KR101334496B1 - Coating liquid for coating film formation, production method thereof, coating film thereof, and antireflection member - Google Patents

Abstract

Provided is a coating liquid for forming a film, a method for producing the same, a film, and an antireflection material that are excellent in storage stability and sufficiently cured by a low temperature heat treatment, and can form a film having excellent scratch resistance.

At least one of polysiloxane (A) which is polysiloxane which has an organic group containing a fluorine atom, and polysiloxane (B) and monoamine compound (C) represented by Formula (1) is contained, and they are melt | dissolved in the organic solvent (D), Coating liquid for forming a film.

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

Description

Coating liquid for film formation, its manufacturing method, its film, and anti-reflective material {COATING LIQUID FOR COATING FILM FORMATION, PRODUCTION METHOD THEREOF, COATING FILM THEREOF, AND ANTIREFLECTION MEMBER}

 This invention relates to the coating liquid for film formation containing polysiloxane, its manufacturing method, the film formed from this coating liquid, and the antireflective material which has this film.

Conventionally, when a film having a low refractive index smaller than the refractive index of the substrate is formed on the surface of the substrate, it is known that the reflectance of light reflected from the surface of the coating is lowered. And the low refractive index film which shows such reduced light reflectance is used as a light reflection prevention film, and is applied to the surface of various base materials.

For example, Patent Literature 1 adds an alcohol dispersion liquid of MgF ₂ fine particles produced by reacting a magnesium salt or an alkoxymagnesium compound as the Mg source with a fluoride salt as the F source, or a tetraalkoxysilane or the like for improving the film strength. A method of applying a liquid as a coating liquid, coating it on a glass substrate, heat treatment at a temperature of 100 to 500 ° C., and forming an antireflection film having a low refractive index on the substrate is disclosed.

In addition, Patent Literature 2, as a hydrolyzed polycondensate such as tetraalkoxysilane, forms a coating liquid by mixing two or more kinds having different average molecular weights with a solvent such as an alcohol, and in forming a coating film with the coating liquid, the mixing ratio at the time of the mixing. It is disclosed to produce a film by adding means such as control of relative humidity. The film is obtained by heating at a temperature of 250 ° C. or higher, exhibits a refractive index of 1.21 to 1.40, and has a thickness of 60 to 160 nm having micro pits or irregularities having a diameter of 50 to 200 nm. A film is formed on a glass substrate and low reflection glass is manufactured.

Further, Patent Document 3 discloses a low reflectance glass made of glass and an underlayer film having a high refractive index formed on its surface, and an upper layer film having a low refractive index formed on the surface thereof. The upper layer is formed of a fluorine-containing silicon compound having a polyfluorocarbon chain such as CF ₃ (CF ₂ ) ₂ C ₂ H ₄ Si (OCH ₃ ) ₃ , and 5 to 90% by mass of Si (OCH ₃ ) _4, etc. The silane coupling agent is hydrolyzed at room temperature in the presence of a catalyst such as acetic acid in an alcohol solvent, and is then applied by a method of applying a liquid of the cocondensate prepared by filtration onto the underlayer film and heating at a temperature of 120 to 250 ° C. have.

Further, Patent Document 4 discloses a silicon compound represented by Si (OR) ₄ and CF ₃ (CF ₂ ) _n CH ₂ CH ₂

Si (OR ¹⁾ application that generated a polysiloxane solution by heating the alcohol and the acid, oxalic acid represented by the silicon-containing compound and, R ² CH ₂ OH represented by ₃ at a temperature 40 ~ 180 ℃ the reaction mixture under a water absence containing a specific ratio mixture Is disclosed. The coating liquid is applied to the surface of the substrate and thermally cured at a temperature of 80 to 450 ° C. to form a film having a refractive index of 1.28 to 1.38 and a water contact angle of 90 to 115 degrees.

Patent Document 1: Japanese Patent Application Laid-Open No. 05-105424

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

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

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

DISCLOSURE OF INVENTION

Problems to be solved by the invention

The above anti-reflection film is used in various display devices and the like, but in recent years, the increase in size, weight, and thickness of display devices such as liquid crystals and plasmas are in progress. It tends to make film thickness thin for the purpose of high transparency, etc., and it becomes a problem that the damage received by heat becomes large. For this reason, the demand for the coating liquid for thermosetting type film formation to harden | cure at the comparatively low temperature which can obtain an anti-reflective base material by the low temperature process to which a film does not receive damage is desired more than before. However, since the hardening temperature of the above conventional low refractive index film is not necessarily low enough, it is desired to lower hardening temperature further.

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

Means for solving the problem

MEANS TO SOLVE THE PROBLEM The present inventors came to complete this invention as a result of earnestly researching in order to achieve the said objective.

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

1. It contains at least one of polysiloxane (A) which is polysiloxane which has an organic group containing a fluorine atom, and polysiloxane (B) and monoamine compound (C) represented by Formula (1), and they are contained in an organic solvent (D). Coating liquid for film formation which melt | dissolves.

[Formula 1]

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

2. Coating liquid for film formation of said 1 whose polysiloxane (A) is polysiloxane obtained by polycondensing the alkoxysilane containing the alkoxysilane represented by Formula (2).

(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. Coating liquid for film formation as described in said 1 or 2 whose polysiloxane (A) is polysiloxane obtained by using at least 1 sort (s) of the alkoxysilane represented by Formula (3) together and polycondensing.

(3)

(R ⁷ is an organic group of 1 to 20 carbon atoms that does not have a hydrogen atom or a fluorine atom, R ⁸ is a hydrocarbon group having a carbon number of 1 to 5, m represents an integer of 0 to 3)

4. Coating liquid for film formation as described in said 1-3 whose organic group which has a fluorine atom of polysiloxane (A) is a perfluoroalkyl group.

5. Coating liquid for film formation as described in said 1-4 whose organic group which has a fluorine atom is 0.05-0.4 mol with respect to 1 mol of total amounts of the silicon atom which polysiloxane (A) has.

6. Coating liquid for film formation as described in said 1-5 whose monoamine compound (C) is at least 1 sort (s) chosen from the group which consists of aliphatic amine and alkanolamine.

7. For film formation as described in said 1-6 whose value which converted the total amount of all the silicon atoms of polysiloxane (A) or polysiloxane (A) and polysiloxane (B) into silicon dioxide is 0.5-15 mass% in a coating liquid. Coating liquid.

8. Coating liquid for film formation as described in said 1-7 in which polysiloxane (B) contains 0.05-0.55 mol of all the silicon atoms of polysiloxane (B) with respect to 1 mol of all the silicon atoms of polysiloxane (A).

9. The nitrogen atom derived from the amino group in a monoamine compound (C) is 0.01-0.2 with respect to 1 mol of total amounts of the total silicon atom of a monoamine compound (C) or polysiloxane (A) and a polysiloxane (A), and a polysiloxane (B). The coating liquid for film formation of the said 1-8 which is molar contained.

10. Furthermore, coating liquid for film formation as described in said 1-9 in which inorganic acid or organic acid contains 0.01-2.5 mol with respect to 1 mol of total amounts of the total silicon atom of polysiloxane (A) or polysiloxane (A), and polysiloxane (B). .

