JP5531614B2 - Coating liquid for forming antireflection coating containing polysiloxane modified with mercapto group - Google Patents

Description

The present invention, antireflective film-forming coating liquid, to a cured film obtained from 及 beauty coating liquid. Furthermore, it is related with the application to the reflection preventing use of the cured film obtained from this coating liquid.

  Conventionally, it is known that when a film having a refractive index lower than the refractive index of a base material is formed on the surface of the base material, the reflectance of light on the surface of the coating film decreases. Such a film showing low reflection characteristics is used as an anti-reflection film for preventing reflection of external light on various displays such as personal computers and televisions, showcases and window glass. Depending on the above, it is applied to various substrate surfaces such as glass and plastic films.

  As means for obtaining a low refractive index film for antireflection, (1) a method using an antireflection layer made of a material containing fluorine having a low refractive index, and (2) air holes are provided in the antireflection layer, air The method is roughly classified into a method of lowering the refractive index by mixing in.

Examples of the method (1) include an alcohol dispersion of MgF ₂ fine particles produced by reacting a magnesium salt, an alkoxymagnesium compound, or the like as an Mg source with a fluoride salt as an F source, or this An antireflective material with a low refractive index on the base material by applying a solution obtained by adding tetraalkoxysilane to a glass base material such as a cathode ray tube and then heat-treating at 100 to 500 ° C. A method of forming a film is disclosed. (See Patent Document 1)

In addition, a silicon compound represented by Si (OR) ₄ , a silicon compound represented by CF ₃ (CF ₂ ) _n CH ₂ CH ₂ Si (OR ¹ ) ₃ , an alcohol represented by R ² CH ₂ OH, and oxalic acid Is heated at 40-180 ° C. in the absence of water to form a polysiloxane solution, the composition containing the solution is applied to the substrate surface, and A method of forming a film having a refractive index of 1.28 to 1.38 and a water contact angle of 90 to 115 ° by forming the film in close contact with the substrate surface by thermosetting at 80 to 450 ° C. It is disclosed. (See Patent Document 2)

Furthermore, a composition A composed of either an organosilicon compound represented by Si (OR) ₄ (R is a linear or branched alkyl group) or a polymer of the compound, and Rf- (OC ₃ F ₆ ) _n − _{O- (CF 2) m - (} CH 2) l -O- (CH 2) s -Si (oR) 3 (Rf is a linear or branched perfluoroalkyl group having 1 to 16 carbon atoms, n represents 1 An integer of ˜50, m is an integer of 0 to 3, l is an integer of 0 to 3, s is an integer of 0 to 6, provided that 6 ≧ m + 1> 0, R is a linear or branched alkyl group) A method of obtaining a low refractive index coating agent and an antireflection film comprising a copolymer with a perfluoropolyether group-containing silicon compound or a composition B comprising a polymer of the compound is disclosed. ing. (See Patent Document 3)

On the other hand, as an example of the above (2), a copolymer composed of Si (OR) ₄ and R ′ _m Si (OR) _4-m , which is a composition composed of either an organosilicon compound or a polymer thereof, Or a copolymer matrix further comprising R ″ _n Si (OR) _4-n [where R is an alkyl group, R ′ is a fluorine-containing substituent, R ″ is a vinyl group, an amino group, an epoxy group, chloro; A substituent having at least one selected from the group consisting of a group, a methacryloxy group, an acryloxy group, and an isocyanate group, and m and n are the number of substitutions], an average particle size of 0.5 to 200 nm, a refractive index of 1 A method for obtaining an antireflection film having a low refractive index coating agent and a low refractive index layer characterized by adding .44 to 1.34 hollow silica fine particles is disclosed. (See Patent Document 4)

JP 05-105424 A JP 09-208898 A JP 2002-265866 A JP 2002-317152 A

  Since the conventional antireflection film as described above is formed on the outermost surface of a display or the like, it is often exposed to external impacts and scratches, fingerprints and dirt, etc. Antifouling properties are required. As disclosed in Patent Document 3 and Patent Document 4 described above, in the conventional antireflection film, a composition containing a polysiloxane-based composition having many condensable groups such as silanol at the terminal is used as a plastic with a hard coat. In many cases, a method of applying a film on a substrate such as a film and forming a film by condensation is used.

  However, even if a polysiloxane having a large number of highly polar silanol groups at the terminal is applied to a hard-coated substrate having a hydrophobic surface, the adhesion is insufficient and good scratch resistance cannot be obtained. Therefore, before forming the anti-reflection film, surface treatment (high frequency discharge plasma method, electron beam method, ion beam method, vapor deposition method, sputtering method, alkali treatment method, acid treatment method, corona discharge treatment method) A glow discharge plasma method or the like is applied. Of these, alkali treatment (saponification) with an aqueous solution of sodium hydroxide, potassium hydroxide or the like is effective. However, if surface treatment such as alkali treatment is performed on the hard coat substrate before forming the antireflection film, there is a problem that the manufacturing cost increases because the number of steps is increased and dedicated equipment is required.

An object of the present invention is to solve the conventional problems, and is excellently adhered to a substrate that has not been surface-treated (such as a plastic film with a hard coat) and exhibits excellent scratch resistance. refractive index, low haze (hAZE), provides a high transmittance antireflection film-forming coating liquid having the cured film and the antireflection film obtained using the coating liquid, and antireflective substrate having a cured film There is.

The inventor has conducted extensive research to achieve the above object, and has reached the present invention. The present invention has the following gist.
1. Via a siloxane bond to the main chain of polysiloxane (a) obtained by polycondensation of an alkoxysilane containing an alkoxysilane represented by formula (1) and an alkoxysilane represented by formula (2) a polysiloxane organic group having a mercapto group is bonded (a), the total molar amount of the sulfur atom of the mercapto group the polysiloxane (a) has a total molar amount of silicon atoms to which the polysiloxane (a) has The coating liquid for anti-reflective coating formation characterized by containing polysiloxane (A) whose ratio (S / Si) is 0.03-0.3 .
Si (OR ¹ ) ₄ (1)
R ³ Si (OR ⁴ ) ₃ (2)
(In the formula (1), R ¹ is a saturated hydrocarbon group having 1 to 5 carbon atoms, in the formula (2), R ³ is a fluorine-containing organic group, and R ⁴ is a hydrocarbon having 1 to 5 carbon atoms. Group.)
2. 2. The coating solution for forming an antireflection coating according to 1 above, wherein R ³ in the formula (2) is a fluoroalkyl group.
3. A polysiloxane (a) is obtained by polycondensation with an alkoxysilane represented by the formula (1), an alkoxysilane represented by the formula (2), and an alkoxysilane represented by the formula (3). 3. The coating liquid for forming an antireflection film as described in 1 or 2 above.
R ⁵ _n Si (OR ⁶ ) _4-n (3)
(In formula (3), R ⁶ is a hydrocarbon group having 1 to 5 carbon atoms, R ⁵ is an organic group not substituted with a hydrogen atom, a halogen atom, or a fluorine atom, and n is 1 to 3. Yes, when n is 2 or 3, a plurality of R ⁵ may be the same or different.
4). The organic group that is not substituted with a fluorine atom represented by R ⁵ in the formula (3) is selected from a chlorine atom, a vinyl group, an amino group, a glycidoxy group, a mercapto group, a methacryloxy group, a ureido group, an isocyanate group, and an acryloxy group. 4. The coating liquid for forming an antireflection coating as described in 3 above, which is a hydrocarbon group which may be substituted with a substituent.
5. 4. The coating liquid for forming an antireflection coating according to 3 above, wherein R ⁵ in the formula (3) is a hydrocarbon group substituted with a ureido group.
6). 6. The coating solution for forming an antireflection coating according to any one of 1 to 5 above, containing polysiloxane (A) in a concentration of 0.08 to 2.5 mol / kg as a concentration of all silicon atoms.
7 . The cured film obtained using the coating liquid for anti-reflective film formation as described in any one of said 1-6 .
8 . The antireflection film forming coating solution according to any one of 1 to 6 above is applied to a base material in which the hard coat layer is semi-cured, dried, and cured at 20 to 150 ° C. after being irradiated with ultraviolet rays. Method for forming a film.
9 . 8. An antireflection substrate having the cured film as described in 7 above.
10 . 8. An antireflection film having the cured film as described in 7 above.

