WO2007102514A1

WO2007102514A1 - Coating liquid for coating film formation, production method thereof, coating film thereof, and antireflection member

Info

Publication number: WO2007102514A1
Application number: PCT/JP2007/054350
Authority: WO
Inventors: Yoshihiro Tani; Kenichi Motoyama
Original assignee: Nissan Chemical Industries, Ltd.
Priority date: 2006-03-07
Filing date: 2007-03-06
Publication date: 2007-09-13
Also published as: CN101395238A; CN101395238B; TW200804542A; JP5382310B2; JPWO2007102514A1; TWI404777B

Abstract

Disclosed is a coating liquid for coating film formation, which can be sufficiently cured by a heat treatment at low temperature while having excellent storage stability. This coating liquid enables to form a coating film having excellent abrasion resistance. Also disclosed are a method for producing such a coating liquid, a coating film and an antireflection member. Specifically disclosed is a coating liquid for coating film formation, which contains a polysiloxane (A) having an organic group containing a fluorine atom, and at least one of a polysiloxane (B) represented by the formula (1) below and a monoamine compound (C). In this coating liquid, the polysiloxane (A) and at least one of the polysiloxane (B) and the monoamine compound (C) are dissolved in an organic solvent (D). (1) (In the formula, R1, R2, R3 and R4 independently represent a hydrogen atom or a saturated hydrocarbon group having 1-5 carbon atoms, and n represents an integer of not less than 2.)

Description

Specification

Coating liquid for coating formation, manufacturing method thereof, coating film thereof, and antireflection material

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

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. Then, such a low refractive index film showing a lowered light reflectance is used as a light reflection preventing film and applied to various substrate surfaces.

For example, Patent Document 1 discloses an alcohol dispersion of MgF fine particles produced by reacting a magnesium salt or an alkoxymagnesium compound as an Mg source with a fluoride salt as an F source, or an improvement in film strength. For this purpose, a solution containing tetraalkoxysilane and the like is used as a coating solution, which is applied on a glass substrate and heat-treated at a temperature of 100 to 500 ° C to form an antireflection film exhibiting a low refractive index on the substrate. Is disclosed.

[0003] Further, 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, and has a refractive index of 1.21 to: 1.40, and has a thickness of 60 to 160 nm with micropits or irregularities having a diameter of 50 to 200 nm. The The coating is formed on a glass substrate to produce a low reflection glass.

[0004] 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. The upper film is formed by using a fluorine-containing silicone compound having a polyfluorocarbon chain such as CF (CF) CH Si (OCH), and a silane coupling agent such as Si (〇CH) at 5 to 90% by mass. In an alcohol solvent in the presence of a catalyst such as acetic acid. It is carried out by a method in which a liquid of a cocondensate prepared by hydrolyzing at a temperature and then filtered is applied onto the lower layer film and heated at a temperature of 120 to 250 ° C.

[0005] Furthermore, Patent Document 4 discloses a silicon compound represented by Si (OR), CF (CF) CH CH

4 3 2 n 2 2

A silicon compound represented by Si (OR ¹ ), an alcohol represented by R ² CH OH, and oxalic acid.

3 2

A coating solution is disclosed in which a polysiloxane solution is produced by heating a reaction mixture contained in a specific ratio at a temperature of 40 to 180 ° C. in the absence of water. By applying this coating solution to the surface of the substrate and thermosetting at a temperature of 80 to 450 ° C, a film having a refractive index of 1.28 to 1.38 and a water contact angle of 90 to 115 degrees is formed. It has been done.

[0006] 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

[0007] The antireflection film as described above is used in various display devices and the like, but is used in recent years as display devices such as liquid crystal and plasma are becoming larger, lighter, and thinner. Antireflective substrates, particularly antireflective films, tend to reduce the film thickness for the purpose of weight reduction and high transparency, and there is a problem that damage caused by heat increases. For this reason, there is an increasing demand for a coating solution for forming a thermosetting film 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. 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.

[0008] By comparison, the object of the present invention is to provide a coating solution that is excellent in storage stability, can be sufficiently cured by low-temperature heat treatment, and can form a coating film having a low refractive index and excellent scratch resistance. Another manufacturing method, a coating obtained from the coating solution, and an antireflection application using the coating.

Means for solving the problem

[0009] As a result of intensive research aimed at achieving the above object, the present inventors have completed the present invention. I got it.

That is, the gist of the present invention is as described below.

1. containing polysiloxane (A), which is a polysiloxane having an organic group having a fluorine atom, and at least one of polysiloxane (B) and monoamine compound (C) represented by formula (1), Coating solution for film formation in which they are dissolved in organic solvent (D).

[Chemical 1]

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

2. The coating solution for forming a coating according to the above 1, which is a polysiloxane obtained by polycondensation of an alkoxysilane containing an alkoxysilane represented by the formula (2).

[Chemical 2]

R ⁵ Si (OR ⁶ ) ₃ (2)

(R ⁵ is an organic group having a fluorine atom, and R ⁶ represents a hydrocarbon group having 1 to 5 carbon atoms.)

3. Polysiloxane (A) force The coating liquid for film formation according to 1 or 2 above, which is a polysiloxane obtained by polycondensation using at least one of alkoxysilanes represented by formula (3)

(R ^/ ) _m Si (OR °) _4. _m (3)

(R ⁷ is a hydrogen atom or an organic group having 1 to 20 carbon atoms having no fluorine atom, R ⁸ is a hydrocarbon group having 1 to 5 carbon atoms, and m represents an integer of 0 to 3.)

4. The coating solution for forming a film according to the above:! To 3, which is an organic basic group perfluoroalkyl group having a fluorine atom of polysiloxane (A).

5.Polysiloxane (A) force The total amount of silicon atoms it has per fluorine The coating solution for forming a coating film according to the above-mentioned :! to 4, wherein the organic group having a child is 0.05 to 0.4 mol:

6. The coating solution for forming a film according to the above:! To 5, wherein the monoamine compound (C) is at least one selected from the group consisting of aliphatic amines and alkanolamines.

7. The value obtained by converting the total amount of all the silicon atoms of polysiloxane (A) or polysiloxane (A) and polysiloxane (B) into silicon dioxide is 0.5 to 15% by mass in the coating solution. The coating liquid for film formation as described in 1 to 6 above.

8. Polysiloxane (B) contains 0.05 to 0.55 mol of all silicon atoms of polysiloxane (B) with respect to 1 mol of all atoms of polysiloxane (A). Coating solution for forming a film according to -7.

9. The monoamine compound (C) is derived from the amino group in the monoamine compound (C) with respect to 1 mol of the total amount of all the atoms of the polysiloxane (A) or the polysiloxane (A) and the polysiloxane (B). The coating solution for forming a film as described in the above:! To 8, containing from 0.01 to 0.2 mol of a nitrogen atom.

10. In addition, the inorganic acid or organic acid is 0 · 01 ~ 2.5 mol per 1 mol of polysiloxane (A) or the total amount of all the silicon atoms of polysiloxane (A) and polysiloxane (B). The coating liquid for forming a film according to any one of the above:! To 9.

