JP5382310B2 - Coating liquid for forming a film, manufacturing method thereof, coating film thereof, and antireflection material - Google Patents

Description

  The present invention relates to a coating liquid for forming a film containing polysiloxane, a production method thereof, a film formed from the coating liquid, and an antireflection material having the film.

Conventionally, it is known that when a coating having a low refractive index smaller than the refractive index of the substrate is formed on the surface of the substrate, the reflectance of light reflected from the surface of the coating is lowered. And the low refractive index film which shows such a reduced light reflectivity is utilized as a light reflection prevention film, and is applied to the surface of various base materials.
For example, Patent Document 1 discloses an alcohol dispersion of MgF ₂ fine particles produced by reacting a magnesium salt or an alkoxymagnesium compound as an Mg source with a fluoride salt as an F source, or an improvement in film strength. For this purpose, a solution obtained by adding tetraalkoxysilane or the like is used as a coating solution, which is coated on a glass substrate and heat-treated at a temperature of 100 to 500 ° C. to form an antireflection film exhibiting a low refractive index on the substrate. A method is disclosed.

  Further, Patent Document 2 discloses a hydrolytic polycondensate such as tetraalkoxysilane, which is a coating liquid obtained by mixing two or more kinds having different average molecular weights and a solvent such as alcohol to form a coating film. It is disclosed that a film is formed by adding means such as mixing ratio at the time of mixing and control of relative humidity. The coating is obtained by heating at a temperature of 250 ° C. or higher, exhibits a refractive index of 1.21 to 1.40, and has a thickness of 60 to 160 nm having micropits or irregularities having a diameter of 50 to 200 nm. The coating is formed on a glass substrate to produce a low reflection glass.

Patent Document 3 discloses a low reflectance glass comprising glass, a lower layer film having a high refractive index formed on the surface thereof, and an upper layer film having a low refractive index formed on the surface thereof. ing. The upper layer film is formed by using a fluorine-containing silicone compound having a polyfluorocarbon chain such as CF ₃ (CF ₂ ) ₂ C ₂ H ₄ Si (OCH ₃ ) ₃ and 5 to 90% by mass of Si (OCH ₃ ) ₄ with respect to this. A hydrolyzed silane coupling agent in an alcohol solvent in the presence of a catalyst such as acetic acid at room temperature, and then filtered to form a cocondensate solution prepared by filtration on the lower layer film. It is performed by heating at ~ 250 ° C.

Further, Patent Document 4 discloses a silicon compound represented by Si (OR) ₄ , a silicon compound represented by CF ₃ (CF ₂ ) _n CH ₂ CH ₂ Si (OR ¹ ) ₃ , and R ² CH ₂ OH. A coating solution is disclosed in which a polysiloxane solution is produced by heating a reaction mixture containing the indicated alcohol and oxalic acid in a specific ratio at a temperature of 40 to 180 ° C. in the absence of water. A coating having a refractive index of 1.28 to 1.38 and a water contact angle of 90 to 115 degrees is formed by applying this coating solution to the surface of the substrate and thermosetting at a temperature of 80 to 450 ° C. .

JP 05-105424 A Japanese Patent Application Laid-Open No. 06-157076 Japanese Patent Laid-Open No. 61-010043 JP 09-208898 A

  The antireflection film as described above is used in various display devices and the like, and in recent years, as the display devices such as liquid crystal and plasma are becoming larger, lighter, and thinner, the antireflection film used for this is being used. Materials, particularly antireflection films, tend to reduce the film thickness for the purpose of weight reduction and high transparency, and there is a problem that damage caused by heat increases. Therefore, there is an increasing demand for a coating solution for forming a thermosetting film that cures at a relatively low temperature, which can obtain an antireflection base material by a low-temperature treatment that does not damage the film. It was. However, the curing temperature of the conventional low refractive index coating as described above is not necessarily low enough, and it is desired to further lower the curing temperature.

  Thus, an object of the present invention is to provide a coating solution that is excellent in storage stability, sufficiently cured by heat treatment at a low temperature, and can form a coating film having a low refractive index and excellent scratch resistance, an efficient production method thereof, It is providing the coating obtained from a coating liquid, and the antireflection use which uses this coating.

As a result of intensive studies to achieve the above object, the present inventors have completed the present invention.
That is, the gist of the present invention is as described below.

（Ｒ ^１ 、Ｒ ^２ 、Ｒ ^３ 及びＲ ^４ はそれぞれ独立に水素原子又は炭素数１〜５の飽和炭化水素基を表し、ｎは２以上の整数を表す。）
３．ポリシロキサン（Ａ）が、式（２）で表されるアルコキシシランを含むアルコキシシランを重縮合して得られるポリシロキサンである上記１または２に記載の被膜形成用塗布液。

（Ｒ^５はフッ素原子を有する有機基であり、Ｒ^６は炭素数１〜５の炭化水素基を表す。）
４．ポリシロキサン（Ａ）が、式（３）で表されるアルコキシシランの少なくとも１種を併用し、重縮合して得られるポリシロキサンである上記１〜３のいずれか一項に記載の被膜形成用塗布液。

（Ｒ^７は水素原子、又はフッ素原子を有しない炭素数１〜２０の有機基であり、Ｒ^８は炭素数１〜５の炭化水素基であり、ｍは０〜３の整数を表す。）
５．ポリシロキサン（Ａ）のフッ素原子を有する有機基が、パーフルオロアルキル基である上記１〜４のうちのいずれか一項に記載の被膜形成用塗布液。
６．ポリシロキサン（Ａ）が、それが有するケイ素原子の合計量１モルに対してフッ素原子を有する有機基が０．０５〜０．４モルである上記１〜５のうちのいずれか一項に記載の被膜形成用塗布液。
７．モノアミン化合物（Ｃ）が、脂肪族アミン及びアルカノールアミンからなる群から選ばれる少なくとも１種である上記１〜６のうちのいずれか一項に記載の被膜形成用塗布液。
８．ポリシロキサン（Ａ）又は、ポリシロキサン（Ａ）とポリシロキサン（Ｂ）の全ケイ素原子の合計量を二酸化ケイ素に換算した値が、塗布液中、０．５〜１５質量％である上記１〜７のうちのいずれか一項に記載の被膜形成用塗布液。
９．ポリシロキサン（Ｂ）が、ポリシロキサン（Ａ）の全ケイ素原子の１モルに対し、ポリシロキサン（Ｂ）の全ケイ素原子が０．０５〜０．５５モル含有される上記２〜８のうちのいずれか一項に記載の被膜形成用塗布液。
１０．モノアミン化合物（Ｃ）が、ポリシロキサン（Ａ）又は、ポリシロキサン（Ａ）とポリシロキサン（Ｂ）の全ケイ素原子の合計量１モルに対し、モノアミン化合物（Ｃ）におけるアミノ基由来の窒素原子が０．０１〜０．２モル含有される上記１〜９のうちのいずれか一項に記載の被膜形成用塗布液。
１１．上記１〜１０のうちのいずれか一項に記載の被膜形成用塗布液を加熱硬化して得られる低屈折率被膜。
１２．上記１１に記載の低屈折率被膜が、より高い屈折率を有する基材の表面上に形成された反射防止材。
１３．上記１〜１２のうちのいずれか一項に記載の被膜形成用塗布液を基材に塗布し、温度２０〜１００℃で１０秒間〜６分間乾燥した後に、温度２０〜７０°Ｃで硬化することを特徴とする低屈折率被膜の形成方法。
１４．無機酸又は有機酸が、ポリシロキサン（Ａ）の全ケイ素原子の合計量１モルに対し、０．０１〜２．５モル含有されたポリシロキサン（Ａ）の有機溶媒の溶液と、モノアミン化合物（Ｃ）と、有機溶媒（Ｄ）と、を混合する上記１〜１０のうちのいずれか一項
に記載の被膜形成用塗布液の製造方法。
１５．無機酸又は有機酸が、ポリシロキサン（Ａ）の全ケイ素原子の合計量１モルに対し、０．０１〜２．５モル含有されたポリシロキサン（Ａ）の有機溶媒の溶液と、ポリシロキサン（Ｂ）と、モノアミン化合物（Ｃ）と、有機溶媒（Ｄ）と、を混合する上記２〜１０のうちのいずれか一項に記載の被膜形成用塗布液の製造方法。
１６．ポリシロキサン（Ａ）の有機溶媒の溶液が、式（２）で表されるアルコキシシランを含むアルコキシシランと酸とを有機溶媒（Ｄ）中で加熱して得られ、かつ上記酸の量が、上記アルコキシシランの全アルコキシ基量の１モルに対し、０．２〜２モルの範囲で得られるポリシロキサンの溶液である上記１４または１５に記載の被膜形成用塗布液の製造方法。 1. It contains polysiloxane (A) , which is a polysiloxane having an organic group having a fluorine atom, and a monoamine compound (C) , and the inorganic acid or organic acid is a total amount of all silicon atoms of the polysiloxane (A) 1 A coating liquid for forming a film , which is contained in an amount of 0.01 to 2.5 mol per mol and dissolved in an organic solvent (D).
2. The coating liquid for film formation according to 1 above, further containing a polysiloxane (B) represented by the formula (1).

