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

Abstract

According to the present invention, it is possible to obtain an anti-reflection film having excellent glass cleaning agent resistance, in which peeling of the anti-reflection film is suppressed when the anti-reflection film is wiped with a glass cleaning agent. A material (P) for forming an antireflection film, which contains the following component (A). Component (A): a polysiloxane (A) having a styryl group and a urea group and / or a urea bond, wherein the molar amount of the styryl group contained in the polysiloxane is 0.1-70 mol% with respect to 100 mol% of Si atoms.

Description

Technical Field

[0001] This invention relates to a plastic substrate having an anti-reflective film with excellent resistance to glass cleaners formed on it. Background Technology

[0002] Previously, it was known that if a coating with a reduced refractive index is formed on the surface of a substrate, the reflectivity of light reflected from the surface of the coating will decrease. Such a refractive index-reducing coating, which exhibits reduced light reflectivity, has been used as an anti-reflective film and applied to various substrate surfaces.

[0003] Methods for forming such anti-reflective films include: chemical vapor deposition (CVD), physical vapor deposition (PVD), sputtering, and other vapor phase methods, or liquid phase methods using alkoxide compounds.

[0004] Typically, vapor-phase methods require expensive and large-scale equipment such as vacuum evaporation apparatus. Furthermore, there are limitations on the size and shape of the substrate from which the film can be formed. On the other hand, liquid-phase methods using alkoxide compounds, such as the so-called sol-gel method, are known. This method offers advantages such as the ability to handle patterning when forming films using large-area coatings or flexible printing methods. Therefore, anti-reflective films formed based on liquid-phase methods are under active research (see, for example, Patent Document 1).

[0005] Existing technical documents Patent documents Patent Document 1: Japanese Patent Application Publication No. 02-258646 Summary of the Invention

[0006] The problem that the invention aims to solve In recent years, plastic substrates have gradually replaced glass substrates in various fields due to their lightweight and ease of molding. To enable plastic substrates to have anti-reflective properties, it is possible to form an anti-reflective film on them. However, the inventors have discovered that anti-reflective films formed using conventional anti-reflective film forming materials tend to peel off when glass cleaner is applied and the substrate is wiped.

[0007] Based on the above, the object of the present invention is to provide an anti-reflective film forming material, an anti-reflective film obtained from the anti-reflective film forming material, and a plastic substrate with an anti-reflective film, wherein the anti-reflective film forming material can produce an anti-reflective film with excellent resistance to glass cleaners, in which peeling of the anti-reflective film is suppressed when wiped with glass cleaner.

[0008] Solution for solving the problem In order to solve the above problems, the inventors conducted in-depth research and found that using an anti-reflective film forming material containing specific components is extremely effective in achieving the above objectives, thus completing the present invention.

[0009] One embodiment of the present invention includes the following solution.

[0010] Antireflective film forming material (P) containing the following component (A).

[0011] (A) Composition: A polysiloxane (A) having styrene groups and urea groups and / or urea bonds, wherein the above polysiloxane (A) contains styrene groups in a molar amount of styrene groups relative to 100 mol% of Si atoms of 0.1 mol% or more and 70 mol% or less.

[0012] One embodiment of the present invention includes the following solution.

[0013] The method for manufacturing a substrate with an anti-reflective film includes the following steps: step (1), coating an anti-reflective film forming material (P) onto a substrate with a heat resistance temperature of 150°C or below to form a coating film; step (2), drying the coating film; and step (3), exposing the dried coating film.

[0014] Antireflective coating forming material (P): An antireflective coating forming material containing the following (A) component.

[0015] (A) Composition: A polysiloxane (A) having styrene groups and urea groups and / or urea bonds, wherein the above polysiloxane (A) contains styrene groups in a molar amount of styrene groups relative to 100 mol% of Si atoms of 0.1 mol% or more and 70 mol% or less.

[0016] In this specification, * in any case represents a bond.

[0017] Invention Effects According to the present invention, an antireflective film forming material, an antireflective film obtained from the antireflective film forming material, and a plastic substrate with an antireflective film can be obtained. The antireflective film forming material can produce an antireflective film with excellent resistance to glass cleaners, in which peeling of the antireflective film is suppressed when wiped with glass cleaner. Detailed Implementation

[0018] <Antireflective film forming material (P)> The antireflective film forming material (P) of the present invention is an antireflective film forming material containing the following component (A). The polysiloxane (A) may be composed of one or more polysiloxanes.

[0019] (A) Composition: A polysiloxane (A) having styrene groups and urea groups and / or urea bonds, wherein the molar amount of styrene groups contained in the polysiloxane is more than 0.1 mol% and less than 70 mol% relative to 100 mol% of Si atoms.

[0020] The aforementioned polysiloxane (A) is a polysiloxane containing styrene groups, and the molar amount of styrene groups contained in the polysiloxane relative to 100 mol% of Si atoms is 0.1 mol% or more and 70 mol% or less, more preferably 1 mol% or more and 30 mol% or less.

[0021] The aforementioned polysiloxane (A) can be obtained, for example, by polycondensation of an alkoxysilane compound component containing an alkoxysilane or its hydrolysate (hereinafter, they are also collectively referred to as compound (St)), wherein the alkoxysilane has at least one styrene group having one or more substituents within the molecule. As a preferred specific example of compound (St), compounds represented by the following formula (0) can be listed. In formula (0), R1 is a hydrogen atom or an alkyl group, and multiple R1s may optionally be the same or different from each other. L is a divalent linking group, and in the presence of multiple Ls, the Ls may optionally be the same or different from each other.

[0022] n is an integer from 1 to 5. n is preferably an integer from 1 to 4, more preferably 1 to 2, and most preferably 1.

[0023] m is an integer from 1 to 3.

[0024] R2 represents a hydrogen atom or any substituent. In the presence of multiple R2s, the R2s may be identical or different from each other, and may be bonded together to form a ring structure with the carbon atoms of the benzene ring.

[0025] 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, wherein any hydrogen atom in R is optionally substituted with a halogen atom, an aromatic ring, or an aliphatic ring. In the presence of multiple Rs, the Rs may optionally be the same as or different from each other.

[0026] The alkyl group represented by R1 in formula (0) is preferably an alkyl group having 1 to 6 carbon atoms, and more preferably methyl, ethyl, or propyl.

[0027] As the divalent linking group represented by L in formula (0), groups represented by single bonds or *-L1-L2-L3-* can be listed. L1, L2, and L3 independently represent groups selected from single bonds and -(CH2). n- (n is an integer from 1 to 5), -NH-, -S-, -O-, -C (=O)-, and groups in the group consisting of phenylene groups that can be substituted by any substituent.

