WO2008044742A1 - Coating solution for formation of low refractive coating film, process for production thereof, and anti-reflection material - Google Patents

Abstract

Disclosed is a coating solution for the coating film formation, which can be cured at a low temperature even on a substrate having a high water contact angle and enables to form a coating film having high light permeability, high hardness, excellent scratch resistance and a low refractivity. Also disclosed is a process for producing the coating solution. Further disclosed is an anti-reflection material prepared by using the coating film. Specifically disclosed is a coating solution for forming a low refractive coating film, which comprises (A) a polysiloxane having a silicon atom to which a fluorinated organic group is attached, (B) a long-chain amine compound having 9 to 20 carbon atoms, and (C) an organic solvent in which the polysiloxane (A) and the long-chain amine compound (B) are dissolved.

Description

 Specification

 Coating liquid for forming low refractive index film, production method thereof and antireflection material

 Technical field

 The present invention relates to a coating solution for forming a low refractive index film containing polysiloxane, and a method for producing the same

, A low refractive index film formed from the coating liquid, and an antireflection material having the film

Yes

 Background art

 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 reduced. Yes. Such a low refractive index film exhibiting a reduced light reflectance is used as a light reflection preventing film and applied to various substrate surfaces.

 [0003] For example, Patent Document 1 discloses an alcohol dispersion of MgF fine particles formed by reacting a magnesium salt or an alkoxymagnesium compound as an Mg source with a fluoride salt as an F source, or a mixture thereof. Anti-reflective film showing low refractive index on the substrate by applying a solution containing tetraalkoxysilane to improve the film strength and applying it to a glass substrate and heat-treating it at a temperature of 100-500 ° C. A method of forming a film is disclosed.

 [0004] In addition, Patent Document 2 discloses a hydrolytic polycondensate such as tetraalkoxysilane, which is a coating liquid obtained by mixing two or more types having different average molecular weights and a solvent such as alcohol. In forming a coating film, it is disclosed that a coating film is prepared 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. 1. 21-; 1. Refractive index of 40, micropits or irregularities having a diameter of 50-200 nm, thickness 60- Has 160 nm. The coating is formed on a glass substrate to produce a low reflection glass.

 [0005] Further, 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. Is disclosed. Formation of the upper layer film is made of polyfluoro, such as CF (CF) C H Si (OCH)

 3 2 2 2 4 3 3

Fluorine-containing silicone compound having carbon chain and 5 to 90% by mass of Si (〇C H) and a silane coupling agent in an alcohol solvent in the presence of a catalyst such as acetic acid.

3 4

 The method is carried out by applying a cocondensate solution prepared by hydrolysis at room temperature, followed by filtration onto the lower layer film and heating at a temperature of 120 to 250 ° C.

[0006] Patent Document 4 discloses a silicon compound represented by Si (OR) and CF (CF) CH CH S

4 3 2 n 2 2 i COR ¹ ), an alcohol represented by R ² CH OH, and oxalic acid.

3 2

 Disclosed is a coating solution in which a polysiloxane solution is produced by heating a reaction mixture containing a constant ratio in the absence of water at a temperature of 40 to 180 ° C. By applying this coating solution to the surface of the substrate and thermosetting at a temperature of 80-450 ° C, a film having a refractive index of 1.28-1.38 and a water contact angle of 90-115 degrees is formed. Yes.

[0007] Patent Document 1: Japanese Patent Laid-Open No. 05-105424

 Patent Document 2: Japanese Patent Laid-Open No. 06-157076

 Patent Document 3: Japanese Patent Laid-Open No. 61-010043

 Patent Document 4: Japanese Patent Laid-Open No. 09-208898

 Disclosure of the invention

 Problems to be solved by the invention

 [0008] The antireflection film used in various display devices as described above is an antireflection base material used for display devices such as liquid crystals and plasmas that have recently become larger, lighter, and thinner. In particular, the antireflection film tends to reduce the thickness of the film for the purpose of weight reduction and high transparency, and there is a problem that damage caused by heat increases. For this reason, there has been an increasing demand for a thermosetting coating film-forming coating solution that can be cured at a relatively low temperature, which can obtain an antireflection substrate by a low-temperature treatment that does not damage the film. It was desired. However, it is desired that the curing temperature of the conventional low refractive index coating as described above is further lowered even if it is not sufficiently low.

[0009] Further, the antireflection film used in the various display devices described above is formed on the surface of a film substrate such as a hard coated triacetinole cellulose film or a hard coated polyethylene terephthalate finalene from the substrate. Is also obtained by forming a film having a low refractive index. In this case, the water contact angle on the surface of the base film on which the low refractive index film is formed may have various sizes depending on the material of the hard coat and the presence or absence of a surface treatment such as a hydrophilic treatment. However, conventionally, it has been difficult to form a high hardness, low refractive index film having high scratch resistance on a substrate film having a high water contact angle.

 Therefore, the object of the present invention is to sufficiently cure even at a relatively low temperature even on a substrate having a high water contact angle, and to have a low refractive index excellent in high light transmission (high transparency), high hardness and scratch resistance. A coating solution for forming a low refractive index film capable of forming a film having a low refractive index, a method for producing the same, a film obtained from the coating liquid for forming a low refractive index film, and an antireflection material using the film. It is in.

 Means for solving the problem

 [0010] As a result of intensive studies to achieve the above object, the present inventors have found that a polysiloxane (A) having a silicon atom to which a fluorine-containing organic group is bonded, and a long-chain amine having 9 to 20 carbon atoms. The film obtained from the coating solution containing the compound (B) and the organic solvent (C) is cured at a low temperature even on a substrate having a high water contact angle exceeding 90 degrees, and has high light transmittance. The present inventors have found that it has a low refractive index with excellent hardness and excellent scratch resistance.

 In the present invention, the mechanism of why the film formed from the coating solution has the above-mentioned excellent properties is not necessarily clear, but the polysiloxane contained in the coating solution of the present invention is not necessarily clear. When (A) does not have a fluorine-containing organic group, a film having a low refractive index cannot be obtained. Further, the long-chain amin compound (B) having 9 to 20 carbon atoms is cured at a relatively low temperature, and gives a coating film having high hardness and excellent scratch resistance. However, if the number of carbon atoms of the amine compound (B) is smaller than 9, sufficient scratch resistance may not be obtained on a surface film substrate having a high water contact angle exceeding 90 degrees. In addition, when the number of carbons exceeds 20, sufficient film forming properties may not be obtained on a film substrate having a surface with a high water contact angle exceeding 90 degrees. May not be achieved.