(R ¹ , R ² , R ³ and R ⁴ each independently represents a hydrogen atom or a saturated hydrocarbon group having 1 to 5 carbon atoms, and n represents an integer of 2 or more.)
3. The coating liquid for film formation according to 1 or 2 above, wherein the polysiloxane (A) is a polysiloxane obtained by polycondensation of an alkoxysilane containing an alkoxysilane represented by the formula (2).

(R ⁵ is an organic group having a fluorine atom, and R ⁶ represents a hydrocarbon group having 1 to 5 carbon atoms.)
4). The film formation according to any one of 1 to 3 above, wherein the polysiloxane (A) is a polysiloxane obtained by polycondensation using at least one alkoxysilane represented by the formula (3). Coating liquid.

^{(R 7} is an organic group having a hydrogen atom, or a fluorine atom having no carbon atoms 1 to 20, ^{R 8} is a hydrocarbon group having 1 to 5 carbon atoms, m represents an integer of 0 to 3.)
5). The coating liquid for film formation according to any one of the above 1 to 4 , wherein the organic group having a fluorine atom of the polysiloxane (A) is a perfluoroalkyl group.
6). The polysiloxane (A) according to any one of 1 to 5 above, wherein the organic group having a fluorine atom is 0.05 to 0.4 mol with respect to 1 mol of the total amount of silicon atoms it has. Coating solution for film formation.
7). The coating liquid for film formation according to any one of the above 1 to 6 , wherein the monoamine compound (C) is at least one selected from the group consisting of an aliphatic amine and an alkanolamine.
8). A value obtained by converting the total amount of all silicon atoms of polysiloxane (A) or polysiloxane (A) and polysiloxane (B) into silicon dioxide is 0.5 to 15% by mass in the coating solution. The coating liquid for film formation according to any one of 7.
9. Of the above 2 to 8 , the polysiloxane (B) contains 0.05 to 0.55 mol of all silicon atoms of the polysiloxane (B) with respect to 1 mol of all silicon atoms of the polysiloxane (A). The coating liquid for film formation as described in any one of Claims.
10. When the monoamine compound (C) is polysiloxane (A) or the total amount of all silicon atoms of the polysiloxane (A) and polysiloxane (B) is 1 mol, the nitrogen atom derived from the amino group in the monoamine compound (C) The coating liquid for forming a film according to any one of the above 1 to 9 , which is contained in an amount of 0.01 to 0.2 mol.
11. The low-refractive-index film obtained by heat-curing the coating liquid for film formation as described in any one of said 1-10.
12 The antireflective material in which the low-refractive-index film of said 11 was formed on the surface of the base material which has a higher refractive index.
13. After apply | coating the coating liquid for film formation as described in any one of said 1-12 to a base material, and drying for 10 seconds-6 minutes at the temperature of 20-100 degreeC, it hardens | cures at the temperature of 20-70 degreeC. A method for forming a low refractive index film.
14 A solution of an organic solvent of polysiloxane (A) containing 0.01 to 2.5 mol of an inorganic acid or an organic acid with respect to 1 mol of the total amount of all silicon atoms of polysiloxane (A), and a monoamine compound ( The manufacturing method of the coating liquid for film formation as described in any one of said 1-10 which mixes C) and an organic solvent (D).
15. A solution of an organic solvent of polysiloxane (A) containing 0.01 to 2.5 mol of an inorganic acid or an organic acid with respect to 1 mol of the total amount of all silicon atoms of polysiloxane (A), and polysiloxane ( The manufacturing method of the coating liquid for film formation as described in any one of said 2-10 which mixes B), a monoamine compound (C), and an organic solvent (D) .
16. A solution of an organic solvent of polysiloxane (A) is obtained by heating an alkoxysilane containing an alkoxysilane represented by formula (2) and an acid in an organic solvent (D), and the amount of the acid is 16. The method for producing a coating liquid for forming a film according to the above 14 or 15 , which is a polysiloxane solution obtained in a range of 0.2 to 2 mol with respect to 1 mol of the total alkoxy group amount of the alkoxysilane.

The coating liquid for forming a film of the present invention is excellent in storage stability, and can provide a film that is sufficiently cured by, for example, a low-temperature heat treatment at a temperature of 20 to 70 ° C. and has a low refractive index and excellent scratch resistance.
And the film obtained from the coating liquid for film formation of this invention can be used suitably for antireflection materials, such as an antireflection film.
In the present invention, the mechanism of why the coating film formed from the coating solution has the above excellent characteristics is not necessarily clear, but is estimated as follows. In the present invention, it is necessary for the coating liquid to contain a combination of fluorine-containing polysiloxane (A) and at least one of hydrocarbon-based polysiloxane (B) and monoamine compound (C). As illustrated in the following examples and comparative examples, in the case of a coating solution in which each of the above components is contained alone, it has excellent storage stability, is thermally cured at a low temperature, and has a low refractive index. A film excellent in scratch resistance cannot be obtained. In the present invention, particularly in the case of a coating solution containing a fluorine-containing polysiloxane (A), a hydrocarbon-based resiloxane (B), and a monoamine compound (C), it is excellent in any of the above characteristics. A cured film can be obtained.

The present invention is described in detail below.
The coating liquid for forming a film of the present invention (also simply referred to as a coating liquid in the present invention) contains polysiloxane (A) , which is a polysiloxane having an organic group having a fluorine atom, and a monoamine compound (C) , Further, a coating film containing an inorganic acid or an organic acid in an amount of 0.01 to 2.5 mol per mol of the total amount of all silicon atoms of the polysiloxane (A ) and dissolved in the organic solvent (D). This is a forming coating solution.

The alkoxysilane represented by the formula (2) imparts water repellency to the coating. Here, R ⁵ in the formula (2) represents an organic group having a fluorine atom, but is not particularly limited as long as it is an organic group having a fluorine atom. Usually, R ⁵ is preferably an alkyl group in which some or all of the hydrogen atoms are substituted with fluorine atoms, or an alkyl group having an ether bond in which some or all of the hydrogen atoms are substituted with fluorine atoms. The number of fluorine atoms that the organic group has is not particularly limited.
R ⁵ is an organic group having a fluorine atom, and is preferably an organic group having 1 to 20, more preferably 3 to 10, and particularly preferably 3 to 8 carbon atoms. Such alkoxysilane is preferable because it is easily available.