According to the present invention, even when applied to a base material (such as a plastic film with a hard coat) that has not been subjected to a surface treatment such as an alkali treatment method (saponification), it exhibits excellent scratch resistance and adheres well. A coating solution for forming an antireflection coating having a low refractive index, low haze (HAZE), and high transmittance is provided.
The above-mentioned effect in the present invention is obtained by using polysiloxane (A) in which an organic group having a mercapto group is bonded to the main chain of polysiloxane (a) via a siloxane bond. Although the mechanism is not necessarily clear, as shown in the comparative examples described later, the polysiloxane (a) has an organic group having a mercapto group without a siloxane bond, even if it has an organic group having a mercapto group. In the case of bonding to the main chain, the effect of the present invention described above cannot be obtained.

<Polysiloxane (a)>
Polysiloxane (a) is a polysiloxane having an organic group in the side chain, since it has a water repellent with antireflection properties to the cured film obtained by the present invention, the polysiloxane (a) has been substituted with a fluorine atom (in the present invention, also referred to as a fluorine-containing organic group.) the organic group that have a in the side chain. In that case, the polysiloxane (a) is a polysiloxane having a fluorine-containing organic group in the side chain .

  The fluorine-containing organic group is an organic group obtained by substituting a part or all of the hydrogen atoms of an aliphatic group or aromatic group with a fluorine atom. Among these, a fluoroalkyl group, preferably a perfluoroalkyl group, is preferable because it is easy to obtain an antireflection coating having high transparency. Moreover, carbon number of the said fluoroalkyl group becomes like this. Preferably it is 3-15, Most preferably, it is 6-12.

Preferable specific examples of the fluoroalkyl group include a trifluoropropyl group, a tridecafluorooctyl group, a heptadecafluorodecyl group, a pentafluorophenyl group, and the like.
The polysiloxane (a) is preferably a polysiloxane having an organic group containing a ureido group in the side chain. By having it in the side chain containing a ureido group, the scratch resistance of the cured film is improved. The method for obtaining the polysiloxane (a) used in the present invention is not particularly limited, but it is usually obtained by polycondensation of alkoxysilane.

In the present invention, when the cured film of the present invention obtained by using the polysiloxane (A) described later has water repellency as well as antireflection performance, the polysiloxane (a) is an alkoxysilane having a fluorine-containing organic group. Those obtained by polycondensation of alkoxysilanes containing are preferred. Further, it is preferable to use tetraalkoxysilane in combination because polysiloxane (a) is easily obtained. The tetraalkoxysilane is preferably an alkoxysilane represented by the following formula (1).
Si (OR ¹ ) ₄ (1)
In the above formula (1), R ¹ represents a hydrocarbon group. However, since the reactivity is higher when the number of carbon atoms is smaller, a saturated hydrocarbon group having 1 to 5 carbon atoms is preferable. More preferred are a methyl group, an ethyl group, a propyl group, and a butyl group. Specific examples of such a tetraalkoxysilane include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, and the like, and are easily available as commercial products. In the present invention, at least one of the alkoxysilanes represented by the formula (1) may be used, but a plurality of types may be used as necessary.

As the alkoxysilane having a fluorine-containing organic group, an alkoxysilane represented by the following formula (2) is preferable.
R ³ Si (OR ⁴ ) ₃ (2)
The alkoxysilane represented by the above formula (2) is an alkoxysilane having the aforementioned fluorine-containing organic group in the side chain, and this alkoxysilane imparts antireflection performance and water repellency to the coating. R ^{3 in the} formula (2) represents the above-described fluorine-containing organic group and is a group having a fluorine atom having 3 to 15 carbon atoms, preferably a group having a fluorine atom having 6 to 13 carbon atoms. is there. The number of fluorine atoms in the organic group is not particularly limited, but is preferably 9-21. R ⁴ in formula (2) represents a hydrocarbon group having 1 to 5 carbon atoms, preferably a saturated hydrocarbon group having 1 to 4 carbon atoms, more preferably a methyl group, an ethyl group, or a propyl group. is there.

Among the alkoxysilanes represented by the above formula (2), an alkoxysilane in which R ³ is preferably a fluoroalkyl group (particularly preferably a perfluoroalkyl group) is preferable, and in particular, R ³ is CF ₃ (CF _{2) k CH 2 CH 2 (} k is more preferably alkoxysilane is an organic group represented by the representative.) an integer from 0 to 12. Specific examples of such alkoxysilanes include trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, tridecafluorooctyltrimethoxysilane, tridecafluorooctyltriethoxysilane, heptadecafluorodecyltrimethoxysilane, heptadecafluorodecyl. Examples include triethoxysilane. In particular, k is preferably an integer of 3 to 9, since the water repellency of the coating becomes good.
In the present invention, at least one of the alkoxysilanes represented by the formula (2) may be used, but a plurality of types may be used as necessary.

The polysiloxane (a) is obtained by polycondensation of alkoxysilanes preferably containing the alkoxysilanes represented by the formulas (1) and (2), but the cured film substrate obtained by the present invention. For the purpose of improving the adhesion to the substrate, it may be further polycondensed with an alkoxysilane represented by the formula (3) as necessary.

R ⁵ _n Si (OR ⁶ ) _4-n (3)

In the above formula (3), R ⁶ is a hydrocarbon group having 1 to 5 carbon atoms, preferably a saturated hydrocarbon group having 1 to 5 carbon atoms, more preferably a saturated hydrocarbon having 1 to 3 carbon atoms. It is a group. Alkoxysilane of formula (3) it is, R ⁵ is a hydrogen atom, a halogen atom, an organic group not substituted by fluorine atom, an alkoxy silane preferably having 1 to 3 alkoxy groups. The organic group having no fluorine which is R ⁵ in formula (3) is preferably a group having 1 to 20 carbon atoms. More preferably, it is a group having 1 to 10 carbon atoms, and more preferably a group having 1 to 5 carbon atoms. Examples of such organic groups include hydrocarbon groups, hydrocarbon groups substituted with chlorine atoms, vinyl groups, amino groups, glycidoxy groups, mercapto groups, methacryloxy groups, ureido groups, isocyanate groups, acryloxy groups, and the like. It is done. Among the hydrocarbon groups, a linear or branched alkyl group is preferable, and substituted with a chlorine atom, a vinyl group, an amino group, a glycidoxy group, a mercapto group, a methacryloxy group, a ureido group, an isocyanate group, an acryloxy group, or the like. May be. When n is 1 to 3 and n is 2 or 3, a plurality of R ⁵ are often the same, but R ⁵ may be the same or different.