[0028] The preferred forms of L are single bonds, alkylene groups with 1 to 4 carbon atoms, and aryl groups with 5 to 12 carbon atoms, with single bonds being the most preferred.

[0029] Preferably, R2 is 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. Furthermore, examples of ring structures formed by multiple R2 bonds together with the carbon atoms of the benzene ring include cyclopentane rings, cyclohexane rings, and other cycloalkyl rings; or aromatic rings such as benzene rings.

[0030] R2 is 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.

[0031] As preferred examples of compounds represented by formula (0), the following compounds (a0-1) to (a0-23) can be listed. (In the formula, Me represents methyl and Et represents ethyl.) i Pr represents isopropyl. From the viewpoint of appropriately obtaining the effects of the present invention, the proportion of the alkoxysilane compound represented by formula (0) or its hydrolysate in the total alkoxysilane used to obtain polysiloxane (A) is more preferably 0.5 mol% or more, and even more preferably 1 mol% or more. Furthermore, from the viewpoint of appropriately obtaining the effects of the present invention, it is preferably 65 mol% or less, and more preferably 30 mol% or less.

[0032] The aforementioned polysiloxane (A) is a polysiloxane having urea groups and / or urea bonds.

[0033] With this configuration, the following effect can be achieved: a high-hardness coating can be obtained even when firing at a relatively low temperature.

[0034] Polysiloxanes having urea groups and / or urea bonds can be obtained, for example, by polycondensation of an alkoxysilane compound component comprising an alkoxysilane compound represented by the following formula (1) (hereinafter also referred to as compound (U)).

[0035] R1 {Si(OR)} 1’ )3} p (1) In equation (1), p represents an integer of 1 or 2.

[0036] R 1 It is an organic group with a carbon number of 2 to 13 and a p-valence having a urea group and / or a urea bond, more preferably an organic group with a carbon number of 2 to 7 and a p-valence. When p is 1, R 1 Preferably, it is a monovalent organic group formed by replacing any hydrogen atom of a hydrocarbon group having 1 to 12 carbon atoms with a urea group; more preferably, it is a monovalent organic group formed by replacing any hydrogen atom of a hydrocarbon group having 1 to 6 carbon atoms with a urea group. When p is 2, R 1 Preferably, it is a divalent organic group formed by inserting a urea bond between any carbon-carbon bonds of a hydrocarbon group having 2 to 12 carbon atoms; more preferably, it is a divalent organic group formed by inserting a urea bond between any carbon-carbon bonds of a hydrocarbon group having 2 to 6 carbon atoms.

[0037] R 1’ It is an alkyl group having 1 to 5 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, and more preferably methyl or ethyl. Multiple R 1’ They can be the same or different.

[0038] R 1 R 1’ It can have a straight chain structure or a branched chain structure.

[0039] Among the alkoxysilane compounds represented by formula (1), when p is 1, it is the alkoxysilane compound represented by formula (1-1).

[0040] R 1 Si(OR) 1’ 3 (1-1) Furthermore, when p is 2, it is an alkoxysilane compound represented by formula (1-2).

[0041] (R) 1’ O)3Si-R 1 -Si(OR) 1’ 3 (1-2) The following are specific examples of alkoxysilane compounds represented by formula (1-1), but are not limited to these. For example, γ-ureopropyltriethoxysilane, γ-ureopropyltrimethoxysilane, γ-ureopropyltripropoxysilane, (R)-N-1-phenylethyl-N'-triethoxysilylpropylurea, (R)-N-1-phenylethyl-N'-trimethoxysilylpropylurea, etc.

[0042] Among them, γ-ureopropyltriethoxysilane or γ-ureopropyltrimethoxysilane is readily available as a commercially available product and is therefore particularly preferred.

[0043] The following are specific examples of alkoxysilane compounds represented by formulas (1-2), but are not limited to these. Examples include: 1,3-bis[3-(triethoxysilyl)propyl]urea, 1,3-bis[2-(triethoxysilyl)ethyl]urea, 1,3-bis[3-(trimethoxysilyl)propyl]urea, 1,3-bis[3-(tripropoxysilyl)propyl]urea, etc. Among these, 1,3-bis[3-(triethoxysilyl)propyl]urea is readily available as a commercially available product and is therefore particularly preferred.

[0044] From the viewpoint of appropriately obtaining the effects of the present invention, 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. Furthermore, from the viewpoint of appropriately obtaining 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.

[0045] From the viewpoint of obtaining a low refractive index coating, the above-mentioned polysiloxane (A) can be a polysiloxane with fluorinated organic groups.

[0046] Such fluorinated organic groups are organic groups in which some or all of the hydrogen atoms of an aliphatic or aromatic group are replaced by fluorine atoms. Specific examples of these groups include: trifluoropropyl, tridecafluorooctyl, heptadecafluorodecyl, pentafluorophenyl, perfluoroalkyl, etc.

[0047] Among these, perfluoroalkyl groups are preferred because they readily produce highly transparent coatings. More preferably, perfluoroalkyl groups have fluorinated organic groups with 3 to 15 carbon atoms.

[0048] Specific examples include perfluoropropyl, perfluorooctyl, and perfluorodecyl.

[0049] In this invention, a variety of polysiloxanes having fluorinated organic groups on their side chains can be used together.

[0050] There are no particular limitations on the method for obtaining the polysiloxane having fluorinated organic groups in the side chain as described above. Generally, it can be obtained by polycondensation of an alkoxysilane having the aforementioned organic groups in the side chain.

[0051] Preferably, the polysiloxane is obtained by polycondensation of an alkoxysilane component containing an alkoxysilane compound represented by formula (2a).

[0052] R2 Si(OR) 2’ 3 (2a) The alkoxysilane compound represented by formula (2a) is an alkoxysilane having the above-mentioned fluorinated organic groups on its side chain.

[0053] Here, R in equation (2a) 2 This refers to the aforementioned fluorine-containing organic group, where the number of fluorine atoms in the organic group is not particularly limited. Multiple R 2’ They can be the same or different.

[0054] Furthermore, R in equation (2a) 2’ The term represents a hydrocarbon group having 1 to 5 carbon atoms, preferably a saturated hydrocarbon group having 1 to 5 carbon atoms, and more preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, or sec-butyl. Here, n- refers to n, i- refers to iso, s- refers to sec, and t- refers to tert.

[0055] In such alkoxysilane compounds represented by formula (2a), R is more preferably preferred. 2 It is a perfluoroalkyl alkoxysilane compound, or, R 2 It is an alkoxysilane compound represented by the organic group of the following formula (2F).