Further, in the equation (2), R ⁶ is a hydrocarbon group of 1 to 5 carbon atoms, particularly saturated hydrocarbon group. Of these, lower alkyl groups such as a methyl group, an ethyl group, a propyl group, and a butyl group are preferable because they are easily available as commercial products. When a plurality of alkoxysilanes represented by the formula (2) are used, their R ⁶ may be the same or different.
In the present invention, among the alkoxysilanes represented by the formula (2), an alkoxysilane in which R ⁵ is an organic group represented by the formula (4) is preferable.

（ｋは０〜１２の整数を表す。）

(K represents an integer of 0 to 12)

Specific examples of the alkoxysilane in which R ⁵ is an organic group represented by the formula (4) include trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, tridecafluorooctyltrimethoxysilane, and trideca Examples include fluorooctyltriethoxysilane, heptadecafluorodecyltrimethoxysilane, and heptadecafluorodecyltriethoxysilane.

In the present invention, at least one of the alkoxysilanes represented by the formula (2) may be used, but a plurality of types may be used as necessary.
The polysiloxane (A) used in the present invention can also be obtained by using together an alkoxysilane represented by the formula (2) and an alkoxysilane represented by the formula (3). In that case, you may use multiple types of alkoxysilane represented by Formula (3).

（Ｒ^７は、水素原子、又はフッ素原子を有しない炭素数１〜２０の有機基であり、Ｒ^８は、それぞれ炭素数１〜５の炭化水素基であり、ｍは０〜３の整数を表す。）

^{(R 7} is a hydrogen atom, or an organic group having 1 to 20 carbon atoms having no fluorine atom, ^{R 8} are each a hydrocarbon group of 1 to 5 carbon atoms, m is an integer of 0 to 3 Represents.)

In the formula (3), R ⁸ represents a hydrocarbon group, but a saturated hydrocarbon group having 1 to 5 carbon atoms is preferable because the reactivity is higher when the number of carbon atoms is smaller. More preferred are a methyl group, an ethyl group, a propyl group, and a butyl group.
When m = 0 in the formula (3), the alkoxysilane represented by the formula (3) represents a tetraalkoxysilane. Specific examples thereof include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane and the like, and are easily available as commercial products.

In the formula (3), in the case of an integer of m = 1 to 3, the alkoxysilane represented by the formula (3) is a C 1-20, preferably 1-10, in which R ⁷ has no hydrogen atom or fluorine atom. An alkoxysilane having an organic group and an alkoxy group. In the present invention, R ⁷ may be the same or different.
Examples of the C1-C20 organic group having no fluorine atom include a saturated hydrocarbon group having a linear or branched structure, an aromatic group having a benzene ring, a glycidyl group, an amino group, a ureido group, or a vinyl group. Or an organic group having an ether bond or an ester bond.

R ^{8 in the} formula (3) is a hydrocarbon group having 1 to 5 carbon atoms. when m is 1 or 2, but is generally preferred if R ⁸ are the same, in the present invention, R ⁸ may be the same or different. Specific examples of alkoxysilane in the case where m is an integer of 1 to 3 in formula (3) are shown below.
For example, trimethoxysilane, triethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, Pentyltrimethoxysilane, pentyltriethoxysilane, heptyltrimethoxysilane, heptyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, hexadecyltrimethoxysilane, hexadecyltriethoxy Silane, octadecyltrimethoxysilane, octadecyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane Vinyltrimethoxysilane, vinyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxy Trialkoxysilanes such as propyltrimethoxysilane and γ-methacryloxypropyltriethoxysilane, dialkoxysilanes such as dimethyldimethoxysilane and dimethyldiethoxysilane, and trialkylalkoxysilanes such as trimethylmethoxysilane and trimethylethoxysilane Can be mentioned.

The polysiloxane (A) used in the present invention is obtained by polycondensation of an alkoxysilane represented by the formula (2) preferably containing 5 to 40 mol% of all alkoxysilanes. 10-40 mol% is preferable when the reflectance of the film is further reduced, and 5-25 mol% is preferable when the hardness of the film is further increased. In that case, the amount of the alkoxysilane represented by the formula (3) used in combination is preferably 60 to 95 mol% in the total alkoxysilane, in other words, with respect to 1 mol of the alkoxysilane represented by the formula (2). 1.5 to 19 mol is preferable.
In addition, when the alkoxysilane of the formula (3) contains an alkoxysilane in which m is 0, in particular, the alkoxysilane alone in which m is 0 or the alkoxysilane in which m of the formula (3) is 0 and m is 1 When using together with the alkoxysilane which is -3, since the storage stability of a coating liquid improves, it is preferable. At that time, the amount of alkoxysilane in which m is 0 is preferably 20 to 95 mol% in the total alkoxysilane, and more preferably 20 to 90 mol% particularly when the reflectance of the coating is further reduced.

Thus, preferred examples of the polysiloxane (A) using the alkoxysilane represented by the formulas (2) and (3) in the present invention are as shown in the following [1] to [4].
[1]: Polysiloxane (A) obtained by polycondensation of 5 to 40 mol% of alkoxysilane represented by formula (2) and 60 to 95 mol% of alkoxysilane represented by formula (3).
[2]: Obtained by polycondensation of alkoxysilane containing 5 to 40 mol% of alkoxysilane represented by formula (2) and 20 to 95 mol% of alkoxysilane represented by m of formula (3). Polysiloxane (A).
[3]: Obtained by polycondensation of alkoxysilane containing 5 to 25 mol% of alkoxysilane represented by formula (2) and 20 to 95 mol% of alkoxysilane represented by m of formula (3) of 0 Polysiloxane (A).
[4]: Obtained by polycondensation of alkoxysilane containing 10 to 40 mol% of alkoxysilane represented by formula (2) and 20 to 90 mol% of alkoxysilane represented by m of formula (3). Polysiloxane (A).

As a method for obtaining polysiloxane (A), for example, alkoxysilane represented by formula (2), alkoxysilane in which m in formula (3) is 0, and m in formula (3) is 1 as necessary. The method of heating and polycondensing at least 1 type of alkoxysilanes of -3 and an organic solvent in presence of oxalic acid is mentioned. Specifically, after adding succinic acid to alcohol in advance to obtain an alcohol solution of succinic acid, the above-mentioned various alkoxysilanes are mixed while the solution is heated.
The amount of the oxalic acid is preferably 0.2 to 2 mol with respect to 1 mol of the total alkoxy group amount of the alkoxysilane used. The heating can be performed at a liquid temperature of preferably 0 to 180 ° C., and preferably several tens of minutes under reflux in a container equipped with a reflux tube so that the liquid does not evaporate or volatilize. ~ Dozens of hours.

When using multiple types of alkoxysilane, you may mix as a mixture which mixed alkoxysilane previously, and may mix multiple types of alkoxysilane sequentially.
In the case of polycondensation of alkoxysilane, the concentration (hereinafter referred to as SiO ₂ conversion concentration) in which all silicon atoms of the prepared alkoxysilane are converted to oxide is 20% by mass or less, particularly preferably 4 to 15% by mass. % Heating is preferable. By selecting an arbitrary concentration within such a concentration range, gel formation can be suppressed and a homogeneous polysiloxane-containing solution can be obtained.

  The organic solvent used for polycondensation of alkoxysilane (hereinafter also referred to as polymerization solvent) is not particularly limited as long as it dissolves the alkoxysilane represented by formula (2) and formula (3). The use of an organic solvent (D) is preferred. Especially, since alcohol produces | generates by the polycondensation reaction of alkoxysilane, the organic solvent favorable with alcohol and alcohol compatibility is used.