 [0011] In summary, the present invention has the gist characterized by the following.

 (1) Contains a polysiloxane (A) having a silicon atom to which a fluorine-containing organic group is bonded, and a long-chain amine compound (B) having 9 to 20 carbon atoms, which are dissolved in an organic solvent (C). A coating solution for forming a low refractive index film, characterized in that

(2) The coating solution according to the above (1), wherein the polysiloxane (A) has 5 to 40 mol% of silicon atoms having fluorine-containing organic groups bonded to all the silicon atoms. (3) The coating solution according to (1) or (2), wherein the long chain amine compound (B) is a linear aliphatic primary amine or secondary amine, or an aliphatic amine having an alicyclic structure.

 (4) Any of (1) to (3) above, wherein the organic solvent (C) comprises at least one selected from the group consisting of alcohols having 1 to 6 carbon atoms and 3 to carbon atoms; glycol ethers having 10 carbon atoms The coating liquid according to Crab.

 (5) Polysiloxane (A) contains a total amount of silicon atoms of 0.;! To 15% by mass in terms of silicon dioxide, and the long chain amine compound (B) is a key of polysiloxane (A). The coating solution according to any one of the above (1) to (4), which is contained in an amount of 0.01 mol to 0.2 mol per mol of the total amount of elementary atoms.

 (6) The coating solution according to any one of (1) to (5) above, further containing a silicon compound (D) represented by the formula (1).

R²、 R³及び R⁴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。 ) (Where

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

 (7) A low refractive index film obtained by curing the coating solution according to any one of (1) to (6) above.

(8) An antireflection material, wherein the low refractive index film according to (7) is formed on the surface of a substrate having a higher refractive index.

(9) The concentration of the alkoxysilane containing 5 to 40 mol% of alkoxysilane having a silicon atom bonded with a fluorine-containing organic group is 4 to 4 in an organic solvent by converting all the silicon atoms of the alkoxysilane to silicon dioxide. A step of polycondensation of a solution of 15% by mass in the presence of 0.2 to 2 mol of oxalic acid with respect to 1 mol of all alkoxide groups of the alkoxysilane to obtain a solution of polysiloxane (A); And a step of mixing a mixed solution of a long chain amine compound (B) having 9 to 20 carbon atoms and an organic solvent (C) with the obtained polysiloxane (A) solution. A method for producing a coating solution for forming a low refractive index film.

 The invention's effect

 [0012] According to the present invention, the water contact angle is high! / Relatively low even on the substrate! / Temperature! / Sufficiently hardened, high light transmission (high transparency), high hardness A coating solution for forming a coating film having a low refractive index excellent in scratch resistance and an efficient production method thereof are provided. In addition, according to the present invention, there are provided a low refractive index coating film obtained from the coating solution and having high hardness and excellent scratch resistance, and an antireflection material using the coating film.

 BEST MODE FOR CARRYING OUT THE INVENTION

 [0013] The present invention is described in further detail below.

 <Polysiloxane (A)>

 The main skeleton has a key atom to which fluorine-containing organic groups contained in the coating solution for forming a low refractive index film of the present invention (hereinafter also simply referred to as a coating solution for forming a film or a coating solution) is bonded. The polysiloxane (A) (hereinafter also simply referred to as polysiloxane (A)) is an organic group bonded to a carbon atom in the main skeleton and substituted with a fluorine atom (in the present invention, a fluorine-containing organic compound). A polysiloxane having a group in which an organic side chain substituted with a fluorine atom is bonded to a carbon atom.

 As the above-mentioned fluorine-containing organic group, an organic group in which part or all is substituted with fluorine, usually an alkyl group in which some hydrogen atoms are substituted with fluorine atoms, or some hydrogen atoms are fluorine atoms. Often it is an alkyl group containing a substituted ether bond! The number of fluorine atoms that the fluorine-containing organic group has is not particularly limited.

 [0014] When the carbon number of the fluorine-containing organic group exceeds 12, the solubility in an organic solvent (C) described later may be insufficient. Therefore, an organic group having 3 to 12 carbon atoms is preferred. More preferably, it has 3 to 10 carbon atoms. Examples of the fluorine-containing organic group include, but are not limited to, a trifluoropropyl group, a tridecafluorooctyl group, a heptadecafluorodecyl group, and a pentafluorophenylpropyl group. ,.

Among the fluorine-containing organic groups, a group having a perfluoroalkyl group at the end and having a hydrocarbon alkylene group bonded to the group, preferably having 3 to 15 carbon atoms, provides a highly transparent coating. Since it is easy, it is suitable. Preferred examples thereof include trifluoropropyl group, tride Examples thereof include a strong fluoroctyl group and a heptadecafluorodecyl group. The polysiloxane (A) may have one or more types of fluorine-containing organic groups as described above.

 [0015] The polysiloxane (A) is not particularly limited as long as it forms a homogeneous solution in the coating solution. In particular, when it is 5 to 40 mol% of all the silicon atoms of the above-described fluorine-containing organic group bonded with the fluorine-containing organic group, a film having a water contact angle of 90 degrees or more can be obtained immediately. This is preferable because a homogeneous polysiloxane (A) solution can be easily obtained. In addition, it is preferable that the number of silicon atoms to which fluorine-containing organic groups are bonded is 10 to 40 mol% of all the silicon atoms of polysiloxane (A) because the reflectance can be further reduced. Further, when it is 5 to 25 mol% in all the silicon atoms of the carbon atomic polysiloxane (A) to which the fluorine-containing organic group is bonded, it is preferable because the scratch resistance can be further improved.

To sum up the above reasons, Kei hydrogen atom bonded to a fluorine-containing organic group, particularly preferably 10 to 25 mole _^0/0 of the total Kei atom of the polysiloxane (A).

 [0016] The method for obtaining the polysiloxane (A) having a fluorine-containing organic group is not particularly limited. In general, it is obtained by condensation polymerization of the above-mentioned alkoxysilane having a fluorine-containing organic group, or the alkoxysilane and another alkoxysilane. In particular, when polycondensing an alkoxysilane having a fluorine-containing organic group, a tetraalkoxysilane, and, if necessary, an alkoxysilane other than the above (hereinafter also referred to as other alkoxysilane), a stable and homogeneous polysilane is used. It is preferable because a solution of siloxane (A) is easily obtained!

