WO2007119805A1

WO2007119805A1 - Phosphoric ester containing coating fluid and antireflection coatings

Info

Publication number: WO2007119805A1
Application number: PCT/JP2007/058120
Authority: WO
Inventors: Ryosuke Shimano; Kenichi Motoyama
Original assignee: Nissan Chemical Industries, Ltd.
Priority date: 2006-04-13
Filing date: 2007-04-12
Publication date: 2007-10-25
Also published as: JPWO2007119805A1; TW200804541A; CN101415789A; TWI473864B; KR101362627B1; KR20080109839A; CN101415789B; JP5293180B2

Abstract

A coating fluid for film formation which is excellent in storage stability and can give a film exhibiting a high water contact angle and excellent dust wipe-off properties; films formed from the fluid; processes for production of both; and antireflection coatings made by using the fluid. A coating fluid for film formation which comprises (A) a polysiloxane having fluorinated organic groups as side chains and (B) a phosphoric ester having hydroxyl attached to the phosphorus atom; films formed from the fluid; and processes for production of both.

Description

Coating liquid for coating formation containing phosphoric ester compound and antireflection film

The present invention relates to a coating liquid for forming a film containing polysiloxane and a phosphate ester compound, a film formed therefrom, and a method for producing them. Specifically, a coating liquid for forming a film containing a polysiloxane having an organic group substituted with a fluorine atom in the side chain, a phosphate ester compound having a hydroxyl group, a film formed therefrom, and a method for forming the film About. Furthermore, the present invention relates to the application of the above-mentioned coating liquid for forming a film and an antireflection application of a film formed therefrom.

Background art

Conventionally, it is known that when a coating film having a refractive index lower than the refractive index of a base material is formed on the surface of the base material, the reflectance of light reflected from the surface of the coating film decreases. Such a film exhibiting a reduced light reflectance is used as a light reflection preventing film and applied to various substrate surfaces.

For example, MgF2 fine particle alcohol dispersion formed by reacting magnesium salt or alkoxymagnesium compound as Mg source with fluoride salt as F source, or tetraalkoxy to improve film strength. A liquid containing silane or the like is used as a coating liquid, which is applied onto a glass substrate such as a cathode ray tube, and then heat-treated at 100 to 500 ° C., whereby an antireflection film exhibiting a low refractive index on the substrate. (See Patent Document 1) o

Also, it is a hydrolytic polycondensate such as tetraalkoxysilane, methyltrialkoxysilane, etyltrialkoxysilane, etc., and it can be used as a coating liquid by mixing two or more kinds having different average molecular weights with a solvent such as alcohol. In forming the coating from the coating solution, a coating is formed by adding means such as the mixing ratio and relative humidity control during the above mixing, and then heated to create a coating from 1.21 to 1.40. There is disclosed a low reflection glass in which a thin film having a refractive index and a thickness of 60 to 160 ηm having micropits or irregularities having a diameter of 50 nm and a force of 200 nm is formed on a glass substrate (see Patent Document 2). Teru. ).

[0003] Further, there is disclosed 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. Yes. (Refer to Patent Document 3.) This publication describes the details of the method of forming the upper layer film as CF

Three

Fluorine-containing silicone with polyfluorocarbon chains such as (CF) C H Si (OCH)

2 2 2 4 3 3

And compound, and a contrast 5 to 90 weight ^_0/0 of Si (OCH) or the like of the silane coupling agent, Al

3 4

After hydrolyzing at room temperature in the presence of a catalyst such as acetic acid in a coal solvent, a cocondensate liquid is prepared by filtration, and then this liquid is applied onto the lower layer film, 120 to 250 °. A method comprising heating at C is described.

In addition, a silicon compound represented by Si (OR) and CF (CF) CH CH Si (OR ¹ )

4 3 2 n 2 2 3 A reaction containing a silicon compound, an alcohol represented by R ² CH OH, and oxalic acid in a specific ratio.

2

The reaction mixture is heated at 40 to 180 ° C. in the absence of water to form a polysiloxane solution, and then a coating solution containing the solution is applied to the substrate surface. A film having a refractive index of 1.28 to 1.38 and a water contact angle of 90 to 115 degrees is disclosed which is formed in close contact with the substrate surface by thermosetting at 450 to 450 ° C. (See Patent Document 4).

[0004] In a display element (particularly a liquid crystal display element) that has been subjected to antireflection treatment by the above-described technology, dust may be attached due to charging due to the influence of the use environment, and the image may become visible. . Further, since the attached dust often cannot be easily wiped off, there is a demand for a display element that can easily wipe off dust attached to the antireflection film. For this reason, the anti-reflection film located on the outermost surface of the display element, especially the anti-reflection layer, has a function (dust wiping function) that suppresses electrification to prevent the adhesion of dust and makes it easier to wipe off the adhering dust. There is a strong demand to grant.

[0005] 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 Application 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

[0006] An object of the present invention is to provide a coating solution for forming a film having excellent storage stability, a high water contact angle and good dust wiping property, a film formed therefrom, and a method for producing them. is there. Another object of the present invention is to use the coating liquid for forming a film and a film formed therefrom for antireflection use.

Means for solving the problem

[0007] As a result of intensive studies in view of the above situation, the present inventors have completed the present invention shown below. That is, the present invention has the following gist.

1. A polysiloxane having an organic group substituted with a fluorine atom as a component (A) in a side chain, and a phosphate ester compound in which a hydroxyl group as a component is bonded to a phosphorus atom. Coating solution for forming a film.

2. The component (A) is a polysiloxane obtained by polycondensation of an alkoxysilane represented by the formula (1) and an alkoxysilane containing the alkoxysilane represented by the formula (2). Coating solution for film formation.

[0008] [Chemical 1]

Si (OR ¹ ) ₄ (1)

(R ¹ represents a hydrocarbon group having 1 to 5 carbon atoms.)

[0009] [Chemical 2]

R ² Si (OR ³ ) ₃ (2)

(R ² represents an organic group substituted with a fluorine atom, and R ³ represents a hydrocarbon group having 1 to 5 carbon atoms.)

[0010] 3. The coating liquid for forming a film according to 2 above, wherein R ^{2 in the} formula (2) is a perfluoroalkyl group.

4. The coating solution for film formation according to 2 or 3 above, wherein the component (A) is a polysiloxane obtained by further polycondensing an alkoxysilane represented by the formula (3).

[0011] [Chemical 3] ^{_{^{R 4 n Si (OR 5)}}} 4. N (3)

(R ⁴ represents an organic group not substituted with a fluorine atom, R ⁵ represents a hydrocarbon group having 1 to 5 carbon atoms, and n represents an integer of 1 to 3.)

[0012] 5. (B) Component power The coating liquid for film formation according to any one of 1 to 4 above, which is a phosphate ester compound represented by formula (4).

[0013] [Chemical 4]

OP (OH) _m (OR ⁶ ) ₃ — _m (4)

(R ⁶ represents an organic group having 1 to 20 carbon atoms, and m represents an integer of 1 or 2.)

[0014] 6. The coating liquid for film formation according to 5 above, wherein R ^{6 in the} formula (4) is an organic group having 1 to 6 carbon atoms.

7. The component according to any one of 1 to 6 above, wherein the phosphorus atom of component (B) is from 0.01 to 0.45 mol with respect to 1 mol of the total amount of silicon atoms of component (A). Coating liquid for film formation.