Although the specific example of the alkoxysilane represented by the said Formula (3) is shown below, it is not limited to this.
Methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, pentyltrimethoxysilane, pentyltriethoxysilane, Heptyltrimethoxysilane, heptyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, hexadecyltrimethoxysilane, hexadecyltriethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane Silane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane , 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyl Triethoxysilane, gamma-mercaptopropyltrimethoxysilane, gamma-mercaptopropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, gamma-methacryloxypropyltrimethoxysilane, gamma-methacrylic Roxypropyltriethoxysilane, ureidomethyltriethoxysilane, ureidomethyltrimethoxysilane, ureidoethyltriethoxysilane, ureidoethyltrimethoxysilane, ureido L-propyltriethoxysilane, ureidopropyltrimethoxysilane, ureidobutyltriethoxysilane, ureidobutyltrimethoxysilane, ureidopentanetriethoxysilane, ureidopentanetrimethoxysilane, dialkoxysilanes such as dimethyldimethoxysilane, dimethyldiethoxysilane, etc. Is mentioned. In the present invention, a plurality of alkoxysilanes represented by the formula (3) may be used as necessary.
Among the alkoxysilanes represented by the above formula (3), an alkoxysilane in which R ⁵ is substituted with a ureido group and has 1 to 20 carbon atoms is preferable because it can improve the scratch resistance of the cured film. More preferably, it is an alkoxysilane represented by the following formula (4).

[H ₂ NCONH (CH ₂ ) _x ] _m Si (OR ² ) _4-m (4)

In said formula (4), x is an integer of 1-6, Preferably it is an integer of 1-5. m is an integer of 0 to 3, and m is preferably 1. R ² 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 and an ethyl group. Specific examples of such alkoxysilanes include ureidomethyltriethoxysilane, ureidomethyltrimethoxysilane, ureidoethyltriethoxysilane, ureidoethyltrimethoxysilane, ureidopropyltriethoxysilane, ureidopropyltrimethoxysilane, ureidobutyltrile. Examples include ethoxysilane, ureidobutyltrimethoxysilane, ureidopentanetriethoxysilane, and ureidopentanetrimethoxysilane.
Among the above formulas (4), a particularly preferred alkoxysilane is an alkoxysilane represented by the following formula (5).

_{(H 2 NCONHCH 2 CH 2 CH} 2) m Si (OR 2) 4-m (5)

Specific examples of the alkoxysilane having a side chain having a ureido group include ureidopropyltriethoxysilane and ureidopropyltrimethoxysilane, and 3-ureidopropyltrimethoxysilane and 3-ureidopropyltriethoxysilane are It is easily available as a commercial product.

The polysiloxane (a) used in the present invention is usually obtained by polycondensing an alkoxysilane represented by the formula (1) and the formula (2) and an alkoxysilane represented by the formula (3) as necessary. Although it can be obtained, the proportion of the alkoxysilane used is not particularly limited as long as it is in a homogeneous solution state in a solvent.
The amount of the tetraalkoxysilane of the formula (1) is preferably 40 to 94 mol%, particularly preferably 56 to 86 mol%, based on the total alkoxysilane used for obtaining the polysiloxane (a).

  The alkoxysilane having a fluorine-containing organic group represented by the formula (2) is preferably 5 mol% or more, particularly preferably 10 mol, based on the total amount of alkoxysilane used for obtaining the polysiloxane (a) component. % Or more is preferable because a film having a water contact angle of 80 ° or more can be easily obtained. On the other hand, the case of preferably 50 mol% or less, particularly preferably 40 mol% or less, is preferable because the formation of gels and foreign substances can be suppressed and a homogeneous polysiloxane (a) solution can be easily obtained.

Moreover, when using the alkoxysilane represented by Formula (3), Preferably it is 1-35 mol% in the alkoxysilane used in order to obtain polysiloxane (a), Especially preferably, 5-20 mol% is suitable. It is.
Among them, the alkoxysilane having a side chain having a ureido group represented by the formula (4), preferably the formula (5) is preferably used with respect to the total amount of alkoxysilane used for obtaining the polysiloxane (a). Is 0.5 to 15 mol%, particularly preferably 4 to 10 mol%, the cured film obtained has good scratch resistance.

  The method for polycondensing the polysiloxane (a) used in the present invention is not particularly limited, and examples thereof include a method of hydrolyzing and polycondensing alkoxysilane in an alcohol or glycol solvent. At that time, the hydrolysis / polycondensation reaction may be either partial hydrolysis or complete hydrolysis. In the case of complete hydrolysis, theoretically 0.5 times mole of water of all alkoxy groups in the alkoxysilane may be added, but usually an excess amount of water is added more than 0.5 times mole. In the present invention, the amount of water used for the reaction can be appropriately selected as desired. Usually, the amount of all alkoxy groups in the alkoxysilane is preferably 0.1 to 2.5 times, particularly preferably 0. .3 to 2.0 moles.

  Usually, for the purpose of promoting hydrolysis / polycondensation reaction, acids such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, formic acid, succinic acid, phosphoric acid, maleic acid or metal salts of these acids; ammonia, methylamine, ethylamine, A catalyst such as an alkali such as ethanolamine or triethylamine is used. The amount of the catalyst is preferably about 0.001 to 0.05 times moles of all alkoxy groups in the alkoxysilane. In addition, it is also common to further promote hydrolysis and polycondensation reactions by heating a solution in which alkoxysilane is dissolved. At that time, the heating temperature and the heating time can be appropriately selected as desired. Preferably, the reaction system is set to 50 to 180 ° C., and the evaporation or volatilization of the liquid does not occur. Done for 10 hours. For example, heating and stirring at 50 ° C. for 24 hours, heating and stirring for 8 hours under reflux, and the like can be mentioned.

As another method, for example, a method of heating a mixture of alkoxysilane, a solvent, and oxalic acid can be mentioned. Specifically, after adding succinic acid to alcohol in advance to make an alcohol solution of succinic acid, the alcohol solution and alkoxysilane are mixed and heated. In this case, the amount of succinic acid is preferably 0.2 to 2 mol, particularly preferably 0.3 to 1.5 mol, relative to 1 mol of all alkoxy groups of the alkoxysilane. The heating in this method can be performed at a liquid temperature of 50 to 180 ° C., and preferably, for example, in a sealed container or under reflux for several tens of minutes to several tens of hours so that the liquid does not evaporate or volatilize. Is called.
In any of the above-described methods, when a plurality of alkoxysilanes are used, a plurality of alkoxysilanes may be mixed in advance, or a plurality of alkoxysilanes may be sequentially added.

