KR20140082924A - Production method of composition for coating-type transparent film formation - Google Patents

Abstract

The task of the present invention is to provide a method of manufacturing a composition for forming a coating-type transparent film with high storage stability capable of forming a transparent film having high transparency, high refractive index, low haze, strong heat resistance, and a wide range of film thickness at low temperatures. To resolve the task, the present invention provides a method of manufacturing a composition for forming a coating-type transparent film which includes a process of mixing (A) metal alkoxide, (B) alcohol, (C) water, and (D) salt acquired by reacting strong acid and at least one selected among a compound represented by the chemical formula (D1) and a nitrogen-containing heterocyclic compound. [In the formula (D1), R1 to R3 are independently hydrogen, an aliphatic with a carbon number 1 - 20, or an aromatic base with a carbon number 4 - 20. At least one among R1 to R3 is an aliphatic with a carbon number 1 - 20 or an aromatic base with a carbon number 4 - 20.].

Description

TECHNICAL FIELD [0001] The present invention relates to a transparent film-forming composition,

The present invention relates to a process for producing a composition for forming a coating type transparent film. More particularly, the present invention relates to a transparent film having a high transparency, a high refractive index, a low haze and a high heat resistance, and a transparent film having a wide range of film thickness can be formed at a low temperature, . Further, the present invention relates to a composition obtained by the above method, a transparent film made of the composition, and a device element having the transparent film.

In an image display apparatus such as a liquid crystal display (LCD), a plasma display panel (PDP), and an organic electroluminescent display, in order to prevent the visibility of the display surface from deteriorating due to the reflection of external light, In most cases, an antireflection film is included. The antireflection film is composed of a multilayer film formed by laminating a plurality of layers having different refractive indexes, and reduces reflected light by using optical interference (see, for example, Non-Patent Document 1).

In the projection-type capacitive touch panel, an indium tin oxide (ITO) electrode, which is a transparent electrode, is patterned on the surface of the substrate. However, since the refractive index difference between the ITO electrode and the glass substrate generally used is large, the pattern of the ITO electrode is conspicuously observed. In order to solve this problem, there is a method of forming a laminate including a film for preventing a pattern composed of a high-refractive-index transparent film from being seen on the upper or lower layer of the ITO electrode.

A film having a high transparency, a high refractive index and a low haze is required for a film which prevents these antireflection films or patterns from being seen. Further, in order to control the reflected light using the interference of light, it is necessary to accurately set the film thickness of each layer in the multilayered film / laminated body. For example, in the high refractive index transparent film, Needs to be. In general, in the manufacturing process of an electronic device, the high-refractive-index transparent film needs to have sufficient heat resistance since it is exposed to the heating process of about 100 to 300 캜 for firing and drying various members a plurality of times.

As the high refractive index transparent film, it is known to use an organic polymer or a metal such as titanium. However, especially for a high refractive index transparent film having a refractive index exceeding 1.7, it is difficult to realize by the former method, and the latter method is generally used. As a method of forming such a high refractive index transparent film containing a metal, dry coating method and wet coating method are generally known.

As the dry coating method, for example, vacuum deposition, sputtering, and chemical vapor deposition (CVD) are known. These methods are advantageous in that a high-purity, high-quality, and high-refractive-index transparent film having a wide film thickness can be obtained. However, since a high vacuum is used, a high device control technology is required and a large- Do. As a result, the dry coating method has a problem of high production cost. Further, the substrate often becomes hot at the time of film formation, which is disadvantageous for film formation on a film substrate or the like.

On the other hand, the wet coating method has a high merit because the manufacturing cost is low and the film forming method is relatively simple. As a method of forming a high refractive index transparent film by a wet coating method, there is known a method of forming a high refractive index transparent film in which metal fine particles are dispersed in a binder by mixing metal oxide fine particles together with a dispersant or a binder and applying a coating. However, these transparent films generally have a high haze, and the metal oxide fine particles are liable to flocculate, which makes it difficult to maintain stability of the ink (see, for example, Patent Document 1).

As another method of forming them, a method of forming a high refractive index transparent film by a colloid solution-gel method is known (see, for example, Non-Patent Document 2). In this method, a compound containing a metal such as metal alkoxide is hydrolyzed in a solution to form a colloidal solution dispersion of metal oxide particles, and this is partially polycondensed to obtain a gel of a metal oxide polymer, And the polycondensation proceeds at the time of firing, thereby forming a dense metal oxide film. This method is advantageous in that a film of a high refractive index can be obtained easily since a film can be formed in the atmosphere, and a metal oxide film having a low manufacturing cost and high denseness can be formed. However, the colloid solution-gel method has the following problems (1) to (5).

(1) It is difficult to appropriately control the reaction in the composition, aggregation of the colloid solution particles occurs, precipitation occurs in the composition, and the optical characteristics of the obtained transparent film are liable to deteriorate.

(2) Gelation of the composition tends to proceed and storage stability is poor.

(3) In general, since a high temperature of 300 to 400 DEG C is required for firing, it is difficult to form a film on a film substrate or a glass substrate including a module having low heat resistance.

(4) In general, the film obtained using the colloid solution-gel method is a thin film having a thickness of about 150 nm or less. In a film having a large film thickness, the flatness of the film is deteriorated or cracks are generated, and the transmittance and haze are remarkably deteriorated.

(5) When the transparent film obtained is exposed to a temperature not lower than the baking temperature for a long time, cracks are likely to occur and heat resistance is low. In the case of a transparent film having a large film thickness, such a tendency is remarkable.

Patent Document 2 and Patent Document 3 disclose a method for producing a film having a high refractive index and high transparency by firing at a low temperature of about 100 캜. However, the problem of lack of storage stability of a composition used in the production of a film has not been solved, and the resulting high refractive index transparent film has low heat resistance and high haze. Also, a thick film exceeding 160 nm can not be obtained.

Japanese Patent Application Laid-Open No. 2004-54161 Japanese Patent No. 4942053 Japanese Patent No. 4208051

Masashi Yoshida, Hiroyoshi Yajima, "Thin-film and optical devices", Tokyo University Publications, 1994 Sakkasumio, "The Science of Colloidal Solution-Gel Method", Agnew Woo-Sha, 1988

It is an object of the present invention to provide a transparent film having a high transparency, a high refractive index, a low haze and a high heat resistance, and also to provide a transparent film having a wide range of film thickness at a low temperature, And to provide a method. It is still another object of the present invention to provide a composition obtained by the above method, a transparent film made of the composition, and a device element having the transparent film.

The inventor of the present invention has repeatedly studied to solve the above problems. As a result, it has been found that the above problems can be solved by the production method having the following constitution, and the present invention has been completed. That is, the present invention relates to, for example, [1] to [15].

[1] A process for producing a compound represented by the formula (1) by reacting at least one member selected from the group consisting of a metal alkoxide (A), an alcohol (B), water (C) And a step of mixing the resulting salt.

[Chemical Formula 1]

Wherein R ¹ to R ³ are each independently hydrogen, an aliphatic group having 1 to 20 carbon atoms or an aromatic group having 4 to 20 carbon atoms, and at least one of R ¹ to R ³ is a group having 1 to 20 carbon atoms Of an aliphatic group or an aromatic group having 4 to 20 carbon atoms]

[2] The salt (D) is a salt obtained by reacting a strong acid with a compound represented by the formula (D1). In the formula (D1), R ¹ to R ³ each independently represent hydrogen or a C 1-20 Wherein at least one of R ¹ to R ³ is an aliphatic hydrocarbon group or R ¹ to R ² are hydrogen and R ³ is an aromatic hydrocarbon group having 6 to 20 carbon atoms. .

[3] A salt obtained by reacting a salt (D) with a strong acid and a nitrogen-containing heterocyclic compound, and the nitrogen-containing heterocyclic compound is at least one selected from the compounds represented by formulas (D2) to , And the production method described in the above [1].