[0017] Examples of the alkoxysilane having a fluorine-containing organic group include alkoxysilanes represented by the following formula (2). In the formula, R ¹ is a fluorine-containing organic group, and R ² is a hydrocarbon group having 1 to 5 carbon atoms.

力、かるアルコキシシランの好まし!/、具体例としては、トリフルォロプロピルトリメトキシ シシラン、ヘプタデカフルォロデシルトリエトキシシラン等が挙げられる。 また、含フッ素有機基を持つアルコキシシランと縮重合されるテトラアルコキシシラン の具体例としては、テトラメトキシシラン、テトラエトキシシラン、テトラプロボキシシラン 、テトライソプロボキシシラン、テトラブトキシシラン等が挙げられる。テトラアルコキシシ ランは一種単独で使用してもよいし、複数種を併用することもできる。 [Chemical 2]

Preferable alkoxy silane! /, For example, trifluoropropyltrimethoxy Examples include silane, heptadecafluorodecyltriethoxysilane, and the like. Specific examples of tetraalkoxysilanes that are polycondensated with alkoxysilanes having fluorine-containing organic groups include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, and tetrabutoxysilane. . Tetraalkoxysilane may be used alone or in combination of two or more.

[0018] The other alkoxysilane is an alkoxysilane in which an organic group other than a fluorine-containing organic group and / or a hydrogen atom is bonded to a silicon atom. Specific examples of such other alkoxysilanes are listed below. Trimethoxysilane, Triethoxysilane, Methyltrimethoxysilane, Methyltriethoxysilane, Ethyltrimethoxysilane, Ethyltriethoxysilane, Propyltrimethoxysilane, Propyltriethoxysilane, Butyltrimethoxysilane, Butinotritriethoxysilane, Pentino Retrimethoxysilane, pentinotritriethoxysilane, octyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, hexadecyltrimethoxysilane, hexadecyltriethoxysilane, octadecyltrimethoxysilane, octadecyl triethoxysilane, phenylalanine trimethoxysilane, Fuenirutori silane, Bulle trimethoxysilane, Bulle triethoxysilane, _I Aminopuropiru Torimetoki _Silane, Ί - § amino propyl _{triethoxysilane,} Ί - glycidoxypropyltrimethoxysilane, _I over-glycidoxy propyl Honoré triethoxysilane, _I over methacryloxy propyl

Other alkoxysilanes may be used alone or in combination of two or more.

[0019] The amount of the alkoxysilane having a fluorine-containing organic group used for obtaining the polysiloxane (Α) is such that the polysiloxane (Α) is in a homogeneous solution state in the organic solvent (C). It is not limited as long as the effect is not impaired. In particular, when the alkoxysilane having a fluorine-containing organic group is 5 to 40 mol% of the total alkoxysilane, the contact angle of water is 90%. It is preferable because a coating of higher degree can be obtained and a homogeneous polysiloxane (A) solution is easily obtained. Moreover, the alkoxysilane force having a fluorine-containing organic group is preferably 10 to 40 mol% of the total alkoxysilane because the reflectance can be further reduced. Moreover, it is preferable that the alkoxysilane having a fluorine-containing organic group is 5 to 25 mol% of the total alkoxysilane because the scratch resistance can be further improved.

To sum up the above reasons, an alkoxysilane having a fluorine-containing organic group, particularly preferably 10 to 25 mole _^0/0 of the total alkoxy Shishiran.

[0020] As a method for obtaining the polysiloxane (A) having a fluorine-containing organic group, for example, an alkoxysilane having a fluorine-containing organic group and, if necessary, an organic solution of tetraalkoxysilane and other alkoxysilanes are oxalic acid. And polycondensation by heating in the presence of. Specifically, after adding succinic acid to alcohol in advance to make an alcohol solution of succinic acid, the above various alkoxysilanes are mixed while the solution is heated. The amount of succinic acid present is preferably 0.2 to 2 moles per mole of all alkoxy groups of the alkoxysilane used. The heating can be performed at a liquid temperature of preferably 0 to 180 ° C, and preferably under reflux in a vessel equipped with a reflux pipe so that the liquid does not evaporate or volatilize. Dozens of tens of thousands of hours.

[0021] In the case of obtaining the polysiloxane (A) having a fluorine-containing organic group, when a plurality of alkoxysilanes are used, a mixture in which alkoxysilanes are mixed in advance may be used, or a plurality of types of alkoxysilanes may be used. You may add to a reaction system one by one.

 When the alkoxysilane is polycondensed, the concentration of all the alkoxysilane atoms in the organic solvent converted to oxide (hereinafter referred to as the SiO equivalent concentration) is preferably 2

 2

 It is suitable to heat in the range of 0% by mass or less, particularly preferably 4 to 15% by mass. By selecting such a concentration range, it is possible to suppress gel formation and obtain a homogeneous polysiloxane (A) solution night.

[0022] The organic solvent used for polycondensation of the alkoxysilane (hereinafter also referred to as a polymerization solvent) is not particularly limited as long as it dissolves the alkoxysilane. In general, since an alcohol is produced by a polycondensation reaction of alkoxysilane, an organic solvent having good compatibility with alcohols and alcohols is used. In particular, alcohols, glyco Nores or dallicol ethers are preferred. Specific examples of such a polymerization solvent include methanol, ethanol, propanol, n-butanol, etc. Examples thereof include glycol ethers such as Noleyatenore and Diethyleneglycolenomethinoretinoetenore. The above organic solvents can be used in combination.

In the present invention, for the polysiloxane (A) having a fluorine-containing organic group, the solution obtained by the above-mentioned method may be used as it is as the polysiloxane (A) solution, and if necessary, The solution obtained by the above method may be concentrated, diluted by adding a solvent, or substituted with another solvent to obtain a polysiloxane (A) solution! /.

 When substituting with another solvent, the solvent (hereinafter, also referred to as “substitution solvent”) may be the same solvent used for polycondensation or may be another solvent. This solvent is not particularly limited as long as the polysiloxane (A) is uniformly dissolved, and it can be selected with one or more kinds and used with a force S.