11. A low refractive index film obtained by heating and curing the coating liquid for forming a film according to the above:! To 10

12. An antireflection material, wherein the low refractive index coating according to 11 above is formed on the surface of a substrate having a higher refractive index.

13. The coating solution for forming a film described in the above:! ~ 10 is applied to a substrate, dried at a temperature of 20 ~: 100 ° C for 10 seconds to 6 minutes, and then cured at a temperature of 20 ~ 70 ° C. A method for forming a low refractive index film.

14. A solution of an organic solvent of polysiloxane (A), at least one of polysiloxane (B) and monoamine compound (C), and organic solvent (D) are mixed. The manufacturing method of the coating liquid for film formation.

15. Solution power of organic solvent (D) of polysiloxane (A) Alkoxysila represented by formula (2) Is obtained by heating an alkoxysilane containing acid and an acid in an organic solvent (D), and the amount of the acid is within a range of 0.2 to 2 mol with respect to 1 mol of the total alkoxy group amount of the alkoxysilane. 15. The method for producing a coating liquid for forming a film as described in 14 above, which is a polysiloxane solution obtained in 1.

The invention's effect

The coating liquid for forming a film of the present invention has excellent storage stability, for example, a film that is sufficiently cured by heat treatment at a temperature of 20 to 70 ° C. and low temperature and excellent in scratch resistance. Can be provided.

The film obtained from the coating liquid for forming a film of the present invention can be suitably used for an antireflection material such as an antireflection film.

In the present invention, the mechanism of why the coating film formed from the coating solution has the above excellent characteristics is not necessarily clear, but is estimated as follows. In the present invention, it is necessary that the coating liquid contains a combination of fluorine-containing polysiloxane (A) and at least one of hydrocarbon-based polysiloxane (B) and monoamine compound (C). As illustrated in the following Examples and Comparative Examples, in the case of a coating solution in which each of the above components is contained alone, it has excellent storage stability, is thermally cured at a low temperature, and has a low content. A film having a refractive index and excellent scratch resistance cannot be obtained. In the present invention, in particular, in the case of a coating solution containing a fluorine-containing polysiloxane (A), a hydrocarbon-based resiloxane (B), and a monoamine compound (C), the above-mentioned characteristics of the deviation and misalignment. However, it is possible to obtain an excellent cured film.

BEST MODE FOR CARRYING OUT THE INVENTION

[0012] The present invention is described in detail below.

The coating liquid for forming a film of the present invention (also simply referred to as a coating liquid in the present invention) is represented by polysiloxane (A), which is a polysiloxane having an organic group having a fluorine atom, and the formula (1). A coating solution for forming a film containing at least one of polysiloxane (B) and monoamine compound (C), which is dissolved in an organic solvent (D).

[Chemical 4]

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

The polysiloxane (A) used in the present invention is a polysiloxane having an organic group having a fluorine atom. The organic group having a fluorine atom is an organic group bonded to a silicon atom of the polysiloxane main chain and partially or entirely substituted with a fluorine atom. The organic group having a fluorine atom is not particularly limited as long as it has a fluorine atom unless the effects of the present invention are impaired. In particular, an alkyl group in which part or all of the hydrogen atoms are substituted with fluorine atoms, an alkyl group having an ether bond in which some or all of the hydrogen atoms are substituted with fluorine atoms, and the like are preferable. At that time, the number of fluorine atoms of the organic group is not particularly limited. More preferred is a perfluoroalkyl group, and still more preferred is an organic group represented by the formula (4).

[Chemical 5]

CF ₃ (CF ₂ ) _k CH ₂ CH ₂ (4)

(k represents an integer from 0 to 12)

Specific examples of the organic group represented by the formula (4) include trifluoropropyl group, tridecafluorooctyl group, heptadecafluorodecinole group and the like.

In the present invention, the polysiloxane (A) may have one or more organic groups having fluorine atoms.

The organic group having a fluorine atom of polysiloxane (A) is reduced from 0.:! To 0.4 mol with respect to 1 mol of all the silicon atoms of polysiloxane (A), thereby further reducing the reflectance. Because it is possible, it is preferred. Further, 0.05 to 25.25 mol is preferable because the hardness of the coating can be further increased.

The polysiloxane (A) of the present invention has an organic group other than the organic group having a fluorine atom. It may be bonded to a silicon atom of the polysiloxane main chain. The organic group is an organic group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, having no fluorine atom.

Examples of such an organic group having no fluorine atom include a saturated hydrocarbon group having a linear or branched structure; an aromatic group having a benzene ring; a glycidyl group, an amino group, a ureido group, or a bur group. Or an organic group having an ether bond or an ester bond.

Specific examples thereof include, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, heptyl group, octyl group, dodecyl group, hexadecyl group, octadecyl group, phenyl group, bur group, γ-aminopropyl. Group, γ-glycidoxypropyl group, _Ί -methacryloxypropyl group and the like.

In the present invention, the amount of the organic group is not particularly limited as long as it does not impair the effects of the present invention, but the polysiloxane (Α) has no fluorine atom. The amount is preferably from 0 · 01 to 0.75 mol per 1 mol of all the silicon atoms. In such a range, a coating with a water contact angle of 90 ° or more can be obtained, and a homogeneous polysiloxane solution can easily be obtained. Also, the case of 0 · 01-0.7 mol is preferable because the hardness of the coating can be further increased.

The method for obtaining such a polysiloxane (Α) is not particularly limited, but polysiloxanes obtained by polycondensation of an alkoxysilane containing an alkoxysilane represented by the following formula (2) are preferred.

[Chemical 6]

R ⁵ Si (OR ") ₃ (2)

(R ⁵ is an organic group having a fluorine atom, and R ⁶ represents a hydrocarbon group having 1 to 5 carbon atoms.) The alkoxysilane represented by the formula (2) imparts water repellency to the film. It is. Here, R ⁵ in the formula (2) represents an organic group having a fluorine atom, but is not particularly limited as long as it is an organic group having a fluorine atom. Usually, R ⁵ is preferably an alkyl group in which some or all of the hydrogen atoms are substituted with fluorine atoms, or an alkyl group having an ether bond in which some or all of the hydrogen atoms are substituted with fluorine atoms. . Fluorine atom of this organic group The number of is also not particularly limited.

R ⁵ is an organic group having a fluorine atom, preferably an organic group having 1 to 20 carbon atoms, more preferably 3 to 10 carbon atoms, and particularly preferably 3 to 8 carbon atoms. Such alkoxysilanes are preferred because they are readily available.

[0014] In the formula (2), R ⁶ represents a hydrocarbon group having 1 to 5 carbon atoms, and a saturated hydrocarbon group is particularly preferred. Of these, lower alkyl groups such as a methyl group, an ethyl group, a propyl group, and a butyl group are preferred because they are readily available as commercial products. When a plurality of alkoxy silanes represented by the formula (2) are used, their R ⁶ may be the same or different.

In the present invention, among the alkoxysilanes represented by the formula (2), an alkoxysilane in which R ⁵ is an organic group represented by the formula (4) is preferred.

