate thereof, and the alkoxysilane compound component contains a compound represented by the following formula (0): (In formula (0), R １ is a hydrogen atom or an alkyl group, and L is a divalent linking group. n is an integer of 1 to 5. m is an integer of 1 to 3. R ２ represents a hydrogen atom or any substituent, R ２ If there are multiple ２ may be the same or different, and may be bonded to each other to form a ring structure together with the carbon atoms of the benzene ring. R represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkynyl group having 2 to 5 carbon atoms, and any hydrogen atom possessed by R may be substituted with a halogen atom, an aromatic ring, or an aliphatic ring. When there are multiple Rs, the Rs may be the same or different.

3. The anti-reflective coating material according to claim 2, wherein the compound represented by formula (0) is selected from the group consisting of the following compounds (a0-1) to (a0-23): (In the formula, Me represents a methyl group, Et represents an ethyl group, i Pr represents an isopropyl group.

4. A method for producing a substrate with an anti-reflective coating, comprising: a step (1) of forming a coating film by applying the anti-reflective coating material (P) according to claim 1 onto a substrate having a heat resistance temperature of 150°C or less; a step (2) of drying the coating film; and a step (3) of exposing the dried coating film to light.

5. The method according to claim 4, further comprising the following step (2'): curing the dried coating film by baking.

6. A substrate with an anti-reflection film, obtained by the method according to any one of claims 4 and 5.

7. An anti-reflective coating obtained by the method according to any one of claims 4 or 5.

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