 [0024] Specific examples of the substitution solvent include alcohols such as methanol, ethanol, isopropanol, butanol, and diacetone alcohol; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ethylene glycol Glyconoles such as propylene glycolenole, hexylene glycolenole; methinorecero sonoleb, ethinorecero sonoleb, butinorecello sonoreb, ethinorecanorebitonore, butinorecanolebitonore, diethyleneglycolenomonoethenore, propylene Examples include glycol ethers such as glyconomonomethinoleethenole and propylene glycolenomonomonobutyl ether; esters such as acetic acid methyl ester, acetic acid ethyl ester, and lactic acid ethyl ester.

 <Long-Chain Amine Compound (B)>

The long-chain amin compound (B) having 9 to 20 carbon atoms (hereinafter also referred to as long-chain ammine compound (B)) contained in the coating liquid of the present invention is a monoamine compound having 9 to 20 carbon atoms. is there. The long chain amine compound (B) may have an alicyclic structure that is preferred by aliphatic amines. When the long chain amine compound (B) has 9 or more carbon atoms, sufficient film formability is easily obtained even on a film substrate having a surface with a high water contact angle exceeding 90 degrees. The number of carbon atoms is preferably 10 or more. On the other hand, when the number of carbon atoms exceeds 20, it is sufficient on a film substrate with a surface with a high water contact angle. In some cases, it is difficult to obtain a good coatability. Of these, the carbon number is preferably 18 or less.

 The long chain amine compound (B) may be any of primary amine, secondary amine or tertiary amine.

. Specific examples of each are listed below, but are not limited thereto.

 [0026] Primary amines include CH (CH) NH, CH (CH) NH, CH (CH) NH, C

 3 2 8 2 3 2 9 2 3 2 10 2

H (CH) NH, CH (CH) NH, CH (CH) NH, CH (CH) NH, CH

3 2 11 2 3 2 12 2 3 2 13 2 3 2 14 2 3

(CH) NH, CH (CH) NH, CH (CH) NH, CH (CH) NH, CH (C

2 15 2 3 2 16 2 3 2 17 2 3 2 18 2 3

H) NH, etc. linear amines; (CH) CH (CH) NH, CH (CH) CH (CH) N

2 19 2 3 2 2 6 2 3 2 6 3

H, CH (CH) CH (CH) NH, CH (CH) CH (CH) NH, CH (CH) CH

2 3 2 8 3 2 3 2 10 3 2 3 2 11

Examples thereof include branched amines such as (CH 2) NH and CH (CH 2) CH (CH 2) NH.

 3 2 3 2 16 3 2

 [0027] Secondary amines include CH (CH) NHCH, CH (CH) NHCH, CH (CH) N

 3 2 7 3 3 2 8 3 3 2 9

HCH, CH (CH) NHCH, CH (CH) NHCH, CH (CH) NHCH, C

3 3 2 10 3 3 2 11 3 3 2 12 3

H (CH) NHCH, CH (CH) NHCH, CH (CH) NHCH, CH (CH)

3 2 13 3 3 2 14 3 3 2 15 3 3 2 1

NHCH, CH (CH) NHCH, CH (CH) NHCH, CH (CH) NHCH C

6 3 3 2 17 3 3 2 18 3 3 2 6 2

H, CH (CH) NHCH CH, CH (CH) NHCH CH, CH (CH) NHCH C

3 3 2 7 2 3 3 2 8 2 3 3 2 9 2

H, CH (CH) NHCH CH, CH (CH) NHCH CH, CH (CH) NHCH

3 3 2 10 2 3 3 2 11 2 3 3 2 12

CH, CH (CH) NHCH CH, CH (CH) NHCH CH, CH (CH) NH

2 3 3 2 13 2 3 3 2 14 2 3 3 2 15

CH CH, CH (CH) NHCH CH, CH (CH) NHCH CH, etc.

 2 3 3 2 16 2 3 3 2 17 2 3

[0028] As tertiary amines, CH (CH) N (CH), CH (CH) N (CH), CH (CH)

 3 2 6 3 2 3 2 7 3 2 3 2 8

N (CH), CH (CH) N (CH), CH (CH) N (CH), CH (CH) N (CH

3 2 3 2 9 3 2 3 2 10 3 2 3 2 11 3

), CH (CH) N (CH), CH (CH) N (CH), CH (CH) N (CH), CH

2 3 2 12 3 2 3 2 13 3 2 3 2 14 3 2

(CH) N (CH), CH (CH) N (CH), CH (CH) N (CH), CH (CH)

3 2 15 3 2 3 2 16 3 2 3 2 17 3 2 3 2

N (CH CH), CH (CH) N (CH CH), CH (CH) N (CH CH), CH (C

4 2 3 2 3 2 5 2 3 2 3 2 6 2 3 2 3

H) N (CH CH), CH (CH) N (CH CH), CH (CH) N (CH CH), CH

2 7 2 3 2 3 2 8 2 3 2 3 2 9 2 3 2

(CH) N (CH CH), CH (CH) N (CH CH), CH (CH) N (CH CH)

3 2 10 2 3 2 3 2 11 2 3 2 3 2 12 2 3

, CH (CH) N (CH CH), CH (CH) N (CH CH), CH (CH) N (CH

2 3 2 13 2 3 2 3 2 14 2 3 2 3 2 15

CH 2) and the like.

 2 3 2

Specific examples of amines having an alicyclic structure include the following formulas (A-1) to (A-7), etc. The compound of this is mentioned.

[Chemical 3]

 (A-7) The long chain amin compound (B) has a high water contact angle. For example, it can be treated with lyophilic treatment such as saponification! In order to increase the scratch resistance of the cured film, primary amine or secondary amine is preferred. More preferred is primary amine. These long chain amin compounds (B) may be used in the form of a salt, but in this case, the stability of the coating solution may be improved.

Further, a linear aliphatic amine is preferable because it has a high effect of accelerating the curing of the film without causing rapid gelation. Furthermore, linear alkylamines have a water contact angle of It is easy to obtain sufficient film formability on a substrate having a high thickness.

 Note that an amine compound having an unsaturated alkyl group or an alkyl group containing an aromatic group can also promote the curing of the film without causing rapid gelation, but in this case, the refractive index of the film becomes high. Therefore, the antireflection function tends to decrease.