[0015] [Chemical 7]

CF ₃ (CF ₂ ) _k CH ₂ CH ₂ (4)

(k represents an integer from 0 to 12)

[0016] Specific examples of the alkoxysilane in which R ⁵ is an organic group represented by the formula (4) include trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, tridecafluoro Citryltrimethoxysilane, tridecafluorooctyltriethoxysilane, heptadecafluorodecyltrimethoxysilane, heptadecafluorodecyltriethoxysilane and the like.

[0017] In the present invention, at least one of the alkoxysilanes represented by the formula (2) may be used, but a plurality of types may be used as necessary.

Further, the polysiloxane (A) used in the present invention can be obtained by using an alkoxysilane represented by the formula (2) and an alkoxysilane represented by the formula (3) in combination. At that time, a plurality of alkoxysilanes represented by the formula (3) may be used.

[0018] [Chemical 8]

^{_{(R,) m Si (OR}} 0) 4. M (R ⁷ is a hydrogen atom or an organic group having 1 to 20 carbon atoms that does not have a fluorine atom, is a hydrocarbon group having 1 to 5 carbon atoms, and m represents an integer of 0 to 3. )

In the formula (3), R ⁸ represents a hydrocarbon group, but a saturated hydrocarbon group having 1 to 5 carbon atoms is preferable because the reactivity is higher when the number of carbon atoms is smaller. More preferred are a methyl group, an ethyl group, a propyl group, and a butyl group.

When m = 0 in formula (3), the alkoxysilane represented by formula (3) represents tetraalkoxysilane. Specific examples thereof include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane, which are easily available as commercial products.

[0020] In the formula (3), when m = an integer of 1 to 3, the alkoxysilane represented by the formula (3) has 1 to 20 carbon atoms in which R ⁷ does not have a hydrogen atom or a fluorine atom, preferably 1 ~: An alkoxysilane having 10 organic groups and an alkoxy group. In the present invention, R ⁷ may be the same or different from each other.

Examples of the organic group having 1 to 20 carbon atoms not having a fluorine atom include a saturated hydrocarbon group having a linear or branched structure, an aromatic group having a benzene ring, a glycidyl group, an amino group, a urea group, or a vinyl group. Or an organic group having an ether bond or an ester bond.

[0021] in the formula (3) is a hydrocarbon group having 1 to 5 carbon atoms. when m is 1 or 2, but is generally preferred if R ⁸ are the same, in the present invention, R ⁸ may be the same or have different from one, respectively. Specific examples of alkoxysilane in the case of m = l to 3 in the formula (3) are shown below.

For example, trimethoxysilane, triethoxysilane, methyltrimethoxysilane, methinoretriethoxysilane, ethinoretrimethoxysilane, ethinoretriethoxysilane, propinotritrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, butyltriethoxy Silane, heptyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, hexadecyltrimethoxysilane, hexadecyltriethoxysilane, octadecyltrimethoxysilane , Octadecyl Triet Xysilane, phenyltrimethoxysilane, phenyltriethoxysilane, butyltrimethoxysilane, vinyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, _Ί -glycidoxypropyltrimethoxysilane , Γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, trialkoxysilane such as γ-methacryloxypropyltriethoxysilane, dialkoxysilane such as dimethyldimethoxysilane and dimethyljetoxysilane, and trimethylmethoxy Examples include trialkylalkoxysilanes such as silane and trimethylethoxysilane.

[0022] The polysiloxane (Α) used in the present invention can be obtained by polycondensation of an alkoxysilane containing the alkoxysilane represented by the formula (2), preferably 5 to 40 mol% in the total alkoxysilane. When the reflectance of the film is further lowered, 10 to 40 mol% is preferable. When the hardness of the film is further increased, 5 to 25 mol% is preferable. In this case, the amount of the alkoxysilane represented by the formula (3) used in combination is preferably 60 to 95 mol% in the total alkoxysilane, in other words, 1 mol of the alkoxysilane represented by the formula (2). In contrast, 1 · 5 to 19 mol is preferred.

In addition, when the alkoxysilane of formula (3) contains an alkoxysilane with m = 0, in particular, alkoxysilane alone with m = 0 or alkoxysilane with m = 0 of m and m When using together with an alkoxysilane having 1 to 3, it is preferable because the storage stability of the coating solution is improved. At that time, the amount of the alkoxysilane m is 0, 20-90 mole ^_0/0 Gayori if more reduce the reflectance of 20 to 95 mol% is preferred instrument particularly coating in the total alkoxysilane preferable.

[0023] In addition, in the present invention, preferred examples of polysiloxane (A) using the alkoxysilane represented by formula (2) and formula (3) are as shown in [1] to [4] below. It is.

[1]: Polysiloxane (A) obtained by polycondensation of 5 to 40 mol% of alkoxysilane represented by the formula (2) and 60 to 95 mol% of alkoxysilane represented by the formula (3).

[2]: Obtained by polycondensation of alkoxysilane containing 5 to 40 mol% of alkoxysilane represented by formula (2) and 20 to 95 mol% of alkoxysilane represented by m of formula (3) of 0 Polysiloxane (A).

[3]: 5 to 25 mol% of alkoxysilane represented by formula (2) and m of formula (3) is represented by 0 Polysiloxane (A) obtained by polycondensation of alkoxysilane containing 20 to 95 mol% of alkoxysilane.

[4]: Obtained by polycondensation of alkoxysilane containing 10 to 40 mol% of alkoxysilane represented by formula (2) and 20 to 90 mol% of alkoxysilane represented by m of formula (3) of 0 Polysiloxane (A).

[0024] As a method for obtaining the polysiloxane (A), for example, an alkoxysilane represented by the formula (2), an alkoxysilane in which m in the formula (3) is 0, and, if necessary, a formula (3) Examples thereof include a method in which at least one alkoxysilane having m of 1 to 3 and an organic solvent are heated and polycondensed in the presence of oxalic acid. Specifically, after adding oxalic acid to alcohol in advance to obtain an alcohol solution of oxalic acid, the above-mentioned various alkoxysilanes are mixed while the solution is heated.

The amount of the oxalic acid is preferably 0.2 to 2 moles per 1 mole of the total alkoxy group content of the alkoxysilane used. The above heating can be performed at a liquid temperature of preferably 0 to 180 ° C., and is preferably performed under reflux in a vessel equipped with a reflux pipe so that the liquid does not evaporate or volatilize. It is carried out for about 10 to 10 hours.

[0025] When a plurality of types of alkoxysilanes are used, they may be mixed as a mixture in which alkoxysilanes are mixed in advance, or a plurality of types of alkoxysilanes may be mixed in sequence.

When polycondensating alkoxysilane, the concentration of all alkoxy atoms in the charged alkoxysilane in terms of oxide (hereinafter referred to as SiO concentration) is 20% by mass or less, especially

2

Preferably it is heated in the range of 4 to 15% by mass. By selecting an arbitrary concentration within such a concentration range, it is possible to suppress gel formation and obtain a homogeneous polysiloxane-containing solution.

[0026] An organic solvent used for polycondensation of alkoxysilane (hereinafter also referred to as polymerization solvent).