Specific examples of the polymerization solvent include alcohols such as methanol, ethanol, propanol, and n-butanol, glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, and diethylene glycol monoethyl ether. .
In the present invention, a plurality of the above organic solvents may be mixed and used.

The coating liquid of the present invention preferably contains polysiloxane (B) , which is at least one polysiloxane represented by the formula (1) .

（Ｒ^１、Ｒ^２、Ｒ^３及びＲ^４はそれぞれ独立に水素原子又は炭素数１〜５の飽和炭化水素基を表し、ｎは２以上、好ましくは２〜５０の整数を表す。）

(R ¹ , R ² , R ³ and R ⁴ each independently represents a hydrogen atom or a saturated hydrocarbon group having 1 to 5 carbon atoms, and n represents 2 or more, preferably an integer of 2 to 50.)

In formula (1), R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom or a saturated hydrocarbon group having 1 to 5 carbon atoms, but specific examples of a saturated hydrocarbon group having 1 to 5 carbon atoms Examples thereof include a methyl group, an ethyl group, a propyl group, and a butyl group.
The polysiloxane (B) is not particularly limited as long as it is at least one polysiloxane represented by the formula (1). That is, a mixture of a plurality of polysiloxanes represented by the formula (1) may be used. In that case, n is preferably an integer of 2 or more, more preferably an integer of 3 to 50. More preferably, it is 4-30.

The method for obtaining the polysiloxane (B) used in the present invention is not particularly limited. For example, the polysiloxane (B) can be obtained by polycondensation of tetraalkoxysilane in an alcohol solvent. In that case, the polycondensation may be any of a method in which partial hydrolysis or complete hydrolysis is carried out and a condensation reaction is carried out. In the case of complete hydrolysis, theoretically, 0.5 times mole of water of all alkoxy groups in tetraalkoxysilane may be added, but usually an excess amount of water is added more than 0.5 times mole.
Specific examples of such a tetraalkoxysilane include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, and the like, and are easily available as commercial products.

In the present invention, the amount of water used in the above reaction can be appropriately selected as desired, but it is usually preferably 0.5 to 2.5 moles of all alkoxy groups in the tetraalkoxysilane.
Also, usually for the purpose of promoting hydrolysis / condensation reaction, inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, hydrofluoric acid or the metal salts thereof; organic acids such as acetic acid, formic acid, succinic acid, maleic acid; A catalyst such as alkali is used. It is also common to further promote polycondensation by heating a solution in which alkoxysilane is dissolved. At that time, the heating temperature and the heating time can be appropriately selected as desired. For example, heating and stirring at room temperature to 100 ° C. for 0.5 to 48 hours, heating and stirring for 0.5 to 48 hours under reflux, etc. Is mentioned.

  The solvent used for polycondensation of tetraalkoxysilane is not particularly limited as long as it dissolves tetraalkoxysilane, but the use of organic solvent (D) is preferred. Especially, since alcohol produces | generates by the polycondensation reaction of tetraalkoxysilane, the organic solvent with favorable compatibility with alcohols and alcohols is used.

  Specific examples of the organic solvent (D) used above include alcohols such as methanol, ethanol, propanol and n-butanol, glycols such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether and diethylene glycol monoethyl ether. Examples include ether. In the present invention, a plurality of the above organic solvents (D) may be mixed and used.

It is preferable that the polysiloxane (B) solution obtained as described above has a SiO ₂ equivalent concentration of 30% by mass or less, preferably 3 to 20% by mass. By selecting an arbitrary concentration within this concentration range, gel formation can be suppressed and a homogeneous solution can be obtained.
In the present invention, when such a polysiloxane (B) is used, the content of the polysiloxane (B) in the coating solution is based on 1 of the mass of all the silicon atoms of the polysiloxane (A) converted to silicon dioxide. The mass in which all silicon atoms of polysiloxane (B) are converted to silicon dioxide is 0.03 to 0.55, preferably 0.05 to 0.55, more preferably 0.05 to 0.45. Is preferred.
In other words, the content of the polysiloxane (B) in the coating solution is such that the total silicon atoms of the polysiloxane (B) are 0.03 to 0.55 mol relative to 1 mol of the total silicon atoms of the polysiloxane (A). , Preferably 0.05 to 0.55 mol, more preferably 0.05 to 0.45 mol.

<Monoamine compound (C)>
The monoamine compound (C) contained in the coating solution of the present invention accelerates polycondensation of alkoxy groups remaining in the coating film without causing rapid gelation, and cures the coating film even at low temperatures. Contributes to progress.
Examples of the monoamine compound (C) include aliphatic amines having preferably 1 to 22 carbon atoms, alkanol amines having preferably 1 to 10 carbon atoms, and aromatic (arylamine).

  Specific examples of the aliphatic amine include methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, N, N-dimethylamine, N, N-diethylamine, N, N-dipropylamine, N, N-di Butylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, methoxymethylamine, methoxyethylamine, methoxypropylamine, methoxybutylamine, ethoxymethylamine, ethoxyethylamine, ethoxypropylamine, ethoxybutylamine, propoxymethylamine, propoxyethylamine, propoxypropyl Amine, propoxybutylamine, butoxymethylamine, butoxyethylamine, butoxypropylamine, butoxybutylamine, cyclohexane Shiruamin and the like.

  Specific examples of the alkanolamine include methanolamine, ethanolamine, propanolamine, butanolamine, N-methylmethanolamine, N-ethylmethanolamine, N-propylmethanolamine, N-butylmethanolamine, N-methylethanolamine, N -Ethylethanolamine, N-propylethanolamine, N-butylethanolamine, N-methylpropanolamine, N-ethylpropanolamine, N-propylpropanolamine, N-butylpropanolamine, N-methylbutanolamine, N-ethyl Butanolamine, N-propylbutanolamine, N-butylbutanolamine, N, N-dimethylmethanolamine, N, N-diethylmethanolamine, N, N-dipropylmethanol Amine, N, N-dibutylmethanolamine, N, N-dimethylethanolamine, N, N-diethylethanolamine, N, N-dipropylethanolamine, N, N-dibutylethanolamine, N, N-dimethylpropanolamine N, N-diethylpropanolamine, N, N-dipropylpropanolamine, N, N-dibutylpropanolamine, N, N-dimethylbutanolamine, N, N-diethylbutanolamine, N, N-dipropylbutanolamine N, N-dibutylbutanolamine, N-methyldimethanolamine, N-ethyldimethanolamine, N-propyldimethanolamine, N-butyldimethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N-propyldiethanol Amine, N-butyldiethanolamine, N-methyldipropanolamine, N-ethyldipropanolamine, N-propyldipropanolamine, N-butyldipropanolamine, N-methyldibutanolamine, N-ethyldibutanolamine, N -Propyldibutanolamine, N-butyldibutanolamine and the like. Specific examples of the arylamine include aniline, N-methylaniline, benzylamine and the like.

  Among them, the monoamine compound (C) is preferably an aliphatic amine having 1 to 22 carbon atoms or an alkanolamine having 1 to 10 carbon atoms. More preferred are ethylamine, N, N-diethylamine, triethylamine, cyclohexylamine, monoethanolamine, diethanolamine, and triethanolamine. In the present invention, a plurality of monoamine compounds may be used.

The content of the monoamine compound (C) in the coating liquid of the present invention is any of the case where the coating liquid contains the polysiloxane (A) alone or the case where the polysiloxane (A) and the polysiloxane (B) are contained. In addition, the nitrogen atom derived from the amino group in the monoamine compound (C) is 0.01 to 0.2 mol, more preferably 0.03 to 0.1 mol, with respect to 1 mol of the total amount of all silicon atoms. It is preferable to do so.
When the monoamine compound (C) is 0.01 mol or more, it is preferable because it is easily cured at a low temperature. Moreover, when the nitrogen atom derived from the amino group in the monoamine compound (C) is 0.20 mol or less, the coating is transparent, uniform, and high coating hardness can be easily obtained.