 [0031] The content of the long chain amine compound (B) in the coating solution of the present invention is preferably the long chain amine compound (B) with respect to 1 mol of the total amount of all the key atoms of the polysiloxane (A). 0.0 to! 2 monolayer, more preferably 0.03 to 0.1 mol. If the long chain amine compound (B) is 0.01 mol or more, it is easy to cure at a low temperature, which is preferable. On the other hand, if it is 0.2 mol or less, the coating is transparent and has high hardness without unevenness. It is preferable because it is easy to obtain.

 [0032] <Organic solvent (C)>

 The organic solvent (C), which is the main solvent of the coating solution of the present invention, is a polysiloxane (A) in which a fluorine-containing organic group is bonded to a silicon atom, a long chain amine compound (B) having 9 to 20 carbon atoms, Any of the following compounds (D) and other components can be used as long as they are dissolved if necessary.

 Specific examples of the organic solvent (C) include aliphatic alcohols such as methanol, ethanol, isopropanol, butanol and diacetone alcohol; alicyclic alcohols such as cyclopentyl alcohol and cyclohexanol; benzyl alcohol and cinnamyl Aromatic alcohols such as Nolecol; Ketones such as acetone, methylethylketone, methylisobutylketone; Glycolanols such as ethylene glycolenol, propyleneglycolanol, hexyleneglycolanol; Noreb, Butinorecerosonolev, Etinore Canorebitonore, Butinorecanorebitonore, Diethyleneglycol Monoremonomethinoreethenore, Propyleneglycolenoremonomethinoreethenore, Propyleneglycolenoremono Glycol ethers such as Chinoreetenore; acid methyl ester, acetic Echiruesuteru, and the like esters such as lactic Echiruesute Le. These single or plural organic solvents are used in combination.

Among these, at least one 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 3 to 10 carbon atoms, more preferably 3 to 7 carbon atoms. Is preferably used. [0033] <Key compound (D)>

 The coating liquid for forming a low refractive index film of the present invention preferably further contains a silicon compound (D) represented by the following formula (1). As a result, the force S further increases the scratch resistance of the coating.

[0034] [Chemical 4]

式（1)における、 R\ R²、 及び R⁴は、それぞれ独立に水素原子又は炭素数;!〜 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。炭素数;!〜 5 の飽和炭化水素基の具体例としては、メチル基、ェチル基、プロピル基、ブチル基な どが挙げられる。

In the formula (1), R \ R ² and R ⁴ each independently represent a hydrogen atom or a saturated hydrocarbon group having from 5 to 5 carbon atoms, n represents an integer of 2 or more, preferably 2 to 50 . Specific examples of the saturated hydrocarbon group having from 5 to 5 carbon atoms include a methyl group, an ethyl group, a propyl group, and a butyl group.

 The key compound (D) may be a mixture of a plurality of compounds represented by the formula (1). In that case, n is preferably an integer of 2 or more, more preferably an integer of 4 or more.

[0035] The method for obtaining the above key compound (D) is not particularly limited. For example, it can be obtained by hydrolytic condensation of tetraalkoxysilane in an organic solvent such as alcohol. At that time, the hydrolysis may be either partial hydrolysis or complete hydrolysis. In the case of complete hydrolysis, it is theoretically necessary to add 0.5 moles of water of all alkoxide groups in the tetraalkoxysilane, but it is usually preferable to add an excess of water over 0.5 moles. Yes. On the other hand, in the case of partial hydrolysis, the amount of water is 0.5 times mol or less, but 0.2 to 0.5 times mol is preferable.

 Specific examples of the tetraalkoxysilane as the raw material include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane, which are easily available as commercial products.

[0036] The amount of water used in the reaction for obtaining the above key compound (D) should be appropriately selected as desired. The ability to produce 0.5 to 2.5 moles of all alkoxide groups in tetraalkoxysilane is preferred. Also, in the reaction, for the purpose of accelerating hydrolysis / condensation reaction, acids such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, formic acid, oxalic acid, phosphoric acid, hydrofluoric acid, maleic acid, alkali such as ammonia, hydrochloric acid, sulfuric acid, sulfuric acid, etc. A catalyst such as a metal salt such as nitric acid 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. A method is mentioned.

 [0037] In the above reaction, the organic solvent used for polycondensation of tetraalkoxysilane is not particularly limited as long as it dissolves tetraalkoxysilane. In general, since an alcohol is generated by a polycondensation reaction of tetraalkoxysilane, an alcohol or an organic solvent having good compatibility with the alcohol is used.

 Specific examples of such organic solvents include methanol, ethanol, propanol, n-butanol, etc., ethylene glycol monoethanolate, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethanol. Examples include glycol ethers such as tilether. The above organic solvents can be used in combination.

 [0038] The organic compound solution of the key compound (D) thus obtained has a SiO equivalent concentration.

 2

 Preferably it is 30 mass% or less. By selecting an arbitrary concentration within this concentration range, gel formation can be suppressed and a homogeneous solution can be obtained.

 A commercially available product can also be used as the key compound (D). For example, methinosilicate 51, methyl silicate 53A, ethyl silicate 40, ethyl silicate 48, SS-C1 and the like, all of which are manufactured by Colcoat.

[0039] <Other ingredients>

The coating liquid for forming a low refractive index film of the present invention includes a polysiloxane (A), an amine compound (B), an organic solvent (C), and a key compound (D) as long as the effects of the present invention are not impaired. Other components other than the above, for example, inorganic fine particles, leveling agents, surfactants, and media such as water may be contained. As the inorganic fine particles, those in a colloidal solution in which fine particles such as silica fine particles, alumina fine particles, titania fine particles, and magnesium fluoride fine particles are preferable are particularly preferable. The colloid solution may be a dispersion of inorganic fine particle powder in a dispersion medium, or a commercially available colloid solution.

 [0040] In the coating liquid of the present invention, by adding inorganic fine particles, it is possible to impart the surface shape of the formed cured film and other functions. As the inorganic fine particles, the average particle size (approx. 0.001−0.2〃111 force << preferably, and (approx. 0.001–0.1〃m force is preferable. The average particle size of the inorganic fine particles is 0.2. If it exceeds 111, the transparency of the cured film formed by the coating solution may be lowered.

 Examples of the dispersion medium of the inorganic fine particles include water or an organic solvent. From the viewpoint of the stability of the coating solution, the colloidal solution preferably has a pH or pKa of 2 to 10, particularly 3 to 7.