(2)

Equation (D2) from, X is, -C (R ⁷⁾ = group or a nitrogen atom represented by a;

In the formula (D3), Y is a group represented by -C (H) (R ⁶ ) - or a group represented by -N (H) -;

In the formula (D4), X is a group represented by -C (R < ¹¹ >) = or a nitrogen atom;

In the formula (D5), Y is a group represented by -C (H) (R ¹¹ ) - or a group represented by -N (H) -;

In formulas (D2) to (D6), R ⁴ to R ¹² are each independently hydrogen, an aliphatic group having 1 to 20 carbon atoms or an aromatic group having ^{4 to} 20 carbon atoms, and any of R ⁴ to R ⁸ Two groups may combine with each other to form a ring, and any two groups selected from R ⁹ to R ¹² may be bonded to each other to form a ring]

[4] Process for mixing 5 to 500 mol of alcohol (B), 0.5 to 5 mol of water (C) and 0.01 to 0.1 mol of salt (D) per mol of metal alkoxide (A) The production method according to any one of [1] to [3] above, further comprising:

[5] The process according to any one of [1] to [4] above, wherein the alcohol-soluble polymer is further mixed in the step of mixing the metal alkoxide (A), alcohol (B), water (C) ≪ / RTI >

[6] A coating type transparent film-forming composition obtained by the production method described in any one of [1] to [5] above.

[7] The composition according to the above-mentioned [6], wherein the viscosity measured at 25 ° C and a shear rate of 383 s ^-1 is 1 to 20 mPa · s.

[8] A method for manufacturing a semiconductor device, comprising the steps of: (1) applying the composition described in [6] or [7] above on a substrate; and (2) A method for producing a transparent film.

[9] A transparent film obtained by the production method described in [8] above.

[10] The transparent film according to the above [9], wherein the film thickness is 1 to 400 nm.

[11] A laminate comprising a substrate and a transparent film as described in [9] or [10], wherein the refractive index of the transparent film at a wavelength of 550 nm is 1.6 or more, the total light transmittance of the laminate is 82% the laminate haze value and haze value of the H _1, only the substrate of the member difference between H ₂ | H ₁ -H ₂ | a laminate of more than 1.5%.

[12] An electronic device comprising a substrate and a transparent film according to [9] or [10].

[13] A method for producing a multilayer structure comprising a transparent conductive film according to the above [9] or [10], wherein a region where a transparent conductive film is present and a region where a transparent conductive film is not present are formed in an upper layer or a lower layer of the patterned transparent conductive film, And the difference in reflectance at 550 nm is 1% or less.

[14] A process for producing a compound represented by the formula (1) by reacting at least one compound selected from the group consisting of (A) a metal alkoxide, (B) an alcohol, (C) water and And a salt to be obtained.

(3)

Wherein R ¹ to R ³ are each independently hydrogen, an aliphatic group having 1 to 20 carbon atoms or an aromatic group having 4 to 20 carbon atoms, and at least one of R ¹ to R ³ is a group having 1 to 20 carbon atoms Of an aliphatic group or an aromatic group having 4 to 20 carbon atoms]

[15] The composition according to the above-mentioned [14], wherein the salt (D) is a salt obtained by reacting a strong acid with at least one member selected from aniline and pyridine.

According to the present invention, there is provided a method for producing a transparent film having a high transparency, a high refractive index, a low haze, and a high heat resistance and capable of forming a transparent film having a wide range of film thickness at a low temperature, A composition obtained by the above method, a transparent film made of the composition, and a device element having the transparent film.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a diagram showing the use of a transparent film made of the composition of the present invention. Fig.

In the present description, among the description of the compound, for example, an alkoxy group, an alkyl group, a phenyl group, a benzyl group, a tolyl group, a naphthyl group and a benzhydryl group are each simply substituted with an alkoxy, alkyl, phenyl, benzyl, tolyl, naphthyl And benzhydryl. The same is true for the other examples. In the present invention, " coating composition " means a composition used for coating.

Hereinafter, the present invention will be described in detail.

[One. Method for producing transparent transparent film-forming composition]

A method of producing a coating type transparent film forming composition of the present invention comprises the steps of (A) mixing a metal alkoxide, (B) an alcohol, (C) water and (D) a strong acid, And a salt obtained by reacting at least one member selected from nitrogen-containing heterocyclic compounds.

Hereinafter, these compounds are also referred to as "component (A)" to "component (D)", respectively, and the composition for forming a coating type transparent film obtained by the production method of the present invention is also referred to as "composition of the present invention". Hereinafter, the components (A) to (D) and optional components will be described, and then the mixing process will be described.

[1-1. Metal alkoxide (A)]

The metal alkoxide (A) is a compound having one or more alkoxy groups bonded to a metal, that is, M-OR (wherein M is a metal and R is alkyl).

Examples of the metal in the metal alkoxide (A) include rare earth metals such as zinc, lead, zirconium, chromium, aluminum, cadmium, tantalum, hafnium, niobium, iron, titanium, magnesium, indium, yttrium, Can be preferably used. Among them, titanium and zirconium are particularly preferable from the viewpoint of balance of the stability and reactivity of the compound, the height of the refractive index of the obtained transparent film, and easiness of obtaining. That is, as the metal alkoxide (A), at least one selected from titanium alkoxide and zirconium alkoxide is preferable.

The alkoxy in the metal alkoxide (A) includes, for example, alkoxy of 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms. Specific examples thereof include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert- N-butoxy, 1,1-dimethyl-n-propoxy, 1,2-dimethyl-n-propoxy, 2,2-dimethyl- N-pentyloxy, 4-methyl-n-pentyloxy, 4-methyl-n-pentyloxy, Dimethyl-n-butoxy, 1,2-dimethyl-n-butoxy, 1,3-dimethyl-n-butoxy, 2,2- N-butoxy, dimethyl-n-butoxy, 3,3-dimethyl-n-butoxy, N-propoxy, 1-ethyl-1-methyl-n-propoxy and 1-ethyl-2-methyl-n-propoxy. Of these, ethoxy, n-propoxy, isopropoxy and n-butoxy are particularly preferable from the viewpoint of balance of the stability and reactivity of the compound and easiness of availability.

In the metal alkoxide (A), the types of the alkoxy on the metal may be all the same or different, but from the viewpoint of balance of the stability and reactivity of the compound and easiness of obtaining the metal alkoxide, desirable. Specifically, tetra-n-butoxytitanium, tetraethoxy titanium, tetraisopropoxy titanium, tetra-n-butoxy zirconium and tetra-n-propoxy zirconium are preferable, and tetra-n- Do.

As the metal alkoxide (A), it is preferable to use a metal alkoxide as a monomer. However, a compound in which a metal alkoxide as a monomer is partially polycondensed, that is, tetrabutoxy titanium dimer, tetrabutoxy titanium tetramer, etc. can be preferably used have. The metal alkoxide (A) may be used singly or in combination of two or more.

[1-2. Alcohol (B)]

As the alcohol (B), any alcohol can be used. Among them, alcohols having 2 to 10 carbon atoms and 1 hydroxyl group in one molecule are preferable, alcohols having 2 to 6 carbon atoms and 1 hydroxyl group in one molecule are more preferable from the standpoint of expressing the functions described later .

As the alcohol (B), for example, a compound represented by R-OH (wherein R is alkyl, the number of carbon atoms thereof is preferably from 2 to 10, more preferably from 2 to 6), and R ² OR ¹ -OH (wherein R ¹ is alkylene, R ² is alkyl, and the total number of carbon atoms of R ¹ and R ² is preferably 2 to 10, more preferably 2 to 6) .

Specific examples of the solvent include ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutanol, Butanol, 3-methyl-1-butanol, 3-methyl-2-butanol, 1-hexanol, 2-hexanol, 3-pentanol, 3-methyl-1-pentanol, 3-methyl-1-pentanol, 1-butanol, 2,2-dimethyl-1-butanol and 1-methoxy-2-propanol are preferable. Among these, at least one species selected from ethanol, 2-propanol, 1-butanol and 1-methoxy-2-propanol is preferable from the viewpoint of balance between solubility of the starting compound and reaction control. Of these, 2-propanol and 1-methoxy-2-propanol are particularly preferable from the viewpoint of balance between the solubility of the starting compound and the reaction control and the suitability of the volatilization rate. The alcohol (B) may be used alone or in combination of two or more.