8. (A) component, the polycondensation of alkoxysilane containing 40 mol% of the alkoxysilane represented by 5 in the formula (1) 60 to 95 mol alkoxysilane represented by ^_0/0 and formula (2) The coating liquid for film formation according to any one of 2 to 7 above, which is polysiloxane obtained by

9. A film formed using the coating liquid for forming a film according to any one of 1 to 8 above.

[0015] 10. An antireflection film formed using the coating liquid for forming a film according to any one of 1 to 8 above.

11. A method for forming a coating, wherein the coating solution for forming a coating described in any one of 1 to 8 above is applied to a substrate, dried at room temperature to 150 ° C, and then cured from room temperature to 150 ° C. .

12. A coating solution for film formation described in any one of 1 to 8 above is applied to a substrate, dried at room temperature to 150 ° C, and then cured from room temperature to 150 ° C. Forming method.

13. An antireflection substrate having the coating according to 9 or the antireflection film according to 10 above.

14. An antireflection film comprising the coating according to 9 or the antireflection film according to 10.

[0016] 15. A polysiloxane having an organic group substituted with a fluorine atom as the component (A) in the side chain. Among all the alkoxysilanes used to obtain, alkoxysilane containing 60 mols of 95 mol% of alkoxysilane represented by formula (1) and 5 to 40 mol% of alkoxysilane represented by formula (2), A solution of polysiloxane (A) obtained by polycondensation of 0.2 to 2 mol of oxalic acid with respect to 1 mol of alkoxy group in an organic solvent at a liquid temperature of 50 to 180 ° C. And a phosphate ester compound bonded to a hydroxyl group atom, and a method for producing a coating solution for forming a coating, characterized by comprising:

[0017] [Chemical 5]

Si (OR ¹ ) ₄ (1)

(R ¹ represents a hydrocarbon group having 1 to 5 carbon atoms.)

[0018] [Chemical 6]

R ² Si (OR ³ ) ₃ (2)

The invention's effect

The coating liquid for forming a film of the present invention is excellent in storage stability, has a high water contact angle, has good dust wiping property, and can form a stable film without change over time. In particular, a coating solution for forming a film exhibiting a low reflectance is useful as a coating solution for forming an antireflection film, and a coating formed using the coating solution should exhibit a low reflectance, a high antifouling property, and a dust wiping property. It is very useful as an antireflection film.

BEST MODE FOR CARRYING OUT THE INVENTION

[0020] The present invention is described in detail below.

The present invention comprises (A) a polysiloxane having a side chain with an organic group substituted with a fluorine atom as a component, and (B) a phosphate ester compound in which a hydroxyl group as a component is bonded to a phosphorus atom. In particular, the present invention relates to a coating liquid for forming a film, a film formed therefrom, and a method for producing the same.

[0021] <(Eight) component> Component (A) is a polysiloxane having an organic group substituted with a fluorine atom in the side chain. In the present invention, the side chains are mainly those that impart a high water contact angle to the coating, and the side chains are not particularly limited as long as they exhibit antifouling properties. Such an organic group substituted with a fluorine atom is an organic group in which part or all of the hydrogen atoms of an aliphatic group or aromatic group are substituted with fluorine atoms. Specific examples of these are given below.

Examples thereof include a trifluoropropyl group, a tridecafluorooctyl group, a heptadecafluorodecyl group, and a pentafluorophenylpropyl group.

Among these, a perfluoroalkyl group is preferable because a highly transparent film can be easily obtained. More preferably, it is a perfluoroalkyl group having 3 to 15 carbon atoms.

Specific examples include trifluoropropyl group, tridecafluorooctyl group, heptadecafluorodecyl group and the like.

In the present invention, a plurality of polysiloxanes having side chains as described above may be used in combination.

[0022] The method for obtaining a polysiloxane having an organic group substituted with a fluorine atom in the side chain as described above is not particularly limited. In general, it can be obtained by polycondensation of the above-mentioned alkoxysilane having an organic group in the side chain with other alkoxysilane.

Of these, polysiloxanes obtained by polycondensation of alkoxysilanes represented by formula (1) and alkoxysilanes represented by formula (2) are preferred.

[0023] [Chemical 7]

Si (OR ¹ ) ₄ (1)

[0024] [Chemical 8]

R ² Si (OR ³ ) ₃ (2)

[0025] R ^{1 in the} formula (1) represents a hydrocarbon group, but since the reactivity is higher when the number of carbon atoms is smaller, a saturated hydrocarbon group having 1 to 5 carbon atoms is preferred, and a methyl group is more preferred. , An ethyl group, a propyl group, and a butyl group.

Specific examples of such tetraalkoxysilane include tetramethoxysilane, tetraeth Examples thereof include xyloxysilane, tetrapropoxysilane, and tetrabutoxysilane, which are readily available as commercial products.

In the present invention, at least one of the alkoxysilanes represented by the formula (1) may be used V, but plural kinds may be used as necessary.

[0026] The alkoxysilane represented by the formula (2) is an alkoxysilane having an organic group substituted with a fluorine atom in the side chain. Accordingly, this alkoxysilane imparts water repellency to the coating film.

Here, R ² in the formula (2) represents an organic group substituted with the above-described fluorine atom, but the number of fluorine atoms of the organic group is not particularly limited.

R ³ in the formula (2) represents a hydrocarbon group having 1 to 5 carbon atoms, preferably a saturated hydrocarbon group having 1 to 5 carbon atoms, more preferably a methyl group, an ethyl group, a propyl group, Butyl group.

Among the alkoxysilanes represented by the formula (2), an alkoxysilane in which R ² is a perfluoroalkyl group is preferred, and more preferably R ² is an organic group represented by the formula (5). Some anoroxysilanes are preferred.

[0027] [Chemical 9]

CF ₃ (CF ₂ ) _k CH ₂ CH ₂ (5) In the formula (5), k represents an integer of 0 to 12.

[0028] Specific examples of the alkoxysilane having an organic group represented by the formula (5) include trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, tridecafluorotrimethoxysilane, and tridecafluoro. Examples include loctyltriethoxysilane, heptadecafluorodecyltrimethoxysilane, heptadecafluorodecyltriethoxysilane, etc.Especially when k is an integer of 2 to 12, the anti-reflective coating has a fingerprint wiping property. Since it becomes favorable, it is preferable.

In the present invention, at least one of the alkoxysilanes represented by the formula (2) may be used as V, but a plurality of types may be used as necessary. In addition, polysiloxane (A) is a polycondensation of alkoxysilanes represented by formula (1) and formula (2) and other alkoxysilanes represented by formula (3) and Z or formula (6). It can also be made. At this time, in addition to the alkoxysilanes represented by the formulas (1) and (2), either the alkoxysilane represented by the formula (3) or the alkoxysilane represented by the formula (6) is used alone. You may use both together.

[0029] [Chemical 10]

R ⁴ _n Si (OR ⁵ ) ₄ — _n (3) In the formula (3), R ⁴ represents an organic group not substituted with a fluorine atom, and R ⁵ is a hydrocarbon having 1 to 5 carbon atoms. N represents an integer of 1 to 3;

[Chemical 11]

(R ⁷ 0) ₃ SiR ⁸ Si (OR ⁷ ) ₃ (6)

In the formula (6), R ⁷ represents a hydrocarbon group having 1 to 5 carbon atoms, and R ⁸ represents an organic chain having 1 to 20 carbon atoms.