When alkoxysilane is polycondensed by the above method, the total concentration of silicon atoms of all alkoxysilanes charged in the solution is preferably 0.07 to 3.5 mol / kg (0.4 to _{4 in} terms of SiO ₂ concentration). 21.4% by mass), particularly preferably 0.17-1.67 mol / kg (1-10% by mass in terms of SiO ₂ ). By selecting such a concentration range, gel formation can be suppressed and a homogeneous polysiloxane solution can be obtained.

  The organic solvent used for polycondensation of alkoxysilane dissolves the alkoxysilane represented by formula (1) and formula (2) and, if necessary, the alkoxysilane represented by formula (3). If there is no particular limitation. In general, since an alcohol is generated by a polycondensation reaction of alkoxysilane, an organic solvent having good compatibility with alcohols and alcohols, in particular, an organic solvent contained in the coating liquid for forming an antireflection coating of the present invention. The use of the same organic solvent as in (B) is preferred.

  Preferable specific examples of the organic solvent include alcohols such as methanol, ethanol, 1-propanol, 2-propanol, n-butyl alcohol and t-butyl alcohol; glycols such as ethylene glycol, propylene glycol and hexylene glycol; Examples include ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, and diethylene glycol monoethyl ether; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone. In the present invention, a plurality of the above organic solvents may be mixed and used.

式中、Ｚはメルカプト基を有する基を表し、好ましくは下記式（ｉｉ）で表される基であり、より好ましくは下記式（ｉｉｉ）で表される基である。

式中ｙは１〜６の整数であるが、好ましくは１〜５の整数である。ｖは１〜３の整数であり、ｖが１であるのが好ましい。
このようなポリシロキサン（Ａ）は、ポリシロキサン（ａ）にメルカプト基を有するアルコキシシランを混合して重縮合させることで得られる。即ち、予め生成したポリシロキサン（ａ）にメルカプト基を有するアルコキシシランを反応させることで、式（ｉ）の構造を生成させて、ポリシロキサン（Ａ）を得ることができる。
上記メルカプト基を有するアルコキシシランとしては、好ましくは下式（６）に示すアルコキシシランが使用される。

〔ＨＳ（ＣＨ_２）_ｙ〕_ｐＳｉ（ＯＲ^７）_４−ｐ （６）

式（６）において、ｙは１〜６の整数であるが、好ましくは１〜５の整数である。Ｐは１〜３の整数であり、Ｐが１に近いほうが反応性が高いので好ましい。また、Ｒ^７は、炭化水素基を表すが、炭素数が少ない方が反応性が高いので、炭素数が好ましくは１〜５、好ましくは１〜４の飽和炭化水素基が好ましい。より好ましくはメチル基、エチル基、プロピル基である。上記式（６）のなかでも下記式（７）のアルコキシシランが好ましい。

（ＨＳＣＨ_２ＣＨ_２ＣＨ_２）_ｐＳｉ（ＯＲ^７）_４−ｐ （７）

式（７）のなかでも、γ−メルカプトプロピルトリメトキシシラン、γ−メルカプトプロピルトリエトキシシランは市販品として入手し易いので好ましい。<Polysiloxane (A)>
The polysiloxane (A) used in the present invention is a polysiloxane in which an organic group having a mercapto group is bonded to the main chain of the polysiloxane (a) having the organic group in the side chain through a siloxane bond. Typically, the polysiloxane (A) is preferably a polysiloxane having a structural unit represented by the following formula (i).

In the formula, Z represents a group having a mercapto group, preferably a group represented by the following formula (ii), and more preferably a group represented by the following formula (iii).

In the formula, y is an integer of 1 to 6, but is preferably an integer of 1 to 5. v is an integer of 1 to 3, and v is preferably 1.
Such polysiloxane (A) can be obtained by mixing polysiloxane (a) with an alkoxysilane having a mercapto group and polycondensing the mixture. That is, the polysiloxane (A) can be obtained by reacting the previously produced polysiloxane (a) with an alkoxysilane having a mercapto group to produce the structure of the formula (i).
As the alkoxysilane having a mercapto group, an alkoxysilane represented by the following formula (6) is preferably used.

[HS _{(CH 2) y] ^{p Si (OR 7) 4-}} p (6)

In formula (6), y is an integer of 1 to 6, preferably an integer of 1 to 5. P is an integer of 1 to 3, and it is preferable that P is close to 1 because the reactivity is high. R ⁷ represents a hydrocarbon group, and since the reactivity is higher when the number of carbon atoms is smaller, a saturated hydrocarbon group having 1 to 5 carbon atoms, preferably 1 to 4 carbon atoms is preferable. More preferred are a methyl group, an ethyl group, and a propyl group. Among the above formulas (6), alkoxysilanes of the following formula (7) are preferable.

(HSCH ₂ CH ₂ CH ₂ ) _p Si (OR ⁷ ) _4-p (7)

Among the formulas (7), γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane are preferable because they are easily available as commercial products.

When polysiloxane (a) and alkoxysilane having a mercapto group are polycondensed, the total concentration of all silicon atoms of polysiloxane (a) is preferably 0.07 to 3.5 mol / kg (SiO ₂ equivalent concentration is 0). .4 to 21.4% by mass), particularly preferably 0.1 to 2.0 mol / kg (SiO ₂ equivalent concentration of 0.6 to 12% by mass) in an organic solvent solution containing an alkoxysilane having a mercapto group. Is preferably added in an amount of 0.03 to 0.3 mol part, particularly preferably 0.04 to 0.22 mol part with respect to 1 mol part of all silicon atoms contained in the resulting polysiloxane (A). The reaction is preferably performed at 20 to 180 ° C, particularly preferably at 25 to 100 ° C.

  The polysiloxane (A) thus obtained is a ratio (S / Si) between the total molar amount of sulfur atoms (S) of mercapto groups and the total molar amount of silicon atoms (Si) of the polysiloxane (A). ) Is preferably 0.03 to 0.3, particularly preferably 0.04 to 0.22. When (S / Si) is less than 0.03, sufficient adhesion between the obtained antireflection coating and the substrate hard coat layer cannot be obtained, resulting in insufficient scratch resistance. The reflectance increases or the transmittance decreases.

  When the polysiloxane (a) and the alkoxysilane having a mercapto group are polycondensed, an organic solvent may be further added to the reaction system. In addition, as the organic solvent here, an organic solvent having good compatibility with alcohols and alcohols, in particular, an organic solvent (B) described later which is a solvent for the coating liquid for forming an antireflection coating of the present invention is suitable. .

When polysiloxane (A) is obtained by polycondensing polysiloxane (a) and alkoxysilane having a mercapto group as described above, a solution of polysiloxane (a) in an organic solvent (B) and an alkoxysilane having a mercapto group. The concentration of all silicon atoms contained in the mixed solution is preferably 3.3 mol / kg or less (20% by mass in terms of SiO ₂ ), particularly preferably 1.7 mol / kg (10% by mass in terms of SiO ₂ conversion). The following is preferable because it can suppress the generation of gel in the polysiloxane (A) solution.