[1-3. Water (C)]

Water derived from ion exchange water, distilled water, RO water, deionized water, purified water, tap water, pure water, ultrapure water, well water, mineral water, mineral water, hot spring water, spring water, fresh water, etc. can be used as the water . It is preferable that the composition of the present invention does not contain any impurities. Therefore, ion-exchanged water, distilled water, RO water, deionized water, purified water, pure water and ultrapure water are preferable. These may be used alone, or two or more of them may be used in combination.

[1-4. Salt (D)]

The salt (D) is a salt obtained by reacting at least one member selected from a strong acid, a compound represented by the formula (D1) (hereinafter also referred to as "compound (D1)") and a nitrogen-containing heterocyclic compound. These compounds (D1) and the nitrogen-containing heterocyclic compounds are collectively referred to as " organic amine compounds ".

As a strong acid as a raw material of the salt (D), a compound having an acid dissociation constant pKa in water at 25 ° C is less than 3, and examples thereof include hydrogen chloride, nitric acid, sulfuric acid, hydrogen fluoride, hydrogen bromide, perchloric acid, Is preferably hydrogen chloride in view of ease of use. The lower limit of the acid dissociation constant pKa in water at 25 DEG C of the strong acid is not particularly limited, and is, for example, -15. The above-described pKa can be measured by a generally known titration method (suitable method), an absorbance method, a capillary electrophoresis method, or the like.

The other raw material of the salt (D) is an organic amine compound.

<Compound ( D1 )>

The compound (D1) is represented by the formula (D1).

[Chemical Formula 4]

In formula (D1), R ¹ to R ³ are each independently hydrogen, an aliphatic group having 1 to 20 carbon atoms or an aromatic group having 4 to 20 carbon atoms, and at least one of R ¹ to R ³ is a group having 1 to 20 carbon atoms An aliphatic group or an aromatic group having 4 to 20 carbon atoms.

The aliphatic group may be a straight chain structure, a branched structure, or a cyclic structure.

The carbon number of the aliphatic group is 1 to 20, preferably 1 to 6.

Examples of the aliphatic group include at least an aliphatic hydrocarbon group and at least one of the carbon atoms excluding the carbon atom bonded to the central nitrogen atom (i.e., the nitrogen atom to which R ¹ to R ³ are bonded) in the formula (D1) in the aliphatic hydrocarbon group And one group is a group substituted with at least one hetero atom selected from nitrogen, oxygen and sulfur.

Examples of the aliphatic hydrocarbon group having 1 to 20 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, sec-butyl, n-pentyl, Alkyl; Cycloalkyl such as cyclopentyl, cyclohexyl and cycloheptyl; Norbornyl, adamantyl, and the like. Among them, an aliphatic hydrocarbon group having 1 to 6 carbon atoms such as methyl, ethyl, isopropyl, n-propyl or n-hexyl is preferable.

The aromatic group is a group containing at least one aromatic ring, for example, an aromatic hydrocarbon group. At least one of the carbon atoms forming the aromatic ring may be substituted with at least one hetero atom selected from oxygen and sulfur. At least one of the hydrogen atoms contained in the aromatic group may be substituted with at least one group selected from the following (1) to (8).

(3) an alkoxycarbonyl group, (4) a carboxyl group, (5) an amide group, (6) a nitro group, (7) a hydrocarbon group having 1 to 12 carbon atoms, (8) Group in which at least one carbon atom of the group is substituted with at least one hetero atom selected from nitrogen, oxygen and sulfur.

Examples of the aromatic group having 4 to 20 carbon atoms include phenyl, benzyl, o-tolyl, m-tolyl, p-tolyl, 1-naphthyl, 2- Aromatic hydrocarbon groups such as pentanenyl, 2-biphenyl, 3-biphenyl, 4-biphenyl, 1-anthracenyl and 9-anthracenyl; Halogenated aromatic groups such as 1-fluorophenyl, 2-fluorophenyl, 3-fluorophenyl and pentafluorophenyl; Hydroxyl group-containing aromatic groups such as 1-hydroxyphenyl, 2-hydroxyphenyl and 3-hydroxyphenyl; Nitro group-containing aromatic groups such as 1-nitrophenyl, 2-nitrophenyl and 3-nitrophenyl; And a heterocyclic group such as 1-furanyl.

The compound (D1) is, for example, a compound wherein R ¹ to R ³ are each independently hydrogen or an aliphatic hydrocarbon group having 1 to 20 carbon atoms, and at least one of R ¹ to R ³ is the aliphatic hydrocarbon group; R ¹ to R ² are hydrogen and R ³ is an aromatic hydrocarbon group having 6 to 20 carbon atoms.

<Nitrogen content Heterocyclic  Compound &gt;

The nitrogen-containing heterocyclic compound means a compound in which at least one of carbon atoms forming a ring in the compound having a cyclic hydrocarbon group is substituted with nitrogen and is a compound other than the compound (D1). At least one of the carbon atoms forming the ring may be substituted with at least one hetero atom selected from oxygen and sulfur. At least one of the hydrogen atoms contained in the compound may be substituted with at least one group selected from the following (1) to (6).

(1) a halogen atom, (2) a hydroxyl group, (3) an alkoxycarbonyl group, (4) a carboxyl group, (5) a hydrocarbon group having 1 to 20 carbon atoms, (6) at least one carbon atom in the hydrocarbon group A group substituted with at least one hetero atom selected.

Specific examples of the nitrogen-containing heterocyclic compound include compounds represented by the formulas (D2) to (D6). Hereinafter, these compounds are also referred to as "compound (D2)" to "compound (D6)".

[Chemical Formula 5]

In the formula (D2), X is a group represented by -C (R &lt; ⁷ &gt;) = or a nitrogen atom. In the formula (D3), Y is a group represented by -C (H) (R ⁶ ) - or a group represented by -N (H) -. In the formula (D4), X is a group represented by -C (R &lt; ¹¹ &gt;) = or a nitrogen atom. In the formula (D5), Y is a group represented by -C (H) (R ¹¹ ) - or a group represented by -N (H) -.

In formulas (D2) to (D6), R ⁴ to R ¹² are each independently hydrogen, an aliphatic group having 1 to 20 carbon atoms or an aromatic group having ^{4 to} 20 carbon atoms, and any of R ⁴ to R ⁸ Two groups may be bonded to each other to form a ring such as an alicyclic ring, an aromatic ring and a heterocyclic ring, or any two groups selected from R ⁹ to R ¹² may bond to each other to form a ring such as an alicyclic ring, May be formed.

The aliphatic group may be a straight chain structure, a branched structure, or a cyclic structure.

The carbon number of the aliphatic group is 1 to 20, preferably 1 to 6. The aliphatic group includes, for example, an aliphatic hydrocarbon group and a group in which at least one of the carbon atoms in the aliphatic hydrocarbon group is substituted with at least one hetero atom selected from oxygen and sulfur. Specific examples of the aliphatic hydrocarbon group having 1 to 20 carbon atoms include the groups described in the description of the formula (D1).

The aromatic group is a group containing at least one aromatic ring, for example, an aromatic hydrocarbon group. At least one of the carbon atoms forming the aromatic ring may be substituted with at least one hetero atom selected from oxygen and sulfur. At least one of the hydrogen atoms contained in the aromatic group may be substituted with at least one group selected from the above (1) to (6) in the description of the nitrogen-containing heterocyclic compound. Specific examples of the aromatic group having 4 to 20 carbon atoms include an aromatic hydrocarbon group, a halogenated aromatic group, a hydroxyl group-containing aromatic group and a heterocyclic group described in the description of the formula (D1).