<Organic solvent (D)>
Any organic solvent (D) can be used as long as it dissolves polysiloxane (A), polysiloxane (B), and monoamine compound (C).
Specific examples of the organic solvent (D) include aliphatic alcohols such as methanol, ethanol, isopropanol, butanol, diacetone alcohol; alicyclic alcohols such as cyclopentyl alcohol, cyclohexanol; benzyl alcohol, cinnamyl alcohol, etc. Aromatic alcohols; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone; glycols such as ethylene glycol, propylene glycol, hexylene glycol; methyl cellosolve, ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, diethylene glycol monomethyl ether , Glycol ethers such as propylene glycol monomethyl ether and propylene glycol monobutyl ether; Glycol ester, ethyl acetate ester, and the like esters such as ethyl lactate ester. These single or plural organic solvents are used in combination.
Among them, at least one use selected from the group consisting of an alcohol having 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, and a glycol ether having preferably 3 to 10 carbon atoms, more preferably 3 to 7 carbon atoms. Is preferred.

<Acid component>
In the coating liquid for forming a film of the present invention, any of the case where the polysiloxane (A) and the monoamine compound (C) are used in combination or the case where the polysiloxane (A), the polysiloxane (B) and the monoamine compound (C) are used together. In this case, an acid component can be contained. This acid component can suppress the formation of gel during the production of the coating liquid for forming a film, and can improve the storage stability of the coating liquid for forming a film.
The acid used here is preferably an inorganic acid such as hydrochloric acid, nitric acid, sulfuric acid or phosphoric acid or an organic acid such as formic acid, acetic acid, malic acid, succinic acid, citric acid, propionic acid or succinic acid. When the acid is contained, the acid may be added directly to the coating solution, but it may be added as a solution dissolved in an organic solvent (D) or water, and polysiloxane (A) or polysiloxane (B). And / or added to the monoamine compound (C) or added to the solution thereof.
The acid content in the coating solution is preferably 0.01 to 2.5 mol, particularly preferably 0.1 to 2 mol, based on 1 mol of all silicon atoms of the polysiloxane (A). It is.

<Other ingredients>
In the present invention, other components other than polysiloxane (A), polysiloxane (B) and / or monoamine compound (C), for example, inorganic fine particles, leveling agent, surface activity, as long as the effects of the present invention are not impaired. A medium such as an agent or water may be contained.
As the inorganic fine particles, fine particles such as silica fine particles, alumina fine particles, titania fine particles, and magnesium fluoride fine particles are preferable, and those of a colloidal solution are particularly preferable. This colloidal solution may be a dispersion of inorganic fine particle powder in a dispersion medium or a commercially available colloidal solution. In the present invention, the inclusion of inorganic fine particles makes it possible to impart the surface shape of the formed cured film and other functions. 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. When the average particle diameter of the inorganic fine particles exceeds 0.2 μm, the transparency of the cured film formed by the prepared coating liquid may be lowered.
Examples of the dispersion medium for the inorganic fine particles include water and organic solvents. As a colloidal solution, it is preferable that pH or pKa is adjusted to 2 to 10 from the viewpoint of the stability of the coating liquid for forming a film. More preferably, it is 3-7.

Organic solvents used for the dispersion medium of colloidal solutions include alcohols such as methanol, isopropyl alcohol, ethylene glycol, butanol and ethylene glycol monopropyl ether, ketones such as methyl ethyl ketone and methyl isobutyl ketone, and aromatic carbonization such as toluene and xylene. Examples include hydrogens, amides such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone, esters such as ethyl acetate, butyl acetate, and γ-butyrolactone, and ethers such as tetrahydrofuran and 1,4-dioxane. . Of these, alcohols and ketones are preferred. These organic solvents can be used alone or in admixture of two or more as a dispersion medium.
Moreover, a leveling agent, surfactant, etc. can use a well-known thing, and since a commercial item is easy to acquire especially, it is preferable.

<Coating liquid for film formation>
The coating liquid for forming a film of the present invention is a solution containing polysiloxane (A) and at least one of polysiloxane (B) and monoamine compound (C), which is dissolved in an organic solvent (D). is there. In the present invention, the preparation method is not particularly limited as long as the coating liquid for forming a film is obtained. For example, you may add and mix sequentially in the organic solvent (D) which uses said each component. In this case, the order of adding each component is not particularly limited. Moreover, you may mix the solution which melt | dissolved in the organic solvent (D) which uses each component, respectively.
Moreover, polysiloxane (A) and polysiloxane (B) can be obtained in a solution state by polycondensation in an organic solvent. Therefore, for example, a method of mixing a solution containing polysiloxane (A) synthesized from polysiloxane (A) with a solution containing polysiloxane (B) synthesized from polysiloxane (B) and / or a monoamine compound (C). Is simple.
If necessary, the polysiloxane (A) solution is concentrated, diluted by adding a solvent, or substituted with another solvent, and then the polysiloxane (B) solution and / or monoamine compound ( It may be mixed with C). Furthermore, after mixing the solution of polysiloxane (A) with the solution of polysiloxane (B) and / or the monoamine compound (C), the organic solvent (D) can be added. In that case, you may use the solution of polysiloxane (B) as a solution which concentrated, diluted by adding a solvent, or substituted with the other solvent as needed.

  Moreover, when the above-mentioned acid component is contained in the coating solution, the acid may be added at any time. For example, a method of adding an acid to a polysiloxane (A) solution, a concentrated solution thereof or a diluted solution thereof, and then adding a monoamine compound (C), a solution of a polysiloxane (A), a concentrated solution thereof or a diluted solution thereof Examples thereof include a method of adding an acid to the mixed solution of polysiloxane (B) and then adding the monoamine compound (C). Moreover, the method etc. which add the solution which mixed the monoamine compound (C) and the acid previously, and add the solution of polysiloxane (A) after that are mentioned.

When preparing the coating solution for forming a film of the present invention, the polysiloxane (A) in the coating solution for forming a film, or the SiO ₂ equivalent concentration of all silicon atoms of the polysiloxane (A) and the polysiloxane (B) is: Preferably it is 0.5-15 mass%, Most preferably, it is 0.5-10 mass%. When the SiO ₂ equivalent concentration is lower than 0.5% by mass, it is difficult to obtain a desired film thickness by a single application, while when it exceeds 15% by mass, the pot life of the solution is less stable. The concentration in terms of SiO ₂ solid content in the coating solution can be determined by adding a solvent to dilute or substituting with another solvent.

The above-mentioned polysiloxane (A), polysiloxane (B), monoamine compound (C), acid component, and further, the solvent used for dilution and replacement of the coating solution are those components and other components added as necessary. It is not particularly limited as long as the compatibility with is not impaired, and one kind or plural kinds can be arbitrarily selected and used. For example, the organic solvent (D), in particular, the same solvent used for the polycondensation of the alkoxysilane may be used, or another solvent may be used.
Specific examples of such solvents include alcohols such as methanol, ethanol, isopropanol, butanol and diacetone alcohol, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, glycols such as ethylene glycol, propylene glycol and hexylene glycol, Methyl cellosolve, ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, glycol ethers such as diethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, esters such as acetic acid methyl ester, acetic acid ethyl ester, and lactate ethyl ester Is mentioned.

  Further, the method for incorporating the above-described other components in the coating solution is not particularly limited. For example, it may be added to any of polysiloxane (A), polysiloxane (B) and / or monoamine compound (C), or a mixture thereof. Further, the polysiloxane (A) and the polysiloxane (B) and / or the monoamine compound (C) may be added after mixing with the organic solvent (D).