11. The low refractive index film obtained by heat-hardening the coating liquid for film formation of said 1-10.

12. The antireflection material formed on the surface of the base material in which the low refractive index film as described in said 11 has a higher refractive index.

13. The coating liquid for film formation as described in said 1-10 is apply | coated to a base material, it is made to dry at the temperature of 20-100 degreeC for 10 second for 6 minutes, and then it hardens at the temperature of 20-70 degreeC of the low refractive index film characterized by the above-mentioned. Forming method.

14. Production of coating liquid for film formation as described in said 1-10 which mixes the solution of the organic solvent of polysiloxane (A), at least one of a polysiloxane (B) and a monoamine compound (C), and an organic solvent (D). Way.

15. The solution of the organic solvent of polysiloxane (A) is obtained by heating the alkoxysilane and acid containing the alkoxysilane represented by Formula (2) in an organic solvent (D), and the quantity of the said acid is the whole of the said alkoxysilane. The manufacturing method of the coating liquid for film formation of said 14 which is a solution of polysiloxane obtained in the range of 0.2-2 mol with respect to 1 mol of alkoxy groups.

Effects of the Invention

The coating liquid for film formation of this invention is excellent in storage stability, for example, can fully provide the film which is hardened | cured by low temperature heat processing of the temperature of 20-70 degreeC, and is low refractive index and excellent in scratch resistance.

And the film obtained from the coating liquid for film formation of this invention can be used suitably for antireflection materials, such as an antireflection film.

In the present invention, the mechanism relating to why the coating formed from the coating liquid has such excellent characteristics is not necessarily clear, but is estimated as follows.

In this invention, it is necessary to contain in combination coating at least one among a fluorine-containing polysiloxane (A), a hydrocarbon type polysiloxane (B), and a monoamine compound (C). As exemplified in Examples and Comparative Examples described later, in the case of the coating liquid in which each of the above components is contained alone, the coating is excellent in storage stability, thermally cured at low temperatures, and has a low refractive index and excellent scratch resistance. Can not get. In the present invention, in particular, in the case of the coating liquid containing a fluorine-containing polysiloxane (A), a hydrocarbon-based siloxane (B), and a monoamine compound (C), an excellent cured coating film can be obtained in any of the above-described properties.

Carrying out the invention  Best form for

EMBODIMENT OF THE INVENTION Below, this invention is demonstrated in detail.

The coating liquid for film formation of this invention (it is also only called coating liquid in this invention) is polysiloxane (A) which is polysiloxane which has an organic group containing a fluorine atom, polysiloxane (B) represented by Formula (1), and monoamine At least one of compound (C) is contained and they are the coating liquid for film formation which is melt | dissolved in the organic solvent (D).

[Formula 4]

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

≪ Polysiloxane (A) >

Polysiloxane (A) used for this invention is polysiloxane which has an organic group containing a fluorine atom. The organic group which has this fluorine atom is an organic group couple | bonded with the silicon atom of the polysiloxane main chain, and is an organic group which one part or all substituted by the fluorine atom. The organic group which has this fluorine atom will not be specifically limited if it has a fluorine atom, unless the effect of this invention is impaired. In particular, an alkyl group in which part or all of the hydrogen atoms are substituted with fluorine atoms, or an alkyl group containing an ether bond in which part or all of the hydrogen atoms are substituted with fluorine atoms is preferable. In that case, the number of the fluorine atoms which this organic group has is not specifically limited, either. More preferably, it is a perfluoroalkyl group, More preferably, it is an organic group represented by Formula (4).

[Chemical Formula 5]

(K represents the integer of 0-12.)

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

In this invention, 1 type may be sufficient as the organic group which has the fluorine atom which polysiloxane (A) has, and multiple types may be sufficient as it.

The organic group having a fluorine atom of the polysiloxane (A) is preferred because the reflectance can be further reduced by 0.1 to 0.4 mole with respect to 1 mole of the total silicon atoms of the polysiloxane (A). Moreover, when it is 0.05-0.25 mol, since the hardness of a film can be raised more, it is preferable.

Moreover, in the polysiloxane (A) of this invention, organic groups other than the organic group which has a fluorine atom may be couple | bonded with the silicon atom of a polysiloxane main chain. The organic group is an organic group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, which does not have a fluorine atom.

As an example of the organic group which does not have such a fluorine atom, Saturated hydrocarbon group which has a linear or branched structure; Aromatic groups having a benzene ring; Organic group which has glycidyl group, an amino group, a ureido group, a vinyl group, etc .; Or organic groups having ether bonds or ester bonds.

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, vinyl group and γ-aminopropyl group. , γ-glycidoxypropyl group, γ-methacryloxypropyl group, and the like.

In the present invention, the amount of the organic group having no fluorine atom in the polysiloxane (A) is not particularly limited as long as the effects of the present invention are not impaired. However, the amount of the organic group preferably has one mole of the total silicon atoms in the polysiloxane (A). Is 0.01-0.75 mol. In the case of such a range, the film whose contact angle of water is 90 degrees or more is easy to be obtained, and the solution of homogeneous polysiloxane (A) is easy to be obtained. Moreover, when it is 0.01-0.7 mol, since the hardness of a film can be raised more, it is preferable.

Although the method of obtaining such a polysiloxane (A) is not specifically limited, The polysiloxane obtained by polycondensing the alkoxysilane containing the alkoxysilane represented by following formula (2) is preferable.

[Chemical Formula 6]

(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 Formula (2) also gives water repellency to a film.

Here, R ⁵ of formula (2) Although represents the organic group which has a fluorine atom, if it is an organic group which has a fluorine atom, it will not specifically limit. Usually, R ⁵ is preferably an alkyl group in which part or all of the hydrogen atoms are substituted with fluorine atoms, or an alkyl group containing an ether bond in which part or all of the hydrogen atoms are substituted with fluorine atoms. The number of fluorine atoms which this organic group has is not specifically limited, either.

R <^5> is an organic group which has a fluorine atom, Preferably carbon number is 1-20, More preferably, it is 3-10, Especially preferably, it is an organic group of 3-8. Such alkoxysilane is preferable because it is easy to obtain.

In addition, in Formula (2), R <^6> represents a C1-C5 hydrocarbon group and especially a saturated hydrocarbon group is preferable. Especially, since lower alkyl groups, such as a methyl group, an ethyl group, a propyl group, and a butyl group, are easy to obtain as a commercial item, it is preferable. When using a some thing as an alkoxysilane represented by Formula (2), those R <^6> may be the same and may differ, respectively.

In this invention, among the alkoxysilanes represented by Formula (2), the alkoxysilane which R <^5> is an organic group represented by Formula (4) is preferable.

[Formula 7]

(k represents an integer of 0 to 12)

As a specific example of the alkoxysilane which such R <^5> is an organic group represented by Formula (4), a trifluoro propyl trimethoxysilane, a trifluoro propyl triethoxysilane, a tridecafluoro octyl trimethoxysilane, and trideca Fluorooctyl triethoxysilane, heptadecafluorodecyltrimethoxysilane, heptadecafluorodecyltriethoxysilane, etc. are mentioned.