[0056] CF3 (CF2) k CH2CH2-*(2F) In equation (2F), k represents an integer from 0 to 12. From the viewpoint of properly obtaining the effects of the present invention, k is preferably an integer from 2 to 12.

[0057] Preferred specific examples of alkoxysilane compounds represented by formula (2a) include: 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, (1H,1H,2H,2H-tridecylfluorooctyl)trimethoxysilane, (1H,1H,2H,2H-tridecylfluorooctyl)triethoxysilane, (1H,1H,2H,2H-heptadecylfluorodecyl)trimethoxysilane, (1H,1H,2H,2H-heptadecylfluorodecyl)triethoxysilane, etc.

[0058] In this invention, at least one of the alkoxysilane compounds represented by formula (2a) may be used, or multiple compounds may be used as needed.

[0059] 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 in the alkoxysilane compound used in the synthesis of polysiloxane (A). Furthermore, from the viewpoint of obtaining a uniform coating solution, it is preferably 20 mol% or less, more preferably 15 mol% or less.

[0060] Polysiloxane (A) can be a polysiloxane having fluorinated organic groups in the main chain direction of the polysiloxane. As a monomeric component for synthesizing such a polysiloxane, an alkoxysilane compound having two trialkoxysilyl groups bonded to a divalent organic group having fluorine atoms can be used, for example. Specific examples of such alkoxysilane compounds include the following alkoxysilane compound represented by formula (2b).

[0061] (R) 2b’ O)3Si-R 2b -Si(OR) 2b’ 3 (2b) Here, R in equation (2b) 2b The above-mentioned fluorine-containing organic group is represented by R, where the number of fluorine atoms in the organic group is not particularly limited. R in formula (2b) 2b Preferably, it is a divalent perfluoroalkyl chain or composed of *-CH2-CH2-(CF2). p -CH2-CH2-* (p is an integer from 1 to 12) represents a divalent organic group.

[0062] Furthermore, R in equation (2b) 2b’ Each R independently represents a hydrocarbon group having 1 to 5 carbon atoms, preferably a saturated hydrocarbon group having 1 to 5 carbon atoms, more preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, or sec-butyl. 2b’ They can be the same or different.

[0063] As specific examples of formula (2b), examples include: 1,6-bis(2-trimethoxysilylethyl)dodecylfluorohexane or 1,6-bis(2-triethoxysilylethyl)dodecylfluorohexane, etc.

[0064] In addition, other alkoxysilane compounds may be used as monomer components for obtaining polysiloxane (A), besides the alkoxysilane compounds shown in formula (0), formula (1), and formula (2a) or (2b) as required. One or more of the aforementioned other alkoxysilane compounds may be used.

[0065] Preferred examples of other alkoxysilane compounds include, but are not limited to, alkoxysilane compounds represented by formula (3), alkoxysilane compounds represented by formula (4), and alkoxysilane compounds represented by formula (5).

[0066] R 3 n Si(OR) 3’ ) 4－n (3) (In equation (3), R) 3 R indicates a monovalent organic group that does not contain any of the following: styrene, urea, urea bond, or fluorine atom. 3’ (This represents a hydrocarbon group with 1 to 5 carbon atoms, where n represents an integer from 1 to 3.) Si(OR) 4 )4(4) (R in equation (4)) 4 (Indicates a hydrocarbon group.) (R) 5’ O)3Si-R 5 -Si(OR) 5’ 3 (5) (In equation (5), R) 5 R represents a divalent organic group with 1 to 20 carbon atoms that does not contain any of the following: styrene, urea, urea bond, or fluorine atom. 5’ (This refers to hydrocarbon groups with 1 to 5 carbon atoms.) R in equation (3) 3 The number of carbon atoms is preferably 1 to 20, more preferably 1 to 15. When n is 2 or 3, R 3 They can be the same or they can be different.

[0067] In equation (3) R 3’ In the case where n is 1 or 2, R 3’ They can be the same or they can be different.

[0068] The following are specific examples of alkoxysilanes represented by formula (3), but are not limited thereto.

[0069] Methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, pentyltrimethoxysilane, pentyltriethoxysilane, heptyltrimethoxysilane, heptyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, hexadecyltrimethoxysilane, hexadecyltriethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane; Vinyltrimethoxysilane, vinyltriethoxysilane; 3-isocyanopropyltrimethoxysilane, 3-isocyanopropyltriethoxysilane; 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane; γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane; γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane; 3-acryloyloxypropyltrimethoxysilane, 3-acryloyloxypropyltriethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyltriethoxysilane, etc., trialkoxysilanes.

[0070] From the viewpoint of appropriately obtaining the effects of the present invention, the proportion of the alkoxysilane compound represented by formula (3) in the total alkoxysilane compound 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. Furthermore, from the viewpoint of appropriately obtaining the effects of the present invention, it is preferably 25 mol% or less, more preferably 20 mol% or less, and even more preferably 15 mol% or less.

[0071] R in equation (4) 4 The term "hydrocarbon group" is preferred from the viewpoint of improving reactivity; saturated hydrocarbon groups with 1 to 5 carbon atoms are preferred, and methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, or sec-butyl are more preferred. 4 They can be the same or they can be different.

[0072] Specific examples of tetraalkoxysilane compounds of formula (4) include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, etc., which are readily available as commercially available products. In this invention, at least one of the alkoxysilane compounds represented by formula (4) may be used, or multiple compounds may be used as needed.

[0073] The amount of alkoxysilane compound used in formula (4) is preferably 40 mol% or more, 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, more preferably 96 mol% or less.

[0074] Furthermore, in the alkoxysilane compounds of formula (5), R 5’ It is a hydrocarbon group with 1 to 5 carbon atoms, preferably a saturated hydrocarbon group with 1 to 4 carbon atoms, and more preferably a saturated hydrocarbon group with 1 to 3 carbon atoms. R 5’ They can be the same or they can be different.

[0075] R 5 It is a divalent organic group with 1 to 20 carbon atoms that does not contain any of the following: styrene, urea, urea bond, or fluorine atom. This divalent organic group may contain cyclic structures or branched structures such as double bonds, triple bonds, or phenyl groups. Furthermore, this divalent organic group may contain heteroatoms such as nitrogen, oxygen, or fluorine atoms.

[0076] In this invention, various alkoxysilane compounds represented by formula (5) may also be used as needed.

[0077] Preferred examples of alkoxysilane compounds represented by formula (5) include: dimethyldimethoxysilane, dimethyldiethoxysilane, etc.

[0078] The proportion of the alkoxysilane compound represented by formula (5) in the total amount of alkoxysilane compounds used in the synthesis of polysiloxane (A) is preferably 1 mol% or more, more preferably 2 mol% or more. Furthermore, it is preferably 20 mol% or less, more preferably 15 mol% or less.