[0030] The alkoxysilane of the formula (3) is an alkoxysilane having 1, 2 or 3 organic groups and 1, 2 or 3 alkoxy groups, wherein R ⁴ is substituted with a fluorine atom. R ^{5 in} formula (3) is a hydrocarbon group having 1 to 5 carbon atoms each. When n is 1 or 2, R ⁵ is generally the same in many cases, but in the present invention, R ⁵ may be the same or different. R ⁴ in the formula (3) is an organic group having 1 to 20 carbon atoms, preferably an organic group having 1 to 15 carbon atoms. When n is 2 or 3, in general, R ⁴ is often the same, but in the present invention, R ⁴ may be the same or different.

The following specific examples of alkoxysilanes represented by formula (3) are not limited to these.

[0031] methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, pentyltrimethoxysilane, pentyltriethoxy Sisilane, heptyltrimethoxysilane, heptyltriethoxysilane, octyltrimethoxy Silane, Octyltriethoxysilane, Dodecyltrimethoxysilane, Dodecyltriethoxysilane, Hexadecyltrimethoxysilane, Hexadecyltriethoxysilane, Octadecyltrimethoxysilane, Octadecyltriethoxysilane, Phenyltrimethoxysilane , Phenyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyl Triethoxysilane, γ-glycidoxy propyl trimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysila , 3 Atarirokishi trimethoxysilane, 3-Atari b trimethoxy silane, .gamma. methacrylonitrile trimethoxysilane, .gamma.-methacryloxypropyl triethoxysilane, gamma - © laid trimethoxysilane, _I - ureidopropyltriethoxysilane Examples thereof include dialkoxysilanes such as ethoxysilane, dimethyldimethoxysilane, and dimethyljetoxysilane.

[0032] R ^{5 in the} formula (3) is a force that is a hydrocarbon group having 1 to 5 carbon atoms, preferably a saturated hydrocarbon group having 1 to 4 carbon atoms, more preferably a saturated carbon group having 1 to 3 carbon atoms. It is a hydrogen group. In the present invention, the alkoxysilane represented by the formula (3) can be used in a plurality of types as required.

[0033] Further, the alkoxysilane of the formula (6) is a hydrocarbon group in which R ⁷ has 1 to 5 carbon atoms, preferably a saturated hydrocarbon group having 1 to 4 carbon atoms, and more A saturated hydrocarbon group having 1 to 3 carbon atoms is preferred.

In the present invention, a plurality of alkoxysilanes represented by the formula (6) may be used as necessary. In general, R ⁷ is often the same, but in the present invention, R ⁷ may be the same or different. R ⁸ is an organic chain having 1 to 20 carbon atoms, and the structure is not particularly limited, and may include cyclic structures such as double bonds, triple bonds, and phenyl groups, and branched structures. Moreover, you may contain hetero atoms, such as nitrogen, oxygen, and fluorine.

[0034] In order to improve the water repellency of the coating film formed according to the present invention, among the alkoxysilanes represented by the formula (6), the R ⁸ moiety contains a perfluoroalkyl chain ( It is preferable to use an alkoxysilane having an organic chain as in 7).

[Chemical 12] -CH ₂ CH ₂ (CF ₂ ) _p CH ₂ CH _2- (7) In formula (7), p represents an integer of 1 to 12.

A specific example of an alkoxysilane having a structure in which R ⁸ in formula (6) is an organic chain containing a perfluoroalkyl chain represented by formula (7) is 1,6-bis. (Trimethoxysilylethyl) dodecafluoro hexane, 1,6-bis (triethoxysilylethyl) dodecafluoro hexane, and the like.

[0035] The component (A) used in the present invention is usually represented by the formula (3) and the formula (6) as necessary, essentially including the alkoxysilane represented by the formula (1) and the formula (2). The ratio of the alkoxysilane used is not particularly limited as long as it is a homogeneous solution in a solvent obtained by polycondensation of one or both of the alkoxysilanes.

When the alkoxysilane represented by the formula (2) is 5 mol% or more with respect to the total amount of alkoxysilane used to obtain the component (A), a film having a water contact angle of 80 ° or more is obtained. When it is 40 mol% or less, the formation of gels and foreign substances can be suppressed, and it is easy to obtain a homogeneous solution of component (A)!

On the other hand, the amount of the alkoxysilane of formula (1) is, (A) in the total amount of Al Kokishishiran used for obtaining the component, 60 mole ^_0/0 Power et al Mashi 95 mol% Ca children! /,.

When only the alkoxysilane represented by the formula (3) is used in combination, it is preferably 0 to 35 mol% in the total amount of alkoxysilane used to obtain the component (A). When only the alkoxysilane represented by the formula (6) is used in combination, 0 to 20 mol% is preferable in the total amount of alkoxysilane used to obtain the component (A). Further, when both alkoxysilanes represented by formula (3) and formula (6) are used in combination, the total amount (A) component of the alkoxysilane represented by formula (3) and formula (6) is The total amount of alkoxysilanes used to obtain the component (A) is 0 to 35 mol% in the total amount of alkoxysilanes used to obtain the component (A). Preferably it is 0 to 15 mol% in quantity! /.

[0036] The method for condensing the polysiloxane that is component (A) used in the present invention is not particularly limited. For example, hydrolysis and condensation of an alkoxysilane in an alcohol solvent is used. Method. In that case, the hydrolysis' condensation reaction may be either partial hydrolysis or complete hydrolysis. In the case of complete three-necked water splitting, theoretically, it is sufficient to cover 0.5 times mole of water of all alkoxy groups in the alkoxysilane, but usually an excess amount of water is more than 0.5 times mole. Yeah.

In the present invention, the amount of water used in the above reaction can be appropriately selected as desired, but is usually 0.1 to 2.5 moles of all alkoxy groups in the alkoxysilane.

[0037] Usually, hydrolysis' acids such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, formic acid, oxalic acid, maleic acid; ammonia, methylamine, ethylamine, ethanolamine, triethylamine, etc. for the purpose of promoting the condensation reaction; Alkali; metal salts such as hydrochloric acid, sulfuric acid, or nitric acid are used as catalysts. In this case, the amount of the catalyst used in the reaction is preferably about 0.05 times the molar amount of all alkoxy groups in the alkoxysilane. In addition, it is also common to further accelerate the hydrolysis and condensation reaction by heating the solution in which the alkoxysilane is dissolved. At that time, the heating temperature and the heating time can be appropriately selected according to need. Preferably, the reaction system is set to 50 to 180 ° C., and several tens of power can be obtained in a sealed container or under reflux so that the liquid does not evaporate or volatilize. Done for tens of hours. For example, methods such as heating and stirring for 24 hours at 50 ° C. and heating and stirring for 8 hours under reflux can be mentioned.

As another method, for example, a method of heating a mixture of alkoxysilane, solvent and oxalic acid can be mentioned. Specifically, after adding oxalic acid to alcohol in advance to obtain an alcohol solution of oxalic acid, the solution and alkoxysilane are mixed and heated. In this case, the amount of oxalic acid is generally set to 0.2 mol, such as 0.2 force, with respect to 1 mol of all alkoxy groups of alkoxysilane. The heating in this method can be performed at a liquid temperature of 50 to 180 ° C, and preferably, for example, in a sealed container or under reflux for several tens of hours for several tens of hours so that the liquid does not evaporate or volatilize. Done.