In this invention, although at least 1 type of alkoxysilane represented by Formula (2) may be used, you may use multiple types as needed.

In addition, the polysiloxane (A) used by this invention can also be obtained using the alkoxysilane represented by Formula (2) and the alkoxysilane represented by Formula (3) together. In that case, you may use multiple types of alkoxysilane represented by Formula (3).

[Formula 8]

(R ⁷ is an organic group of 1 to 20 carbon atoms that does not have a hydrogen atom or a fluorine atom, R ⁸ are each a carbon number of 1-5 hydrocarbon group, m represents an integer of 0 to 3)

In Formula (3), although R <^8> represents a hydrocarbon group, since a carbon number has low reactivity, the C1-C5 saturated hydrocarbon group is preferable.

More preferably, they are a methyl group, an ethyl group, a propyl group, and a butyl group.

In the case of m = 0 in Formula (3), the alkoxysilane represented by Formula (3) represents tetraalkoxysilane. Specific examples thereof include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane and the like, which can be easily obtained as a commercial item.

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

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

R <^8> of Formula (3) is a C1-C5 hydrocarbon group. When m is 1 or 2, when R <^8> is generally the same in general, in this invention, R <^8> may be the same and may differ, respectively. The specific example of the alkoxysilane in the case of integer of m = 1 to 3 of such Formula (3) is shown below.

For example, trimethoxysilane, triethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, Butyltrimethoxysilane, Butyltriethoxysilane, Pentyltrimethoxysilane, Pentyltriethoxysilane, Heptyltrimethoxysilane, Heptyltriethoxysilane, Octyltrimethoxysilane, Octyltriethoxysilane, Dodecyl Trimethoxysilane, dodecyltriethoxysilane, hexadecyltrimethoxysilane, hexadecyltriethoxysilane, octadecyltrimethoxysilane, octadecyl triethoxysilane, phenyltrimethoxysilane, phenyltriethoxy Silane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltri Ethoxysilane, γ-methacryl jade Trialkoxysilanes, such as propyl trimethoxysilane and (gamma)-methacryloxypropyl triethoxysilane, and dialkoxysilanes, such as dimethyldimethoxysilane and dimethyl diethoxysilane, and trimethylmethoxysilane, trimethylethoxysilane, etc. Trialkylalkoxysilane, etc. are mentioned.

Polysiloxane (A) used by this invention is obtained by polycondensing the alkoxysilane which preferably contains 5-40 mol% of the alkoxysilane represented by Formula (2) in all the alkoxysilanes. When reducing the reflectance of a film further, 10-40 mol% is preferable, and when increasing the hardness of a film further, 5-25 mol% is preferable. In that case, 60-95 mol% in all the alkoxysilanes is preferable, and, as for the quantity of the alkoxysilane represented by Formula (3) to use together, 1.5-19 mol is preferable with respect to 1 mol of the alkoxysilane represented by Formula (2). Do.

Moreover, when m is 0 as an alkoxysilane of Formula (3), especially the alkoxysilane which m is 0 or the alkoxysilane whose m is 0 of Formula (3), and the alkoxy of m is 1-3 When using silane together, since the storage stability of a coating liquid improves, it is preferable. In that case, 20-95 mol% is preferable in all the alkoxysilanes, and, as for the quantity of the alkoxysilane whose m is 0, 20-90 mol% is more preferable especially when further reducing the reflectance of a film.

In this way, the preferable example of polysiloxane (A) using the alkoxysilane represented by Formula (2) and Formula (3) in this invention is as follows [1]-[4].

[1]: Polysiloxane (A) obtained by polycondensing 5-40 mol% of the alkoxysilanes represented by Formula (2) and 60-95 mol% of the alkoxysilanes represented by Formula (3).

[2]: Polysiloxane (A) obtained by polycondensing the alkoxysilane containing 5-40 mol% of the alkoxysilane represented by Formula (2) and 20-95 mol% of the alkoxysilane represented by m of Formula (3) to 0.

[3]: Polysiloxane (A) obtained by polycondensing the alkoxysilane containing 5-25 mol% of the alkoxysilane represented by Formula (2), and 20-95 mol% of the alkoxysilane represented by m of Formula (3) to 0.

[4]: Polysiloxane (A) obtained by polycondensing the alkoxysilane containing 10-40 mol% of the alkoxysilane represented by Formula (2), and 20-90 mol% of the alkoxysilane represented by m of Formula (3) to 0.

As a method of obtaining polysiloxane (A), For example, the alkoxysilane represented by Formula (2), the alkoxysilane represented by m of Formula (3) to 0, and m of Formula (3) are 1-3 as needed. The method of heating and polycondensing at least 1 type of alkoxysilane and an organic solvent in presence of oxalic acid is mentioned. Specifically, after adding oxalic acid to alcohol beforehand to make it an alcohol solution of oxalic acid, it is a method of mixing said various alkoxysilanes in the state which heated the solution.

The amount of oxalic acid present is preferably 0.2 to 2 moles with respect to 1 mole of the total amount of alkoxy groups of the alkoxysilane to be used. The heating is preferably carried out at 0 to 180 ° C, and is preferably carried out for several tens of minutes to several tens of hours under reflux in a vessel equipped with a reflux tube so that the liquid does not evaporate, volatilize, or the like.

When using multiple types of alkoxysilanes, you may mix as a mixture which mixed the alkoxysilane beforehand, and may mix several types of alkoxysilanes sequentially.

In the case of polycondensing the alkoxysilane, the concentration (hereinafter referred to as SiO ₂ conversion concentration) in which all silicon atoms of the injected alkoxysilane are converted into oxides is 20% by mass or less, particularly preferably in the range of 4 to 15% by mass. It is preferred to be heated. By selecting an arbitrary concentration in such a concentration range, it is possible to suppress the formation of a gel and obtain a homogeneous polysiloxane-containing solution.

Although the organic solvent (henceforth a polymerization solvent) used when polycondensing an alkoxysilane dissolves the alkoxysilane represented by Formula (2) and Formula (3), it will not specifically limit, but use of an organic solvent (D) is preferable. Do. Especially, since alcohol is produced | generated by the polycondensation reaction of an alkoxysilane, the organic solvent with favorable compatibility with alcohols or alcohols is used.

Specific examples of the polymerization solvent described above include alcohols such as methanol, ethanol, propanol, n-butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and the like. Can be mentioned.

In this invention, you may mix and use multiple types of said organic solvent.

<Polysiloxane (B)>

Polysiloxane (B) contained in the coating liquid of this invention is polysiloxane which is at least 1 sort (s) represented by Formula (1).

[Chemical Formula 9]

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

In Formula (1), although R <^1> , R <^2> , R <^3> and R <^4> represent a hydrogen atom or a C1-C5 saturated hydrocarbon group each independently, As a specific example of a C1-C5 saturated hydrocarbon group, a methyl group, an ethyl group, A propyl group, a butyl group, etc. are mentioned.

The polysiloxane (B) is not particularly limited as long as it is at least one polysiloxane represented by formula (1). That is, the thing of multiple types of polysiloxane represented by Formula (1) may be mixed. In that case, it is preferable that n is an integer of 2 or more, More preferably, it is an integer of 3-50. More preferably, it is 4-30.