In the present invention, specific examples of the coating liquid for forming a film are given below.
[1] A coating solution containing polysiloxane (A) and polysiloxane (B) and dissolved in an organic solvent (D).
[2] A coating solution containing the polysiloxane (A) and the monoamine compound (C) and dissolved in the organic solvent (D).
[3] A coating solution containing polysiloxane (A), polysiloxane (B), and monoamine compound (C), which are dissolved in an organic solvent (D).
[4] A coating solution containing inorganic fine particles in the above [1], [2] or [3].
[5] A coating liquid containing at least one selected from the group consisting of a leveling agent and a surfactant in the above [4].

In the coating liquid for forming a film of the present invention, the polysiloxane (A) is preferably 0.5 to 15% by mass, as the mass of all silicon atoms of the polysiloxane (A) converted to silicon dioxide. Preferably it is contained 0.5 to 10% by mass.
And when polysiloxane (B) is contained, the content of polysiloxane (B) is that of polysiloxane (B) with respect to 1 of the mass of all the silicon atoms of polysiloxane (A) converted to SiO ₂ . The mass of all silicon atoms converted to SiO ₂ is preferably 0.03 to 0.55, more preferably 0.05 to 0.55. If the mass of all the silicon atoms of polysiloxane (B) converted to SiO ₂ exceeds 0.55, sufficient film formability may not be obtained or the refractive index of the paint film may increase.

  Moreover, in the case where the monoamine compound (C) is contained, the monoamine compound (C) contains either the polysiloxane (A) alone or the polysiloxane (A) and the polysiloxane (B) in combination. In addition, the nitrogen atom derived from the amino group in the monoamine compound (C) is preferably 0.01 to 0.2 mol, more preferably 0.03 to 0.3 mol, with respect to 1 mol of the total amount of all silicon atoms of each. 1 mole. When the nitrogen atom derived from the amino group in the monoamine compound (C) is 0.01 mol or more, it is preferable because it is easily cured at a low temperature. Moreover, when it is 0.20 mol or less, the coating film is transparent, uniform, and high hardness of the coating film is easily obtained, which is preferable.

  In the present invention, a coating liquid for forming a film containing polysiloxane (A), polysiloxane (B) and monoamine compound (C) is preferable because it is easy to obtain a film having excellent scratch resistance.

<Formation of coating>
The coating liquid for forming a film of the present invention can be applied to a substrate and thermally cured to obtain a desired film. A known or well-known method can be adopted as the coating method.
For example, methods such as a dip method, a flow coating method, a spray method, a bar coating method, a gravure coating method, a roll coating method, a blade coating method, and an air knife coating method can be employed.
Examples of the base material include base materials such as plastic, glass, and ceramics. Examples of the plastic include polycarbonate, poly (meth) acrylate, polyethersulfone, polyarylate, polyurethane, polysulfone, polyether, and polyetherketone. And sheets and films of trimethylpentene, polyolefin, polyethylene terephthalate, (meth) acrylonitrile, triacetylcellulose, diacetylcellulose, acetate butyratecellulose, and the like.

The coating film formed on the substrate may be heat-cured as it is at a temperature of 20 to 70 ° C., for example, but prior to this, it may be dried at a temperature of 20 to 100 ° C. and then heat-cured. At that time, the time required for drying is preferably 10 seconds to 6 minutes. The time required for thermosetting can be appropriately selected according to desired film properties, but is usually 1 hour to 7 days. When a low curing temperature is selected, it is easy to obtain a coating film having sufficient scratch resistance by increasing the curing time.
Moreover, the coating liquid for forming a film of the present invention can provide a film having excellent scratch resistance even at a curing temperature exceeding 70 ° C.

<Applications such as antireflection materials>
The film formed from the coating liquid of the present invention has a feature that it has a low refractive index of 1.4 or less and excellent scratch resistance, and therefore it is particularly suitable for antireflection applications. it can.
When the coating of the present invention is used for antireflection applications, the coating of the present invention is formed on the surface of a substrate having a refractive index higher than that of the coating of the present invention, for example, a plastic film substrate. The base material can be easily converted into a base material having an antireflection ability, that is, an antireflection base material such as an antireflection film or antireflection glass. The coating of the present invention is effective when used as a single coating on the substrate surface, but is also effective when used in an antireflection laminate in which a coating is formed on a lower coating having a high refractive index. .

  The relationship between the thickness of the coating and the wavelength of light is described. Between the thickness d (nm) of the coating having a refractive index a and the wavelength λ (nm) of light for which a reduction in reflectance due to this coating is desired, It is known that the relational expression d = (2b−1) λ / 4a (wherein b represents an integer of 1 or more) is established. Therefore, by using this formula to determine the thickness of the coating, it is possible to easily prevent reflection of light having a desired wavelength. As a specific example, in order to form a film having a refractive index of 1.32 for light having a wavelength of 550 nm and prevent reflected light from the glass surface, these numerical values are substituted into λ and a in the above formula. Thus, the optimum film thickness can be calculated. At that time, any positive integer may be substituted for b. For example, the film thickness obtained by substituting 1 for b is 104 nm, and the film thickness obtained by substituting 2 for b is 312 nm. By adopting the film thickness thus calculated, it is possible to easily impart antireflection ability.

The thickness of the coating film formed on the substrate can be adjusted by the thickness of the coating film, but can also be easily adjusted by adjusting the SiO ₂ equivalent concentration of the coating solution.
The coating of the present invention can be suitably used in fields where antireflection of light is desired, such as a glass cathode ray tube, a computer display, a mirror having a glass surface, and a glass showcase. Furthermore, the coating film of the present invention has sufficient practicality in terms of antifouling properties such that fingerprints and oil-based inks can be easily wiped off, and can be sufficiently cured by a low-temperature treatment at a temperature of 20 to 70 ° C. It is particularly useful for an antireflection film for display devices such as plasma and display monitors.

Hereinafter, although a synthesis example, an Example, and a comparative example are shown and this invention is demonstrated concretely, this invention is restrict | limited to these following synthesis examples and examples, and is not interpreted.
Explanation of abbreviations in this embodiment.
TEOS: Tetraethoxysilane GPS: γ-Glycidoxypropyltrimethoxysilane FS-13: Tridecafluorooctyltrimethoxysilane
MEA: monoethanolamine CHA: cyclohexylamine IPA: isopropanol BCS: butyl cellosolve The measurement method in the following synthesis examples is shown below.

[Measurement of residual alkoxysilane monomer]
The residual alkoxysilane monomer in the polysiloxane (A) solution was measured by gas chromatography (hereinafter referred to as GC).
The GC measurement was performed under the following conditions using Shimadzu GC-14B manufactured by Shimadzu Corporation.
Column: Capillary column CBP1-W25-100 (length 25 m, diameter 0.53 mm, wall thickness 1 μm)
Column temperature: The temperature was raised at a starting temperature of 50 ° C. to 15 ° C./min to reach an ultimate temperature of 290 ° C. (holding time 3 minutes).
Sample injection volume: 1 μL, injection temperature: 240 ° C., detector temperature: 290 ° C., carrier gas: nitrogen (flow rate 30 mL / min), detection method: FID method.

[Synthesis Example 1]
57.26 g of methanol was put into a four-necked reaction flask equipped with a reflux tube, and 18.01 g of oxalic acid was added little by little with stirring to prepare a methanol solution of oxalic acid. The solution was then heated and a mixture of TEOS (17.71 g) and FS-13 (7.02 g) was added dropwise under reflux. After dropping, the mixture was refluxed for 5 hours and allowed to cool to room temperature to prepare a polysiloxane (A) solution (PF-1). When this polysiloxane (A) solution (PF-1) was measured by GC, no alkoxysilane monomer was detected.