[0079] (Polysiloxane (B)) The antireflective film forming material (P) of the present invention can be an antireflective film forming material containing the following (B) component.

[0080] (B) Ingredients: Polysiloxane (B) is different from polysiloxane (A).

[0081] Polysiloxane (B) is a polysiloxane that is different from polysiloxane (A). As a more preferred embodiment, examples include: polysiloxanes that do not contain styrene groups, polysiloxanes that do not contain either urea groups or urea bonds.

[0082] As a monomeric component for obtaining polysiloxane (B), examples include alkoxysilane compounds or derivatives thereof exemplified in polysiloxane (A). Wherein, as a monomeric component for obtaining polysiloxane (B), it does not simultaneously include an alkoxysilane compound or derivative thereof containing a styrene group and an alkoxysilane compound or derivative thereof having at least one of a urea group and a urea bond.

[0083] From the viewpoint of properly obtaining the effects of the present invention, it is preferred that the monomer component used to obtain polysiloxane (B) preferably includes at least one compound selected from the group consisting of alkoxysilane compounds represented by the above formulas (1) to (5).

[0084] The polysiloxane (B) may be a polysiloxane containing at least one functional group selected from the group consisting of urea groups and urea bonds.

[0085] Polysiloxane (B) can be a polysiloxane having fluorinated organic groups.

[0086] Polysiloxane (B) may be a polysiloxane obtained using the other alkoxysilane compounds described above.

[0087] From the viewpoint of properly obtaining the effects of the present invention, other alkoxysilane compounds used in the synthesis of polysiloxane (B) may be at least one compound selected from the group consisting of alkoxysilane compounds represented by formula (3) and alkoxysilane compounds represented by formula (4).

[0088] The polysiloxane (B) may be composed of one or more 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.

[0089] The method for polycondensing polysiloxanes used in this invention is not particularly limited. For example, a method of hydrolyzing / condensing an alkoxysilane compound in an organic solvent such as an alcohol or glycol can be listed. In this case, the hydrolysis / condensation reaction can be either partial hydrolysis or complete hydrolysis. In the case of complete hydrolysis, water at least 0.5 times the molar amount of all alkoxy groups in the alkoxysilane compound can be added.

[0090] In this invention, the amount of water used in the above reaction can be appropriately selected as desired, typically 0.1 to 2.5 times the molar amount of all alkoxy groups in the alkoxysilane compound, preferably 0.1 to 2.0 times the molar amount.

[0091] In addition, acids or bases can be added as catalysts to promote hydrolysis / condensation reactions. 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, or formic acid. Examples of base catalysts include inorganic salts such as sodium and potassium; and various amines (for example, methylamine, ethylamine, ethanolamine, triethylamine, and ammonia).

[0092] In this case, the amount of catalyst used in the reaction is preferably 0.001 to 0.05 moles of all alkoxy groups in the alkoxysilane compound, more preferably 0.01 to 0.03 moles. Furthermore, the hydrolysis / condensation reaction can be promoted by heating the solution containing the alkoxysilane compound.

[0093] At this point, the heating temperature can be appropriately selected as desired, preferably 50°C or higher, and more preferably 180°C or lower. Furthermore, the heating time can be appropriately selected as desired, preferably 10 minutes or more, and more preferably 24 hours or less. As more preferred reaction conditions, examples include methods such as heating at 50°C for 24 hours while stirring, and heating under reflux for 2 to 10 hours while stirring.

[0094] In addition, another method, for example, is to heat a mixture of an alkoxysilane compound, a solvent, and an acid. Specifically, this involves preparing an alcoholic solution of an acid by first adding an acid to an alcoholic solvent, and then mixing the solution with an alkoxysilane and heating it.

[0095] At this point, the amount of acid is preferably 0.2 to 2 moles relative to 1 mole of all the alkoxy groups in the alkoxysilane compound, more preferably 0.5 to 2 moles.

[0096] In this method, the heating temperature is preferably set to 50°C or higher, and more preferably to 180°C or lower, using a liquid thermometer. The reaction time is preferably set to 10 minutes or more, and more preferably to 24 hours or less.

[0097] In the above methods, when using multiple alkoxysilane compounds, the multiple alkoxysilane compounds can be mixed beforehand, or multiple alkoxysilane compounds can be added sequentially.

[0098] When polycondensing alkoxysilane compounds using the above method, the concentration at which the total stoichiometry of silicon atoms in the alkoxysilane compound used in the reaction is converted into SiO2 (hereinafter referred to as SiO2 conversion concentration) is preferably set to 20% by mass or less, and more preferably to 15% by mass or less. Selecting any concentration within such a range is preferable from the viewpoint of suppressing gel formation and obtaining a homogeneous polysiloxane solution.

[0099] The solvent used for polycondensing alkoxysilane compounds is not particularly limited as long as it can dissolve the alkoxysilane compound represented by formula (1) and, if necessary, the alkoxysilane compound represented by formula (2a), the alkoxysilane compound represented by formula (2b), and the alkoxysilane compounds represented by formulas (3) to (5). Alcohols and organic solvents with good compatibility with alcohols are preferred.

[0100] Specific examples of organic solvents used in the polycondensation of alkoxysilane compounds 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.

[0101] In this invention, a variety of the above-mentioned organic solvents can be used in combination.

[0102] <Molecular weight of polysiloxane> The polysiloxane used in this invention has a weight-average molecular weight (Mw) equivalent to polystyrene, determined by gel permeation chromatography (GPC), preferably between 500 and 500,000, more preferably between 1,000 and 300,000. Furthermore, the molecular weight distribution (Mw / Mn) of the polysiloxane used in this invention, expressed as the ratio of Mw to the number-average molecular weight (Mn) equivalent to polystyrene determined by GPC, is preferably 15 or less, more preferably 10 or less. From the viewpoint of appropriately obtaining the effects of this invention, this molecular weight range is preferred.

[0103] <Antireflective film forming material (P)> The antireflective film forming material (P) of the present invention is preferably a coating liquid containing a polymer component and a solvent, wherein the polymer component contains a polysiloxane (A) and a polysiloxane (B) as needed.

[0104] The following solvents can be listed as specific examples of solvents that can be used in antireflective coating forming materials (P).