Although the method of obtaining polysiloxane (B) used for this invention is not specifically limited, For example, it can be obtained by the method of polycondensing tetraalkoxysilane in an alcohol solvent. In that case, polycondensation may be any of the method of partial hydrolysis or complete hydrolysis, and making it condensation reaction. In the case of complete hydrolysis, theoretically, 0.5 times mole of water of all the alkoxy groups in tetraalkoxysilane may be added, but an excess amount of water is usually added more than 0.5 times mole.

Specific examples of such tetraalkoxysilanes include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane and the like, which can be easily obtained as commercially available products.

In this invention, although the quantity of water used for the said reaction can be suitably selected as desired, Usually, Preferably it is 0.5-2.5 times mole of all the alkoxy groups in tetraalkoxysilane.

Moreover, inorganic acids, such as hydrochloric acid, a sulfuric acid, nitric acid, phosphoric acid, hydrofluoric acid, or its metal salt, for the purpose of promoting a hydrolysis-condensation reaction normally; Organic acids such as acetic acid, formic acid, oxalic acid and maleic acid; Alkali such as ammonia; Catalysts are used. Moreover, it is also common to accelerate polycondensation by heating the solution which the alkoxysilane melt | dissolved. In that case, heating temperature and a heat time can be suitably selected according to what you want, For example, methods, such as heating and stirring for 0.5 to 48 hours at room temperature-100 degreeC, or heating and stirring for 0.5 to 48 hours under reflux, are mentioned. have.

The solvent used for polycondensing the tetraalkoxysilane is not particularly limited as long as it dissolves the tetraalkoxysilane, but the use of an organic solvent (D) is preferable. Especially, since alcohol is produced | generated by the polycondensation reaction of tetraalkoxysilane, the organic solvent with favorable compatibility with alcohols or alcohols is 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, diethylene glycol monoethyl Glycol ether, such as ether, etc. are mentioned. In this invention, you may mix and use multiple types of said organic solvent (D).

Solution of the polysiloxane (B) obtained as described above is preferably in terms of SiO ₂ concentration of 30% by mass or less, preferably 3 to 20 mass%. By selecting an arbitrary concentration in this concentration range, the formation of a gel can be suppressed to obtain a homogeneous solution.

In this invention, when using such polysiloxane (B), content in the coating liquid of polysiloxane (B) is polysiloxane (B) with respect to 1 of the mass which converted all the silicon atoms of polysiloxane (A) into silicon dioxide. It is preferable that the mass which converted all the silicon atoms of into silicon dioxide is 0.03-0.55, Preferably it is 0.05-0.55, More preferably, it is 0.05-0.45.

In other words, as for content in the coating liquid of polysiloxane (B), all silicon atoms of polysiloxane (B) are 0.03-0.55 mol with respect to 1 mol of all the silicon atoms of polysiloxane (A), Preferably it is 0.05-0.55 mol, More preferable Preferably it is 0.05-0.45 mol.

 <Monoamine Compound (C)>

The monoamine compound (C) contained in the coating liquid of this invention promotes the polycondensation of the alkoxy group which remain | survives in a coating film, without causing gelatinization rapidly and contributes to advancing hardening of a coating film even at low temperature.

As monoamine compound (C), C1-C22 aliphatic amine, C1-C10 alkanolamine, Aromatic (arylamine), etc. are mentioned preferably.

Specific examples of aliphatic amines include methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, N, N-dimethylamine, N, N-diethylamine, N, N-dipropylamine, N, N-dibutylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, methoxymethylamine, methoxyethylamine, methoxypropylamine, methoxybutylamine, ethoxymethylamine, ethoxyethylamine , Ethoxypropylamine, ethoxybutylamine, propoxymethylamine, propoxyethylamine, propoxypropylamine, propoxybutylamine, butoxymethylamine, butoxyethylamine, butoxypropylamine, butoxybutylamine , Cyclohexylamine, etc. are mentioned.

Specific examples of the alkanolamine include methanolamine, ethanolamine, propanolamine, butanolamine, N-methylmethanolamine, N-ethylmethanolamine, N-propylmethanolamine, N-butylmethanolamine, N-methylethanolamine, N-ethylethanolamine, N-propylethanolamine, N-butylethanolamine, N-methylpropanolamine, N-ethylpropanolamine, N-propylpropanolamine, N-butylpropanolamine, N-methylbutanolamine, N- Ethylbutanolamine, N-propylbutanolamine, N-butylbutanolamine, N, N-dimethylmethanolamine, N, N-diethylmethanolamine, N, N-dipropylmethanolamine, N, N-dibutylmethanolamine , N, N-dimethylethanolamine, N, N-diethylethanolamine, N, N-dipropylethanolamine, N, N-dibutylethanolamine, N, N-dimethylpropanolamine, N, N-diethyl Propanolamine, N, N-dipropylpropanolamine, N, N-dibutylpropanolamine, N, N-dimethylbutanolamine, N, N-diethylbutanolamine, N, N-dipropylbutanol Min, N, N-dibutylbutanolamine, N-methyldimethanolamine, N-ethyldimethanolamine, N-propyldimethanolamine, N-butyldimethanolamine, N-methyldiethanolamine, N-ethyldi Ethanolamine, N-propyldiethanolamine, N-butyldiethanolamine, N-methylpropanolamine, N-ethyldipropanolamine, N-propyldipropanolamine, N-butylbutanolamine, N-methyldibutanolamine, N-ethyldibutanolamine, N-propyldibutanolamine, N-butyldibutanolamine, etc. are mentioned. Specific examples of the arylamine include aniline, N-methylaniline, benzylamine, and the like.

As a monoamine compound (C), a C1-C22 aliphatic amine or a C1-C10 alkanolamine is especially preferable. More preferably, they are ethylamine, N, N-diethylamine, triethylamine, cyclohexylamine, monoethanolamine, diethanolamine, and triethanolamine. In the present invention, a plurality of monoamine compounds may be used.

The content of the monoamine compound (C) in the coating liquid of the present invention is the total silicon atom even when the coating liquid contains polysiloxane (A) alone or when it contains polysiloxane (A) and polysiloxane (B). It is preferable that the nitrogen atom derived from the amino group in a monoamine compound (C) becomes 0.01-0.2 mol with respect to 1 mol of the total amount of, More preferably, it is 0.03-0.1 mol.

When monoamine compound (C) is 0.01 mol or more, since it is easy to harden at low temperature, it is preferable. Moreover, when the nitrogen atom derived from the amino group in a monoamine compound (C) is 0.20 mol or less, since a film is transparent, there is no stain and it is easy to obtain the hardness of a high film, it is preferable.

<Organic Solvent (D)>

The organic solvent (D) contained in the coating liquid of this invention can be used as long as it dissolves polysiloxane (A), polysiloxane (B), and a monoamine compound (C).

As an example of such an organic solvent (D), Aliphatic alcohols, such as methanol, ethanol, isopropanol, butanol, diacetone alcohol; Alicyclic alcohols such as cyclopentyl alcohol and cyclohexanol; Aromatic alcohols such as benzyl alcohol and cinnamyl alcohol; Ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; Glycols such as ethylene glycol, propylene glycol and hexylene glycol; Glycol ethers such as methyl cellosolve, ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, diethylene glycol monomethyl ether, propylene glycol monomethyl ether and propylene glycol monobutyl ether; Ester, such as methyl acetate, ethyl acetate, and lactic acid ethyl ester, etc. are mentioned.