In each of the above methods, when a plurality of alkoxysilanes are used, a plurality of alkoxysilanes may be mixed and used in advance, or a plurality of alkoxysilanes may be added sequentially.

[0038] When the alkoxysilane is polycondensed by the above method, the concentration obtained by converting the total amount of silicon atoms of the prepared alkoxysilane into SiO (hereinafter referred to as SiO converted concentration) is 20 quality. Generally, the amount is not more than%. By selecting an arbitrary concentration within such a concentration range, gel formation can be suppressed and a homogeneous polysiloxane solution can be obtained. Solvents used for polycondensation of alkoxysilanes include alkoxysilanes represented by formula (1) and formula (2) and, if necessary, alkoxysilanes represented by formula (3) and formula (6). If it melt | dissolves, it will not specifically limit. In general, alcohols are produced by the polycondensation reaction of alkoxysilanes, and therefore, alcohols and organic solvents having good compatibility with alcohols are used.

Specific examples of such an organic solvent include alcohols such as methanol, ethanol, propanol, and butanol; ethylene glycol monomethyl ether, ethylene glycol monoremonoethylenoatenore, diethyleneglycolenomonomethinoreatenore, diethylene Examples include ethers such as glycol monoethyl ether; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone.

In the present invention, a mixture of the above organic solvents may be used.

[0039] <Component (B)>

The component (B) used in the present invention is a phosphate ester compound having a hydroxyl group.

In order to exhibit good dust wiping properties, which is an effect of the present invention, a phosphate ester compound having one or two hydroxyl groups bonded to a phosphorus atom in one molecule is preferable.

Among such phosphate ester compounds, the phosphate compound represented by the formula (4) is preferable.

[0040] [Chemical 13]

OP (OH) _m (OR ⁶ ) ₃ — _m (4)

[0041] R ^{6 in the} formula (4) may include a cyclic structure such as a force double bond, a triple bond, and a phenol group, which is an organic group having 1 to 20 carbon atoms, and a branched structure. It may also contain heteroatoms such as nitrogen and oxygen.

If the carbon number of R ⁶ is 21 or more, the compatibility with polysiloxane (A) may be insufficient, or the storage stability of the coating solution may not be sufficiently obtained. Twenty organic groups are preferred. When the coating of the present invention is used for an antireflection film, A case of 10 is more preferable because it can suppress an increase in reflectance, and a case of 1 to 6 carbon atoms is preferable because there is almost no increase in reflectance.

M in the formula (4) is an integer of 1 or 2, but when m is 0, the compound of the formula (4) becomes a phosphate ester compound having no hydroxyl group, and is an antistatic effect that is an effect of the present invention. It is difficult to obtain an effect. On the other hand, when m is 3, the compound of formula (4) represents phosphoric acid, and the coating formed due to insufficient affinity with polysiloxane (A) may become unstable and whiten over time. Therefore, a compound that has antistatic properties while maintaining the stability of the coating, and thereby exhibits dust wiping properties, which is the effect of the present invention, is a phosphorous having both a hydroxyl group in which m is 1 or 2 and an alkyl ester moiety. It is an acid ester compound. Many hydroxyl groups! Since the antistatic effect is so strong that m is 2, particularly when m is 2, the effect of the present invention can be achieved with a small amount.

Specific examples of such phosphate ester compounds are not limited to these.

For example, methyl phosphate (also known as phosphoric acid methyl ester, monoester: diester = 50: 5 0 (wt%) mixture), E chill phosphate (also known as phosphoric acid Echiruesuteru, monoester: diester = 37: 63 (mass ^_0/0 ) Mixture), isopropyl phosphate (also known as isopropyl phosphate ester, monoester: diester = 30:70 (mass ⁰ /.) Mixture), di-n-butyl phosphate (monoester: diester = 36: 64 (mass ⁰⁾ /.) Mixture), di-n-butyl phosphate (isolated diester), phenol phosphate (also known as phosphoric acid monophenyl ester, monoester isolated), phosphoric acid diphenyl (also known as phosphoric acid diphenyl ester) , diesters isolated product), hexyl phosphoric acid 2 E Ji Le (aka phosphate - hexyl ester to Echiru, monoester: diester = 40: 60 (mass ^_0/0) mixture), mono-n- Dodeshiruri Acid (also known as mono n-dodecyl phosphate, isolated monoester), n-tridecyl phosphate (also known as phosphoric acid n-tridecyl ester, monoester 'diester mixture), 1-aminopropyl phosphate (also known as phosphoric acid) Mono 1-aminopropyl ester, monoester isolated product), 1 amino-2-methylpropyl phosphate (also known as phosphoric acid 1-amino-2-methylpropyl phosphate, monoester isolated product) burulinic acid, 3 acryloxy Examples thereof include propyl phosphoric acid and 3-methacryloxypropyl phosphoric acid. In the present invention, the component (B) is not limited as long as it is well compatible with the component (A), and a plurality of them can be used.

[0043] The content of the component (B) is such that the phosphorus atom of the component (B) is 0.01 mol or more with respect to 1 mol of the total amount of silicon atoms in the component (A). preferable. More preferably, it is 0.1 mol or more, and particularly preferably 0.15 mol or more. When the amount is less than 0.01 mol, it may be difficult to obtain good dust wiping properties, which is the effect of the present invention. On the other hand, even if it exceeds 0.45 mol, the effect of dust wiping is hardly improved, so 0.45 mol or less is preferable. When used in an antireflection film, the amount is more preferably 0.4 mol or less, and particularly preferably 0.25 mol or less.

[0044] <(C) Solvent>

The coating liquid for forming a film of the present invention is usually in a solution state in which the component (A), the component (B), and other components described later as required are dissolved in a solvent.

Therefore, the (C) solvent used in the present invention is not particularly limited as long as it can uniformly dissolve the component (A), the component (B), and other components described later as required. Usually an organic solvent.

Specific examples of such solvents include alcohols such as methanol, ethanol, propanol, butanol and diacetone alcohol; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; ethylene glycol, propylene glycol and hexylene glycol. Glycols such as ethylene glycol monomethyl ether, ethylene glycol monoethyl enore ethere, ethylene glycol monobutino ree enore, ethenorecanolitol, butyl carbitol, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, Ethers such as propylene glycol monobutyl ether and tetrahydrofuran; esters such as methyl acetate, ethyl acetate, and ethyl lactate Etc. The.

In the present invention, a plurality of solvents may be used.

[0045] <Other ingredients>

In the present invention, as long as the effects of the present invention are not impaired, the component (A) and other components other than the component (B), for example, inorganic fine particles, fillers, leveling agents, surface modification Components such as an agent and a surfactant may be contained.

[0046] Examples of the inorganic fine particles include metal oxide fine particles, metal double oxide fine particles, and magnesium fluoride fine particles.

Examples of metal oxides include silica, alumina, titanium oxide, zirconium oxide, tin oxide, and zinc oxide. Examples of metal double oxides include ITO, copper, silver, and zinc antimonate. Etc. Moreover, hollow silica fine particles, porous silica fine particles, and the like can also be exemplified.