<Organic solvent (B)>
The coating liquid for forming a film of the present invention is a solution in which polysiloxane (A) and other components described later as required are dissolved in an organic solvent (B). Therefore, the organic solvent (B) used in the present invention is not particularly limited as long as it dissolves the polysiloxane (A) and other components described later as uniformly as possible.

  Specific examples of such an organic solvent (B) include alcohols such as methanol, ethanol, 1-propanol, 2-propanol, n-butyl alcohol, cyclohexanol, diacetone alcohol; acetone, methyl ethyl ketone, methyl isobutyl ketone, and the like. Ketones such as ethylene glycol, propylene glycol, hexylene glycol; methyl cellosolve, ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, tetrahydrofuran, etc. Ethers; esters such as acetic acid methyl ester, acetic acid ethyl ester, and lactate ethyl ester; In the present invention, a plurality of organic solvents (B) can also be used.

<Other components in coating liquid for film formation>
In the present invention, other components other than the polysiloxane (A) and the organic solvent (B) component, for example, inorganic fine particles, fillers, leveling agents, surface modifiers, surfactants, as long as the effects of the present invention are not impaired. Components such as an agent may be included.

Examples of the inorganic fine particles include metal oxide fine particles, metal double oxide fine particles, and magnesium fluoride fine particles. Examples of the metal oxide include silica, alumina, titanium oxide, zirconium oxide, tin oxide, and zinc oxide. Examples of the metal double oxide include ITO, ATO, AZO, and zinc antimonate. Moreover, hollow silica fine particles, porous silica fine particles, and the like can also be exemplified. Such inorganic fine particles may be either powder or colloidal solution, but those of colloidal solution are preferable because they are easy to handle. This colloidal solution may be a dispersion of inorganic fine particle powder in a dispersion medium or a commercially available colloidal solution. In the present invention, the inclusion of inorganic fine particles makes it possible to impart the surface shape of the formed cured film and other functions. The inorganic fine particles preferably have an average particle diameter of 0.001 to 0.2 μm, more preferably 0.001 to 0.1 μm. When the average particle diameter of the inorganic fine particles exceeds 0.2 μm, the transparency of the cured film formed by the prepared coating liquid may be lowered.
Examples of the dispersion medium of the inorganic fine particles include water or an organic solvent. The colloidal solution is preferably adjusted to pH or pKa of preferably 2 to 10, more preferably 3 to 7, from the viewpoint of the stability of the film-forming coating solution.

Examples of the organic solvent used for the dispersion medium of the colloidal solution include alcohols such as methanol, propanol, and butanol; glycols such as ethylene glycol; ketones such as methyl ethyl ketone and methyl isobutyl ketone; aromatic hydrocarbons such as toluene and xylene; Amides such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone; Esters such as ethyl acetate, butyl acetate and γ-butyrolactone; Ethers such as ethylene glycol monopropyl ether, tetrahydrofuran and 1,4-dioxane be able to. Of these, alcohols or ketones are preferable. Moreover, the same organic solvent as the organic solvent (B) contained in the coating liquid for forming an antireflection coating of the present invention can also be used. These organic solvents can be used as a dispersion medium alone or in admixture of two or more.
In addition, known fillers, leveling agents, surface modifiers, surfactants and the like can be used, and commercially available products are particularly preferable because they are easily available.

<Antireflection coating forming coating solution>
The coating solution for forming an antireflective coating of the present invention (also referred to as a composition for forming an antireflective coating) contains the polysiloxane (A) and other components as required, and these components are organic solvents (B). Dissolved uniformly inside. The coating solution for forming a film of the present invention appropriately uses a plurality of organic solvents (B) so that a good film free from defects such as foreign matter, unevenness, and pinholes can be obtained when applied to a desired substrate. You can also The coating liquid of the present invention is coated and cured on a desired substrate according to the film forming method described later, whereby an antireflection coating having good antireflection properties, scratch resistance and antifouling properties is obtained.

  The method for preparing the coating liquid for forming a film of the present invention is not particularly limited, and can be obtained by uniformly dissolving the polysiloxane (A) and other components as required in an organic solvent (B). Usually, the polysiloxane (A) is polycondensed in an organic solvent, preferably in an organic solvent (B) as described above, and obtained in a solution state. Therefore, the method of using the solution containing polysiloxane (A) as it is and mixing with an organic solvent (B) and other components as needed is suitable.

  In addition, if necessary, the polysiloxane (A) solution is concentrated, further diluted with organic solvent (B), or substituted with another solvent, and then mixed with other components as necessary. May be. Furthermore, the organic solvent (B) can be added after mixing the polysiloxane (A) solution and other components as necessary. If necessary, other components may be dissolved in the organic solvent (B) and then mixed with the polysiloxane (A) solution.

Polysiloxane film-forming coating solution (A) of the present invention, the concentration of total silicon atoms having its preferably 2.5 mol / kg (15 wt% in terms of SiO ₂ concentration) or less, particularly preferably 1.7mol / Kg (10% by mass in terms of SiO ₂ ) or less is preferable, and preferably 0.08 mol / kg (0.5% by mass in terms of SiO ₂ ) or more, particularly preferably 0.12 mol. / Kg (0.7% by mass in terms of SiO ₂ ) or more is preferable. When the concentration of the total silicon atoms is smaller than 0.08 mol / kg, it is difficult to obtain a desired film thickness by one coating, and when the concentration is higher than 2.5 mol / kg (SiO ₂ equivalent concentration of 15% by mass). The storage stability of the coating liquid for forming a film tends to be insufficient.

  The organic solvent (B) in the coating solution for forming a film of the present invention is preferably 26.5 to 98.5% by mass, particularly preferably 50 to 95% by mass in the coating solution. One or more organic solvents (B) can be arbitrarily selected and used. The above-described method of mixing the other components may be performed simultaneously with the solution of the polysiloxane (A) and the organic solvent (B) or after the mixing of the polysiloxane (A) and the organic solvent (B). It is not limited.

Specific examples of the coating liquid for forming a film in the present invention are listed below.
[1] A coating-forming coating solution containing all the silicon atoms of polysiloxane (A) at a concentration of 0.08 to _2.5 mol / kg (0.5 to 15% by mass in terms of SiO ₂ ).
[2] A coating liquid for forming a coating film comprising the above [1] and inorganic fine particles.
[3] A coating solution for forming a film, comprising [1] or [2] and at least one selected from the group consisting of a filler, a leveling agent, a surface modifier, and a surfactant.

<Coating and cured film forming method and coating substrate>
The coating liquid for forming a film of the present invention is applied to a substrate, then temporarily dried, irradiated with a predetermined amount of ultraviolet light, and then thermally cured at a predetermined temperature to obtain a desired cured film. .
A known or well-known method can be adopted as the coating method. For example, dip coating method, flow coating method, spin coating method, flexographic printing method, ink jet coating method, spray coating method, bar coating method, gravure roll coating method, roll coating method, blade coating method, air doctor coating method, air knife Methods such as a coating method, a wire doctor coating method, a reverse coating method, a transfer roll coating method, a micro gravure coating method, a kiss coating method, a cast coating method, a slot orifice coating method, a calendar coating method, and a die coating method can be employed.