[0041] Examples of the organic solvent used as a dispersion medium for the colloidal solution include alcohols such as methanol, isopropyl alcohol, ethylene glycol, butanol, ethylene glycol monopropinoatenole; methyl ethyl ketone, methyl isobutyl ketone, and the like. Ketones; aromatic hydrocarbons such as toluene and xylene; amides such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone; esters such as ethyl acetate, butyl acetate, and _{butyrolataton} ; tetrahydrofuran; 4 Can list ethers such as dioxane.

 Of these, alcohols or ketones are preferable. These organic solvents can be used as a dispersion medium alone or in admixture of two or more.

 Further, as the leveling agent and surfactant, known ones can be used, and in particular, commercially available products are preferred because they are easily available.

[0042] <Coating liquid for film formation>

The coating solution for forming a film of the present invention contains polysiloxane (Α), a long chain amine compound (Β), and optionally a silicon compound (D) and other components, which are contained in the organic solvent (C). It is a dissolved solution. In the present invention, the preparation method is not limited as long as the coating solution is obtained. For example, in the organic solvent (C) that uses each of the above components, Next, it may be added and mixed. In this case, the order of adding each component is not particularly limited. Alternatively, a solution obtained by dissolving each component in an organic solvent (C) that uses each component may be mixed. In particular, when the polysiloxane (A) solution is mixed with the mixed solution of the long chain amine compound (B) and the organic solvent (C), it is preferable because the generation of precipitates can be suppressed! /.

[0043] Especially, when the polysiloxane (A) is obtained as a solution of the organic solvent (C), the solution of the polysiloxane (A) can be used as it is, which is preferable. When the polysiloxane (A) is obtained as a solution of the organic solvent (C), as described above, the solution of the organic solvent (C) of the alkoxysilane having a silicon atom to which the fluorine-containing organic group is bonded is used as the solution of the alkoxysilane. It is preferably obtained by condensation polymerization in the presence of 0.2 to 2 moles of succinic acid per mole of alkoxide group.

 [0044] In the coating solution of the present invention, for the purpose of adjusting the pH, an acid can be mixed in advance with the polysiloxane (A) solution. The amount of the acid is preferably 0.01-2.5 Monoreca S, more preferably 0. !! to 2 mol, relative to 1 mol of the polysiloxane (A).

 As the acid used above. Examples include inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, and phosphoric acid; monocarboxylic acids such as formic acid, acetic acid, and phosphoric acid; and organic acids such as polyvalent carboxylic acids such as oxalic acid, citrate, propionic acid, and succinic acid. . Of these, the acid in the solution state can be used as it is. It is preferably diluted with a polymerization solvent. It is preferable to use other acids by dissolving them in a suitable concentration in the polymerization solvent.

 [0045] In the coating solution of the present invention, polysiloxane (A) force The silicon atom of the polysiloxane (A) is preferably converted into silicon dioxide, preferably from 0 .;! To 15% by mass, more preferably 0.5 to 10% by mass, and the long chain amine compound (B) is 0.01 to 0.2 monole, preferably 0.03 to 0 per monoe of the polysiloxane (A) Contains 1 monole.

 In addition, when the key compound (D) is contained, the key compound (D) is preferably in the range of 0 · 03-0.55 moles, more preferably with respect to 1 mole of the key atom of the polysiloxane (A). Is preferably contained in an amount of 0.05 to 0.45 mol.

 [0046] In the present invention, the concentration in terms of SiO solid content in the coating liquid for forming a film is preferably 0.

 2

5% by mass, more preferably 0.5 to 10% by mass is suitable. SiO concentration is 0.1 quality If it is lower than the amount%, it is difficult to obtain a desired film thickness by a single application. Conversely, if it is 15% by mass or less, the pot life of the solution tends to be more stable. The SiO solid content equivalent concentration mentioned here is

 2

 It means the concentration in which the silicon atoms in the coating solution are converted to silicon dioxide. For example, when the coating solution contains only polysiloxane (A), it means the concentration of polysiloxane (A) key atom converted to silicon dioxide, and the coating solution contains polysiloxane (A). When A) and the key compound (D) are contained, it means the concentration obtained by converting the total amount of key atoms of the polysiloxane (A) and the key compound (D) into silicon dioxide.

 If necessary, add the organic solvent to the coating solution above to increase the SiO solid content equivalent concentration.

 2

 The power to be prepared to be within the above range The organic solvent used for this is the organic solvent used for polycondensation of alkoxysilane when producing the polysiloxane (A), the concentration of the polysiloxane (A) solution, The organic solvent used when diluting or substituting with another organic solvent can be used. One or more organic solvents can be arbitrarily selected and used.

[0047] Specific examples of the coating solution for forming a low refractive index film in the present invention are listed below.

 [1] A coating solution containing polysiloxane (A) and a long chain amine compound (B), which are dissolved in an organic solvent (C).

 [2] A coating solution containing polysiloxane (A), a long chain amine compound (B), and a key compound (D), which are dissolved in an organic solvent (C).

 [3] A coating solution containing inorganic fine particles in the above [1] or [2].

 [4] A coating liquid containing a leveling agent or a surfactant in the above [1], [2] or [3].

[0048] <Formation of film>

 The coating liquid for forming a low refractive index 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, a dipping method, a flow coating method, a spraying method, a no-coating method, a gravure coating method, a rhono-recording method, a blade coating method, an air knife coating method and the like can be employed.

Examples of the base material include base materials made of plastic, glass, ceramics and the like. Plastics include polycarbonate, poly (meth) acrylate, polyethersulfone, polyarylate, polyurethane, polysulfone, polyether, polyetherketone, polymethylpentene, polyolefin, polyethylene terephthalate, poly (meth) acrylonitrile. And sheets and films such as triacetyl cellulose, diacetyl cellulose, and acetate butyrate cellulose.

[0049] In the present invention, a substrate having a high water contact angle, for example, a substrate that has not been subjected to a treatment for enhancing hydrophilicity such as a saponification treatment, that is, a table having a high water contact angle of, for example, 90 degrees or more. Even when a substrate having a surface is used, it is possible to form a low refractive index film having a high light transmittance and excellent scratch resistance and a refractive index of preferably 1.4 or less on the surface of the substrate.

 The thickness of the coating film formed on the surface of the substrate can be adjusted by the thickness of the coating film, but can also be easily adjusted by adjusting the SiO equivalent concentration of the coating solution.