These solvents alone or a plurality of organic solvents are used in combination.

Especially, carbon number becomes like this. Preferably it is 1-6, More preferably, 1-4 alcohol and carbon number Preferably it is 3-10, More preferably, it is the at least 1 sort (s) chosen from the group which consists of 3-7 glycol ethers. Use is preferred.

<Acid component>

In the coating liquid for film formation of this invention, even when using together a polysiloxane (A) and a monoamine compound (C), or when using together a polysiloxane (A), polysiloxane (B), and a monoamine compound (C) It may contain an acid component. This acid component can suppress generation | occurrence | production of a gel at the time of manufacture of the coating liquid for film formation, and can improve the storage stability of the coating liquid for film formation.

As the acid used herein, inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid or organic acids such as formic acid, acetic acid, malic acid, oxalic acid, citric acid, propionic acid and succinic acid are preferable. In the case of containing an acid, the acid may be added directly to the coating liquid, or may be added as a solution dissolved in an organic solvent (D) or water, and a polysiloxane (A), polysiloxane (B) and / or a monoamine compound ( It can be added to C) or contained in the form added to these solutions.

Content of the acid with respect to a coating liquid becomes like this. Preferably it is 0.01-2.5 mol with respect to 1 mol of all the silicon atoms of polysiloxane (A), Especially preferably, it is 0.1-2 mol.

&Lt; Other components >

In the present invention, other components other than polysiloxane (A), polysiloxane (B) and / or monoamine compound (C), for example, inorganic fine particles, leveling agents, surfactants, etc., so long as the effects of the present invention are not impaired. Media such as water may be contained.

As the inorganic fine particles, fine particles such as silica fine particles, alumina fine particles, titania fine particles and magnesium fluoride fine particles are preferable, and particularly preferably a colloidal solution. The colloidal solution may be obtained by dispersing the inorganic fine particle powder in a dispersion medium, or may be a commercially available colloid solution. In the present invention, by containing the inorganic fine particles, the surface shape of the cured coating film to be formed and other functions can be imparted. It is preferable that the average particle diameter is 0.001-0.2 micrometer as an inorganic fine particle, More preferably, it is 0.001-0.1 micrometer. When the average particle diameter of an inorganic fine particle exceeds 0.2 micrometer, transparency of the cured film formed with the coating liquid prepared may fall.

Water and an organic solvent are mentioned as a dispersion medium of an inorganic fine particle. As a colloidal solution, it is preferable that pH or pKa is adjusted to 2-10 from a viewpoint of stability of the coating liquid for film formation. More preferably, it is 3-7.

Examples of the organic solvent used in the dispersion medium of the colloidal solution include alcohols such as methanol, isopropyl alcohol, ethylene glycol, butanol and ethylene glycol monopropyl ether, ketones such as methyl ethyl ketone and methyl isobutyl ketone, toluene and xylene. Aromatic hydrocarbons, amides such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, esters such as ethyl acetate, butyl acetate and γ-butyrolactone, tetrahydrofuran, 1,4-dioxane and the like Ethers may be mentioned. Among these, alcohols and ketones are preferable. These organic solvents may be used alone or as a dispersion medium by mixing two or more kinds thereof.

In addition, a well-known thing can be used for a leveling agent, surfactant, etc., Especially a commercial item is easy to obtain and is preferable.

&Lt; Coating liquid for forming a film &

The coating liquid for film formation of this invention contains the polysiloxane (A), at least one of a polysiloxane (B), and a monoamine compound (C), and is a solution which melt | dissolved in the organic solvent (D). In this invention, the preparation method is not specifically limited as long as this coating liquid for film formation is obtained. For example, you may add and mix sequentially in the organic solvent (D) which uses each said component. In this case, the order of addition of the respective components is not particularly limited. Moreover, you may mix the solution melt | dissolved in the organic solvent (D) which uses each component, respectively.

In addition, polysiloxane (A) and polysiloxane (B) can be polycondensed in an organic solvent and can be obtained in a solution state. Therefore, for example, the method of mixing the solution containing the polysiloxane (A) which synthesize | combined the polysiloxane (A) with the solution containing the polysiloxane (B) which synthesize | combined the polysiloxane (B), and / or the monoamine compound (C) easy.

Further, if necessary, the solution of polysiloxane (A) may be concentrated, diluted with the addition of a solvent, or replaced with another solvent, followed by mixing with a solution of polysiloxane (B) and / or a monoamine compound (C). Moreover, after mixing the solution of polysiloxane (A), the solution of polysiloxane (B), and / or a monoamine compound (C), an organic solvent (D) can also be added. In that case, the solution of polysiloxane (B) may be concentrated as needed, the solvent may be diluted by adding a solvent, or a solution substituted with another solvent may be used.

In addition, when containing said acid component in a coating liquid, acid may be added at any time. For example, a method of adding an acid to a solution of the polysiloxane (A), the concentrate or a dilution thereof, and then adding a monoamine compound (C), or a solution of the polysiloxane (A), the concentrate or the dilution thereof and a polysiloxane. The method of adding an acid to the mixed solution of (B), and adding a monoamine compound (C) after that is mentioned. Moreover, the method of adding the solution which mixed the monoamine compound (C) and an acid previously, and then adding the solution of polysiloxane (A), etc. are mentioned.

To prepare a coating liquid for film formation of the invention, SiO ₂ in terms of the concentration of total silicon atoms is a polysiloxane (A) in the coating film-forming liquid, or a polysiloxane (A) and polysiloxane (B) which is preferably from 0.5 to It is 15 mass%, Especially preferably, it is 0.5-10 mass%. If the SiO ₂ conversion concentration is lower than 0.5% by mass, the desired film thickness is difficult to be obtained by one coating. On the other hand, when it exceeds 15% by mass, the pot life of the solution is more difficult to stabilize. SiO ₂ solid content conversion density | concentration in a coating liquid can be performed by adding and diluting a solvent or substituting with another solvent.

The solvent used for dilution or substitution of the said polysiloxane (A), polysiloxane (B), a monoamine compound (C), an acid component, and a coating liquid is compatible with each of these components, and the other components added as needed. It does not specifically limit, unless it impairs a sex, It can select arbitrarily and use one paper or multiple papers. For example, the same solvent as that used for the polycondensation of the organic solvent (D) and the above-mentioned alkoxysilane may be used, and other solvents are used.

Specific examples of such a solvent include alcohols such as methanol, ethanol, isopropanol, butanol and diacetone alcohol, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, glycols such as ethylene glycol, propylene glycol and hexylene glycol, Glycol ethers such as methyl cellosolve, ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, and propylene glycol monobutyl ether, and methyl acetate And esters such as ethyl acetate and ethyl lactate.

In addition, the method of making another component mentioned above in a coating liquid is not specifically limited. For example, you may add to any of polysiloxane (A), polysiloxane (B), and / or a monoamine compound (C), or in mixtures thereof. Moreover, you may add, after mixing a polysiloxane (A), a polysiloxane (B), and / or a monoamine compound (C) with an organic solvent (D).