Such inorganic fine particles may be either powder or colloidal solution, but those of colloidal solution are preferable because they are easy to handle. 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 force to 0.2 m, and more preferably 0.001 force to 0.1 m. When the average particle size of the inorganic fine particles exceeds 0.2 μχη, 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. From the viewpoint of the stability of the coating solution for forming a film, the colloidal solution is preferably adjusted to ρΗ or pKa from 2 to 10, more preferably from 3 to 7.

[0047] Examples of the organic solvent used for the dispersion medium of the colloidal solution include alcohols such as methanol, ethanol, propanol, and butanol; glycols such as ethylene glycol; ketones such as methyl ethyl ketone and methyl isobutyl ketone; toluene, Aromatic hydrocarbons such as xylene; Amides such as dimethylformamide, dimethylacetamide, and N methylpyrrolidone; Esters such as ethyl acetate, butyl acetate, and γ-butyroratatone; Ethylene glycol monopropyl ether, tetrahydrofuran, 1,4 dioxane And ethers such as 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.

Also, known fillers, leveling agents, surface modifiers, surfactants and the like are used. Especially, since the commercial product is easy to obtain, it is preferable.

[0048] <Coating liquid for film formation>

The method for preparing the coating liquid for forming a film of the present invention is not particularly limited. The components (A) and (B) may be in a uniform solution state. Usually, the component (A) is polycondensed in a solvent, and thus is obtained in a solution state. Therefore, a method of using the solution containing the component (A) (hereinafter referred to as the solution of the component (A)) as it is and mixing it with the component (B) is simple. If necessary, the solution of component (A) may be concentrated, diluted by adding a solvent, or replaced with another solvent, and then mixed with component (B). Furthermore, the solvent can be added after mixing the solution of component (A) and component (B). Alternatively, the component (B) may be dissolved in the solvent (C) and then mixed with the solution (A).

The SiO equivalent concentration in the coating solution is preferably from 0.5 to 15% by mass.

2

6 mass% is more preferable. If the SiO equivalent concentration is lower than 0.5% by mass, it is desirable to apply it once.

2

If the content is higher than 15% by mass, the storage stability of the solution tends to be insufficient. The solvent used for dilution, substitution or the like may be the same solvent as used for the polycondensation of alkoxysilane described above, or may be a different solvent. The solvent is not particularly limited as long as the compatibility with the component (A) and the component (B) is not impaired, and one kind or a plurality of kinds can be arbitrarily selected and used.

[0049] The method for mixing the other components described above is not particularly limited, either at the same time as component (A) and component (B) or after mixing components (A) and (B). ! ヽ.

In the present invention, specific examples of the coating liquid for forming a film are given below.

[1] A coating solution for forming a coating, comprising (A) component and 0.01 to 0.45 mol of phosphorus atoms in component (B) with respect to 1 mol of the total amount of silicon atoms in component (A).

[2] A coating liquid for forming a coating film comprising the above [1] and inorganic fine particles.

[3] A coating forming coating solution containing at least one selected from the group consisting of the above [1] or [2] and a filler, a leveling agent, a surface modifier, and a surfactant.

[0050] Formation of film>

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, dip coating method, flow coating method, spin coating method, flexographic printing method, ink jet coating method, spray coating method, bar coating method, gravure roll coating method, roll coating method, blade coating method, air doctor one coating method, air knife Methods such as a coating method, a wire doctor coating method, a reverse coating method, a transfer roll coating method, a micro gravure coating method, a kiss coating method, a cast coating method, a slot orifice coating method, a calendar coating method, and a die coating method can be employed. In this case, examples of the substrate used include known or well-known substrates such as plastic, glass, and ceramics. Plastics include polycarbonate, poly (meth) acrylate, polyethersulfone, polyarylate, polyurethane, polysulfone, polyether, polyetherketone, trimethylpentene, polyolefin, polyethylene terephthalate, (meth) acrylonitrile, triacetyl cellulose And plates and films of diacetyl cellulose and acetate butyrate cellulose.

The coating film formed on the substrate may be thermally cured as it is at a room temperature force of 450 ° C, preferably 40 to 450 ° C, but prior to this, preferably in the temperature range of room temperature to 150 ° C, preferably After drying in the temperature range of 10 ° C to 150 ° C, heat curing may be performed. In this case, the time required for drying is preferably 10 seconds to 10 minutes.

The time required for thermosetting can be appropriately selected according to the desired film properties, but is usually 1 hour to 10 days. When a low curing temperature is selected, it is easy to obtain a film having sufficient scratch resistance by increasing the curing time.

In particular, when the substrate is an organic substrate such as a TAC (triacetylcellulose) film or PET (polyester) film, the curing temperature of the coating film is from room temperature to 150 ° C in consideration of the heat resistance of the substrate. The temperature is preferably 10 ° C to 150 ° C. In that case, when using a drying process, it is preferable to dry in the temperature range from room temperature to 150 ° C, preferably in the temperature range from 10 ° C to 150 ° C for 10 seconds to 10 minutes.

The coating film of the present invention thus obtained has a feature that the water contact angle is 80 ° or more, and the dust wiping property is excellent. Power! In particular, the coating film formed by the present invention having a low reflectance can be suitably used particularly as a low refractive index layer for antireflection applications. [0052] When the coating of the present invention is used for antireflection applications, the surface of a substrate having a refractive index higher than that of the coating of the present invention, such as ordinary glass or TAC (triacetylcellulose) film, is used. By forming the coating film of the present invention, this base material can be easily converted into a base material having an antireflection function. At that time, the coating of the present invention is effective even when used as a single coating on the substrate surface, but it can also be used as an antireflection laminate in which a coating is formed on a lower coating having a high refractive index. It is valid.

[0053] Here, the relationship between the thickness of the coating and the wavelength of light is described. The thickness d (nm) of the coating having a refractive index a and the wavelength (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) Z4a (where b represents an integer of 1 or more) holds between. Therefore, by using this equation to determine the thickness of the coating, it is possible to easily prevent reflection of light having a desired wavelength.

As a specific example, for light with a wavelength of 550 nm, 1. To form a film with a refractive index of 32 and prevent reflected light from the glass surface, substitute these values in equation (a) above. By doing so, the optimum film thickness can be calculated. In that case, b can substitute any positive integer. 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 calculated in this way, it is possible to easily impart antireflection ability.

[0054] Although the thickness of the coating film formed on the substrate can be adjusted by the film thickness at the time of coating,

2. It can be easily adjusted by adjusting the equivalent concentration.

[0055] In addition to having water repellency (antifouling properties) and good dust wiping properties, the coating of the present invention has the characteristics of low reflectance. Therefore, it can be suitably used in fields where light reflection prevention is desired, such as glass cathode ray tubes; displays for televisions, computers, car navigation systems, mobile phones, etc .; mirrors with glass surfaces; glass showcases. In particular, it is useful for antireflection films used for liquid crystal displays, plasma displays, projection displays, EL displays, polarizing plates such as SED, FET, CRT, and front plates.

Example

[0056] Synthesis examples, examples and comparative examples are shown below to specifically explain the present invention. The description is not to be construed as limited to these examples.

Abbreviations in this embodiment will be described.