[0105] Examples include: methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, hexanol, heptanol, octanol, nonanol, decanol, undecylol, dodecanol, diacetone alcohol, etc.; cyclic alcohols such as cyclopropanol, cyclobutanol, cyclopentanol, cyclohexanol, 2-methylcyclohexanol, cycloheptanol, cyclooctanol, cyclononanol, cyclodecanol, etc.; and diols such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, butanediol (1,3-butanediol, 2,3-butanediol, etc.), 2-methyl-2,4-pentanediol (also known as hexanediol), pentanediol, hexanediol, heptanol, etc. 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, diethylene glycol dibutyl ether, etc., glycol ethers; tetrahydrofuran, 1,4-dioxane, etc.; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; esters such as methyl acetate, ethyl acetate, and ethyl lactate; lactams such as N-methyl-2-pyrrolidone; amides such as N,N-dimethylformamide, N,N-dimethylacetamide, tetramethylurea, or hexamethylphosphoric triamine; lactones such as γ-butyrolactone; and dimethyl sulfoxide, etc.

[0106] Regarding the solvents that can be used in the antireflective film forming material (P), it is preferable that one or more solvents are selected from the group consisting of cyclic alcohols having 3 to 10 carbon atoms and diols having 3 to 10 carbon atoms (e.g., ethylene glycol, propylene glycol, 2-methyl-2,4-pentanediol, etc.).

[0107] Regarding the solvents that can be used in the antireflective film forming material (P), it is preferable that they contain one or more glycol ethers having 4 to 8 carbon atoms (for example, among the above-mentioned glycol ethers, solvents 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).

[0108] There are no particular limitations on the method for preparing the antireflective film forming material (P). For example, it is simple to use a polymerization solution containing polysiloxane (A) and / or polysiloxane (B) as is and dilute it by mixing the solvents. Alternatively, the polymerization solution can be concentrated and diluted with solvent as needed, or diluted by mixing the solvents after replacing them with other solvents.

[0109] The content of polysiloxane (A) in the antireflective film forming material (P), which is the concentration of SiO2 converted from the total amount of silicon atoms in polysiloxane (A) (SiO2 conversion concentration), is preferably 0.1% by mass or more, more preferably 0.3% by mass or more. Furthermore, from the viewpoint of improving the storage stability of the solution, it is preferably 15% by mass or less, more preferably 8% by mass or less.

[0110] Furthermore, when the antireflective film forming material (P) contains polysiloxane (B), the total content of polysiloxane (A) and polysiloxane (B), which is the concentration of SiO2 converted from the total amount of silicon atoms in polysiloxane (A) and polysiloxane (B) (SiO2 conversion concentration), is preferably 0.1% by mass or more, more preferably 0.3% by mass or more. Moreover, from the viewpoint of improving the storage stability of the solution, it is preferably 15% by mass or less, more preferably 8% by mass or less.

[0111] From the viewpoint of properly obtaining the effects of this disclosure, the content of polysiloxane (A) in the antireflective film forming material (P) is preferably 10% by mass or more, and more preferably 20% by mass or more, relative to the total mass of the solid components contained in the antireflective film forming material (P).

[0112] When the antireflective film forming material (P) contains other components described later, the content of polysiloxane (A) is preferably 99.9% by mass or less, more preferably 99% by mass or less, relative to the total mass of the solid components contained in the antireflective film forming material (P).

[0113] Furthermore, when the antireflective film forming material (P) contains polysiloxane (B), from the viewpoint of appropriately obtaining the effects of this disclosure, the total content of polysiloxane (A) and polysiloxane (B) in the antireflective film forming material (P) is preferably 10% by mass or more, more preferably 20% by mass or more, relative to the total mass of the solid components contained in the antireflective film forming material (P).

[0114] In cases where the antireflective film forming material (P) contains other components described below, in addition to the above-described cases, the total amount of polysiloxane (A) and polysiloxane (B) relative to the total mass of the solid components contained in the antireflective film forming material (P) is preferably 99.9% by mass or less, more preferably 99% by mass or less.

[0115] In this specification, "total mass of the solid components of the antireflective film forming material (P)" refers to the total mass of the antireflective film forming material (P) when the antireflective film forming material (P) does not contain solvent, and to the mass of the antireflective film forming material (P) after subtracting the mass of the solvent from the total mass of the antireflective film forming material (P) when the antireflective film forming material (P) contains solvent.

[0116] <Other Ingredients> In this invention, other components besides polysiloxane (A), polysiloxane (B), and solvents may be included. Specific examples of other components include: inorganic microparticles, fillers, leveling agents, surface modifiers, or surfactants.

[0117] As inorganic particles, examples include: metal oxide particles, metal composite oxide particles, magnesium fluoride particles, etc.

[0118] Examples of metal oxide particles include: silicon dioxide, aluminum oxide, titanium oxide, zirconium oxide, tin oxide, and zinc oxide. Furthermore, these particles can be in a beaded form.

[0119] Examples of metal composite oxide particles include: ITO (Indium Tin Oxide), ATO (Antimony Trioxide), AZO (Aluminium Zinc Oxide), and zinc antimonate.

[0120] In addition, examples can be given of hollow silica particles, porous silica particles, etc. The aforementioned hollow silica particles can be in the form of beads.

[0121] Inorganic microparticles can be either powders or colloidal solutions, but colloidal solutions are preferred due to their ease of handling. The colloidal solution can be a solution obtained by dispersing inorganic microparticle powder in a dispersion medium, or it can be a commercially available colloidal solution. Examples of commercially available inorganic microparticles include organosilica sols manufactured by Nissan Chemical Co., Ltd. (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, NPC-ST-30, etc.). One type of inorganic microparticle can be used alone, or two or more can be used in combination.

[0122] In this invention, by including inorganic microparticles, the surface shape and other functions of the cured film to be formed can be imparted.

[0123] The inorganic microparticles preferably have an average particle size of 0.001 to 0.2 μm, more preferably 0.001 to 0.1 μm. When the average particle size of the inorganic microparticles exceeds 0.2 μm, the transparency of the cured coating formed from the prepared antireflective film forming material is sometimes reduced.

[0124] Here, "average particle size" can be expressed as the value obtained by observing the average primary particle size of inorganic particles using the BET method (based on the specific surface area obtained by nitrogen adsorption) and by transmission electron microscopy. In this invention, it is expressed by the BET method (based on the specific surface area obtained by nitrogen adsorption).

[0125] Water and organic solvents can be listed as dispersion media for inorganic particles. As a colloidal solution, from the viewpoint of the stability of the antireflective film forming material, the pH or pKa is preferably adjusted to 2–10, more preferably 3–7.

[0126] Organic solvents used as dispersion media in colloidal solutions include: alcohols such as methanol, ethanol, propanol, and butanol; diols 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; diol ethers such as ethylene glycol monopropyl ether; and ethers such as tetrahydrofuran and 1,4-dioxane.