[Synthesis Examples 2-3]
With the composition shown in Table 1, polysiloxane (A) solutions (PF-2 to PF-3) were obtained in the same manner as in Synthesis Example 1. At that time, as in Synthesis Example 1, a plurality of types of alkoxysilanes were mixed and used in advance.
When the obtained polysiloxane (A) solutions (PF-2 to PF-3) were measured by GC, no alkoxysilane monomer was detected.

[Synthesis Example 4]
A 4-necked reaction flask equipped with a reflux tube was charged with 31.78 g of ethanol, 0.18 g of oxalic acid and 10.80 g of pure water, 29.16 g of TEOS and FS-1328.08 g were added with stirring, and the mixed solution was added. Prepared. The solution was then heated to reflux for 3 hours and then allowed to cool to room temperature to prepare a polysiloxane (A) solution (PF-4A). When this polysiloxane (A) solution (PF-4A) was measured by GC, no alkoxysilane monomer was detected.
Meanwhile, 81.99 g of ethanol and 18.01 g of oxalic acid were charged into a four-necked reaction flask equipped with a reflux tube, and heated for 5 hours with stirring to prepare an acidic solution (PF-4B).
Then, 50.00 g of the polysiloxane (A) solution (PF-4A) and 50.00 g of the acidic solution (PF-4B) were mixed to prepare a polysiloxane (A) solution (PF-4).

[Synthesis Example 5]
Into a four-necked reaction flask equipped with a reflux tube, 33.35 g of ethanol was added, 34.79 g of TEOS was added with stirring, and then 0.15 g of oxalic acid, 14.99 g of water and 16.68 g of ethanol were mixed uniformly in advance. The solution was added dropwise little by little. Then, this solution was heated, stirred under reflux for 1 hour, and allowed to cool to room temperature to prepare a polysiloxane (B) solution (PS-1). When this polysiloxane (B) solution (PS-1) was measured by GC, no alkoxysilane monomer was detected.

[Synthesis Example 6]
To the eggplant flask, 48.59 g of ethanol was added, 34.68 g of TEOS was added with stirring, and then a diluted solution obtained by adding 1.74 g of 60% nitric acid aqueous solution to 14.99 g of water was added dropwise little by little. Then, it stirred at room temperature for 1 hour, and prepared the solution (PS-2) of polysiloxane (B). When this polysiloxane (B) solution (PS-2) was measured by GC, no alkoxysilane monomer was detected.

[ Examples 1 to 12, Comparative Example 1]
With the composition shown in Table 2, a coating solution for forming a film (Q1 to Q12) was prepared by mixing a solution of polysiloxane (A), a solution of polysiloxane (B), a monoamine compound and a solvent.
Of Examples 1 to 12, Examples 1 to 5 are reference examples, and Examples 6 to 12 are examples of the present invention. In Comparative Example 1 , a coating solution (T1) was prepared by mixing a polysiloxane (A) solution and a solvent having the composition shown in Table 2.
About these Q1-Q12 and T1, or the coating film using them, evaluation shown below was performed.

The Si molar ratio of (A) / (B) represents the molar ratio of Si atoms of polysiloxane (A) and Si atoms of polysiloxane (B).

Example 13 ( Example )
PF-4 (33.33 g), CHA 0.20 g, cyclohexyl alcohol 5.00 g, propylene glycol monomethyl ether 20.00 g, and IPA 41.47 g were mixed to prepare a coating forming coating solution (Q13).
The coating film using Q13 was evaluated as follows.

<Storage stability>
The coating solution was allowed to stand at a temperature of 25 ° C. for 1 month, and then 100 cc was filtered through a non-aqueous polytetrafluoroethylene filter having a pore diameter of 0.45 μm and Φ × L: 18 × 22 mm (Chromatodisc 13N manufactured by Kurashiki Boseki Co., Ltd.). What was possible was marked with ◯, and what was clogged was marked with ×.
The results are shown in Table 3.
<Evaluation of cured film>
The prepared coating liquids (Q1 to Q13 and T1) were applied to a triacetyl cellulose (hereinafter referred to as TAC) film (film thickness of 80 μm, reflectance at a wavelength of 550 nm of 4.5%) subjected to the following treatment. Coating was performed using a coater (No. 3) to form a coating film. After leaving at a temperature of 23 ° C. for 30 seconds, it was dried in a clean oven at 100 ° C. for 5 minutes and then cured at a temperature of 60 ° C. for 3 days. About the obtained hardened film, water contact angle, oil-based pen wiping property, fingerprint wiping property, adhesion, reflectance, and scratch resistance were evaluated.

The refractive index was measured using a cured film formed as follows. The prepared coating solutions (Q1 to Q13 and T1) are spin-coated on a silicon wafer to form a coating film, left at a temperature of 23 ° C. for 30 seconds, and then dried at 100 ° C. for 5 minutes in a clean oven. Then, it was cured at a temperature of 60 ° C. for 3 days to obtain a cured film having a film thickness of 100 nm.
These evaluation methods are as follows, and the evaluation results are shown in Tables 3 and 4.

[TAC film surface treatment method]
A TAC film with a hard coat (film thickness of 80 μm) manufactured by Nippon Paper Industries Co., Ltd. was immersed in a 5% by weight aqueous potassium hydroxide (KOH) solution heated to 40 ° C. for 3 minutes for alkali treatment, then washed with water, The mixture was neutralized by immersing in a 5% by mass sulfuric acid (H ₂ SO ₄ ) aqueous solution (liquid temperature: 23 ° C.) for 30 seconds, washed with water and dried.
[Water contact angle]
Using an automatic contact angle meter CA-Z type manufactured by Kyowa Interface Science Co., Ltd., the contact angle when 3 microliters of pure water was dropped was measured.

[Oil pen wiping off]
The ink applied to the surface of the cured coating using a Pentel oil pen was wiped off using Asahi Kasei Bencot M-3, and the ease of removal was visually determined. The ink was completely wiped off, and the others were marked with x.
[Fingerprint wiping properties]
Fingerprints were attached to the surface of the cured coating, wiped with Bencot M-3 manufactured by Asahi Kasei Co., Ltd., and the ease of removal was visually determined. The fingerprint was completely wiped off, and the others were marked with x.

[Adhesion]
Cut 100 points in a grid pattern at 1 mm intervals on the cured film on the substrate, and strongly attach cello tape (Nichiban Co., Ltd., 24 mm width) to the cured film, then peel off the cello tape rapidly to remove the cured film. The presence or absence was confirmed visually. The case where there was no peeling was marked with ◯, and the case where there was peeling was marked with ×.

[Reflectance]
Using a spectrophotometer UV3100PC manufactured by Shimadzu Corporation, light having a wavelength of 550 nm was incident on the cured film at an incident angle of 5 degrees, and the reflectance was measured.

[Abrasion resistance]
The cured film was rubbed 10 reciprocally at 400 g / cm ² using steel wool # 0000 manufactured by Nippon Steel Wool Co., Ltd., and the scratched surface of the cured film was visually determined.
Judgment criteria are as follows.
A: No scratch ~ 5, B: 6-10 scratches, C: 11-20 scratches, D: 21 or more scratches

[Refractive index]
The refractive index of light having a wavelength of 633 nm was measured using Ellipsometer DVA-36L manufactured by Mizoji Optical Co., Ltd.

As shown in Tables 3 and 4, the cured coatings obtained from the coating liquids of Examples 1 to 13 had excellent characteristics of scratch resistance of B or higher at a curing temperature of 60 ° C. and a water contact angle of 100. Excellent characteristics were exhibited.
In particular, in Examples 6 to 10, which are examples of the present invention, a cured film obtained from a coating solution containing polysiloxane (A), polysiloxane (B) and monoamine compound (C) was manufactured by Nippon Steel Wool Co., Ltd. Using steel wool # 0000, rubbing 10 reciprocations at 400 g / cm ² , and visually determining how the cured film surface was scratched, all the cured films showed excellent characteristics of scratch resistance A. .