TEOS: Tetraethoxysilane

UPS: γ-Ureidopropyltriethoxysilane

MAS: γ-Methacryloxypropyltrimethoxysilane

MPS: γ-Mercaptopropyltrimethoxysilane

APS: 3-Aminopropyltriethoxysilane

F3: trifluoropropyltrimethoxysilane

F13: Tridecafluorooctyltrimethoxysilane

F17: Pentadecafluorodecyltrimethoxysilane

F12: 1,6-Bis (trimethoxysilylethyl) dodecafluoro oral hexane

MeOH: Methanol

IPA: isopropyl alcohol (2-propanol)

n BuOH: n Butinoreare no Reno 1 (1 Butanore)

PG: Propylene glycol

PA: phosphoric acid

MePA: Methyl phosphate (also known as phosphoric acid methyl ester, monoester: diester = 50: 50 (mass%) mixture)

EtPA: Ethyl phosphate (also known as ethyl phosphate, monoester: diester = 37:63 (mass%) mixture)

IPPA: isopropyl phosphate (also known as isopropyl phosphate, monoester: diester = 30: 70 (mass%) mixture)

PhPA: Phenylphosphoric acid (also known as phosphoric acid monophenyl ester, isolated monoester) EhPA: 2-ethylhexyl phosphate (also known as 2-ethylhexyl phosphate, monoester: diester = 40: 60 (mass) ^_0/0) mixture)

DdPA: Mono n dodecyl phosphate (also known as mono n dodecyl phosphate, isolated mono ester) TMePA: Trimethyl phosphate (also known as trimethyl phosphate, triester isolate)

[0057] Measurement methods in the following synthesis examples are 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). GC measurements were made by Shimadzu GC— 1

Measurement was performed using 4B under the following conditions.

Column: One power ram CBP1— W25— 100 (25mm X O. 53πιπιΦ X 1, um) Column temperature: Start temperature is 50 ° C, temperature is increased by 15 ° CZ minutes, and final temperature is 290 ° C (3 minutes) It was.

Sample injection volume: 1 L

Injection temperature: 240 ° C

Detector temperature: 290 ° C

Carrier gas: Nitrogen (flow rate 30mLZ)

Detection method: FID method

[0058] [Synthesis Example 1]

Into a four-necked reaction flask equipped with a reflux tube was charged 32.54 g of MeOH, and 18.OO g of oxalic acid was added in small portions with stirring to prepare a MeOH solution of oxalic acid. The oxalic acid methanol solution is then heated to reflux, followed by MeOH 24.73 g, TEOS 17.71 g, F13

7. 02 g of the mixture was added dropwise. After completion of the dropwise addition, the reaction was continued for 5 hours under reflux, and then allowed to cool to prepare a polysiloxane (A) solution (P1). When this polysiloxane (A) solution (P 1) was measured by GC, no alkoxysilane monomer was detected.

[0059] [Synthesis Examples 2 to 11]

Polysiloxane (A) solutions (P2 to P11) were obtained in the same manner as in Synthesis Example 1 with the compositions shown in Table 1. At that time, as in Synthesis Example 1, a mixture of a plurality of types of alkoxysilanes (hereinafter referred to as monomers) was used. When the obtained polysiloxane (A) solutions (P2 to P11) were measured by GC, no monomer was detected.

[0060] [Table 1] Borisyloxy / Recoxysilane

MeOI I

Sun (A) Succinic acid-methanol solution

(g)

Solution (mol) (K) Succinic acid (g) MeOH (g)

TEOS F13

Synthesis example 1 P1 17. 71 7. 02 24. 73 18. 00 32. 54

0.085 0.015

F13 UPS

Synthesis example 2 P2 7. 02 1. 29 25. 08 18. 00 31. 84

0.015 0.0045

TEOS F13 UPS

Synthesis example 3 P3 19. 06 1. 87 1. 29 22. 22 18. 00 37. 56

0.0915 0.004 0.0045

TEOS F13 UPS

Synthesis Example 4 P4 16. 25 8. 19 1. 29 25. 73 18. 00 30. 54

0.078 0.0175 0.0045

TEOS F3 UPS

Synthesis example 5 P5 15. 73 4. 36 1. 29 21. 38 18. 00 39. 24

0.0755 0.02 0.0045

TEOS F17 UPS

Synthesis example 6 P6 17. 81 5. 68 1. 29 24. 78 18. 00 32. 44

0.0855 0.01 0.0045

TEOS F13 MAS

Synthesis Example 7 P7 16. 77 7. 02 1. 12 24. 91 18. 00 32. 18

0.0805 0.015 0.0045

TEOS F13 MPS

Synthesis example 8 P8 16. 77 7. 02 0. 88 24. 67 18. 00 32. 66

0.0805 0.015 0.0045

TEOS F13 GPS

Synthesis Example 9 P9 l b. 77 7. 02 1. 06 24. 85 18. 00 32. 30

0.0805 0.015 0.0045

TEOS F13 APS GPS

Synthesis example 10 P10 13. 85 9. 36 1. 00 2. 12 26. 33 18. 00 29. 34

0.0665 0.02 0.0045 0.009

TEOS F13 F12 UPS

Synthesis example 11 P11 9. 08 3. 12 3. 99 0. 86 17. 05 12. 00 53. 89

0.0437 0.0067 0.0067 0.003

[0061] [Synthesis Example 12]

Add 28.83g of MeOH to a four-necked reaction flask equipped with a reflux tube, add TEOS 27. 91g, F13 11.70g, UPS 1.98g in small amounts under stirring to mix several kinds of alkoxysilanes. Mixing of products A MeOH solution was prepared. Next, while stirring this mixed solution at room temperature, a mixture of 14.42 g of MeOH, 15.01 g of water and 0.15 g of oxalic acid was added dropwise. After completion of the dropwise addition, heating was started, and the reaction was continued for 1 hour from the start of refluxing, and then allowed to cool to prepare a solution (P12) of polysiloxane (A). When this polysiloxane (A) solution (P12) was measured by GC, no monomer was detected.

[0062] [Table 2] Coxisilane 1 MeOH melt y night

Polysiloxane Alkoxysilane Water monosuccinic acid One MeOH solution Sun (Λ) MeOH

(g) MeOH solution

(mol) (g) Water (g) Succinic acid (g)

TEOS F13 UPS

Synthesis example 12 P12 27. 91 1.98 28. 83 0. 15

0. 134 0.025 0.0075

[0063] [Examples 1 to 20]

With the composition shown in Table 3, the coating solution for forming a film was prepared by mixing the phosphate compound (B) and the solvent into the polysiloxane (A) solution. Using this coating solution, the storage stability and the film were evaluated as follows.

Yes

[0064] [Comparative Examples 1 to 8]

With the composition shown in Table 3, a solvent was mixed with the polysiloxane (A) solution to prepare a coating solution. Using this coating solution, the storage stability and coating film shown below were evaluated in the same manner as in the Examples. However, in Comparative Example 6, the coating solution using PA instead of the phosphoric acid ester compound (B) in the example was used, and in Comparative Example 7, the coating solution using TMoePA was evaluated. .