Any two groups selected from R ⁴ to R ⁸ , for example, a pair of R ⁴ and R ⁵ , a pair of R ⁵ and R ⁶ , a pair of R ⁶ and R ⁷ , and a pair of R ⁷ and R ⁸ . Any two groups selected from R ⁹ to R ¹² are, for example, a pair of R ⁹ and R ¹⁰ , a pair of R ¹⁰ and R ¹¹ , and a pair of R ¹¹ and R ¹² . Specific examples thereof include compounds represented by formulas (D2-1) to (D2-3) or (D4-1) to (D4-2). Hereinafter, these compounds are also referred to as "compound (D2-1)" to "compound (D2-3)" and "compound (D4-1)" to "compound (D4-2)".

[Chemical Formula 6]

R ⁴ to R ⁶ , R ⁸ to R ¹⁰ and R ¹² to R ¹³ in the formulas (D2-1) to (D2-3) and (D4-1) to (D4-2) An aliphatic group having 1 to 20 carbon atoms or an aromatic group having 4 to 20 carbon atoms. Specific examples of the aliphatic group and the aromatic group include those described in the description of the formulas (D2) to (D6).

Examples of the nitrogen-containing heterocyclic compound include pyrrole, pyrrolidine, imidazole, pyridine, piperidine, pyrimidine, indole, quinoline, isoquinoline, purine, Picoline, imidazolidine, piperazine, and pyrazine.

&Lt; Preferred examples of organic amine compound >

As the organic amine compound, the following compounds are preferable from the viewpoints of cost, ease of availability and safety. Compound (D1) as the compound having an R ¹ ~R ³ shown in Table 1, and preferably, monomethyl amine, benzylamine, and aniline, and o- toluidine are more preferred, and more preferred is aniline. As the compound (D2), a compound having R ⁴ to R ⁸ shown in Table 2 is preferable, and pyridine is more preferable.

That is, it is preferable to use an amine such as monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, benzylamine, o-toluidine, m-toluidine, At least one member selected from the group consisting of choline, p-picoline, y-picoline, pyridine and quinoline is preferable and at least one member selected from monomethylamine, benzylamine, o-toluidine, aniline and pyridine, And pyridine.

[Table 1]

[Table 2]

The salt (D) is a salt obtained by reacting a strong acid with an organic amine compound. Examples of the salt include monomethylamine hydrochloride, dimethylamine hydrochloride, trimethylamine hydrochloride, monoethylamine hydrochloride, diethylamine hydrochloride, triethylamine hydrochloride, monoisopropylamine hydrochloride, benzylamine hydrochloride, o-toluidine hydrochloride, m- Picoline hydrochloride,? -Picoline hydrochloride, pyridine hydrochloride, and quinoline hydrochloride are preferable as the hydrochloride, aniline hydrochloride, benzhydrylamine hydrochloride,? -Picoline hydrochloride,? -Picoline hydrochloride,? -Picoline hydrochloride, These salts (D) are excellent in ease of acquisition, cost, stability and safety. Instead of these hydrochlorides, nitrate, sulfate, hydrofluoride, hydrobromide, perchlorate, and chlorate are examples.

Of these, monomethylamine hydrochloride, benzylamine hydrochloride, o-toluidine hydrochloride, aniline hydrochloride and pyridine hydrochloride are more preferable from the viewpoint of balance of ease of reaction control, ease of acquisition, cost, stability and safety, Particularly preferred are aniline hydrochloride and pyridine hydrochloride because of their excellent stability, optical properties such as haze of the obtained transparent film, heat resistance and flatness in a thick film.

The reaction ratio of the strong acid to the organic amine compound is, for example, as follows. The salt (D) can be obtained by reacting usually 1 to 50 mol, preferably 1 to 10 mol, of strong acid with 1 mol of the organic amine compound. The salt (D) may be used singly or in combination of two or more.

[1-5. Optional ingredients]

In the present invention, components other than the components (A) to (D) may be mixed as optional components in the preparation of the composition. Examples of optional components include a binder, a surfactant, an adhesion promoter, and a corrosion inhibitor.

The binder is a resin that can be used for dispersing and supporting the metal oxide polymer in the transparent film formed using the composition of the present invention. The binder is not particularly limited as long as it is a resin that is generally used as a binder of a sol-gel composition and does not significantly impair the transparency of the formed film. Examples of the binder include polyvinyl alcohol, epoxy resin, silicone resin, fluorine resin, , Polypropylene, polyvinyl chloride, polystyrene, acrylic resin, styrene-methyl methacrylate copolymer, styrene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene block copolymer, polyethylene terephthalate, polybutylene terephthalate , Polyethylene naphthalate, polycarbonate, nylon 6, nylon 66, polyester, polyacetal, polyether ether ketone, polyether nitrile, polysulfone, polyether sulfone, polyimide and polyamideimide.

As the binder, an alcohol-soluble polymer obtained by polymerizing a plurality of arbitrary radically polymerizable monomers may be used. The "alcohol-soluble polymer" is a polymer having solubility in alcohol to such an extent that when the polymer is added in an amount of 0.1 to 50% by weight based on the alcohol, it is well dispersed and a transparent composition can be obtained. Here, the alcohol is preferably an alcohol having 2 to 10 carbon atoms and one hydroxyl group in one molecule. Examples of the alcohol include those exemplified as the alcohol (B). The alcohol-soluble polymer is not particularly limited as long as it is a polymer satisfying the above-mentioned conditions, and for example, it is a polymer having an acidic group (e.g., an acrylic resin having an acidic group). The acidic group may be any acidic group generally known, such as a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, or a phosphoric acid group, but a carboxyl group is preferable from the viewpoint of low manufacturing cost and ease of molecular design. The further use of the alcohol-soluble polymer is preferable because it is possible to precisely control the refractive index and the film thickness.

The binder may be used in an amount of, for example, 0.05 to 300 parts by weight, preferably 0.1 to 200 parts by weight, based on 100 parts by weight of the metal alkoxide. The binder may be used alone or in combination of two or more.

The surfactant has the effect of further improving the coatability of the composition of the present invention on the substrate. As a result, for example, the uniformity of the film thickness of the obtained transparent film becomes good. As the surfactant, generally known silicon-based, fluorine-based, or acrylic-based surfactants can be used. Examples of commercially available products include Zonyl FSO-100, Zonyl FSN, Zonyl FSO, Zonyl FSH (trade name, DuPont), Triton X-100, Triton X-114 and Triton X- Dynol 604, Dynol 607 (trade name, manufactured by Air Products Japan), n-Dodecyl-β-D-maltoside, Novek, Byk-300, Byk-306, Byk-335, Byk- DFX-18, POTGENT 250, POTGENT 251 (trade name, manufactured by Nippon Kayaku Co., Ltd.), trade name: F-477, F-472SF, TF-1366 (trade name, manufactured by DIC Corporation) and KP-341 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.). The surfactant may be used alone or in combination of two or more.

As the adhesion promoter, for example, there is known a compound which forms a bond between a substrate and a component in the composition, and a compound which has a functional group exhibiting affinity between the substrate and a component in the composition. Further, adhesion between the substrate and the composition may be promoted by two or more kinds of adhesion promoters depending on different mechanisms. Specific examples of the adhesion promoter include a silane coupling agent such as 3- (3-aminopropyl) triethoxysilane, 3- (3-mercaptopropyl) trimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, And a silane coupling agent such as isopropyltrimethoxysilane. The adhesion promoter may be used alone or in combination of two or more.

As the corrosion inhibitor, known compounds such as hindered amine compounds and hindered phenol compounds can be used. Examples of commercially available products include Irgafos XP40, IRGANOX 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1135 and IRGANOX 1520L (trade names, BASF Japan). The corrosion inhibitor may be used alone or in combination of two or more.

[1-6. Action of each component]

(A), alcohol (B), water (C) and salt (D) used in the production method of the present invention or contained in the composition of the present invention, .