[0127] Alcohols and ketones are preferred. These organic solvents can be used as dispersion media, either alone or in combination of two or more.

[0128] In addition, fillers, leveling agents, surface modifiers, surfactants, etc., can be well-known substances, especially commercially available ones, which are preferred.

[0129] <Substrate with anti-reflective coating> The substrate with an anti-reflective film of the present invention includes an anti-reflective film. Furthermore, the anti-reflective film of the present invention is obtained using the aforementioned anti-reflective film forming material (P).

[0130] One embodiment of the antireflective film of the present invention is a substrate with an antireflective film obtained by the following manufacturing method, which includes: step (1), coating an antireflective film forming material (P) on a substrate (also referred to as substrate (A)) with a heat resistance temperature of 150°C or below to form a coated film; step (2), drying the coated film; and step (3), exposing the coated film dried in step (2) above.

[0131] <Substrate (A)> The substrate (A) is a substrate with a heat resistance temperature of 150°C or below.

[0132] Here, the heat resistance temperature is the temperature at which the substrate will not deform or cause other problems even when exposed during processing such as forming a resin film on the substrate. For resin substrates, it also varies depending on the degree of stretching treatment and must not exceed the glass transition temperature (Tg).

[0133] Materials used 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), or cellulose acetate butyrate, etc. Heat resistance temperatures are disclosed, for example, in Japanese Patent Application Publication No. 09-100363.

[0134] 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.

[0135] The antireflective coating material (P) can be coated using conventional coating methods. Examples of coating methods include dip coating, spin coating, spray coating, slot coating, brush coating, roller transfer printing, screen printing, inkjet printing, or flexographic printing.

[0136] When using flexographic printing to form the film, in order to obtain in-plane uniformity during film formation, the viscosity of the antireflective film forming material (P) is preferably 8 mPa·s or more, more preferably 9 mPa·s or more. Furthermore, the viscosity of the antireflective film forming 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.

[0137] When using a spray coating method to form the film, in order to obtain in-plane uniformity during film formation, the viscosity of the antireflective film forming material (P) is more preferably 0.5 mPa·s or more, and even more preferably 0.8 mPa·s or more. Furthermore, the viscosity of the antireflective film forming material (P) is more preferably 80 mPa·s or less, and even more preferably 50 mPa·s or less.

[0138] The thickness of the coating formed on the substrate can be adjusted by the parameters described above during coating, and can also be easily adjusted by the SiO2 concentration of the antireflective film forming material.

[0139] The above-described step (2) is a drying step to remove the solvent. It is suitable for cases where the time from coating to firing or exposure is not fixed for each substrate, or where firing or exposure is not performed immediately after coating. The drying only needs to remove the solvent to the extent that the shape of the coating film will not be deformed due to substrate transport, etc., and the drying method is not particularly limited. For example, a method of drying on a heating plate at a drying temperature of 30 to 150°C (set to not exceed the heat resistance temperature of the substrate), preferably 40 to 100°C, for 0.5 to 30 minutes, preferably 1 to 5 minutes, can be listed.

[0140] In the method for manufacturing the substrate with anti-reflective film of the present invention, the following step (2') may be performed after the above-described step (2). It should be noted that step (2') may also be performed after the above-described step (3).

[0141] “Process (2'): The process of curing the dried coating film by firing” At this point, the firing temperature can be any temperature between 70 and 150°C, preferably between 80 and 120°C. Heating can be performed using common methods, such as heating plates, hot air circulating ovens, far-infrared heating furnaces (IR ovens), belt furnaces, etc. The coating obtained in this way has good film-forming properties and high transmittance.

[0142] In step (3), the irradiation light can be, for example, ultraviolet light and visible light containing wavelengths of 150 to 800 nm, preferably ultraviolet light containing wavelengths of 300 to 400 nm.

[0143] As a light source for illumination, for example, low-pressure mercury lamps, high-pressure mercury lamps, deep ultraviolet (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, light-emitting diode (LED) lamps, halogen lamps (e.g., sodium lamps), microwave-excited electrodeless lamps, etc.

[0144] The preferred light irradiation intensity is 1000–200000 J / m². 2 More preferably, it is 1000 to 100000 J / m 2 .

[0145] When the coating obtained according to the method of the present invention is used as an anti-reflective film, the coating is formed on the surface of a substrate having a refractive index higher than that of the coating, such as ordinary glass, film, etc., according to the method of the present invention, thereby converting it into a substrate with anti-reflective capabilities. In this case, the coating is effective as a single coating on the substrate surface, and it is also effective as an anti-reflective laminate on which the coating is formed on a lower coating having a high refractive index.

[0146] The antireflective film of the present invention preferably has an average visible light reflectance of 3.0% or less for visible light with wavelengths from 380 nm to 800 nm, more preferably 2.0% or less.

[0147] The average visible light reflectance is determined from the spectral reflectance curve. The spectral reflectance curve is obtained by applying a black coating to the side of the anti-reflective substrate opposite to the low-refractive-index layer to remove gloss, or by attaching a black film. The incident angle is set to 5 degrees from a direction perpendicular to the surface of the low-refractive-index layer, using a C-light source, and the result is obtained under a 2-degree field of view. The average visible light reflectance is obtained by averaging the reflectance of each wavelength of visible light using relative visibility correction. In this case, photopic visual standard relative visibility is used.

[0148] Here, the relationship between the thickness of the coating and the wavelength of light is described.

[0149] It is known that the relationship between the thickness d (nm) of a coating with refractive index a and the wavelength λ (nm) of light for which the reflectivity is to be reduced by the coating is d = (2b - 1)λ / 4a (where b represents an integer greater than 1). Therefore, by using this formula to determine the thickness of the coating, the reflection of light of the desired wavelength can be easily prevented.

[0150] Furthermore, the substrate with the anti-reflective film of the present invention can be further laminated with an anti-fouling film on the aforementioned anti-reflective film. The anti-fouling film is a film that inhibits the adhesion of organic or inorganic substances to the surface, or a film that allows for easy removal of the adhered substances by wiping or other cleaning methods even when organic or inorganic substances are already attached to the surface.

[0151] The thickness of the antifouling membrane is not particularly limited. When the antifouling membrane is composed of a fluorinated organosilicon compound coating, the membrane thickness is preferably 2 to 20 nm, more preferably 2 to 15 nm, and even more preferably 2 to 10 nm. If the membrane thickness is 2 nm or more, it becomes a state of uniform coverage by the antifouling layer, which is durable from the point of view of abrasion resistance.