[0065] [Table 3]

Polysiloxane Phosphate ester Solvent

(A) Solution Compound (B) PG n-BuOH ΙΡΑ P / Si ω ω ω ω Molar ratio Example 1 PI PhPA 7. 00 10. 00 48. 80 0. 1 5

33. 33 0. 87

Example 2 P2 MePA 7.00 10. 00 49. 07 0. 15

33. 33 0. 60

Example 3 P2 [PPA 7.00 10. 00 48. 82 0. 15

33. 33 0. 85

Example 4 P2 PhPA 7.00 10. 00 49. 55 0. 02

33. 33 0. 1 2

Example 5 P2 PhPA 7.00 10. 00 49. 09 0. 10

33. 33 0. 58

Example 6 P2 PhPA 7.00 10. 00 48. 80 0. 15

33. 33 0. 87

Example 7 P2 EhPA 7.00 10. 00 48. 25 0. 15

33. 33 1. 42

Example 8 P2 DdPA 7.00 10. 00 48. 34 0. 15

33. 33 1. 33

Example 9 P3 PhPA 7.00 10. 00 48. 80 0. 15

33. 33 0. 87

Example 10 P4 PhPA 7.00 10. 00 48. 80 0. 15

33. 33 0. 87

Example 1 1 P5 PhPA 7.00 10. 00 48. 80 0. 15

33. 33 0. 87

Example 12 P6 PhPA 7.00 10. 00 48. 80 0. 15

33. 33 0. 87

Example 13 P7 PhPA 7.00 10. 00 48. 80 0. 15

33. 33 0. 87

Example 14 P8 PhPA 7.00 10. 00 48. 80 0. 15

33. 33 0. 87

Example 15 P9 PhPA 7.00 10. 00 48. 80 0. 15

33. 33 0. 87

Example 16 P 10 PhPA 7.00 10. 00 48. 80 0. 15

33. 33 0. 87

Example 1 7 P 12 PhPA 7.00 10. 00 62. 1 3 0. 15

20. 00 0. 87

Example 18 P2 EtPA 7.00 10. 00 48. 71 0. 20

33. 33 0. 96

Example 19 P2 EtPA 7.00 10. 00 47. 75 0. 40

33. 33 1. 92

Example 20 P l l PhPA 7.00 10. 00 32. 13 0. 15

50. 00 0. 87

Comparative Example 1 PI — 7. 00 10. 00 49. 67

33. 33

Comparative Example 2 P2 — 7. 00 1 0. 00 49. 67

33. 33

Comparative Example 3 P5 — 7. 00 10. 00 49. 67

33. 33

Comparative Example 4 P6 — 7. 00 10. 00 49. 67

33 .: r

Comparative Example 5 P12 — 7. 00 10. 00 63. 00

20.00

Comparative Example 6 P2 PA 7. 00 10. 00 49. 18 0. 15

33. 33 0. 49

Comparative Example 7 P2 TMePA 7.00 10. 00 48. 97 0. 15

33. 33 0. 70

Comparative Example 8 P l l 7. 00 10. 00 33. 00 —

50. 00

[0066] The PZSi molar ratio in Table 3 represents the molar ratio of the phosphorus atom of the phosphate ester compound (B) to the silicon atom of the polysiloxane (A).

[0067] <Storage stability>

After the coating solution for film formation prepared with the composition shown in Table 3 was allowed to stand at room temperature for 1 month, the pore size was 0. 45 m, Φ XL: 18 X 22 mm non-aqueous polytetrafluoroethylene filter (Kurashita Boshoku Co., Ltd., Chromatodisc 13N), lOOcc filtered, ○ can be filtered, X is clogged did. Table 4 shows the results of evaluating the storage stability of the coating solution.

[0068] <Evaluation of coating>

The prepared coating-forming coating solution was applied to a triacetyl cellulose (hereinafter referred to as TAC) film (film thickness of 80 m, reflectance at a wavelength of 550 nm of 4.5%) subjected to the treatment described below to a wire bar (No. 3) was applied to form a coating film. Then, it was left at room temperature for 1 minute, dried for 5 minutes at a temperature of 100 ° C using a clean oven, and then cured at a temperature of 40 ° C for 3 days.

The TAC film used at that time was immersed for 3 minutes in a 5% by weight potassium hydroxide (KOH) aqueous solution of a TAC film with a hard coat (film thickness 80 μm) manufactured by Nippon Paper Industries Co., Ltd. heated to 40 ° C. After alkaline treatment, clean with pure water, then immerse in 0.5% by weight aqueous sulfuric acid (H2S04) at room temperature for 30 seconds and finally clean with pure water, and then in an oven at 70 ° C for 1 hour It is a dried film.

The obtained coating film was evaluated for water contact angle, magic wiping property, fingerprint wiping property, HAZE, transmittance, reflectance, surface resistance, triboelectric charge index, and dust wiping property. These evaluation methods are as follows, and the evaluation results are shown in Tables 4 and 5.

[0069] [Water contact angle]

Using an automatic contact angle measuring device FACE (CA—W type) manufactured by Kyowa Interface Science Co., Ltd., the liquid was measured with an average of five points. At that time, a water drop of 3.01 pure water was made at the tip of the needle in an environment of 23 ° C. and 50% relative humidity, and this was dropped on the surface of the coating to measure the contact angle.

[0070] [Magic wiping off]

After writing on the coating surface with black magic (M700-T1 manufactured by Magic ink), it was dried and wiped with a force tissue paper, and the wiping level was visually evaluated according to the following criteria.

〇: Magic can be completely wiped off.

Δ: Most of the magic remains with a wiping force mark.

X: Magic remains and can hardly be wiped off. [0071] [Fingerprint wiping property]

After the fingerprint was attached to the coated surface, it was wiped off with a tissue paper, and the level of wiping was visually evaluated according to the following criteria.

○: Both fingerprints and oil can be completely wiped off.

Δ: The oil can be wiped off, but a fingerprint mark remains.

X: Neither fingerprint nor oil can be wiped off.

[0072] [HAZE and transmittance]

Measurement was performed using SPECIAL HAZE METER TC-1800H manufactured by Tokyo Denshoku.

[0073] [Reflectance]

After rubbing the film surface (back surface) opposite to the coated surface with sandpaper and applying a black paint with a matte finish, the UV reflectance measuring device MPC-3100 is installed on the spectrophotometer UV-3100PC manufactured by Shimadzu Corporation. Connected and measured in wavelength range 400-800nm. The reflectance at a wavelength of 550 nm and an incident angle of 5 ° was measured.

[0074] [Surface resistance]

The surface resistance value was measured using a digital insulation meter DSM-8103 manufactured by Toa DDK Corporation. At that time, a sample that was left in an environment of 23 ° C and 50% relative humidity for 3 hours or more was used.

[0075] [friction band voltage]

Using Kanebo-type Kanebo-type friction band voltage measuring device EST-8 with a Western blanket (for muslin JIS L 0803) as a friction cloth, leave it for 3 hours or more in an environment of 23 ° C and 50% relative humidity. After the sample coating surface was rubbed 10 times, the surface voltage was measured for 60 seconds. The triboelectric charging index IFC (integrated value of the charged voltage time curve) obtained as a result of this evaluation was used to evaluate the chargeability of the coating (the smaller the value, the better the ability to wipe off dust that is difficult to charge). This evaluation method is based on JIS L 1094.