&Lt; Metal alkoxide (A) >

The metal alkoxide (A) reacts with water (C), and some alkoxy in the metal alkoxide (A) undergoes hydrolysis to generate a hydroxyl group. Thereafter, among the molecules, hydroxyl groups or some polycondensation of the hydroxyl group and alkoxy generate a metal-oxygen-metal bond, and a metal oxide polymer is produced. In the present invention, it is presumed that the polymer is a polymer having an appropriate degree of polymerization and a polycondensation reaction proceeding two-dimensionally, so that the polymer is well dispersed in the composition and a transparent composition can be obtained. When the composition is applied and baked on a substrate, the polycondensation reaction described above proceeds further in the film to form a dense metal oxide film. As a result, a film having high transparency and high refractive index can be obtained.

&Lt; Alcohol (B) >

The alcohol (B) is used not only as a solvent for dissolving other raw materials such as the metal alkoxide (A) and the salt (D), but also for improving the stability of the composition of the present invention and for forming a film having a high transparency and refractive index Is used for the purpose of expressing suitable characteristics. These properties are estimated as follows.

The alcohol (B) is obtained by a reaction between an alkoxy of the metal alkoxide (A) and an alcohol (B), a hydrolysis reaction of the alkoxide of the metal alkoxide (A) with water (C) The progress of the polycondensation reaction between the alkoxy and the hydroxyl group of the polymer is controlled to a good balance. As a result, a metal oxide polymer is produced in the composition of the present invention. This polymer is a polymer having an appropriate degree of polymerization and proceeding in a two-dimensional manner through the polycondensation reaction, and therefore has high dispersibility in the composition, and the composition is transparent. Since the growth of the polymer, that is, the polycondensation reaction, is suppressed by the presence of the alcohol (B), the viscosity of the composition is stabilized and the storage stability is excellent.

When the composition thus obtained is coated and sintered on a substrate, the aforementioned alcohol (B) is volatilized from the film, and as a result, the polycondensation reaction between the polymers dispersed in the composition proceeds further.

It is presumed that the polymer dispersed in the composition of the present invention is not three-dimensionally but two-dimensional, so that it is presumed that the film obtained as a result of the polycondensation reaction becomes a dense metal oxide film in which a two-dimensional bulk structure is superimposed. As a result, a film having high transparency and high refractive index can be obtained. Further, since the flexibility of the film is good, cracking due to heat shrinkage when the film is exposed at a high temperature is suppressed.

Further, since the volatilization rate of the alcohol (B) at the time of firing is appropriate, the curing rate of the film is appropriately controlled. As a result, it is possible to obtain a film having excellent properties such as good flatness, low haze, and cracking even when the film thickness is large.

&Lt; Water (C) >

Water (C) has a function of promoting the hydrolysis of the metal alkoxide (A) and a function of promoting the dissolution of the salt (D) in the composition of the present invention.

<Salt (D)>

The salt (D) has a function of appropriately controlling the reaction in the composition of the present invention. In addition, the presence of the salt (D) enables the transparent film having a high refractive index to be formed at a lower temperature than in the prior art using the composition of the present invention. These are estimated as follows.

The salt (D) has a function of appropriately suppressing the hydrolysis of alkoxy in the metal alkoxide (A), and has a function of hydrolyzing a part of the metal alkoxide (A) Hit. Further, the salt (D) has a function of appropriately promoting the polycondensation reaction between the hydroxyl group and the alkoxy between the molecules which occurs thereafter, and therefore, in the relatively short time after the hydrolysis, the subsequent polycondensation reaction . As a result, generation of the metal oxide polymer grown two-dimensionally, not three-dimensionally, is promoted.

The dispersion composition of the two-dimensionally grown polymer is very suitable for forming a film having high heat resistance, transparency and high refractive index as described in the description of the mechanism of action of alcohol (B).

Further, since the salt (D) has a function of promoting the polycondensation reaction described above, when a film is formed using the composition of the present invention, for example, a dense metal oxide film can be formed at a low temperature of 50 to 270 캜 have.

Further, since the promoting effect of the polycondensation reaction of the salt (D) is not excessively large and appropriate, the curing of the film proceeds at a proper speed. Thus, the resulting film has good flatness and low haze, and even a thick film having a thickness exceeding 300 nm, for example, maintains a sufficient level of flatness and suppresses the occurrence of cracks. Therefore, by using the salt (D), it becomes possible to produce a transparent film having a low haze, a large film thickness and an excellent heat resistance.

[1-7. Mixing process]

The method for producing a transparent film forming composition of the present invention includes a step of mixing the above-mentioned components (A) to (D). The temperature of the liquid at the time of mixing is usually 18 to 35 占 폚, preferably 20 to 30 占 폚; The stirring time is usually 1 to 48 hours, preferably 4 to 24 hours; The reaction is carried out under atmospheric pressure, for example.

Under such a mixing condition, it is presumed that the polycondensation reaction of the metal alkoxide (A) proceeds appropriately, that is, not only the proper degree of polymerization is obtained but also the metal oxide polymer in which the polycondensation reaction proceeds two-dimensionally is produced .

In the mixing step, it is preferable to set the amounts of the components (A) to (D) to the ranges described below. This makes it possible to (1) improve the stability of the composition, and (2) to provide a film having a higher transparency, a refractive index, a higher heat resistance and a lower haze and a lower film thickness , And also at low firing temperatures.

The alcohol (B) is preferably mixed in the range of 5 to 500 moles, more preferably 15 to 250 moles, per 1 mole of the metal alkoxide (A). When the amount of the alcohol (B) is not less than the lower limit value described above, the stability of the obtained composition is high and, for example, thickening and precipitation do not occur, and a film having a high transparency and a low haze can be obtained when the composition is coated. When the amount of the alcohol (B) is not more than the above-mentioned upper limit value, a film having a sufficient film thickness and a high refractive index can be obtained when the composition is coated.

Water (C) is preferably mixed in the range of 0.5 to 5 moles, more preferably 0.8 to 3 moles, per 1 mole of the metal alkoxide (A). When the amount of the water (C) is not less than the lower limit value described above, the hydrolysis of the metal alkoxide (A) proceeds appropriately, the salt (D) sufficiently dissolves, the reaction in the composition proceeds appropriately, The refractive index of the film obtained when the film is formed becomes high. When the amount of water (C) is not more than the above-mentioned upper limit value, the hydrolysis of the metal alkoxide (A) does not proceed excessively and the stability of the obtained composition is high. For example, the thickening such as gelation, And a film having a high transparency and a low haze can be obtained when the composition is coated by coating.

The salt (D) is preferably mixed in the range of 0.01 to 0.1 mol, more preferably 0.02 to 0.06, per mol of the metal alkoxide (A). When the amount of the salt (D) is not less than the lower limit value described above, the polycondensation reaction can be sufficiently promoted at a low firing temperature, and a film excellent in transparency and refractive index can be obtained. When the amount of the salt (D) is within the above-mentioned range, the stability of the composition is high, for example, the precipitation does not occur in the composition and the optical characteristics of the resulting film become high.

In the mixing step, the components (A) to (D) and, if necessary, the above-mentioned arbitrary components, for example, a binder such as an alcohol-soluble polymer are appropriately selected by stirring, mixing, , Whereby the composition of the present invention can be prepared. In the mixing step, it is preferable to mix the components (A) to (D) in the composition ratio.

The mixing method of the raw material compound is not particularly limited and the components (A) to (D) may be mixed at one time, but considering the reaction in the presumed composition, the following methods (1) to (3) desirable. The above-mentioned optional components may also be added to the composition thus obtained.

(1) First, all the metal alkoxides (A) and all the alcohols (B) are mixed and reacted sufficiently. Next, water (C) and salt (D) How to do it.

(2) First, all the metal alkoxides (A) and some alcohols (B) are mixed and reacted sufficiently. Next, water (C), salt (D) and remaining alcohol ) Is added to the reaction mixture, followed by sufficient reaction.

(3) The mixture solution (1) is prepared by mixing all of the metal alkoxide (A) and a part of the alcohol (B) To prepare a mixed solution (2), followed by mixing the mixed solution (1) and the mixed solution (2) and sufficiently reacting them.