) Is not particularly limited as long as it dissolves the alkoxysilane represented by formula (2) and formula (3), but the use of organic solvent (D) is preferred. In particular, alcohols are produced by the polycondensation reaction of alkoxysilanes, and therefore alcohols and organic solvents having good compatibility with alcohols are used.

[0027] Specific examples of the polymerization solvent include methanol, ethanol, propanol, and _η -buta Examples include alcohols such as diols, glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, and diethylene glycol monoethyl ether.

In the present invention, a plurality of the above organic solvents may be mixed and used.

[0028] Polysiloxane (B)>

The polysiloxane (B) contained in the coating solution of the present invention is at least one polysiloxane represented by the formula (1).

[0029] [Chemical 9]

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, preferably 2 to 50. )

In the formula (1), R ² , R ³ and R ⁴ each independently represent a hydrogen atom or a saturated hydrocarbon group having 1 to 5 carbon atoms, but specific examples of the saturated hydrocarbon group having 1 to 5 carbon atoms Examples include methyl, ethyl, propyl, butyl and the like.

The polysiloxane (B) is not particularly limited as long as it is at least one polysiloxane represented by the formula (1). That is, it may be a mixture of a plurality of polysiloxanes represented by the formula (1). In that case, n is preferably an integer of 2 or more, more preferably an integer of 3 to 50. More preferably, it is 4-30.

[0031] The method for obtaining the polysiloxane (B) used in the present invention is not particularly limited. For example, it can be obtained by polycondensation of tetraalkoxysilane in an alcohol solvent. In this case, the polycondensation may be any of a method in which partial hydrolysis or complete hydrolysis is carried out and a condensation reaction is carried out. In the case of complete hydrolysis, theoretically 0.5 moles of water of all alkoxy groups in tetraalkoxysilane should be added, but usually more than 0.5 moles of water is added.

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

[0032] In the present invention, the amount of water used in the above reaction can be appropriately selected as desired, but it is generally preferably 0.5 to 2.5 times as much as that of all alkoxy groups in tetraalkoxysilane. It is.

Also, usually for the purpose of accelerating hydrolysis and condensation reactions, inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and hydrofluoric acid, or metal salts thereof; organic acids such as acetic acid, formic acid, oxalic acid, and maleic acid; A catalyst such as an alkali is used. It is also common to further promote polycondensation by heating a solution in which alkoxysilane is dissolved. At that time, the heating temperature and 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, or heating and stirring at reflux for 0.5 to 48 hours. And the like.

[0033] The solvent used for polycondensation of tetraalkoxysilane is not particularly limited as long as it dissolves tetraalkoxysilane, but the use of organic solvent (D) is preferred. In particular, alcohols are generated by polycondensation reaction of tetraalkoxysilane, and therefore, organic solvents having good compatibility with alcohols and alcohols are used.

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

[0035] The polysiloxane (B) solution obtained as described above has a SiO equivalent concentration of 30% by mass.

2

Hereinafter, it is preferably 3 to 20% by mass. By selecting an arbitrary concentration within this concentration range, gel formation can be suppressed and a homogeneous solution can be obtained.

In the present invention, when such a polysiloxane (B) is used, the content of the polysiloxane (B) in the coating solution is 1 in the mass obtained by converting all the silicon atoms of the polysiloxane (A) to silicon dioxide. On the other hand, the mass force of all the silicon atoms of polysiloxane (B) converted to silicon dioxide is 0.03 to 0.55, preferably f or 0.05 to 0.55, and more preferably f or 0.05 to 0.45. so Preferably there is.

In other words, the content of the polysiloxane (B) in the coating solution is such that the total amount of all the atoms of the polysiloxane (B) is from 0.03 to 0.001 mol per mol of all the atoms of the polysiloxane (A). 55 monole, preferably f 0.05-0.55 monole, more preferably f 0.05-0.45 monole.

[0036] <Monoamine compound (C)>

The monoamine compound (C) contained in the coating solution of the present invention promotes polycondensation of the alkoxy groups remaining in the coating without causing rapid gelation, and progresses curing of the coating even at low temperatures. Contributes to

Examples of the monoamine compound (C) include aliphatic amines having preferably carbon atoms:! -22, alkanolamines having preferably 1 to 10 carbon atoms, and aromatic amines.

[0037] Specific examples of the aliphatic amine include methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, N, N-dimethylamine, N, N-jetylamine, N, N-dipropylamine, N, N-dibutylamine, trime Tinoleamine, triethylamine, tripropylamine, tributylamine, methoxymethylamine, methoxyethylamine, methoxypropylamine, methoxybutylamine, ethoxymethylamine, ethoxyethylamine, ethoxypropyl Amines, ethoxybutyramine, propoxymethylamine, propoxyethylamine, propoxypropylamine, propoxypetite / leamine, butoxymethylamine, butoxystilamine, butoxypropylamine, butoxybutylamine, cyclo Such as key Shiruamin and the like.

[0038] Specific examples of alkanolamines include methanolamine, ethanolamine, propanolanolamine, butanolamine, N-methylmethanolamine, N-ethylmethanolamine, N-propylmethanolamine, N_ Butylmethanolamine, N_methylethanolamine, N-ethylethanolamine, N-propylethanolamine, N-butylethanolamine, N-methylpropanolamine, N-ethylpropanolamine, N- Propinopropanolamine, N-butylpropanolamine, N-methylbutanolamine, N-ethylbutanolamine, N-propylbutanolamine, N-butylbutanolamine, N, N-dimethylmethanolamine, N , N—Jetylmethanolamine, N, N- Dipropylmethanolamine, N, N-dibutylmethanolamine, N, N-dimethylethanolanolamine, N, N-jetylethanolamine, N, N-dipropylethanolamine, N, N-dibutylethanolamine , N, N-dimethylpropanolamine, N, N-diethylpropanolamine, N, N-dipropylpropanolamine, N, N-dibutinolpropanolamine, N, N-dimethylbutanolamine, N , N-Jetylbutanolamine, N, N-dipropylbutanolamine, N, N-dibutylbutanolamine, N-methyldimethanolamine, N-ethyldimethanolamine, N_propyldimethanolamine N-Butyldimethanolamine, N-Methyljetanolamine, N-Ethyljetanolamine, N-Propyldiethanolamine N-butyljetanolamine, N-methyldipropanolamine, N-ethyldipropanolamine, N_propyldipropanolamine, N-butyldipropanolamine, N_methyldibutanolamine, N- Examples include tildibutanolamine, N-propyldibutanolamine, and N-butyldibutanolamine. Specific examples of arylamine include aniline, N-methylaniline, benzylamine and the like.

[0039] The monoamine compound (C) is preferably an aliphatic amine having 1 to 22 carbon atoms or an alkanolamine having 10 carbon atoms. More preferred are ethylamine, N, N-jetolamine, triethylamine, cyclohexylamine, monoethanolamine, diethylanolamine, and triethanolamine. In the present invention, a plurality of monoamine compounds may be used.