In this invention, the specific example of the coating liquid for film formation is given to the following.

[1] A coating liquid containing polysiloxane (A) and polysiloxane (B) and dissolved in an organic solvent (D).

[2] A coating liquid containing polysiloxane (A) and a monoamine compound (C), and they are dissolved in an organic solvent (D).

[3] A coating liquid containing polysiloxane (A), polysiloxane (B), and a monoamine compound (C), and they are dissolved in an organic solvent (D).

[4] The coating liquid containing inorganic fine particles in [1], [2] or [3].

[5] The coating liquid containing [4] at least one selected from the group consisting of a leveling agent and a surfactant.

In the coating liquid for film formation of this invention, polysiloxane (A) is 0.5-15 mass% as mass which converted all the silicon atoms which the polysiloxane (A) has in terms of silicon dioxide, More preferably, it is 0.5-10. It is contained by mass%.

Then, the polysiloxane, if (B) is contained, the content of the polysiloxane (B) is in terms of the whole silicon atoms in the polysiloxane (B) in one of the mass in terms of total silicon atoms of the polysiloxane (A) to the SiO ₂ in SiO ₂ One mass is preferably 0.03 to 0.55, more preferably 0.05 to 0.55. When the mass in terms of the whole silicon atoms in the polysiloxane (B) in excess of 0.55 SiO ₂ film forming property of the coating film is not sufficiently obtained, or, in some cases the refractive index of the coating film to be increased.

In addition, when a monoamine compound (C) is contained, when a monoamine compound (C) contains polysiloxane (A) alone, or when it contains polysiloxane (A) and polysiloxane (B) together, respectively, The nitrogen atom derived from the amino group in a monoamine compound (C) with respect to 1 mol of the total amount of all the silicon atoms which it has becomes like this. Preferably it is 0.01-0.2 mol, More preferably, it is 0.03-0.1 mol. When the nitrogen atom derived from the amino group in a monoamine compound (C) is 0.01 mol or more, since it is easy to harden at low temperature, it is preferable. Moreover, when it is 0.20 mol or less, since a film is transparent, there is no stain, and it is easy to obtain the hardness of a high film, it is preferable.

In this invention, since the coating liquid for film formation containing polysiloxane (A), polysiloxane (B), and a monoamine compound (C) is easy to obtain the film excellent in scratch resistance, it is preferable.

<Formation of film>

The coating liquid for film formation of this invention is apply | coated to a base material, and a desired film can be obtained by thermosetting. As a coating method, a well-known or well-known method can be employ | adopted.

For example, methods such as a dip method, a flow coat method, a spray method, a bar coat method, a gravure coat method, a roll coat method, a blade coat method and an air knife coat method can be adopted.

Substrates, such as plastics, glass, and ceramics, are mentioned as a base material, As a plastics, polycarbonate, poly (meth) acrylate, polyether sulfone, polyarylate, polyurethane, polysulfone, polyether, polyether ketone, trimethyl Sheets and films, such as a pentene, a polyolefin, a polyethylene terephthalate, (meth) acrylonitrile, a triacetyl cellulose, a diacetyl cellulose, an acetate butyrate cellulose, etc. are mentioned.

Although the coating film formed in the base material may be thermoset as it is at the temperature of 20-70 degreeC as it is, for example, you may thermoset after drying at the temperature of 20-100 degreeC previously. In that case, the time required for drying is preferably 10 seconds to 6 minutes. Although the time required for thermosetting can be suitably selected according to desired film characteristics, it is usually 1 hour-7 days. When selecting a low hardening temperature, it is easy to obtain the film which has sufficient scratch resistance by lengthening hardening time.

Moreover, the coating liquid for film formation of this invention can obtain the film excellent in scratch resistance even at the curing temperature exceeding 70 degreeC.

&Lt; Use of antireflective material &

Since the film formed from the coating liquid of this invention has the low refractive index whose refractive index is 1.4 or less, and is excellent in scratch resistance, it can be used especially for antireflection use.

When the coating of the present invention is used for antireflection applications, the substrate is easily reflected by forming the coating of the present invention 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. It can convert into the base material which has an prevention ability, ie, antireflection base materials, such as an antireflection film and antireflection glass. Although the film of this invention is effective even if it uses as a single film on the surface of a base material, it is effective also to use for the antireflective laminated body in which the film was formed on the lower layer film which has high refractive index.

As for the relationship between the thickness of the film and the wavelength of the light, d = (2b-1) λ between the thickness d (nm) of the film having the refractive index a and the wavelength? It is known that a relational expression of / 4a (wherein b represents an integer of 1 or more) is established. Therefore, the reflection of light of a desired wavelength can be easily prevented by determining the thickness of the film using this equation. For example, in order to form the film which has a refractive index of 1.32 with respect to the light of wavelength 550nm, and to prevent the reflected light from a glass surface, the optimal film thickness is substituted by substituting these numerical values into (lambda) and a of said formula. Can be calculated. In that case, b should just substitute arbitrary positive integers. For example, the film thickness obtained by substituting 1 into b is 104 nm, and the film thickness obtained by substituting 2 into b is 312 nm. By employing the film thickness calculated in this manner, the antireflection performance can be easily provided.

Although the thickness of the film formed on substrate may be controlled by the coating film thickness, even it can be easily adjusted as to adjust the concentration of Si0 ₂ in terms of the coating liquid.

The coating of the present invention can be suitably used in a field where antireflection of light is desired, such as a glass CRT, a computer display, a mirror having a glass surface, a glass showcase, and the like. Moreover, since the film of this invention has sufficient practicality in terms of antifouling property which is easy to wipe a fingerprint and an oil ink, and can harden | cure sufficiently by low-temperature processing of the temperature of 20-70 degreeC, display apparatuses, such as a liquid crystal and a plasma, and a display monitor It is especially useful for the antireflection film.

Hereinafter, although a synthesis example, an Example, and a comparative example are shown and this invention is demonstrated concretely, this invention is limited to these synthesis examples and an Example, and is not interpreted.

Explanation of abbreviations in this embodiment.

TEOS: tetraethoxysilane

GPS: γ-glycidoxypropyltrimethoxysilane

FS-13: tridecafluoroctyltrimethoxysilane

MEA: Monoethanolamine

CHA: cyclohexylamine

IPA: isopropanol

BCS: butyl cellosolve

The measurement method in the following Synthesis Example is shown below.

[Residual Alkoxysilane Monomer Measurement Method]

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

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

Column: Capillary column CBP1-W25-100 (length 25m, diameter 0.53mm, thickness 1㎛)

Column temperature: It heated up at the starting temperature of 50 degreeC-15 degreeC / min, and set it as the arrival temperature of 290 degreeC (holding time 3 minutes).