The stirring time in the above methods (1) and (2) is usually 1 to 48 hours, preferably 4 to 24 hours. In the above method (3), the stirring time at the time of preparing each of the mixed solution (1) and mixed solution (2) is usually 5 minutes to 2 hours, preferably 10 minutes to 1 hour, ) And the mixed solution (2) is usually 1 to 48 hours, preferably 4 to 24 hours.

[2. Composition for forming a coating type transparent film]

The coating type transparent film forming composition of the present invention is a composition for forming a coating film for a transparent conductive film which comprises (A) a metal alkoxide, (B) an alcohol, (C) water and (D) a strong acid, Or a salt thereof. This composition is obtained, for example, by mixing the components (A) to (D). Specifically, this composition can be obtained by the above-described production method.

The composition of the present invention preferably has a viscosity of 1 to 20 mPa · s, more preferably 1 to 10 mPa · s. The viscosity is measured at 25 DEG C and a shear rate of 383 s &lt; ^-1 &gt;, and details of the measurement conditions are as described in the examples.

The composition of the present invention has a stable viscosity and excellent storage stability. Further, by using the composition of the present invention, a metal oxide film having high transparency, refractive index, heat resistance and flatness and having low haze can be obtained at a low firing temperature.

The composition of the present invention can be identified by a method described in Non-Patent Document 2, that is, by an analytical method such as NMR, ESR, Raman spectrum, infrared spectrum, gas chromatography, liquid chromatography and the like. Further, the reaction of the raw materials with each other is overwhelmingly caused when the composition is applied and baked, and rarely occurs in the solution in the raw material compounding step. Therefore, the composition of the raw material compound used in preparing the composition of the present invention can be identified by the above-described analytical method.

[3. Method for producing transparent film using composition for forming transparent transparent film]

A method for forming a transparent film on a substrate by using the composition for forming a transparent film of the present invention will be described below. The method for producing a transparent film of the present invention comprises the steps of (1) applying the coating type transparent film forming composition of the present invention onto a substrate, and (2) applying the coating film obtained in the step (1) And then firing it by a method.

[3-1. Step (1)]

In the step (1), the composition for forming a transparent film of the present invention is applied on a substrate.

As the substrate, for example, a glass substrate made of soda lime glass, low alkali borosilicate glass, alkali-free aluminoborosilicate glass, or the like; There are polymeric groups composed of polycarbonate, polyester, aromatic polyamide, polyamideimide, polyimide, polyethylene terephthalate, polymethylmethacrylate and the like. The substrate may be plate-shaped or film-shaped. A transparent electrode made of indium oxide, tin oxide, silver, gold, carbon, an organic compound or the like, an insulating film, a color filter, various driving circuits, or the like may be formed on the surface of the substrate.

The composition of the present invention can form a film by low-temperature baking. Therefore, among these substrates, it is particularly useful for film formation on a plastic substrate having low heat resistance or a substrate having a drive circuit susceptible to adverse effects due to heat.

An example of the thickness of the substrate is 0.1 to 3 mm, but is not particularly limited. As a coating method, general methods such as a spin coating method, a slit coating method, a dip coating method, a blade coating method, a spraying method, a convex printing method, a concave printing method, a flat printing method, a dispensing method and an ink jet method can be used . From the viewpoints of uniformity of film thickness and productivity, the spin coat method and the slit coat method are preferable, and the slit coat method is more preferable.

The coating film obtained in the step (1) is preferably subjected to a drying step appropriately after application. The drying method includes, for example, vacuum drying, room temperature drying, heat drying, and air drying. By these methods, the solvent in the coating film, for example, the alcohol (B) is removed to dry the coating film. The drying conditions include, for example, drying at a temperature of from room temperature to 100 ° C for 30 seconds to 5 minutes. The reduced pressure drying is carried out at a temperature of 20 to 25 캜 under a pressure of 50 to 150 Pa, for example. From the viewpoint of the production cost, it is preferable to dry at room temperature under atmospheric pressure, but if drying takes a long time, it is preferable to heat and dry at about 50 캜. The drying process is performed at a temperature lower than that of the step (2).

[3-2. Step (2)]

In the step (2), the coating film obtained in the step (1) is baked.

By this step, the solvent in the coating film, for example, the alcohol (B) is removed, and the polycondensation reaction of the metal alkoxide (A) and its lower condensate in the coating film proceeds to form a dense metal oxide film, The coating film is cured. Not all solvents need to be removed.

For firing, for example, a hot plate or an oven can be used. The firing temperature varies depending on the kind of the solvent such as the alcohol (B), but is usually from 50 to 270 캜, preferably from 70 to 270 캜. The firing temperature is, for example, the temperature of the plate when using a hot plate and the temperature measured using a thermocouple provided in the oven when using an oven. The baking time is usually 1 to 60 minutes. In the present invention, since the composition for forming a transparent film having the above-described characteristics is used, such low-temperature firing is possible.

A condition of baking at a temperature of 70 ° C or higher and lower than 160 ° C is preferable from the viewpoint of the heat load and the production cost for the substrate and the condition of baking at 160 ° C or higher and 270 ° C or lower is preferable from the viewpoint of the characteristics of the obtained transparent film. And a condition of baking at 80 DEG C for 60 minutes is preferable in view of the characteristics of the transparent film, the manufacturing cost, and the balance of the heat load to the substrate.

[3-3. Any process]

Before and after each of the above-described processes, one or more processes selected from an appropriate process, a cleaning process, and a drying process may be appropriately added. Examples of the treatment process include a chemical treatment using a silane coupling agent and the like, a plasma surface treatment, an ultrasonic treatment, an ozone treatment, a cleaning treatment using a suitable solvent, and a heat treatment.

The plasma surface treatment can be used for improving the applicability to a composition for forming a transparent film or a developer. For example, the surface of the substrate or the coating film can be treated using oxygen plasma under conditions of 100 watts, 90 seconds, an oxygen flow rate of 50 sccm (sccm; standard cc / min), and a pressure of 50 pascals.

In the ultrasonic treatment, the substrate is immersed in a solution, and ultrasonic waves of about 200 kHz, for example, are propagated to remove fine particles physically attached to the substrate.

The ozone treatment can effectively remove adherents and the like on the substrate due to the oxidizing power of ozone generated by the ultraviolet light, while emitting air to the substrate and irradiating the ultraviolet light.

The cleaning treatment can be carried out by, for example, spraying pure water in a mist state or a shower state, and washing out impurities of fine particle type with solubility and pressure.

The heat treatment is a method of removing the compound in the substrate by volatilizing the compound to be removed. The heating temperature is appropriately set in consideration of the boiling point of the compound to be removed. For example, when the compound to be removed is water, it is heated in the range of about 50 to 80 占 폚.

[3-4. The transparent film and The laminate ]

The film thickness of the transparent film obtained by the above production method is preferably 1 to 400 nm, and more preferably 2 to 400 nm. The refractive index of the film is preferably 1.6 or more, and more preferably 1.7 to 2.1.

The laminate of the present invention is a film-attached substrate including a substrate and the transparent film, for example, the transparent film formed on the substrate. The total light transmittance of the laminate such as the film-adhered substrate is preferably 82% or more, and more preferably 85 to 93%. The haze H ₁ of the layered product such as a film-attached substrate or the like is preferably such that the difference | H ₁ -H ₂ | from the haze value H ₂ of the substrate alone is preferably 1.5% or less, more preferably 0.5% to be.

When these properties are within the above-mentioned ranges, the transparent film of the present invention can sufficiently exhibit the functions as the antireflection application and the application for preventing the appearance of the pattern.

The &quot; total light transmittance &quot; is the ratio of the transmitted light to the incident light, and the transmitted light is composed of the direct transmission component and the scattering component. &Quot; Haze &quot; is a ratio of light scattered by 2.5 degrees or more from the incident light axis in the total light-transmitted light. The light source is the C light source, and the spectrum is the CIE luminance function y. The &quot; refractive index &quot; is the refractive index at a wavelength of 550 nm. Details of these measurement conditions are as described in the examples.