[0040] The content of the monoamine compound (C) in the coating solution of the present invention includes the case where the coating solution contains the polysiloxane (A) alone, or the polysiloxane (A) and the polysiloxane (B). In any of the cases, the nitrogen atom derived from the amino group in the monoamine compound (C) is from 0.01 to 0.2 mol, more preferably from 0.03 to 0.1 mol, based on 1 mol of the total amount of all the silicon atoms. 0.1 mol is preferable.

When the monoamine compound (C) is 0.01 mol or more, it is preferable because it is easily cured at a low temperature. In addition, when the nitrogen atom derived from the amino group in the monoamine compound (C) is 0.20 mol or less, the coating is transparent and it is preferable to obtain a high coating hardness without unevenness.

[0041] <Organic solvent (D)> Any organic solvent (D) can be used as long as it dissolves polysiloxane (A), polysiloxane (B), and monoamine compound (C).

Specific examples of such organic solvents (D) include aliphatic alcohols such as methanol, ethanol, isopropanol, butanol and diacetone alcohol; alicyclic alcohols such as cyclopentyl alcohol and cyclohexanol; benzyl alcohol and cinnamic Aromatic alcohols such as alcohols; ketones such as acetone, methyl ethyl ketone, methyl isobutanol ketone; glycols such as ethylene glycol, propylene glycol, hexylene glycol; Echinorecanorebitonore, butinorecanorebitonore, diethyleneglycolenomonomethinoatenore, propyleneglycolenomonomethinoatenore, propyleneglycolenobutenorenore Glycol ether Norre such Honoré; acid methyl ester, acetic Echiruesuteru, and the like esters such as lactic Echinore ester. These single or plural organic solvents are used in combination.

Among them, 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. Use is preferred.

In the coating liquid for forming a film of the present invention, when polysiloxane (A) and monoamine compound (C) are used in combination, or when polysiloxane (A), polysiloxane (B) and monoamine compound (C) are used in combination. In any case, an acid component can be contained. This acid component can suppress the formation of gel during the production of the coating liquid for forming a film, and can improve the storage stability of the coating liquid for forming a film.

The acid used here is preferably an inorganic acid such as hydrochloric acid, nitric acid, sulfuric acid or phosphoric acid or an organic acid such as formic acid, acetic acid, malic acid, oxalic acid, succinic acid, propionic acid or succinic acid. When an acid is contained, the acid may be added directly to the coating solution, but it may be added as a solution dissolved in an organic solvent (D) or water. Polysiloxane (A) or polysiloxane may also be added. Power added to (B) and Z or monoamine compound (C) \ or contained in the form added to their solution It is possible to make it S.

The acid content in the coating solution is preferably from 0 · 01 to 2.5 monolayers, particularly preferably from 0 · :! to 2 mol, based on 1 mol of all the silicon atoms of polysiloxane (A). Is preferred.

[0043] <Other ingredients>

In the present invention, as long as the effects of the present invention are not impaired, other components other than polysiloxane (A), polysiloxane (B) and Z or monoamine compound (C), such as inorganic fine particles, leveling agents, A medium such as a surfactant and water may be contained. As the inorganic fine particles, those having 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. 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 size of 0.001−0.2 / im, more preferably 0.001−0.1 μΐη. When the average particle size of the inorganic fine particles exceeds 0.2 μΐη, the transparency of the cured film formed by the prepared coating liquid may be reduced. Water and organic solvents are used as the dispersion medium for the inorganic fine particles. Can be mentioned. As the colloidal solution, it is preferable that pH or pKa is adjusted to 2 to 10 from the viewpoint of the stability of the coating solution for film formation. More preferably, it is 3-7.

[0044] Examples of the organic solvent used for the dispersion medium of the colloidal solution include alcohols such as methanol, isopropyl alcohol, ethylene glycol, butanol, ethylene glycol monopropinoreateol, methyl ethyl ketone, methyl isobutyl ketone, and the like. Ketones, aromatic hydrocarbons such as toluene and xylene, amides such as dimethylenolenolemamide, dimethylacetamide, N-methylpyrrolidone, esters such as ethyl acetate, butyl acetate, and γ-butarate rataton, Examples include ethers such as tetrahydrofuran and 1,4-dioxane. Of these, alcohols and ketones are preferred. These organic solvents can be used alone or in combination of two or more as a dispersion medium. Further, as the leveling agent and the surfactant, known ones can be used, and in particular, commercially available products are preferable because they are easily available.

[0045] <Coating liquid for film formation>

The coating liquid for forming a film of the present invention contains polysiloxane (A) and at least one of polysiloxane (B) and monoamine compound (C), which are dissolved in the organic solvent (D). It is a solution. In the present invention, the preparation method is not particularly limited as long as the coating liquid for forming a film is obtained. For example, the above components may be sequentially added and mixed in the organic solvent (D) using the above components. In this case, the order of adding each component is not particularly limited. Further, a solution in which each component is dissolved in the organic solvent (D) to be used may be mixed. Further, polysiloxane (A) and polysiloxane (B) can be obtained in a solution state by polycondensation in an organic solvent. Therefore, for example, a method of mixing a solution containing polysiloxane (A) synthesized from polysiloxane (A) with a solution containing polysiloxane (B) synthesized from polysiloxane (B) and / or a monoamine compound (C) Is simple.

If necessary, the polysiloxane (A) solution is concentrated, diluted by adding a solvent or substituted with another solvent, and then the polysiloxane (B) solution and / or monoamine compound ( You can mix it with C). Further, the organic solvent (D) can be added after mixing the polysiloxane (A) solution with the polysiloxane (B) solution and / or the monoamine compound (C). At that time, the polysiloxane (B) solution may be concentrated, diluted with a solvent, or replaced with another solvent, if necessary.

[0046] When the above acid component is contained in the coating solution, the acid may be added at any time. For example, a method of adding an acid to a solution of polysiloxane (A), a concentrated solution thereof or a diluted solution thereof, and then covering the monoamine compound (C), a solution of polysiloxane (A), a concentrated solution thereof or a diluted solution thereof Examples thereof include a method in which an acid is added to a mixed solution of a liquid and polysiloxane (B), and then a monoamine compound (C) is added. Further, there may be mentioned a method in which a solution in which a monoamine compound (C) and an acid are premixed is prepared and then a solution of polysiloxane (A) is prepared.

[0047] When preparing the coating solution for forming a film of the present invention, the polysiloxane in the coating solution for forming a film

(A), or SiO of all the silicon atoms of polysiloxane (A) and polysiloxane (B) The converted concentration is preferably 0.5 to 15% by mass, and particularly preferably 0.5 to 10% by mass. If the SiO equivalent concentration is lower than 0.5% by mass, a desired film thickness can be obtained by a single application.

2

On the other hand, if it exceeds 15% by mass, the pot life of the solution is less stable. The concentration of Si 0 solids in the coating solution must be diluted with a solvent or replaced with another solvent.

2

Can be performed.