Sample injection amount: 1 占 퐇, injection temperature: 240 占 폚, detector temperature: 290 占 폚, carrier gas: nitrogen (flow rate: 30 ml / min)

Synthesis Example 1

57.26 g of methanol was added to a four-neck reaction flask equipped with a reflux tube, and 18.01 g of oxalic acid was added in small portions under stirring to prepare a methanol solution of oxalic acid. Subsequently, this solution was heated and the mixture of TEOS (17.71 g) and FS-13 (7.02 g) was dripped under reflux. After dropping, the mixture was refluxed for 5 hours, cooled to room temperature to prepare a solution (PF-1) of polysiloxane (A). The alkoxysilane monomer was not detected when the solution (PF-1) of this polysiloxane (A) was measured by GC.

Synthesis Examples 2-3

By the composition shown in Table 1, the solution (PF-2-PF-3) of polysiloxane (A) was obtained by the method similar to the synthesis example 1. In that case, similarly to the synthesis example 1, several types of alkoxysilane was mixed previously and used.

The alkoxysilane monomer was not detected when the solution (PF-2-PF-3) of the obtained polysiloxane (A) was measured by GC, respectively.

[Synthesis Example 4]

Into a four-necked reaction flask equipped with a reflux tube, 31.78 g of ethanol, 0.18 g of oxalic acid, and 10.80 g of pure water were added thereto, and 29.16 g of TEOS and 28.08 g of FS-13 were added thereto under stirring to prepare a mixed solution. Subsequently, this solution was heated to reflux for 3 hours, and thereafter cooled to room temperature to prepare a solution (PF-4A) of polysiloxane (A). The alkoxysilane monomer was not detected when the solution (PF-4A) of this polysiloxane (A) was measured by GC.

On the other hand, 81.99 g of ethanol and 18.01 g of oxalic acid were added to a four-neck reaction flask equipped with a reflux tube, and heated under stirring for 5 hours to prepare an acidic solution (PF-4B).

And 50.00 g of solution (PF-4A) of polysiloxane (A) and 50.00 g of acidic solution (PF-4B) were mixed to prepare a solution (PF-4) of polysiloxane (A).

Synthesis Example 5

33.35 g of ethanol was added to a four-necked reaction flask equipped with a reflux tube, and 34.79 g of TEOS was added under stirring, and then a solution obtained by uniformly mixing 0.15 g of oxalic acid, 14.99 g of water, and 16.68 g of ethanol in advance was added dropwise. Then, this solution was heated, it stirred at reflux for 1 hour, it was left to cool to room temperature, and the solution (PS-1) of polysiloxane (B) was prepared. The alkoxysilane monomer was not detected when the solution (PS-1) of this polysiloxane (B) was measured by GC.

[Synthesis Example 6]

48.59 g of ethanol was added to a Nasu flask, and 34.68 g of TEOS was added under stirring, and a dilute solution in which 1.74 g of an aqueous 60% nitric acid solution was added to 14.99 g of water was added dropwise. Thereafter, the mixture was stirred at room temperature for 1 hour to prepare a solution (PS-2) of polysiloxane (B). The alkoxysilane monomer was not detected when the solution (PS-2) of this polysiloxane (B) was measured by GC.

[Examples 1 to 12 and Comparative Example 1]

In the composition shown in Table 2, the solution of polysiloxane (A), the solution of polysiloxane (B), the monoamine compound, and the solvent were mixed, and the coating liquids (Q1-Q12) for film formation were prepared.

In addition, in the comparative example, in the composition shown in Table 2, the solution and the solvent of polysiloxane (A) were mixed, and the coating liquid (T1) was prepared.

Evaluation shown below was performed about these Q1-Q12 and T1 or the coating film using them.

Si molar ratio of (A) / (B) shows the molar ratio of the Si atom of polysiloxane (A) and the Si atom of polysiloxane (B).

[Example 13]

PF-4 (33.33g), CHA 0.20g, cyclohexyl alcohol 5.00g, propylene glycol monomethyl ether 20.00g, and IPA 41.47g were mixed, and the coating liquid Q13 for film formation was prepared.

Evaluation shown below was performed about the coating film using Q13.

<Storage stability>

After the coating solution was allowed to stand at a temperature of 25 ° C. for 1 month, 100 cc of filtration was performed using a non-aqueous polytetrafluoroethylene filter (Chromasiki Spinning Co., Ltd. chromatodis 13N manufactured by Kurashiki Spinner) having a pore diameter of 0.45 μm and φ × L: 18 × 22 mm. (Circle) and what clogging generate | occur | produced were made what was able to be x.

The results are shown in Table 3.

&Lt; Evaluation of cured film &

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

In addition, the refractive index was measured using the cured film formed as follows. After the prepared coating liquids (Q1 to Q13 and Tl) were spin-coated on a silicon wafer to form a coating film, the mixture was left at a temperature of 23 ° C. for 30 seconds and then dried at 100 ° C. for 5 minutes in a clean oven, followed by a temperature of 60 ° C. It hardened | cured for 3 days, and the cured film whose film thickness is 100 nm was obtained.

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

 [TAC film surface treatment method]

Nippon Paper Co., Ltd. hard coat formed TAC film (film thickness: 80 micrometers) was immersed in 5 mass% potassium hydroxide (KOH) aqueous solution heated at 40 degreeC for 3 minutes, and it alkaline-treated, and then washed with water, and 0.5 mass% sulfuric acid then, It was immersed in (H ₂ SO ₄ ) aqueous solution (liquid temperature 23 ° C.) for 30 seconds to neutralize, washed with water and dried.

[Water contact angle]

The contact angle when 3 microliters of pure water was dripped using the automatic contact angle meter CA-Z type by Kyowa Interface Science, Inc. was measured.

[Wipe off the oil repellent]

The ink treated on the surface of the cured film using a penterus oil-based pen was wiped off using Bencott M-3, manufactured by Asahi Kasei Co., Ltd. to visually determine whether it was wiped well. (Circle) and thing other than that which ink was wiped off completely were made into x.

 [Fingerprints]

Fingerprints were affixed on the hardened film surface, and it wiped using Bencott M-3 by Asahi Kasei Co., Ltd., and visually judged whether it wiped well. The thing wiped off the fingerprint completely was made into (circle) and the other thing x.

[Adhesion]

Cut 100 points in a checkerboard graduation shape at intervals of 1 mm to the cured film on the substrate, and strongly adhere the cellop tape (Nichi-Sanregistered Trademark 24 mm width) to the cured film, and then peel off the cello tape sharply to see if the cured film is peeled off. Was visually confirmed. And those with no peeling were rated as &quot;? &Quot;

[reflectivity]

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

[Scratch resistance]

Using the Nippon Steel Wool Co., Ltd. steel wool # 0000, the hardened film was rubbed 10 reciprocally at 400 g / cm <2>, and it visually judged that the flaw of the hardened film surface generate | occur | produced.

The criteria are as follows.

A: 5 or more scratches, B: 6-10 scratches, C: 11-20 scratches, D: 21 or more scratches

[Refractive index]

The refractive index in the light of wavelength 633nm was measured using the episometer DVA-36L made by Mizo Geographic Co., Ltd.

As shown in Table 3 and Table 4, in the cured film obtained from the coating liquid of Examples 1-13, the outstanding property of the scratch resistance B or more and the water contact angle of 100 degree or more appeared at the curing temperature of 60 degreeC. .