In the present invention, it is possible to form a transparent film which is a thick film as described above and which has excellent optical properties such as total light transmittance, haze, refractive index, and the like. That is, according to the present invention, for example, a transparent film having various film thicknesses and excellent optical characteristics can be formed by appropriately selecting conditions such as the amount of alcohol (B) to be used and the number of revolutions of the spin coat.

[3-5. High refractive index  Use of transparent film]

Hereinafter, the use of the high refractive index transparent film of the present invention will be described. The high-refractive-index transparent film formed by using the coating type transparent film-forming composition of the present invention and the laminate using the high-refractive-index transparent film are used, for example, in electronic devices from their optical properties. An example of the electronic device has a substrate and a high refractive index transparent film of the present invention.

Examples of the electronic device include a flat panel display (FPD) such as a liquid crystal display element, an organic electroluminescent display, and an electronic paper, a touch panel element, and a solar cell element.

The electronic device may be fabricated using a rigid substrate, a substrate that is susceptible to bending, or a combination thereof. Further, the substrate used for the electronic device may be transparent or colored.

As the high refractive index transparent film used for FPD, for example, there is an antireflection film. The touch panel element can be divided into a resistive film type or a capacitive type in accordance with the detection method, but in any of these methods, a high refractive index transparent film is used as the antireflection film. In particular, in the projection-type electrostatic capacity type, a high-refractive-index transparent film is used as an application for preventing the pattern of the ITO film from being seen. The high refractive index transparent film may be patterned into an arbitrary shape, respectively.

The solar cell element can be divided into a silicon system, a compound system, an organic system, a quantum dot system and the like depending on the material of the light absorption layer, and a high refractive index transparent film is used as an antireflection film even if any material is used. The high refractive index transparent film may be patterned into an arbitrary shape, respectively.

&Lt; Use of antireflection film &

In one example, the film formed using the composition of the present invention is used as an antireflection film, for example, as a single layer. In general, if the refractive index n film is formed of a transparent substrate, the refractive index on the n _2, the thickness d _{2 1,} the light reflection factor of incident medium of a refractive index n ₀ from the surface in a vertical film is, n ₀ <n ₂ < n ₁ and has a minimum value when n ₂ · d ₂ is an odd multiple of 1/4 of the wavelength of light, and the value is represented by R below.

R = [(n ₀ n ₁ -n ₂ ² ) / (n ₀ n ₁ + n ₂ ² )] ²

Therefore, the condition that R becomes zero is n ₂ = (n ₀ n ₁ ) ^0.5 . For example, when the medium is air (n ₀ = 1), on the semiconductor material having the refractive index of about 3.4, By forming a high-refractive-index transparent film (refractive index: about 1.85, for example), its reflectance can be lowered. The composition of the present invention can be preferably used for such an antireflection use because of high stability, high transparency of the obtained film, low haze, and high refractive index.

Further, in another example, a laminated film including a film formed using the composition of the present invention is used as an antireflection film. Generally, when a laminated film composed of a film having a refractive index of about 1.35 as a first layer and a film having a refractive index of about 1.85 as a second layer is formed on a glass substrate as an antireflection film on a glass substrate, Is known to have a lower reflectance than a case where an antireflection film is not formed in a wide range of wavelengths from 400 to 800 nm. The film formed using the composition of the present invention can be preferably used as the film of the second layer in this example.

<Uses to prevent visible patterns>

In one example, the film formed using the composition of the present invention is used as a transparent conductive film pattern formed on a transparent substrate, for example, to prevent a pattern of a touch electrode pattern on a capacitive touch panel from being seen.

When the difference in refractive index between the transparent conductive film and the transparent substrate is large in the transparent conductive film pattern formed on the transparent substrate, the reflected light in the region where the transparent conductive film exists on the transparent substrate and the reflected light And as a result, the transparent conductive film pattern becomes conspicuous. In order to prevent this, a laminated film including the high refractive index transparent film of the present invention is formed on a transparent substrate on which a transparent conductive film pattern is formed (FIG. 1A), or a high refractive index transparent film of the present invention A transparent conductive film pattern is formed on the laminated film (FIG. 1 (B)). In these cases, it is preferable that the difference in reflectance between the reflected light in the region where the transparent conductive film exists and the reflected light in the region where the transparent conductive film does not exist is 550 nm or less within 1%.

That is, as an example of an electronic device, a layered structure including a high-refractive-index transparent film of the present invention is formed on an upper layer or a lower layer of a patterned transparent conductive film so that a region of the transparent conductive film, And the difference in reflectance at 550 nm is 1% or less.

Since the composition of the present invention has high stability of the composition, can form a film having a wide range of film thickness at a low temperature, has a high transparency, a low haze, a high refractive index and a high heat resistance, It can be suitably used for the purpose of preventing the pattern from being seen.

Examples of the transparent substrate used for preventing the pattern from being seen include a glass substrate made of soda lime glass, low alkali borosilicate glass, alkali-free aluminoborosilicate glass, or the like; There is a polymer substrate composed of polycarbonate, polyester, aromatic polyamide, polyamideimide, polyimide, polyethylene terephthalate, polymethylmethacrylate and the like. These may be plate-shaped or film-shaped.

Examples of the transparent conductive film used for preventing the pattern from being seen include organic film, metal oxide film such as ITO, indium zinc oxide (IZO), gallium oxide zinc oxide (GZO), metal nano- Film, metal nanowire dispersion film, metal nanotube dispersion film, organic nanoparticle dispersion film, organic nanowire dispersion film, and organic nanotube dispersion film.

[Example]

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In the examples and the comparative examples, ultrapure water was used as water as a component, but in the following, it may be simply referred to as &quot; water &quot;. Ultrapure water was prepared using Furik FPC-0500-0M0 (trade name, manufactured by ORGANO CO., LTD.). The preparation of the composition was carried out at room temperature of 25 캜, unless otherwise specified.

The measurement method or evaluation method in each evaluation item was as follows.

(1) Viscosity

For the measurement of the viscosity of the composition, a TV-22 type viscometer (manufactured by Toki Kogyo Co., Ltd.) was used. The viscosity at 25 ° C and a shear rate of 383 s ^-1 was measured. The viscosity stability of the composition was evaluated by comparing the viscosity measurement value a (mPa · s) at the start of storage and the viscosity measurement value b (mPa · s) after storage at the time of storing the composition at 25 ° C for 180 hours (BB) &quot;, a composition having a viscosity increasing rate of 10% or more and a rate of increasing viscosity of 10% or more and 60% or less is referred to as &quot; good & , And a composition whose rate of rise exceeds 60% is referred to as &quot; poor (CC) &quot;.

(2) Total light transmittance and haze ( Hayes )

A haze guard plus (manufactured by BYK Gardner Co., Ltd.) was used for measurement of the total light transmittance and haze (haze) of the substrate with a transparent film. The reference was air. The evaluation of the haze of the transparent film was evaluated as "very good (AA)" when the difference between the haze value of the substrate only and the haze value of the substrate with the transparent film was less than 0.5% ) &Quot;, and those exceeding 1.5% were determined as &quot; poor (CC) &quot;. The Eagle XG glass substrate having a thickness of 0.7 mm had a haze value of 0.0%.

(3) Refractive index

For measurement of the refractive index of the transparent film, a reflective film thickness meter FE-3000 (manufactured by Otsuka Electronics Co., Ltd.) was used. The measured value at a wavelength of 550 nm was defined as the refractive index of the sample.

(4) Thickness

For measurement of the film thickness of the transparent film, a stepped P-16 + (trade name; manufactured by Keel A Tencor Co., Ltd.) was used. A part of the film formed on the substrate was scraped off and the step on the interface was measured. The measured value was defined as the film thickness of the sample. The measurement of the film thickness was carried out in accordance with "Method of measuring film thickness of fine ceramics thin film-method of measuring with a stylus type roughness tester (JIS-R-1636)".