And the storage stability of the coating liquid (Q1-Q13) was also favorable, and was stable after storage for 6 months at a temperature of 23 ° C.
Furthermore, the cured coatings obtained from the coating liquids of Examples 1 to 13 exhibited characteristics such as a low refractive index of 1.400 or less and a low reflectance.
On the other hand, Comparative Example 1 using the coating solution (T1) having no solution of the monoamine compound (C) and the polysiloxane (B) had an insufficient scratch resistance of D at a curing temperature of 60 ° C. It was.
In addition, as shown in Tables 3 and 4, the cured coatings obtained from the coating liquids of Examples 1 to 13 were excellent in antifouling properties such as fingerprint wiping properties and oil-based pen wiping properties, and adhered to the substrate. It was highly probable.

[ Examples 14 to 15 (Examples) ]
The prepared coating liquid Q6 was applied to the TAC film (film thickness 80 μm, reflectance 4.5% at a wavelength of 550 nm) subjected to the alkali treatment described above using a bar coater (No. 3), and the coating film Formed. After leaving at a temperature of 23 ° C. for 30 seconds, it was dried in a clean oven at 100 ° C. for 5 minutes, and then Example 14 was at a temperature of 23 ° C. for 5 days, and Example 15 was at a temperature of 40 ° C. for 3 days. A cured film was obtained under the following curing conditions. The obtained cured film was evaluated for adhesion, reflectance and scratch resistance. These evaluation methods are as follows, and the evaluation results are shown in Table 5.

As shown in Example 14 and Example 15, the cured film of the present invention, the curing temperature has been shown to be excellent in 23 ° C. and 40 ° C. But scratch resistance.

[Reference example]
The prepared coating solution Q1 was applied to the TAC film (film thickness of 80 μm, reflectance at a wavelength of 550 nm of 4.5%) subjected to the alkali treatment described above using a bar coater (No. 3). Formed. After leaving at a temperature of 23 ° C. for 30 seconds, it was dried in a clean oven at 100 ° C. for 5 minutes. And immediately after standing to cool to the temperature of 23 degreeC, the water contact angle, oil-based pen wiping property, fingerprint wiping property, adhesiveness, reflectance, and scratch resistance were evaluated about this film by the same method as an Example. As a result, the water contact angle is larger than 100 ° (> 100 °), the oil pen wiping property is ○, the fingerprint wiping property is ○, the adhesion property is ○, the reflectance is 1.4%, and the scratch resistance is 400 g / cm. D at ² loads.

The coating liquid for forming a film of the present invention is excellent in storage stability, can be sufficiently cured by a low-temperature heat treatment at a temperature of 20 to 70 ° C., and can provide a film having a low refractive index and excellent scratch resistance. Therefore, it can be suitably used particularly for an antireflection substrate, and in particular, can be suitably used for an antireflection film for a display element.

The specification, claims and abstract of Japanese Patent Application No. 2006-060808 filed on March 7, 2006 and Japanese Patent Application No. 2006-356192 filed on December 28, 2006 are as follows. The entire contents are hereby incorporated by reference as the disclosure of the specification of the present invention.

Claims (16)

Polysiloxane (A) and the motor Noamin compound is a polysiloxane having an organic group having a fluorine atom (C) contains a further inorganic or organic acids, the total amount of the silicon atoms of the polysiloxane (A) A coating liquid for forming a film , which is contained in an amount of 0.01 to 2.5 moles per mole and dissolved in an organic solvent (D).   The coating liquid for film formation according to claim 1, further comprising a polysiloxane (B) represented by the formula (1).

(R ¹ , R ² , R ³ And R ⁴ Each independently represents a hydrogen atom or a saturated hydrocarbon group having 1 to 5 carbon atoms, and n represents an integer of 2 or more. ) The coating solution for forming a film according to claim 1 or 2 , wherein the polysiloxane (A) is a polysiloxane obtained by polycondensation of an alkoxysilane containing an alkoxysilane represented by the formula (2).

(R ⁵ is an organic group having a fluorine atom, and R ⁶ represents a hydrocarbon group having 1 to 5 carbon atoms.) The film formation according to any one of claims 1 to 3, wherein the polysiloxane (A) is a polysiloxane obtained by polycondensation using at least one alkoxysilane represented by the formula (3). Coating liquid.

^{(R 7} is an organic group having a hydrogen atom, or a fluorine atom having no carbon atoms 1 to 20, ^{R 8} is a hydrocarbon group having 1 to 5 carbon atoms, m represents an integer of 0 to 3.) The coating liquid for film formation according to any one of claims 1 to 4 , wherein the organic group having a fluorine atom of the polysiloxane (A) is a perfluoroalkyl group. The organic group which has a fluorine atom is 0.05-0.4 mol with respect to 1 mol of total amounts of the silicon atom which polysiloxane (A) has, It is any one of Claims 1-5 The coating liquid for film formation as described. The coating liquid for film formation according to any one of claims 1 to 6 , wherein the monoamine compound (C) is at least one selected from the group consisting of aliphatic amines and alkanolamines. The value obtained by converting the total amount of all silicon atoms of polysiloxane (A) or polysiloxane (A) and polysiloxane (B) into silicon dioxide is 0.5 to 15% by mass in the coating solution. film-forming coating liquid according to any one of 1-7. Polysiloxane (B) is, relative to 1 mole of total silicon atoms of the polysiloxane (A), of the claims 2-8 in which all the silicon atoms of the polysiloxane (B) is contained 0.05 to 0.55 moles The coating liquid for film formation as described in any one of these. When the monoamine compound (C) is polysiloxane (A) or the total amount of all silicon atoms of the polysiloxane (A) and polysiloxane (B) is 1 mol, the nitrogen atom derived from the amino group in the monoamine compound (C) The coating liquid for film formation according to any one of claims 1 to 9 , which is contained in an amount of 0.01 to 0.2 mol.   The low-refractive-index film obtained by heat-curing the coating liquid for film formation as described in any one of Claims 1-10.   The antireflective material in which the low-refractive-index film of Claim 11 was formed on the surface of the base material which has a higher refractive index.   The coating solution for forming a film according to any one of claims 1 to 12 is applied to a substrate, dried at a temperature of 20 to 100 ° C for 10 seconds to 6 minutes, and then cured at a temperature of 20 to 70 ° C. A method for forming a low refractive index film. A solution of an organic solvent of polysiloxane (A) containing 0.01 to 2.5 mol of an inorganic acid or an organic acid with respect to 1 mol of the total amount of all silicon atoms of polysiloxane (A), and a monoamine compound ( The manufacturing method of the coating liquid for film formation as described in any one of Claims 1-10 which mixes C) and an organic solvent (D).   A solution of an organic solvent of polysiloxane (A) containing 0.01 to 2.5 mol of an inorganic acid or an organic acid with respect to 1 mol of the total amount of all silicon atoms of polysiloxane (A), and polysiloxane ( The manufacturing method of the coating liquid for film formation as described in any one of Claims 2-10 which mixes B), a monoamine compound (C), and an organic solvent (D). A solution of an organic solvent of polysiloxane (A) is obtained by heating an alkoxysilane containing an alkoxysilane represented by formula (2) and an acid in an organic solvent (D), and the amount of the acid is The method for producing a coating liquid for forming a film according to claim 14 or 15 , which is a polysiloxane solution obtained in a range of 0.2 to 2 mol with respect to 1 mol of the total alkoxy group amount of the alkoxysilane.