[0048] The above-mentioned polysiloxane (A), polysiloxane (B), monoamine compound (C), acid component, and a solvent used for dilution or replacement of the coating solution are added to each of these components and as necessary. As long as the compatibility with other components to be obtained is not impaired, it is not particularly limited, and one kind or plural kinds can be arbitrarily selected and used. For example, the organic solvent (D) may be the same solvent used for the polycondensation of the above alkoxysilane, or another solvent may be used. Specific examples of such solvents include methanol, ethanol, isopropanol, butanol and diacetone alcohol, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, ethylene glycol, propylene glycol and hexylate. Glycols such as N-glycol, methyl cetyl sorb, ethyl cetol sorb, butyl cello soleb, ethyl carbitol, butino recano levitol, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether Examples include esters such as glycol ether, acetic acid methyl ester, acetic acid ethyl ester, and lactic acid ethyl ester.

[0049] In addition, the method of incorporating the above-described other components into the coating solution is not particularly limited.

For example, it may be added to any of polysiloxane (A), polysiloxane (B) and / or monoamine compound (C), or a mixture thereof. Further, the polysiloxane (A) and the polysiloxane (B) and Z or the monoamine compound (C) may be added after mixing with the organic solvent (D).

[0050] In the present invention, specific examples of the coating liquid for forming a film are given below.

[1] A coating solution containing polysiloxane (A) and polysiloxane (B), which are dissolved in an organic solvent (D).

[2] A coating solution containing polysiloxane (A) and monoamine compound (C), which are dissolved in an organic solvent (D). [3] A coating solution containing polysiloxane (A), polysiloxane (B) and monoamine compound (C), which are dissolved in an organic solvent (D).

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

[5] A coating solution containing at least one selected from the group consisting of a leveling agent and a surfactant in [4] above.

[0051] In the coating solution for forming a film of the present invention, the polysiloxane (A) force is preferably 0.5 to 15 as the mass of all the silicon atoms of the polysiloxane (A) in terms of silicon dioxide. It is contained in mass%, more preferably 0.5 to 10 mass%.

When polysiloxane (B) is contained, the content of polysiloxane (B) is 1 for the mass of all the silicon atoms of polysiloxane (A) converted to SiO.

2

) The total mass of all the silicon atoms converted to SiO is preferably 0.03 to 0.55, more preferably 0

2

It is preferable that it is from 05 to 0.55. Convert all silicon atoms of polysiloxane (B) to Si〇

2 If the mass exceeds 0.55, sufficient film formability may not be obtained, or the refractive index of the paint film may increase.

[0052] When the monoamine compound (C) is contained, the monoamine compound (C), the polysiloxane (A) is contained alone, or the polysiloxane (A) and the polysiloxane (B) are used in combination. In any case, the nitrogen atom derived from the amino group in the monoamine compound (C) is preferably from 0 · 01 to 0.2 mol, more preferably 0 mol, based on 1 mol of the total amount of all the carbon atoms each has. · 03-0. 1 mole. When the nitrogen atom derived from the amino group in the monoamine compound (C) is 0.01 mol or more, it is preferable because it is easily cured at a low temperature. In addition, the amount of 0.20 mol or less is preferable because the coating is transparent, has no unevenness, and high coating hardness is easily obtained.

[0053] In the present invention, a coating solution for forming a film containing polysiloxane (A), polysiloxane (B) and monoamine compound (C) is preferable because it is easy to obtain a film having excellent scratch resistance. Les.

[0054] <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, methods such as a dip method, a flow coating method, a spray method, a bar coating method, a gravure coating method, a roll coating method, a blade coating method, and an air knife coating method can be employed. Examples of the base material include base materials such as plastic, glass, and ceramics, and examples of the plastic include polycarbonate, poly (meth) acrylate, polyethersulfone, polyarylate, polyurethane, polysulfone, polyether, and poly Examples thereof include sheet films such as ether ketone, trimethyl pentene, polyolefin, polyethylene terephthalate, (meth) acrylonitrile, triacetinoresenorelose, dicetinoresenorelose, and acetate butyrate cenorelose.

[0055] The coating film formed on the substrate may be heat-cured as it is at a temperature of 20 to 70 ° C, for example, but prior to this, it is dried at a temperature of 20 to 100 ° C and then heat-cured. May be. At this time, the time required for drying is preferably 10 seconds to 6 minutes. The time required for thermosetting can be appropriately selected according to the desired film properties, but is usually 1 hour to 7 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 addition, the coating liquid for forming a film of the present invention can provide a film having excellent scratch resistance even at a curing temperature exceeding 70 ° C.

[0056] <Applications such as antireflection materials>

The film formed from the coating solution of the present invention has a low refractive index of 1.4 or less and excellent scratch resistance, and therefore is particularly suitable for use in antireflection applications. Can do.

When the coating of the present invention is used for antireflection applications, the coating of the present invention is formed on the surface of a substrate having a refractive index higher than that of the coating of the present invention, for example, a plastic film substrate. The substrate can be easily converted into an antireflection substrate such as an antireflection film such as an antireflection film or an antireflection glass. The coating of the present invention is effective when used as a single coating on the substrate surface, but is also effective when used in an antireflection laminate in which a coating is formed on a lower coating having a high refractive index. .

[0057] The relationship between the thickness of the film and the wavelength of light is described as follows: between the thickness d (nm) of the film having a refractive index a and the wavelength λ (nm) of the light whose reflectance is desired to be reduced by this film. Has d = (2b- 1) It is known that the relational expression of / 4a (where b represents an integer of 1 or more) holds. 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, to form a film with a refractive index of 1. 3 2 and prevent reflected light from the glass surface, substitute these values for λ and a in the above equation By doing so, the optimum film thickness can be calculated. In that case, b can be substituted with 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 S.

[0058] The thickness of the coating film formed on the substrate can be adjusted by the thickness of the coating film, but can also be easily adjusted by adjusting the SiO equivalent concentration of the coating solution. . The coating of the present invention can be suitably used in fields where antireflection of light is desired, such as glass cathode ray tubes, computer displays, mirrors having glass surfaces, and glass showcases. Furthermore, the coating film of the present invention has sufficient practicality in terms of antifouling properties such that fingerprints and oil-based inks can be easily wiped off, and can be sufficiently cured by low-temperature treatment at a temperature of 20 to 70 ° C. It is particularly useful for antireflection films for display devices such as plasma and display monitors.

Example

[0059] Hereinafter, the present invention will be specifically described with reference to synthesis examples, examples and comparative examples. However, the present invention is not construed as being limited to these synthesis examples and examples. .

Explanation of abbreviations in this embodiment.

TEOS: Tetraethoxysilane

FS-13: Tridecafluorooctyltrimethoxysilane

MEA: Monoethanolanolamine

CHA: Cyclohexylamine

IPA: Isopropanol

BCS: Butyl Seguchi Solve Measurement methods in the following synthesis examples are shown below.

[0060] [Measurement method of residual alkoxysilane monomer]

The residual alkoxysilane monomer in the polysiloxane (A) solution was measured by gas chromatography (hereinafter referred to as GC).

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

Column: Capillary column CBP1 _W25_ 100 (length 25m, diameter 0.53mm, wall thickness

1 β ΤΩ.)

Column temperature: Starting temperature 50 ° C ~: Temperature is raised in 15 ° CZ minutes and the final temperature is 290 ° C (holding time 3 minutes)

).