Yes

 [0050] The coating film formed on the substrate may be heat-cured as it is at a temperature of 20 to 150 ° C, but prior to this, it is dried at a temperature of 20 to 100 ° C and then thermally cured. Also good. At this time, the time required for drying is preferably 10 seconds to 6 minutes.

 The time required for thermosetting is usually 1 hour to 7 days, which can be appropriately selected according to the desired film properties. When a low curing temperature is selected, a coating film having sufficient scratch resistance can be easily obtained by increasing the curing time.

 Further, the coating liquid for forming a water repellent film of the present invention can provide a film having excellent scratch resistance even at a curing temperature exceeding 150 ° C. At that time, it is preferable to adjust the curing temperature and the curing time according to the heat-resistant temperature of the substrate.

[0051] <Uses of antireflection materials, etc.>

 Since the coating film formed from the coating liquid of the present invention has a low refractive index of, for example, 1.4 or less as described above, it can be suitably used particularly for applications as an antireflection material. it can.

 When the coating of the present invention is used as an antireflection material, the antireflection ability can be easily imparted by forming the coating of the present invention on a substrate having a higher refractive index than the coating of the present invention. That is, an antireflection substrate such as an antireflection film or an antireflection glass is formed by forming the coating of the present invention on the surface of a substrate such as a plastic film having a higher refractive index than the coating of the present invention. can do.

The film of the present invention is effective even when formed as a single film on the substrate surface. It is also effective as an antireflector having a stacked structure in which the coating of the present invention is formed on a coating that forms one or more lower layers having a ratio.

[0052] The coating of the present invention can be suitably used in fields where antireflection of light is desired, such as televisions, glass cathode ray tubes, computer displays, mirrors having glass surfaces, and glass showcases.

 Furthermore, since the coating film of the present invention has a water contact angle of 90 degrees or more, it has water repellency and has sufficient practicality in terms of antifouling property that fingerprints and oil-based inks can be easily wiped off. Therefore, it can be cured sufficiently even in a curing process at a relatively low temperature of 20 to 150 ° C., which is very advantageous in the production process of an antireflection substrate.

 Since the coating film of the present invention has the above-mentioned advantages, it is particularly useful for antireflection films for display devices such as liquid crystal and plasma, and display monitors.

 Example

 EXAMPLES 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 the following synthesis example and Example, and is not interpreted.

 Abbreviations in this example are as follows.

 TEOS: Tetraethoxysilane

FS—13:

 CCSS-88 ::

 MMEEAA :: Momonono Etata Noor Lumin Minn

 HHAA :: Hexylylamine

 LLAA :: Laura Uri Lino Norrea Amimin

 SSAA :: Stteare Allyl Luamin Min

 IIPPAA :: isopsoprolopapananol

 ccHHeexxOOHH :: Cyclochlorohexanosanonorere

 PPGGMMEE :: Puplopipirenren Glycocor Lurumo Monome Methytylru Aetherell

[[00005544]] Below, the measurement measurement standard method in the following synthesis synthesis example is shown below. .

Gas chromatography of residual residual aralkoxixisilaran monomonomer in a solution of polypolysiloxyloxasan ((AA)) (Hereinafter referred to as GC).

 GC measurement was performed under the following conditions using Shimadzu GC-14B manufactured by Shimadzu Corporation.

 Column: One power lamb CBP1—W25—100 (length 25mm, diameter 0 · 53mm, wall thickness β m)

 Column temperature: Start temperature from 50 ° C to 15 ° C / min to reach 290 ° C (3 min)

Yes

 Sample injection volume: 1, 1 L, injection temperature: 240 ° C, detector temperature: 290 ° C, carrier gas: nitrogen (flow rate 30 mL / min), detection method: FID method.

[0055] [Synthesis Example 1]

 A 4-necked reaction flask equipped with a reflux tube was charged with 57.26 g of methanol, and 18. Olg of oxalic acid was added in small portions with stirring to prepare a methanol solution of oxalic acid. Then, this solution was heated, and a mixture of TEOS (17.71 g) and FS-13 (7.02 g) was added dropwise under reflux. After the dropwise addition, the mixture was refluxed for 5 hours and allowed to cool to room temperature to prepare a polysiloxane (A) solution (PF). When this polysiloxane (A) solution (PF) was measured by GC, no alkoxysilane monomer was detected.

[0056] [Synthesis Example 2]

 To a four-necked reaction flask equipped with a reflux tube, 47.36 g of ethanol, 0.18 g of oxalic acid and 10.80 g of pure water were added, and 41.66 g of TEOS was added with stirring to prepare a mixed solution. Next, this solution was heated to V for 3 hours under reflux, and then allowed to cool to room temperature to prepare a polysiloxane solution (PS). When this polysiloxane solution (PS) was measured by GC, no alkoxysilane monomer was detected.

[0057] [Synthesis Example 3]

60.13 g of methanol was put into a four-necked reaction flask equipped with a reflux tube, and 18. Olg of oxalic acid was added in small portions with stirring to prepare a methanol solution of oxalic acid. The solution was then heated, and a mixture of TEOS (17.71 g) and CS-8 (4.15 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 solution (PC) of polysiloxane (A). When this polysiloxane (A) solution (PC) was measured by GC, alkoxysilane monomer was measured. One was not detected.

[0058] [Table 1]

[0059] [Examples;! To 4, Comparative examples;! To 6]

 With the composition shown in Table 2, the coating solution for forming a film (Q1 to Q4) was prepared by mixing the polysiloxane solution obtained in the above synthesis example, an amine compound and an organic solvent.

 In Comparative Examples, coating solutions (T1 to T6) were prepared with the compositions shown in Table 2. These Q1 to Q4 and Τ1 to Τ6 or coatings using them were evaluated as follows.

[0060] [Table 2]

[0061] <Storage stability>

 After the coating solution for film formation was allowed to stand at a temperature of 25 ° C for 1 month, a polytetrafluoroethylene filter having a pore diameter of 0.45 ^ 111, an inner diameter of 18 mm and a length of 22 mm (Chromato Disc 13N manufactured by Kurashiki Boseki Co., Ltd.) ) Was lOOcc filtered, and the one that could be filtered was marked with ◯, and the one with clogging was marked with X. Table 3 shows the results.