In addition, in Examples 6-10, the hardened film obtained from the coating liquid containing polysiloxane (A), polysiloxane (B), and a monoamine compound (C) is 400 g using steel wool # 0000 by the Japan Steel Wool Company. As a result of visually determining that scratches occurred on the surface of the cured film by rubbing 10 round trips at / cm 2, excellent cured resistance was A in all cured films.

And storage stability of coating liquids (Q1-Q13) was also favorable, and was stable even after storing for 6 months at the temperature of 23 degreeC.

Moreover, in the cured film obtained from the coating liquid of Examples 1-13, the characteristic of the low refractive index and low reflectance of 1.400 or less appeared.

On the other hand, the comparative example 1 using the coating liquid (T1) which does not have the solution of a monoamine compound (C) and a polysiloxane (B) was insufficient in scratch resistance D at 60 degreeC curing temperature.

In addition, as shown in Tables 3 and 4, the cured coating film obtained from the coating liquids of Examples 1 to 13 was excellent in antifouling properties such as fingerprint wiping and oil pen wiping and high adhesion to the substrate. .

[Examples 14-15]

The prepared coating liquid Q6 was applied to the alkali-treated TAC film (reflectance of 4.5% in film thickness and wavelength of 550 nm of 4.5%) described above using a bar coater (No. 3) to form a coating film. After standing at a temperature of 23 ° C. for 30 seconds, it was dried for 5 minutes at 100 ° C. in a clean oven, followed by Example 14 for 5 days at a temperature of 23 ° C., and Example 15 for 3 days at a temperature of 40 ° C. for each curing condition. The cured film was obtained. Adhesiveness, reflectance, and scratch resistance were evaluated about the obtained cured film. These evaluation methods are as above-mentioned, and the evaluation result is shown in Table 5.

As shown in Example 14 and Example 15, the cured film of this invention was shown to be excellent in abrasion resistance even when hardening temperature is 23 degreeC and 40 degreeC.

[Referential Example 1]

The prepared coating solution Q1 was applied to a TAC film (reflectance of 4.5% in film thickness of 550 nm and a wavelength of 550 nm) subjected to alkali treatment as described above using a bar coater (No. 3) to form a coating film. After standing at the temperature of 23 ° C. for 30 seconds, the resultant was dried for 5 minutes at 100 ° C. in a clean oven. Immediately after cooling to a temperature of 23 ° C., the water contact angle, oil pen wiping, fingerprint wiping, adhesiveness, reflectance and scratch resistance were evaluated in the same manner as in Example. As a result, the water contact angle was larger than 100 ° (> 100 °), the oil pen wiping was ○, the fingerprint wiping was ○, the adhesion was ○, the reflectance was 1.4%, and the scratch resistance was D at 400 g / cm 2 load.

The coating liquid for film formation of this invention is excellent in storage stability, can fully be hardened by the low temperature heat processing of the temperature of 20-70 degreeC, and can provide the film excellent in low refractive index and scratch resistance. Therefore, it can use especially suitably for an antireflection base material, and can use especially for the antireflection film for display elements especially.

In addition, the JP Patent application 2006-060808 filed on March 7, 2006 and the Japanese patent application 2006-356192 filed on December 28, 2006 are hereby incorporated by reference in their entirety. It introduces as disclosure of the specification of this invention.

Claims (15)

Polysiloxane (A) which is polysiloxane which has an organic group containing a fluorine atom, and a monoamine compound (C) are contained, or the polysiloxane (A) represented by the said Formula (A), Formula (1), and a monoamine compound (C) are contained And as those coating liquids for film formation dissolved in the organic solvent (D), The nitrogen atom derived from the amino group in the monoamine compound (C) is 0.01 to 1 mol of the total amount of the total silicon atoms of the polysiloxane (A) or the polysiloxane (A) and the polysiloxane (B) in the monoamine compound (C). Coating liquid for film formation contained in 0.2 mol.      [Formula 1]

(R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom or a saturated hydrocarbon group having 1 to 5 carbon atoms, n represents an integer of 2 or more) The method of claim 1, Coating liquid for film formation whose polysiloxane (A) is polysiloxane obtained by polycondensing the alkoxysilane containing the alkoxysilane represented by Formula (2). (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. The method according to claim 1 or 2, Coating liquid for film formation whose polysiloxane (A) is polysiloxane obtained by using together at least 1 sort (s) of the alkoxysilane represented by Formula (3), and polycondensing. (3)

(R ⁷ is an organic group of 1 to 20 carbon atoms that does not have a hydrogen atom or a fluorine atom, R ⁸ is a hydrocarbon group having a carbon number of 1 to 5, m represents an integer of 0 to 3) 3. The method according to claim 1 or 2, Coating liquid for film formation whose organic group which has a fluorine atom of polysiloxane (A) is a perfluoroalkyl group. 3. The method according to claim 1 or 2, Coating liquid for film formation whose organic group which has a fluorine atom is 0.05-0.4 mol with respect to 1 mol of total amounts of the silicon atom which polysiloxane (A) has. 3. The method according to claim 1 or 2, Coating liquid for film formation whose monoamine compound (C) is at least 1 sort (s) chosen from the group which consists of aliphatic amine and alkanolamine. 3. The method according to claim 1 or 2, Coating liquid for film formation whose value which converted the total amount of all the silicon atoms of polysiloxane (A) or polysiloxane (A) and polysiloxane (B) into silicon dioxide is 0.5-15 mass% in a coating liquid. 3. The method according to claim 1 or 2, Coating liquid for film formation in which the polysiloxane (B) contains 0.05-0.55 mol of all the silicon atoms of polysiloxane (B) with respect to 1 mol of all the silicon atoms of polysiloxane (A). delete 3. The method according to claim 1 or 2, Furthermore, the coating liquid for film formation in which an inorganic acid or an organic acid contains 0.01-2.5 mol with respect to 1 mol of total amounts of all the silicon atoms of polysiloxane (A) or polysiloxane (A), and polysiloxane (B). The low refractive index film obtained by heat-hardening the coating liquid for film formation of Claim 1 or 2. The antireflection material formed on the surface of the base material in which the low refractive index film of Claim 11 has a higher refractive index. The coating liquid for film formation of Claim 1 or 2 is apply | coated to a base material, it is made to dry at the temperature of 20-100 degreeC for 10 second for 6 minutes, and then it hardens at the temperature of 20-70 degreeC, The low refractive index film characterized by the above-mentioned. Method of formation. The manufacturing method of the coating liquid for film formation of Claim 1 or 2 which mixes the solution of the organic solvent of polysiloxane (A), a monoamine compound (C), and an organic solvent (D); Or the manufacturing method of the coating liquid for film formation which mixes the solution of the organic solvent of polysiloxane (A), a polysiloxane (B), and a monoamine compound (C) and an organic solvent (D). 15. The method of claim 14, The solution of the organic solvent of polysiloxane (A) is obtained by heating the alkoxysilane and acid containing the alkoxysilane represented by Formula (2) in an organic solvent (D), and the quantity of the said acid is the total amount of the alkoxy groups of the said alkoxysilane. The manufacturing method of the coating liquid for film formation which is a solution of polysiloxane obtained in the range of 0.2-2 mol with respect to 1 mol of the. (2)

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