[0076] [Dust wiping property]

The tissue paper was torn finely on the coated surface and paper dust was adhered to the coated surface, and then wiped off with a tissue paper. The level of wiping was visually evaluated according to the following criteria. ○: Remove 70% or more of dust adhered before wiping △: Remove 40 to 70% of dust adhered before wiping X: Almost no wiping

[Table 4]

[Table 5]

HAZE Transmittance Reflectivity Surface resistance Friction electrification index Example Dust wiping property Immediately after film formation After 1 week (%) (%) (Ω / α) (FC (kV / min) Example 1 0. 2 0. 2 94. 7 1. 4 10 ¹¹ 0. 01 ○ Example 2 0. 2 0. 2 95. 0 1. 5 10 ¹² 0. 08 ○ Example 3 0. 2 0. 2 94. 4 1. 5 10 ¹² 0. 12 ○ Example 4 0. 2 0. 2 94. 7 1. 4 10 ¹³ 0. 20 ○ Example 5 0. 2 0. 2 94. 5 1. 5 10 ¹² 0. 02 ○ Example 6 0 2 0. 2 94. 6 1. 5 10 ¹¹ 0. 00 ○ Example 7 0. 2 0. 2 94. 0 1. 8 10 ¹³ 0. 05 ○ Example 8 0. 2 0. 2 93. 0 1. 7 10 ¹² 0. 05 Yes Example 9 0. 2 0. 2 93. 7 2. 0 10 ^{1 0} 0. 00 Yes Example 10 0. 2 0. 2 94. 5 1. 4 10 ¹² 0. 00 ○ Example 11 0. 2 0. 2 93. 5 2. 2 10 ¹⁰ 0. 00 ○ Example 12 0. 2 0. 2 94. 2 1. 7 10 ¹¹ 0. 00 ○ Example 13 0. 2 0. 2 94. 0 1. 7 10 ¹⁰ 0. 00 ○ Example 14 0. 2 0. 2 94. 2 1. 7 10 ¹¹ 0. 00 ○ Example 15 0. 2 0. 2 94. 3 1. 5 10 ¹⁰ 0. 00 ○ Example 16 0. 2 0. 2 93. 4 1. 8 10 ¹¹ 0. 01 ○ Example 17 0. 2 0. 2 94. 6 1. 7 10 ¹² 0. 01 O Implementation Example 18 0. 2 0. 2 94. 7 1. 7 10 ¹¹ 0. 02 ○ Example 19 0. 2 0. 2 94. 4 1. 8 10 ¹⁰ 0. 01 ○ Example 20 0. 2 0. 2 94. 1 1 9 10 ¹² 0. 04 〇 Comparative example 1 0. 2 0. 2 95. 0 1. 3 10 ¹⁵ 1. 00 X Comparative example 2 0. 2 0. 2 94. 8 1. 4 10] ⁵ 0. 60 X Comparative Example 3 0. 2 0. 2 94. 1 1. 9 10 ¹⁴ 0. 30 X Comparative Example 4 0. 2 0. 2 94. 7 1. 5 10 ¹⁵ 0. 48 X Comparative Example 5 0. 2 0 2 94. 9 1. 6 10 ¹⁵ 2. 99 X Comparative example 6 0. 4 0. 8 94. 2 1. 4 10 ¹⁰ 0. 00 ○ Comparative example 7 0. 2 0. 2 94. 5 1. 9 10 ¹⁵ 0. 55 X Comparative Example 8 0. 2 0. 2 94. 3 1. 8 10 ¹⁵ 0. 62 X

[0079] In Examples 1 to 20, a film having a high water contact angle and a good dust wiping property was obtained. In Comparative Examples 1 to 5, Comparative Example 7, and Comparative Example 8, dust was removed. The wipeability was poor.

In addition, Comparative Example 6 had a high water contact angle and good dust wiping properties, as in the Example, but the HAZE value increased after 1 week and was stable as in Examples 1 to 20. A film could not be obtained.

Industrial applicability

The coating liquid for forming a film of the present invention is excellent in storage stability, has a high water contact angle, has good dust wiping properties, and can form a stable film without change over time. Among them, those showing a low reflectance are useful as coating solutions for forming an antireflection film, and are formed using them. The coated film is very useful as an antireflection film.

Therefore, it is very useful as an antireflection film for use in display elements such as liquid crystal display elements and plasma displays. It should be noted that the entire contents of the specification, claims, and abstract of Japanese Patent Application No. 2006-110725 filed on April 13, 2006 are cited herein as the disclosure of the specification of the present invention. Incorporate.

Claims

Claims [1] A polysiloxane having an organic group substituted with a fluorine atom as the component (A) in the side chain, and a phosphate ester compound in which the hydroxyl group as the component is bonded to the phosphorus atom A coating solution for forming a film, characterized in that: [2] The component (A) is a polysiloxane obtained by polycondensation of an alkoxysilane represented by the formula (1) and an alkoxysilane containing the alkoxysilane represented by the formula (2). The coating liquid for film formation as described in 1.

[Chemical 1]

Si (OR ¹ ) ₄ (1)

(R ¹ represents a hydrocarbon group having 1 to 5 carbon atoms.)

[Chemical 2]

R ² Si (OR ³ ) ₃ (2)

[3] Equation (2) in which R ² is perfluoro full O b alkyl group, film-forming coating liquid according to claim 2.

[4] The coating liquid for film formation according to claim 2 or 3, wherein the component (A) is a polysiloxane obtained by polycondensation of an alkoxysilane represented by the formula (3).

[Chemical 3]

R ⁴ _n Si (OR ⁵ ) ₄ — _n (3)

[5] The coating liquid for film formation according to any one of claims 1 to 4, wherein the component (B) is a phosphate ester compound represented by the formula (4).

[Chemical 4] OP (OH) _m (OR ⁶ ) ₃ — _m (4)

[6] The coating liquid for film formation according to [5], wherein R ^{6 in the} formula (4) is an organic group having 1 to 6 carbon atoms.

[7] With respect to 1 mol of the total amount of silicon atoms in component (A), phosphorus atoms in component (B)

The coating solution for forming a film according to any one of claims 1 to 6, which contains 0.5 mol.

[8] (A) component, heavy an alkoxysilane containing 5 to 40 mol% of the alkoxysilane table by the formula 60 to 95 mol of alkoxysilane represented by (1) ^_0/0 and formula (2) The coating solution for forming a film according to any one of claims 2 to 7, which is a polysiloxane obtained by condensation.

[9] A film formed using the coating liquid for forming a film according to any one of claims 1 to 8.

[10] An antireflection film formed by using the coating liquid for forming a film according to any one of claims 1 to 8.

[11] The film-forming coating solution according to any one of claims 1 to 8 is applied to a substrate, dried at room temperature to 150 ° C, and then cured at room temperature to 150 ° C. Method for forming a film.

[12] The coating solution for forming a film according to any one of claims 1 to 8 is applied to a substrate, dried from room temperature to 150 ° C, and then cured from room temperature to 150 ° C. Forming method of antireflection film.

[13] The antireflection substrate having the coating according to claim 9 or the antireflection film according to claim 10.

[14] An antireflection film having the coating according to claim 9 or the antireflection film according to claim 10.

[15] An alkoxysilane containing 60 to 95 mol% of the alkoxysilane represented by the formula (1) and 5 to 40 mol% of the alkoxysilane represented by the formula (2), and the alkoxy group of all alkoxysilanes. 0.2 to 2 moles of oxalic acid and 1 to 2 moles of oxalic acid in organic solvent A method for producing a coating liquid for coating formation, comprising: mixing a polysiloxane solution obtained by heating and polycondensation at ° C; and a phosphate compound in which a hydroxyl group is bonded to a phosphorus atom.

[Chemical 5]

Si (OR ¹ ) ₄ (1)

(R ¹ represents a hydrocarbon group having 1 to 5 carbon atoms.)

[Chemical 6]

R ² Si (OR ³ ) ₃ (2)