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

[0061] [Synthesis Example 1]

Into a four-necked reaction flask equipped with a reflux tube, 57 · 26 g of methanol was added, 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-1). When this polysiloxane (A) solution (PF-1) was measured by GC, no alkoxysilane monomer was detected.

[0062] [Synthesis Examples 2 to 3]

Polysiloxane (A) solutions (PF-2 to PF-3) 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 plurality of types of alkoxysilanes were mixed and used.

When the obtained polysiloxane (A) solutions (PF — 2 to PF — 3) were measured by GC, no alkoxysilane monomer was detected.

[0063] [Table 1] Polysiloxane Silicon compound Succinic acid Methanol (A) solution (g) (g) (g)

TEOS FS- 1 3

Synthesis example 1 PF- 1 1 7. 71 7. 02 1 8. 01

0. 0850mol 0. 01 50mol

TEOS FS- 1 3 GPS

Synthesis example 2 1 7. 71 4. 68 1. 1 8

0. O850mol 0. Ol OOmol 0. 0050mol

TEOS FS- 1 3

Synthesis example 3 1 8. 02 6. 32 1 8. 01 57. 47

0. 0865mol 0. 01 35mol

[0064] [Synthesis Example 4]

A 4-necked reaction flask equipped with a reflux tube was charged with 31.78g of ethanol, 0.18g of shinonoic acid and 10.80g of pure water, and TEOS29.16g and FS—1328.08g were added under the carrying frame. ? A kongo solution was prepared. The solution was then heated to reflux for 3 hours and then allowed to cool to room temperature to prepare a polysiloxane (A) solution (PF-4A). When this polysiloxane (A) solution (PF-4A) was measured by GC, no alkoxysilane monomer was detected. On the other hand, 81 · 99 g of ethanol and 18.01 g of oxalic acid were charged into a four-necked reaction flask equipped with a reflux tube, and heated with stirring for 5 hours to prepare an acidic solution (PF-4B).

Then, 50.00 g of the polysiloxane (A) solution (PF-4Α) and 50.00 g of the acidic solution o (PF-4Β) were mixed to prepare a polysiloxane (A) solution (PF-4).

[0065] [Synthesis Example 5]

In a four-necked reaction flask equipped with a reflux tube, add 33-35 g of ethanol, stir TEOS34.79 g with stirring, and then add 0.15 g of oxalic acid, 14.99 g of water and 16.68 g of ethanol in the next stage. Therefore, the uniformly mixed solution was added dropwise little by little. Then, this solution was heated, stirred under reflux for 1 hour, and allowed to cool to room temperature to prepare a polysiloxane (B) solution (PS-1). When this polysiloxane (B) solution (PS-1) was measured by GC, the alkoxysilane monomer was not detected.

[0066] [Synthesis Example 6]

The eggplant flask was charged with 48.59 g of ethanol, 34.68 g of TEOS was added under stirring, and then a diluted solution obtained by adding 1.74 g of 60% nitric acid aqueous solution to 14.99 g of water was added dropwise little by little. Thereafter, the mixture was stirred at room temperature for 1 hour to prepare a polysiloxane (B) solution (PS-2). this When the polysiloxane (B) solution (PS-2) was measured by GC, no alkoxysilane monomer was detected.

[0067] [Example:! To 12, Comparative Example 1]

With the composition shown in Table 2, a coating solution for forming a film (Q1 to Q12) was prepared by mixing a solution of polysiloxane (A), a solution of polysiloxane (B), a monoamine compound and a solvent.

In the comparative example, a coating solution (T1) was prepared by mixing a polysiloxane (A) solution and a solvent having the composition shown in Table 2.

These Q1 to Q12 and T1 or coatings using them were evaluated as follows.

[0068] [Table 2]

[0069] The Si molar ratio of (A) / (B) is calculated as follows: Si atom of polysiloxane (A) and Si atom of polysiloxane (B) Represents the molar ratio.

[0070] [Example 13]

PF-4 (33. 33 g), CHAO. 20 g, cyclohexenolelenolene 5. OOg, propylene glycol, 'recall monomethyl ether 20.00 g, and IPA41. ) Was prepared.

The coating film using Q13 was evaluated as follows.

[0071] <Storage stability>

The coating solution was allowed to stand at a temperature of 25 ° C for 1 month, and then lOOcc with a non-aqueous polytetrafluoroethylene filter with a pore size of 0.45 μm and Φ XL: 18 X 22 mm (Chromatodisc 13N, Kurashiki Boseki) Filters were marked with ◯, and those with clogging were marked with X.

The results are shown in Table 3.

Evaluation of cured film>

The prepared coating solutions (Q1 to Q13 and T1) were triacetyl cellulose (hereinafter referred to as TAC) film treated as shown below (film thickness 80 μm, reflectivity at wavelength 550 nm is 4.5%) A bar coater (No. 3) was applied to form a coating film. After standing at a temperature of 23 ° C for 30 seconds, it was dried in a clean oven at 100 ° C for 5 minutes and then cured at a temperature of 60 ° C for 3 days. The cured film thus obtained was evaluated for water contact angle, oil pen wiping property, fingerprint wiping property, adhesion, reflectance and scratch resistance.

[0072] The refractive index was measured using a cured film formed as follows. The prepared coating solutions (Q1 to Q13 and T1) are spin-coated on a silicon wafer to form a coating film, then left at a temperature of 23 ° C for 30 seconds, and then in a clean oven at 100 ° C for 5 seconds. The film was dried for 3 minutes and then cured at 60 ° C for 3 days 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.

[0073] [TAC film surface treatment method]

40 TAC films with a hard coat made by Nippon Paper Industries Co., Ltd. (film thickness 80 μm). After being immersed in a 5% by mass potassium hydroxide (KOH) aqueous solution heated to C for 3 minutes and alkali-treated, washed with water, then 0.5% by mass sulfuric acid (H 2 SO 4) aqueous solution (liquid temperature 23 ° C) for 30 seconds

twenty four

Neutralized, washed with water and dried. [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.

[0074] [Oil pen wiping off]

The ink applied to the surface of the cured coating with 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.

[Fingerprint wiping properties]

Fingerprints were attached to the surface of the cured coating, wiped with Bencot M-3 manufactured by Asahi Kasei Co., Ltd., and the ease of removal was visually determined. The fingerprint was completely wiped off, and the others were marked X.

[0075] [Adhesion]

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

[0076] [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.

[0077] [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 11-20, D: Scratch 21 or more

[0078] [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.

[0079] [Table 3] Water contact angle Oil pen Fingerprint

Coating solution Storage stability (°) Wiping property Wiping property

Example 1 Q1 ○> 100 ○ o

Example 2 Q2 ○> 100 ○ o

Example 3 Q3 ○> 100 o o

Example 4 Q4 ○> 100 o o

Example 5 Q5 ○> 100 o o

Example 6 Q6 ○> 100 ○ ○

Example 7 Q7 ○> 100 ○ ○

Example 8 Q8 ○> 100 ○ o

Example 9 Q9 ○> 100 ○ ○

Example 10 Q10 ○> 100 ○ ○

Example 11 Q11 ○> 100 ○ ○

Example 12 Q12 ○> 100 ○ ○

Example 13 Q13 ○> 100 ○ ○

Comparative Example 1 T1 ○> 100 ○ ○

[0080] [Table 4]

[0081] As shown in Table 3 and Table 4, the cured coatings obtained from the coating solutions of Examples:! To 13 had excellent characteristics of scratch resistance of B or more at a curing temperature of 60 ° C. Excellent characteristics with a water contact angle of 100 degrees or more were shown.