  In that case, the base material to be used can be a known base material made of plastic, glass, ceramics or the like. Plastics include polycarbonate, poly (meth) acrylate, polyethersulfone, polyarylate, polyurethane, polysulfone, polyether, polyetherketone, polytrimethylpentene, polyolefin, polyethylene terephthalate, poly (meth) acrylonitrile, triacetylcellulose, Examples include substrates or films of diacetyl cellulose, acetate butyrate cellulose, and the like. However, since these substrates may have low mechanical strength and solvent resistance, a hard coat material is applied on the surface and cured to apply the coating solution of the present invention (base material with hard coat). Is preferred. For example, it is preferable to use a substrate in which an arbitrary hard coat layer is formed on the surface of a triacetylcellulose (TAC) substrate or the like before applying the coating liquid of the present invention. The hard coat material is not particularly limited as long as it is an energy ray curable hard coat material. A heat, ultraviolet ray, or electron beam curing type is preferable, and a material in which a double bond group is polymerized and cured by ultraviolet irradiation is particularly preferable.

  Conventionally, when an antireflection coating is formed on a substrate with a hard coat, a surface treatment (high frequency discharge plasma method, electron beam method, ion beam method, vapor deposition method, sputtering method) for easy adhesion to the film surface with a hard coat. , Alkali treatment method, acid treatment method, corona discharge treatment method, atmospheric pressure glow discharge plasma method, etc.), but when a cured film is formed using the coating liquid of the present invention, surface treatment is not required. Good scratch resistance is obtained. Further, by controlling the curing conditions (temperature, energy ray irradiation amount, etc.) when forming the hard coat layer of the substrate with hard coat within an arbitrary range, the anti-reflection coating of the present invention has better scratch resistance. I can do it.

That is, in the process of applying a hard coat material to a plastic substrate and curing it by irradiating energy rays, the hard coat material is not completely cured, but in a semi-cured state (the antireflection coating liquid of the present invention is hard-coated). It has a hardness that does not cause scratches even when applied on the layer, but the hard coat is not sufficiently cured and the unreacted part remains in the hard coat layer) By applying and curing the coating liquid of the present invention thereon, the scratch resistance of the cured film of the present invention can be made better than when applied to a completely cured base material with a hard coat. For example, a hard coat material (RC-610R) used as a hard coat layer of the base material of the present invention is applied onto triacetyl cellulose, and is irradiated with all light from a high-pressure mercury lamp, and integrated in terms of ultraviolet light with a wavelength of 250 nm. and those cured 60 mJ / cm ² irradiation, the 300 mJ / cm ² irradiation (full cure conditions RC-610R) was prepared separately which was cured, a coating solution of the present invention applied, cured thereto, respectively When the hard coat layer is cured, the cured film of the present invention obtained by irradiation with 60 mJ / cm ² has better scratch resistance.

The coating film of the coating solution applied to the base material is dried for an arbitrary time in the temperature range of 10 to 150 ° C. according to the heat resistance of the base material, and then applied to all light from a high-pressure mercury lamp and integrated in terms of ultraviolet light with a wavelength of 250 nm. Then, it is preferably irradiated with 50 to 1500 mJ / cm ² and thermally cured in a temperature range of room temperature to 450 ° C. The time required for drying is preferably 10 seconds to 10 minutes, and the time required for thermosetting can be appropriately selected according to desired cured film properties, but is usually 1 hour to 10 days. When a low thermosetting temperature is selected, a cured film having sufficient scratch resistance can be easily obtained by increasing the curing time. In particular, when the substrate is an organic substrate such as a TAC film or a polyester (PET) film, the thermosetting temperature is preferably room temperature (20 ° C.) to 150 ° C. in consideration of the heat resistance of the substrate, 40 to 150 ° C. is more preferable.
The cured film of the present invention thus obtained is characterized by low reflection, a water contact angle of 80 ° or more, and excellent scratch resistance. Therefore, it can be suitably used as a low refractive index layer for antireflection applications.

  In the present invention, the antireflection coating of the present invention is formed on the surface of a substrate having a refractive index higher than that of the antireflection coating of the present invention, such as a hard coated TAC (triacetylcellulose) film. Thus, the base material can be easily converted into a base material having an anti-light reflection ability. Although it is effective to form the antireflection coating of the present invention as a single cured film on the surface of the substrate, the antireflection coating of the present invention is formed on the lower layer coating or the hard coating layer having a high refractive index. It is also effective to use it as an antireflection laminate.

Here, the relationship between the thickness of the antireflection coating and the wavelength of light will be described. The thickness d (nm) of a cured film having a refractive index a and the wavelength λ (nm) of light for which a decrease in reflectance due to the cured film is desired. )), It is known that a relational expression of d = (2b−1) λ / 4a (where b represents an integer of 1 or more) holds. Therefore, by using this equation to determine the thickness of the antireflection coating, it is possible to easily prevent reflection of light having a desired wavelength. As a specific example, in order to form a film having a refractive index of 1.32 for light having a wavelength of 550 nm and prevent reflected light from the glass surface, these numerical values are substituted into λ and a in the above formula. Thus, the optimum film thickness can be calculated. At that time, any positive integer may be substituted for b. For example, the film thickness obtained by substituting 1 for b is 104 nm, and the film thickness obtained by substituting 2 for b is 312 nm. By adopting the thickness of the coating thus calculated, the antireflection ability can be easily imparted.
The thickness of the antireflection coating formed on the substrate can be adjusted by the film thickness at the time of coating, but can also be easily adjusted by changing the SiO ₂ equivalent concentration in the coating forming coating solution. .

Synthesis Examples, Examples, and Comparative Examples are shown below to specifically describe the present invention, but the present invention is not construed as being limited to the following examples. Abbreviations in this embodiment will be described.
TEOS: Tetraethoxysilane UPS: γ-Ureidopropyltriethoxysilane MPS: γ-mercaptopropyltrimethoxysilane F13: Tridecafluorooctyltrimethoxysilane
APS: 3-aminopropyltrimethoxysilane
GPS: γ-glycidoxypropyltrimethoxysilane MeOH: methanol IPA: isopropyl alcohol (2-propanol)
n-BuOH: n-butyl alcohol (1-butanol)
PG: Propylene glycol

Measurement methods in the following synthesis examples are shown below.
[Measurement of residual alkoxysilane monomer]
The residual alkoxysilane monomer in the polysiloxane (A) solution was measured by gas chromatography (hereinafter referred to as GC). GC measurement was performed under the following conditions using Shimadzu GC-14B manufactured by Shimadzu Corporation.
Column: Capillary column CBP1-W25-100 (25 mm × 0.53 mmΦ × 1 μm)
Column temperature: The starting temperature was set to 50 ° C., and the temperature was raised at 15 ° C./minute to reach the ultimate temperature of 290 ° C. (3 minutes).
Sample injection volume: 1 μL
Injection temperature: 240 ° C
Detector temperature: 290 ° C
Carrier gas: Nitrogen (flow rate 30mL / min)
Detection method: FID method

[Synthesis Example 1]
Into a four-necked reaction flask equipped with a reflux tube, 31.84 g of MeOH was added, and 18.00 g of oxalic acid was added in small portions with stirring to prepare a MeOH solution of oxalic acid. Next, this succinic acid-MeOH solution was heated to reflux, and then a mixture of MeOH 25.08 g, TEOS 16.77 g, F13 7.02 g and UPS 1.29 g was added dropwise. After completion of the dropwise addition, the reaction was continued for 5 hours under reflux, and then allowed to cool to prepare a polysiloxane (a) solution (P1). When this polysiloxane (a) solution (P1) was measured by GC, no alkoxysilane monomer was detected.