<Hardened film evaluation> Coating liquid for coating formation (Q1 to Q4 and T1 to T6) was applied to hard-coated triacetyl cellulose (hereinafter referred to as HC-TAC) film (film thickness 80 ^ 111, water contact angle on the hard coat surface was 83 degrees, Coating was performed using a bar coater (No. 6) at a reflectance of 4.5% at a wavelength of 550 nm. 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 90 ° C for 15 hours. The resulting cured coating was evaluated for water contact angle, oil pen wiping property, fingerprint wiping property, adhesion, reflectance and scratch resistance.

 [0063] The refractive index was measured using a cured film formed as follows. The prepared coating solutions (Q1-Q4 and T1-T6) are spin-coated on a silicon wafer to form a coating film, and then left at a temperature of 23 ° C for 30 seconds, and then in a clean oven at 100 ° C. The film was dried for 5 minutes and then cured at 90 ° C for 15 hours to obtain a cured film having a film thickness of lOOnm.

 These evaluation methods are as follows, and the evaluation results are shown in Tables 3 and 4.

 [0064] [Water contact angle]

 Using an automatic contact angle meter CA-Z manufactured by Kyowa Interface Science Co., Ltd., the contact angle when 3 microliters of pure water was dropped was measured.

 The water contact angle on the hard coat surface of the HC-TAC film used in the examples was also measured by this method.

[0065] [Oil pen wiping off]

 The ink applied to the surface of the cured coating using a Pentel oil pen was wiped off with Asahi Kasei Bencot M-3, and the ease of removal was visually determined. The ink was completely wiped off, and the others were X.

[0066] [Fingerprint wiping property]

 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 X.

[0067] [Adhesion]

Cut 100 points in a grid pattern on the cured film on the substrate at lmm intervals, and strongly adhere the cello tape (Nichiban Co., Ltd. 24mm width) to the cured film, and then remove the cello tape rapidly. With force S, the presence or absence of peeling of the cured film was visually confirmed. The case where there was no peeling was indicated as ◯, and the case where there was peeling was indicated as X.

[0068] [Reflectance]

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

[0069] [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: Scratch 6 ~: 10, C: Scratch; ;! ~ 20, D: Scratch 2;! ~ 30, E: 31 or more

 [0070] [Refractive index]

 The refractive index of light having a wavelength of 633 nm was measured using an Ellipsometer 1 DVA-36L manufactured by Mizoji Optical Co., Ltd.

[0071] [Table 3]

[0072] [Table 4]

[0073] As shown in Tables 3 and 4, in Examples;! To 4, excellent properties with scratch resistance of C or higher at a curing temperature of 90 ° C and water contact angle of 100 degrees or higher Excellent properties were shown.

 The storage stability of the coating solutions (Q1 to Q4) was also good and stable after storage at a temperature of 23 ° C for 6 months.

 Further examples! In ~ 4, 1. Low refractive index of less than 400 and low reflectivity were shown.

 On the other hand, Comparative Examples 1 to 5 using the coating solution (Tl to 5) in the case of not having the long chain amine compound (B) or in the case of an amine compound having a carbon number of less than the carbon number, at a curing temperature of 90 ° C, Scratch resistance 1 · Life was insufficient, D or less.

[0074] Further, as shown in Tables 3 and 4, Examples 1 to 4 are excellent in antifouling properties such as fingerprint wiping properties and oily pen wiping properties, and have high adhesion to the substrate. there were. In addition, coating solution (T6) using polysiloxane substituted with fluorine atoms and organic group has insufficient water contact angle of 90 degrees or less, low antifouling property and high reflectivity. It was something.

 Industrial applicability

[0075] The coating liquid for forming a water-repellent film of the present invention has excellent storage stability, is sufficiently cured by heat treatment at a temperature of 20 ° C to 150 ° C, and has low refractive index and scratch resistance. An excellent coating can be provided. Therefore, it can be particularly suitably used for an antireflection substrate, and in particular, can be suitably used for an antireflection film for a display element. The specification of Japanese Patent Application No. 2006-279219 filed on October 12, 2006 It is something that is incorporated.

Claims

The scope of the claims  [1] Polysiloxane (A) having a silicon atom to which a fluorine-containing organic group is bonded, and having 9 to 9 carbon atoms A coating solution for forming a low refractive index film, comprising 20 long-chain amine compounds (B), which are dissolved in an organic solvent (C). [2] The coating solution according to claim 1, wherein the polysiloxane (A) has 5 to 40 mol% of the C atom bonded with the fluorine-containing organic group with respect to all the C atoms. [3] The coating solution according to claim 1 or 2, wherein the long chain amine compound (B) is a linear aliphatic primary amine or secondary amine, or an aliphatic amine having an alicyclic structure. [4] The organic solvent (C) according to any one of claims 1 to 3, wherein the organic solvent (C) comprises at least one selected from the group consisting of an alcohol having 1 to 6 carbon atoms and 3 to 3 carbon atoms; glycol ether having 10 carbon atoms. Coating liquid described in 1.  [5] The polysiloxane (A) contains a total amount of silicon atoms of 0.;! To 15% by mass in terms of silicon dioxide, and the long chain amine compound (B) is a polysiloxane (A) key. The coating solution according to any one of claims 1 to 4, which is contained in an amount of 0.01 to 0.2 mol per mol of the total amount of elementary atoms.  [6] The coating liquid according to any one of claims 1 to 5, further comprising a key compound (D) represented by the formula (1).

(Where

R ² and R ⁴ each independently represent a hydrogen atom or a saturated hydrocarbon group having 1 to 5 carbon atoms, and n represents an integer of 2 or more. ) [7] A low-refractive-index film obtained by heat-curing the coating solution according to any one of Claims! [8] An antireflection material, wherein the low refractive index film according to claim 7 is formed on the surface of a substrate having a higher refractive index. [9] The concentration of alkoxysilane containing 5 to 40 mol% of alkoxysilane having a silicon atom to which a fluorine-containing organic group is bonded is determined by converting all the silicon atoms of the alkoxysilane to silicon dioxide in an organic solvent. To obtain a solution of polysiloxane (A) by polycondensation of a solution of 15% by mass in the presence of 0.2 to 2 mol of succinic acid with respect to 1 mol of all alkoxide groups of the alkoxysilane. And mixing the resulting polysiloxane (A) solution with a mixed solution of a long chain amin compound (B) having 9 to 20 carbon atoms and an organic solvent (C). A method for producing a coating solution for forming a low refractive index film.