Further, in Examples 6 to 10: the cured coating obtained from the coating solution containing polysiloxane (A), polysiloxane (B) and monoamine compound (C) was manufactured by Nippon Steel Wool Co., Ltd. Using 0000, rubbing 10 reciprocations at 400 g / cm ² , and visually judging how the cured film surface was scratched, all the cured films exhibited excellent scratch resistance A.

[0082] The storage stability of the coating solutions (Q1 to Q13) was also good, and was stable after storage at a temperature of 23 ° C for 6 months. Furthermore, the cured films obtained from the coating solutions of Examples:! To 13 showed characteristics of a low refractive index of 1.400 or less and a low reflectance.

On the other hand, Comparative Example 1 using the coating solution (T1) without a solution of the monoamine compound (C) and the polysiloxane (B) has an insufficient scratch resistance of D at a curing temperature of 60 ° C. It was a good thing.

In addition, as shown in Tables 3 and 4, the cured films obtained from the coating solutions of Examples:! To 13 are excellent in antifouling properties such as fingerprint wiping properties and oil-based pen wiping properties, and the base material. The adhesiveness was high.

[0083] [Examples 14 to 15]

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

[0084] [Table 5]

[0085] As shown in Example 14 and Example 15, it was shown that the cured film of the present invention was excellent in scratch resistance even at curing temperatures of 23 ° C and 40 ° C.

[0086] [Reference Example 1]

Apply the prepared coating solution Q1 to the TAC film (film thickness 80 / im, reflectivity 4.5% at a wavelength of 550 nm) with the alkali treatment described above using a bar coater (No. 3). Then, a coating film was formed. After leaving at a temperature of 23 ° C for 30 seconds, it was dried in a clean oven at 100 ° C for 5 minutes. Immediately after being allowed to cool to a temperature of 23 ° C, this film was subjected to the same method as in the examples in the water contact angle, oil pen wiping property, fingerprint wiping property, and adhesion. , Reflectance and scratch resistance were evaluated. As a result, the water contact angle is greater than 100 ° (> 100 °), the oil pen wiping property is ○, the fingerprint wiping property is ○, the adhesion property is ○, the reflectance is 1.4%, and the scratch resistance is 400 g / D at cm ² load.

Industrial applicability

The coating solution for forming a film of the present invention is excellent in storage stability, can be sufficiently cured by a low temperature heat treatment of 20 to 70 ° C., and can provide a film having a low refractive index and excellent scratch resistance. 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. In addition, the Japanese patent application 2006- 060808 filed on March 7, 2006 and the Japanese patent application 2006- 356192 filed on December 28, 2006 Description and scope of claims , And the entire contents of the abstract are hereby incorporated by reference as the disclosure of the specification of the present invention.

Claims

Claims containing polysiloxane (A), which is a polysiloxane having an organic group having a fluorine atom, and at least one of polysiloxane (B) and monoamine compound (C) represented by formula (1) A coating solution for forming a film in which they are dissolved in an organic solvent (D).

[Chemical 1]

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

[2] The coating liquid for film formation according to [1], wherein the polysiloxane (A) is a polysiloxane obtained by polycondensation of an alkoxysilane containing an alkoxysilane represented by the formula (2).

[Chemical 2]

R ⁵ Si (OR ⁶ ) ₃ (2)

(R ⁵ is an organic group having a fluorine atom, and R ⁶ represents a hydrocarbon group having 1 to 5 carbon atoms.) [3] Polysiloxane (A) At least of the alkoxysilane represented by the formula (3) The coating liquid for film formation according to claim 1 or 2, which is a polysiloxane obtained by polycondensation using one kind in combination.

[Chemical 3]

^{_{(R 7) m Si (OR}} 8) 4. M (3)

[4] The coating liquid for forming a film according to any one of claims 1 to 3, wherein the organic group having a fluorine atom of the polysiloxane (A) is a perfluoroalkyl group.

[5] Polysiloxane (A) force Fluorine raw material per 1 mol of total amount of silicon atoms it has The coating liquid for film formation according to any one of claims 1 to 4, wherein the organic group having a molecular weight is 0.05 to 0.4 mol.

[6] The coating liquid for film formation according to any one of claims 1 to 5, which is at least one selected from the group consisting of monoamine compound (C) 1S aliphatic amine and alkanolamine.

[7] Polysiloxane (Α) or the total amount of all the silicon atoms of polysiloxane (Α) and polysiloxane (Β) converted to silicon dioxide is 0.5 to 15% by mass in the coating solution. Claim 1

The coating solution for forming a coating film according to one of items 1 to 6 above.

[8] The polysiloxane (Β) force The claim wherein all the silicon atoms of the polysiloxane (Β) are contained in an amount of 0.05 to 0.55 mol with respect to 1 mol of all of the silicon atoms of the polysiloxane (Α). The coating liquid for forming a film according to any one of 1 to 7.

[9] The monoamine compound (C) is derived from the amino group in the monoamine compound (C) with respect to 1 mol of the total amount of all the atoms of the polysiloxane (原子) or polysiloxane (Α) and polysiloxane (Β). The coating solution for forming a film according to claim 1, wherein the nitrogen atom is contained in an amount of 0.01 to 0.2 mol.

[10] Furthermore, the inorganic acid or organic acid is 0 · 01-2.5 per 1 mol of polysiloxane (量) or the total amount of all the atoms of polysiloxane (Α) and polysiloxane (Β). The coating liquid for forming a film according to any one of claims 1 to 9, which is contained in moles.

[11] A low refractive index film obtained by heat-curing the coating liquid for forming a film according to any one of claims 1 to 10.

[12] An antireflection material, wherein the low refractive index film according to claim 11 is formed on the surface of a substrate having a higher refractive index.

[13] Claims 1 to: A coating solution for forming a film according to any one of 10 is applied to a substrate.

, Temperature 20 ~: A method for forming a low refractive index film, characterized by drying at 100 ° C for 10 seconds to 6 minutes and then curing at a temperature of 20 ~ 70 ° C.

[14] An organic solvent solution of polysiloxane (A), polysiloxane (B) and monoamine compound (

The method for producing a coating liquid for forming a film according to any one of claims 1 to 10, wherein at least one of C) and an organic solvent (D) are mixed. [15] Solution power S of an organic solvent of polysiloxane (A) S, obtained by heating an alkoxysilane containing an alkoxysilane represented by formula (2) and an acid in an organic solvent (D), and the above acid The production of a coating solution for forming a film according to claim 14, wherein the amount of is a polysiloxane solution obtained in a range of 0.2 to 2 mol per 1 mol of the total alkoxy group amount of the alkoxysilane. Method