[Synthesis Examples 2-3]
With the composition shown in Table 1, polysiloxane (a) solutions (P2 to P3) were obtained in the same manner as in Synthesis Example 1. At that time, in the same manner as in Synthesis Example 1, a plurality of types of alkoxysilanes (hereinafter also referred to as monomers) were mixed with MeOH and used. When the obtained polysiloxane (a) solutions (P2 to P3) were measured by GC, no monomer was detected.

[Comparative Synthesis Examples 1 to 9]
With the composition shown in Table 1, polysiloxane (a) solutions (Q1 to Q9) were obtained in the same manner as in Synthesis Example 1. At that time, in the same manner as in Synthesis Example 1, a plurality of types of alkoxysilanes (hereinafter also referred to as monomers) were mixed with MeOH and used. When the obtained polysiloxane (a) solutions (Q1 to Q9) were measured by GC, no monomer was detected.

[Synthesis Example 4]
Into a four-necked reaction flask equipped with a reflux tube, 28.68 g of MeOH was added, and 27.95 g of TEOS, 11.70 g of F13, and 2.16 g of UPS were added little by little with stirring to mix a plurality of types of monomers. A MeOH solution was prepared. Next, while stirring this mixed solution at room temperature, a mixture of 14.34 g of MeOH, 15.02 g of water, and 0.15 g of oxalic acid was added dropwise. After completion of the dropwise addition, the mixture was stirred for 10 minutes, and then heating was started. The reaction was continued for 1 hour from the start of reflux, and then allowed to cool to prepare a polysiloxane (a) solution (P4). When this polysiloxane (a) solution (P4) was measured by GC, no monomer was detected.

[Synthesis Examples 5-6]
Polysiloxane (a) solutions (P5 to P6) were obtained in the same manner as in Synthesis Example 4 with the compositions shown in Table 2. At that time, as in Synthesis Example 4, a plurality of types of monomers were mixed with MeOH in advance. When the obtained solutions (P5 to P6) of polysiloxane (a) were measured by GC, no monomer was detected.

[Comparative Synthesis Examples 10 to 18]
With the composition shown in Table 2, polysiloxane (a) solutions (Q10 to Q18) were obtained in the same manner as in Synthesis Example 4. At that time, as in Synthesis Example 4, a plurality of types of monomers were mixed with MeOH in advance. When the obtained polysiloxane (a) solutions (Q10 to Q18) were measured by GC, no monomer was detected.

[Examples 1 to 15]
In the composition shown in Table 3, MPS and a solvent are mixed in a solution of polysiloxane (a), and stirred at a temperature of 30 ° C. for 1 hour to react polysiloxane (a) and MPS to obtain a solution of polysiloxane (A). (E1 to E15) were prepared. When this polysiloxane (A) solution (E1 to E15) was measured by GC, no monomer was detected. Table 3 shows the results of evaluating the storage stability of these solutions by the method described below.

[Comparative Examples 1 to 24]
With the composition shown in Table 3, a solvent was mixed with the polysiloxane (a) solutions (P1 to P6 and Q1 to Q18) to prepare coating solutions (S1 to S24). The storage stability shown below was evaluated using these coating solutions. The results are shown in Table 3.

<Storage stability of coating solution>
The film-forming coating solution prepared with the composition shown in Table 3 was allowed to stand at room temperature for 1 month, and then a non-aqueous polytetrafluoroethylene filter having a pore diameter of 0.45 μm and Φ × L: 18 × 22 mm (Chromatodisc manufactured by Kurashiki Boseki Co., Ltd.) 13N), 100 cc was filtered, and what was able to be filtered was marked with ◯, and clogged with x.

表３のＳ／Ｓｉモル比は、実施例においては表３の組成で調製した塗布液に含まれるポリシロキサン（Ａ）の有するメルカプト基の硫黄原子とポリシロキサン（Ａ）との全珪素原子のモル比を表し、また、比較例においては塗布液中に含まれるポリシロキサン（ａ）のメルカプト基の硫黄原子と全珪素原子とのモル比を表す。

In the examples, the S / Si molar ratio in Table 3 is the ratio of the total silicon atoms of the mercapto group sulfur atoms and polysiloxane (A) contained in the polysiloxane (A) contained in the coating solution prepared in the composition shown in Table 3. In the comparative example, the molar ratio of the sulfur atom of the mercapto group and the total silicon atom of the polysiloxane (a) contained in the coating solution is represented.

<Preparation of base film with hard coat>
The base material which apply | coats the coating liquid for film formation of this invention was produced as follows. A hard coat material (manufactured by Sanyo Kasei Kogyo Co., Ltd., RC-610R, solid content 33% by mass) is attached to a triacetylcellulose film (manufactured by FUJIFILM Corporation) with a wire bar no. 8 and dried in a clean oven at 60 ° C. for 1 minute, and then exposed to all light from a high-pressure mercury lamp, and the integrated values (60 mJ / cm ²⁾ shown in Table 4 in terms of ultraviolet light at a wavelength of 250 nm. Or 300 mJ / cm ² ).

[Examples 16 to 34]
Using the solution (E1 to E15) of polysiloxane (A) prepared with the composition shown in Table 3 as the coating liquid for film formation, with the hard coat prepared by the method described above in <Preparation of substrate film with hard coat> A TAC film (film thickness of 80 μm, reflectance at a wavelength of 550 nm is 4.3%) and a wire bar No. Then, the film was allowed to stand at room temperature for 1 minute and further dried at a temperature of 100 ° C. for 5 minutes using a clean oven to obtain a coated film. Next, the film-coated film was irradiated with all the light from a high-pressure mercury lamp, irradiated with the integrated value shown in Table 4 in terms of ultraviolet light having a wavelength of 250 nm, and cured at a temperature of 40 ° C. for 3 days.
About the obtained cured film, HAZE, transmittance, reflectance, scratch resistance, water contact angle, magic wiping property, and fingerprint wiping property were evaluated. These evaluation methods are as follows, and the evaluation results are shown in Tables 4 and 5.

[Comparative Examples 25-48]
The coating liquids (S1 to S24) prepared with the composition shown in Table 3 were applied to the BAR film with hard coat (thickness 80 μm, reflectance at a wavelength of 550 nm of 4.3%) prepared as described above. Then, the film was allowed to stand at room temperature for 1 minute and further dried at a temperature of 100 ° C. for 5 minutes using a clean oven to obtain a coated film. Next, the film-coated film was irradiated with all the light from a high-pressure mercury lamp, irradiated with the integrated value shown in Table 4 in terms of ultraviolet light having a wavelength of 250 nm, and cured at a temperature of 40 ° C. for 3 days.
About the obtained cured film, the result evaluated similarly to the Example is shown in Table 4 and Table 5.