[0152] The antireflective film forming material (P) of the present invention is preferably used in displays for televisions, computers, car navigation systems, mobile phones, etc.; mirrors with glass surfaces; solar cells, and other fields where it is desirable to prevent light reflection. It is particularly useful for lens covers of liquid crystal displays, plasma displays, projection displays, electroluminescent (EL) displays, surface-conduction electron-emitter displays (SED), field emission displays (FED), cathode ray tubes (CRTs), solar cells, and for antireflective films used in front panels.

[0153] Example The following examples illustrate the invention in further detail, but the invention is not limited to these examples. It should be noted that the abbreviations for compounds and solvents are as follows.

[0154] STMS: p-Styrenetrimethoxysilane (included in compound (St)).

[0155] UPS: γ-ureopropyltriethoxysilane (included in compound (U)).

[0156] TEOS: Tetraethoxysilane.

[0157] F13: (1H,1H,2H,2H-tridecylfluorooctyl)trimethoxysilane.

[0158] GPS: γ-glycidoxypropyltrimethoxysilane.

[0159] MPMS: γ-methacryloyloxypropyltrimethoxysilane.

[0160] MeOH: Methanol.

[0161] EtOH: Ethanol.

[0162] HG: 2-Methyl-2,4-pentanediol.

[0163] PB: Propylene glycol monobutyl ether.

[0164] <Synthesis example 1> To a 200 mL four-necked flask equipped with a reflux flask, TEOS (18.7 g, 90.0 mmol), STMS (1.12 g, 5.0 mmol), and MeOH (18.6 g) were added, stirred, and cooled in an ice bath at 10 °C. Then, MeOH (9.4 g), water (8.8 g), and nitric acid (0.5 g) were added, and the mixture was stirred in an ice bath at 10 °C for 30 minutes. Afterward, the mixture was stirred at 65 °C for 2 hours. Then, UPS (1.32 g, 5.0 mmol) and MeOH (1.4 g) were added, and the reaction was further carried out at 65 °C for 2 hours. Finally, the mixture was cooled to room temperature, and EtOH (40.0 g) was added. The mixture was stirred at room temperature for 30 minutes to obtain solution K1.

[0165] <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-necked flask equipped with a reflux duct. The mixture was stirred and cooled in an ice bath at 10 °C. Then, MeOH (9.2 g), water (8.8 g), and nitric acid (0.5 g) were added, and the mixture was stirred in an ice bath at 10 °C for 30 minutes. Afterward, the mixture was stirred at 65 °C for 2 hours. Then, UPS (1.32 g, 5.0 mmol) and MeOH (1.4 g) were added, and the reaction was further carried out at 65 °C for 2 hours. Finally, the mixture was cooled to room temperature, and EtOH (40.0 g) was added. The mixture was stirred at room temperature for 30 minutes to obtain solution K2.

[0166] <Synthesis Example 3> To a 200 mL four-necked flask equipped with a reflux flask, TEOS (13.5 g, 65.0 mmol), STMS (6.73 g, 30.0 mmol), and MeOH (18.4 g) were added, stirred, and cooled in an ice bath at 10 °C. Then, MeOH (9.2 g), water (8.8 g), and nitric acid (0.5 g) were added, and the mixture was stirred in an ice bath at 10 °C for 30 minutes. Afterward, the mixture was stirred at 65 °C for 2 hours. Then, UPS (1.32 g, 5.0 mmol) and MeOH (1.4 g) were added, and the reaction was further carried out at 65 °C for 2 hours. Finally, the mixture was cooled to room temperature, and EtOH (40.0 g) was added. The mixture was stirred at room temperature for 30 minutes to obtain solution K3.

[0167] <Synthesis example 4> TEOS (19.8 g, 95.0 mmol) and MeOH (19.7 g) were added to a 200 mL four-necked flask equipped with a reflux tube. The mixture was stirred and cooled in an ice bath at 10 °C. Then, MeOH (8.4 g), water (8.8 g), and nitric acid (0.5 g) were added, and the mixture was stirred in an ice bath at 10 °C for 30 minutes. Afterward, the mixture was stirred at 60 °C for 2 hours. Then, UPS (1.32 g, 5.0 mmol) and MeOH (1.4 g) were added, and the mixture was further reacted at 60 °C for 1 hour. Afterward, the mixture was cooled to room temperature, and EtOH (40.0 g) was added. The mixture was stirred at room temperature for 30 minutes to obtain solution K4.

[0168] <Synthesis example 5> To a 200 mL four-necked flask equipped with a reflux flask, TEOS (13.5 g, 65.0 mmol), GPS (7.09 g, 30.0 mmol), and MeOH (18.1 g) were added, stirred, and cooled in an ice bath at 10 °C. Then, MeOH (9.1 g), water (8.8 g), and nitric acid (0.5 g) were added, and the mixture was stirred in an ice bath at 10 °C for 30 minutes. Afterward, the mixture was stirred at 65 °C for 2 hours. Then, UPS (1.32 g, 5.0 mmol) and MeOH (1.4 g) were added, and the reaction was further carried out at 65 °C for 2 hours. Finally, the mixture was cooled to room temperature, and EtOH (40.0 g) was added. The mixture was stirred at room temperature for 30 minutes to obtain solution K5.

[0169] <Synthesis Example 6> To a 200 mL four-necked flask equipped with a reflux flask, TEOS (13.5 g, 65.0 mmol), MPMS (7.45 g, 30.0 mmol), and MeOH (17.9 g) were added, stirred, and cooled in an ice bath at 10 °C. Then, MeOH (9.0 g), water (8.8 g), and nitric acid (0.5 g) were added, and the mixture was stirred in an ice bath at 10 °C for 30 minutes. Afterward, the mixture was stirred at 65 °C for 2 hours. Then, UPS (1.32 g, 5.0 mmol) and MeOH (1.4 g) were added, and the reaction was further carried out at 65 °C for 2 hours. Finally, the mixture was cooled to room temperature, and EtOH (40.0 g) was added. The mixture was stirred at room temperature for 30 minutes to obtain solution K6.

[0170] <Synthesis Example 7> To a 200 mL four-necked flask equipped with a reflux flask, TEOS (18.7 g, 90.0 mmol), F13 (2.34 g, 5.0 mmol), and MeOH (17.9 g) were added, stirred, and cooled in an ice bath at 10 °C. Then, MeOH (8.9 g), water (8.8 g), and nitric acid (0.5 g) were added, and the mixture was stirred in an ice bath at 10 °C for 30 minutes. Afterward, the mixture was stirred at 65 °C for 2 hours. Then, UPS (1.32 g, 5.0 mmol) and MeOH (1.4 g) were added, and the reaction was further carried out at 65 °C for 2 hours. Finally, the mixture was cooled to room temperature, and EtOH (40.0 g) was added. The mixture was stirred at room temperature for 30 minutes to obtain solution K7.

[0171] <Synthesis example 8> To a 200 mL round-bottom flask equipped with a reflux tube, 30.0 g of silica particles MA-ST-UP (manufactured by Nissan Chemical Co., 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 in an ice bath at 10 °C for 30 minutes. Afterward, the mixture was stirred under reflux for 1 hour and cooled to room temperature to obtain solution K8.

[0172] Table 1 summarizes the types and amounts of monomer components used in synthesis examples 1 to 7. <Example 1> Add K8 (36.2 g) to a 200 mL flask and stir at room temperature. Then add K1 (13.8 g) and stir for another 30 minutes at room temperature. After that, add HG (5.0 g) and PB (45.0 g) and stir for another 30 minutes at room temperature to obtain the antireflective film forming material KL1.

[0173] <Examples 2-7, Comparative Examples 1-4> As shown in Table 2, the type and amount of the polysiloxane solution used were changed, except that the process was carried out in the same manner as in Example 1, thereby obtaining antireflective film forming materials KL2-7 and KM1-4. In the table, the values ​​in parentheses indicate the proportions of each component in the antireflective film forming material when the total amount of polysiloxane and silica particles is 100% by mass.

[0174] It should be noted that the antireflective film forming material KL7 of Example 7 was prepared in the following manner: the total proportion of polysiloxane contained in K3 and K6 to the proportion of silica particles contained in K8 were 27.5% and 72.5%, respectively, and the proportion of polysiloxane (A) contained in K3 to polysiloxane (B) contained in K6 was 1:1. <Example 8> HG (1.0g) and PB (9.0g) were added to KL1 solution (10.0g) and stirred to obtain solution KL1'.

[0175] <Examples 9-14, Comparative Examples 5-8> The same procedure as in Example 8 was performed, except that solutions KL2 to KL7 and KM1 to KM4 were used instead of KL1 solution, thereby obtaining solutions KL2' to KL7' and KM1' to KM4'.

[0176] <Fabrication of substrates with anti-reflective coating> Solutions from Examples 8-14 and Comparative Examples 5-8 were pressure-filtered onto a 50mm × 50mm × 2.0mm thick PMMA (polymethyl methacrylate) substrate using a 0.5μm pore size membrane filter. A film was then formed on the substrate using spin coating to achieve a 100nm thickness after firing. The substrate was dried on a heated plate at 30°C for 5 minutes. Afterward, it was fired in a hot air circulating oven at 90°C for 1 hour. Further, an ultraviolet irradiation device (EYE GRAPHICS, UB011-3A type) and a high-pressure mercury lamp (1000W input power) at 50mW / cm² were used. 2 (Converted to wavelength 365nm) Irradiation for 20 seconds (cumulative 1000mJ / cm²) 2 This yielded a substrate with an anti-reflective coating.

[0177] <Evaluation of Reflectivity> Using the substrate with anti-reflective coating obtained by the above method, a black film (kukkiri mieru) is pasted onto the back side (uncoated side). The reflectance of the coated surface was measured using a UV-3600 UV-Vis-NIR spectrophotometer manufactured by Shimadzu Corporation at an incident angle of 5° within a wavelength range of 380 nm to 800 nm. Based on the obtained spectral reflectance curve, the average visible light reflectance of a single side (coated surface) was calculated according to JIS R 3106. The evaluation results are shown in Table 3.

[0178] <Chemical Resistance Test> Glass cleaner (manufactured by HondaAccess Co., Ltd., model 08CBC-A030L1) was sprayed in a mist onto the substrate with the anti-reflective coating obtained by the above method, and left to stand for 24 hours. Afterwards, the agent adhering to the surface was wiped off with a dry cloth, the surface was cleaned with EtOH, and then dried by blowing air. The surface was then visually inspected, and the following conditions were evaluated: 0% peeling of the film from the entire substrate; 1% peeling of only a portion of the remaining agent; 2% peeling of a portion of the remaining agent; and 3% complete absence of peeling. The evaluation results are shown in Table 3. As shown in Table 3, by using polysiloxanes with styrene and urea groups as substituents, it is possible to obtain antireflective coatings and substrates with excellent chemical resistance.

[0179] Industrial availability The present invention has excellent anti-reflective properties and is also resistant to chemicals, and therefore is expected to be used in various displays, especially in vehicle lens covers for automobiles, motorcycles and the like, where cleaning with various chemicals is performed during maintenance.

[0180] It should be noted that the entire contents of the specification, technical solution and abstract of Japanese Patent Application No. 2023-134269, filed on August 21, 2023, are incorporated herein by reference as a disclosure of the specification of this invention.

Claims

1. An antireflective film forming material, comprising an antireflective film forming material P containing component A below. Component A: Polysiloxane A containing styrene groups and urea groups and / or urea bonds, wherein the molar amount of styrene groups contained in the polysiloxane is more than 0.1 mol% and less than 70 mol% relative to 100 mol% of Si atoms.

2. The antireflective film forming material according to claim 1, wherein, The polysiloxane A is obtained by polycondensation of an alkoxysilane compound comprising an alkoxysilane or its hydrolysate, wherein the alkoxysilane has at least one styrene group having one or more substituents within its molecule. The alkoxysilane compound component comprises a compound represented by the following formula (0), In formula (0), R1 is a hydrogen atom or an alkyl group, and L is a divalent linker. n is an integer from 1 to 5, and m is an integer from 1 to 3. R2 represents a hydrogen atom or any substituent. In the presence of multiple R2 atoms, the R2 atoms may be identical or different from each other, and may optionally bond together with each other to form a ring structure 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. Any hydrogen atom in R may optionally be replaced by a halogen atom, an aromatic ring, or an aliphatic ring. In the presence of multiple Rs, the Rs may optionally be the same as or different from each other.

3. The antireflective film forming material according to claim 2, wherein, The compound represented by the formula (0) is selected from the group consisting of the following compounds (a0-1) to (a0-23). In the formula, Me represents methyl and Et represents ethyl. i Pr represents isopropyl.

4. A method for manufacturing a substrate with an anti-reflective film, comprising: Step 1: A coating film is formed by coating an anti-reflective film forming material P as described in claim 1 onto a substrate with a heat resistance temperature below 150°C. Step 2, drying the coated film; and Step 3: Expose the dried coating film.

5. The manufacturing method according to claim 4, wherein, It also includes the following process 2', Step 2': The process of curing the dried coating film by firing.

6. A substrate with an anti-reflective film, obtained by the method described in any one of claims 4 or 5.

7. An antireflective film obtained by the method of any one of claims 4 or 5.

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