[Comparative Examples 49-54]
A TAC film with a hard coat (thickness 80 μm, reflectance at a wavelength of 550 nm) prepared as described above using the film-forming coating solutions (E2, E4, E7, E10, E12, and E14) prepared with the composition of Table 3 is 4. 3%) wire bar No. After coating using No. 3, it was allowed to stand at room temperature for 1 minute, further dried at 100 ° C. for 5 minutes using a clean oven, and cured at 40 ° C. for 3 days without being irradiated with ultraviolet rays.
About the obtained cured film, the result evaluated similarly to the Example is shown in Table 4 and Table 5.

[HAZE and transmittance]
It measured using SPECIAL HAZE METER TC-1800H by Tokyo Denshoku.
[Reflectance]
After rubbing the film surface (back surface) opposite to the coated surface with sandpaper and applying a matte black paint, a UV reflectance measuring device (Shimadzu Corporation) is applied to a spectrophotometer (Shimadzu Corporation, UV-3100PC). Measurement was performed in a wavelength range of 400 to 800 nm by connecting an MPC-3100 manufactured by KK The reflectance at a wavelength of 550 nm and an incident angle of 5 ° was measured.

[Abrasion resistance]
Steel wool (Nihon Steel Co., Ltd., Bonster, # 0000) is attached to a friction tester (manufactured by Daiei Seiki Co., Ltd.), and a constant load (200 g / cm ² and 500 g / cm ² ) is applied to the coated surface. After reciprocating friction, the number of scratches on the cured film was visually evaluated according to the following criteria.
A: No damage to 5 wounds B: 6 to 15 wounds C: 16 to 30 wounds D: 31 or more wounds E: The entire film is peeled from the surface of the substrate

[Water contact angle]
Using an automatic contact angle measuring device (manufactured by Kyowa Interface Science Co., Ltd., FACE (CA-W type)), the measurement was carried out with a five-point average of the liquid suitable method. At that time, a water droplet of 3.0 μL of pure water was formed on the needle tip in an environment of 23 ° C. and 50% relative humidity, and this was dropped on the surface of the cured film, and the contact angle was measured.

[Magic wiping off]
After writing on the cured film surface with black magic (M700-T1 manufactured by Magicink), the film was dried and then wiped with tissue paper, and the level of wiping was visually evaluated according to the following criteria.
○: Magic can be completely wiped off.
Δ: Most of the magic can be wiped off, but marks remain.
X: Magic itself remains and can hardly be wiped off.

[Fingerprint wiping properties]
After the fingerprint was attached to the cured film surface, it was wiped off with a tissue paper, and the wiping level was visually evaluated according to the following criteria.
○: Both fingerprints and oil can be completely wiped off.
Δ: The oil can be wiped off, but a fingerprint mark remains.
×: Neither fingerprint nor oil can be wiped off.

  Examples 16 to 34 exhibited water repellency with a water contact angle of 100 ° or more, had good magic wiping properties and fingerprint wiping properties, and had a low reflectance of less than 2%. Furthermore, the scratch resistance was also evaluated as A with a load of 200 g and as A or B with a load of 500 g, indicating high scratch resistance.

  Further, when Example 17 and Example 18 are compared, the scratch resistance is higher in Example 17, which has a lower UV irradiation amount when the base material hard coat is cured, and the antireflection is better when the hard coat is in a semi-cured state. The adhesion of the film is good. Similar results were obtained in the comparison between Example 20 and Example 21, Example 27 and Example 28, Example 30 and Example 31.

In addition to having water repellency (antifouling property) and good scratch resistance, the antireflection coating obtained by the present invention has a feature of low reflectance. Therefore, it can be suitably used in fields where antireflection of light is desired, such as glass cathode ray tubes, televisions, computers, car navigation systems, mobile phone displays, glass surface mirrors, glass showcases, and the like. In particular, liquid crystal displays, plasma displays, projection displays, EL displays, SEDs, etc. that require external impacts, friction, and antifouling properties (property of easily removing attached sebum, fingerprints, magic inks, cosmetics, etc.) It is useful for antireflection films used for polarizing plates such as FETs and CRTs and front plates.

The entire contents of the specification, claims, and abstract of Japanese Patent Application No. 2007-103296 filed on April 10, 2007 are incorporated herein as the disclosure of the specification of the present invention. Is.

Claims (10)

And alkoxysilane represented by the formula (1), through a siloxane bond to the main chain of the formula the alkoxysilane emissions containing alkoxysilane represented by (2) polycondensation and resulting polysiloxane (a) Te is a polysiloxane organic group bonded with a mercapto group (a), it said the total molar amount of the sulfur atom of the mercapto group polysiloxane (a) has a total moles of silicon atoms to which the polysiloxane (a) has A coating solution for forming an antireflective coating, comprising polysiloxane (A) having a ratio (S / Si) to the amount of 0.03 to 0.3 .
Si (OR ¹ ) ₄ (1)
R ³ Si (OR ⁴ ) ₃ (2)
(In the formula (1), R ¹ is a saturated hydrocarbon group having 1 to 5 carbon atoms, in the formula (2), R ³ is a fluorine-containing organic group, and R ⁴ is a hydrocarbon having 1 to 5 carbon atoms. Group.) The coating solution for forming an antireflection coating according to claim 1, wherein R ³ in the formula (2) is a fluoroalkyl group. A polysiloxane (a) is obtained by polycondensation with an alkoxysilane represented by the formula (1), an alkoxysilane represented by the formula (2), and an alkoxysilane represented by the formula (3). The coating liquid for antireflection film formation according to claim 1 or 2.
R ⁵ _n Si (OR ⁶ ) _4-n (3)
(In formula (3), R ⁶ is a hydrocarbon group having 1 to 5 carbon atoms, R ⁵ is an organic group not substituted with a hydrogen atom, a halogen atom, or a fluorine atom, and n is 1 to 3. Yes, when n is 2 or 3, a plurality of R ⁵ may be the same or different. The organic group not substituted with a fluorine atom as R ⁵ in the formula (3) is selected from a chlorine atom, a vinyl group, an amino group, a glycidoxy group, a mercapto group, a methacryloxy group, a ureido group, an isocyanate group, and an acryloxy group. The coating solution for forming an antireflection coating according to claim 3, which is a hydrocarbon group that may be substituted with a substituent. The coating solution for forming an antireflection coating according to claim 3, wherein R ⁵ in the formula (3) is a hydrocarbon group substituted with a ureido group. The coating liquid for forming an antireflection film according to any one of claims 1 to 5 , comprising polysiloxane (A) in a concentration of 0.08 to 2.5 mol / kg as a concentration of all silicon atoms. The cured film obtained using the coating liquid for anti-reflective film formation as described in any one of Claims 1-6 . The reflection liquid which hardens | cures at 20-150 degreeC after apply | coating the coating liquid for anti-reflective film formation as described in any one of Claims 1-6 to a base material with a hard-coat layer semi-hardened, drying, and irradiating with an ultraviolet-ray Method for forming a protective coating. An antireflection substrate having the cured film according to claim 7 . An antireflection film having the cured film according to claim 7 .