(5) Heat resistance

The heat resistance of the transparent film was evaluated by the following procedure. A sample on which a film was formed was placed in a thermostatic chamber LC-114 (trade name, manufactured by Espace Co., Ltd.) set at 230 DEG C, taken out after 30 hours, magnified at a magnification of 100 times using an optical microscope And the film state was observed. The evaluation result was defined as "good (AA)" when no cracks were observed on the film at all, and "bad" (CC) when cracks were observed at one or more locations on the film.

[Example 1]

[Preparation of composition for forming a transparent film]

10.0 g of tetrabutyl orthotitanate (manufactured by Tokyo Chemical Industry Co., Ltd.) and 13.4 g of 2-propanol were mixed and stirred for 10 minutes to obtain a mixed solution (1). Further, 0.0790 g of monomethylamine hydrochloride (manufactured by Tokyo Chemical Industry Co., Ltd.), 1.06 g of water and 26.7 g of 2-propanol were mixed and stirred for 10 minutes to obtain a mixed solution (2). Next, all the mixed solution 2 was added to the mixed solution 1 while stirring the mixed solution 1, and the mixture was stirred for 4 hours to obtain a composition I. The molar ratio of the feed amount of the raw material used is shown in Table 3.

[Formation of a transparent film]

0.5 mL of the obtained composition I was dropped onto an EagleXG glass substrate having a thickness of 0.7 mm and spin-coated at 500 rpm using a spin coater (trade name: MS-A150, manufactured by Mikasa). The glass substrate was allowed to stand for 30 seconds at room temperature and dried, and then baked for 1 hour on a hot stage at 80 캜 to prepare a substrate I with a transparent film.

[Evaluation of transparent substrate-attached substrate]

The obtained transparent-film-adhered substrate I had a total light transmittance of 89.6%, a haze of 0.2%, a refractive index of 1.87, and a film thickness of 400 nm. The evaluation of Haze was "very good (AA)". The evaluation of the heat resistance was "good (AA)". The evaluation results are shown in Table 3. Since the transparent film of the substrate I with the transparent film was formed using the composition of the present invention, it had high transparency, low haze, high refractive index and high heat resistance.

[Evaluation of stability of viscosity]

The viscosity of the obtained composition I at the start of storage was 3.58 mPa,, the viscosity increase rate was 52%, and the viscosity stability was "good (BB)". The evaluation results are shown in Table 3. Since the composition I was prepared by mixing the appropriate compound shown in the present invention, the viscosity stability was high.

[Examples 2 to 9, Example 11 and Comparative Example 3]

Except that the mixed solutions (1) and (2) were prepared and the mixed solution (1) and the mixed solution (2) were mixed in the conditions described in Tables 3 to 4 and Table 6 Compositions II to VIV, XII and IIIc were prepared in the same manner as in Example 1.

Substrates II to VIV, XII and IIIc having transparent films were produced in the same procedure as in Example 1 except that the compositions II to VIV, XII and IIIc were used. In Example 3, a transparent film-attached substrate III-1 was prepared in the same procedure as in Example 1 except that the composition III was used, and further, the composition III was used, and further, on a hot stage at 230 캜 for 30 minutes Except that the substrate III-2 having a transparent film was produced in the same procedure as in Example 1 except that the composition III was used and spin coating was carried out at 2000 rpm. , A transparent film-adhered substrate III-3 was prepared, and the same procedure was followed as in Example 1 except that the composition III was used and spin coating was carried out at 5500 rpm.

In Example 6, a transparent film-attached substrate VI-1 was prepared in the same procedure as in Example 1 except that the composition VI was used. Further, the composition VI was used and spin coating was carried out at 5500 rpm A transparent-film-attached substrate VI-2 was produced in the same procedure as in Example 1 except for the above. In Comparative Example 3, a transparent film-attached substrate IIIc was prepared in the same procedure as in Example 1 except that the composition IIIc was used and spin coating was performed at 400 rpm.

In Example 11, a transparent film-attached substrate XII-1 was prepared in the same procedure as in Example 1 except that the composition XII was used and spin coating was carried out at 300 rpm. Further, the composition XII was used , A transparent film-adhered substrate XII-2 was produced in the same procedure as in Example 1 except that the film was further spin-coated at 300 rpm and further baked on a hot stage at 150 ° C for 30 minutes. Further, the composition XII was used , And the substrate was subjected to spin coating at 300 rpm and further baked for 30 minutes on a hot stage at 230 ° C, a substrate XII-3 with a transparent film was produced in the same procedure as in Example 1, , And a transparent film-adhered substrate XII-4 was prepared in the same procedure as in Example 1 except that spin coating was performed at 2000 rpm. Further, the composition XII was used and spin coating was performed at 2000 rpm, A substrate XII-5 with a transparent film was produced in the same procedure as in Example 1 except that the substrate was fired on a hot stage at 150 캜 for 30 minutes. Further, the substrate XII-5 was further subjected to spin coating at 2000 rpm A substrate XII-6 having a transparent film was produced in the same procedure as in Example 1 except that the substrate was fired on a hot stage at 230 캜 for 30 minutes.

[Preparation of alcohol-soluble polymer solution (3)] [

In a four-necked flask equipped with a stirrer, 200.0 g of diethylene glycol ethyl methyl ether as a polymerization solvent, 10.0 g of methoxypolyethylene glycol methacrylate, 30.0 g of methacrylic acid, 30.0 g of dicyclopentanyl methacrylate as a radical polymerizable monomer , 30.0 g of N-cyclohexylmaleimide and 5.0 g of 2,2'-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator were added, respectively, and 4 And polymerization was carried out by heating for a time.

The reaction solution was cooled to room temperature to obtain an alcohol-soluble polymer solution (3). A part of the solution (3) was sampled and the weight average molecular weight was measured by GPC analysis (polystyrene standard). As a result, the weight average molecular weight was 3600.

[Example 10]

0.005 g of the alcohol-soluble polymer solution (3) was added to 3.00 g of Composition VI to obtain Composition X. Further, 0.300 g of the alcohol-soluble polymer solution (3) was added to 1.51 g of Composition VI to obtain Composition XI.

[Formation of a transparent film]

A substrate X-1 with a transparent film was produced in the same procedure as in Example 1 except that the composition X was used. Further, a transparent-film-attached substrate X-2 was produced in the same procedure as in Example 1 except that the composition X was used and that the substrate was fired on a hot stage at 230 캜 for 30 minutes. Further, a transparent-film-attached substrate XI-1 was produced in the same procedure as in Example 1 except that the composition XI was used. Further, a transparent-film-attached substrate XI-2 was produced in the same procedure as in Example 1 except that the composition XI was used and that the substrate was fired on a hot stage at 230 ° C for 30 minutes.

The transparent films of the transparent film-adhered substrates X-1, X-2, XI-1 and XI-2 were formed using the composition of the present invention, and thus had high transparency, low haze, high refractive index and high heat resistance. Since the compositions X and XI were prepared by mixing the appropriate compound shown in the present invention, the viscosity stability was high.

[Comparative Example 1]

Based on Example 4 disclosed in Japanese Patent No. 4942053, the following composition Ic was prepared. 12.8 g of tetrabutyl orthotitanate and 17.0 g of 2-propanol were mixed and stirred for 1 hour to obtain a mixed solution 1. Further, 0.103 g of hydrazine monohydrochloride and 1.35 g of distilled water were stirred for 10 minutes using an ultrasonic agitator (USK-1R, manufactured by Asuzon Co., Ltd.) while maintaining the temperature at 10 to 30 占 폚, 2-propanol (34.1 g) was added, and ultrasonic agitation was performed for 10 minutes while maintaining the temperature at 20 to 50 占 폚 to obtain a mixed solution 2. Next, the total amount of the mixed solution 2 was added to the mixed solution 1, and the mixture was stirred at a temperature of 25 DEG C and a rotation speed of 550 rpm for 6 hours to obtain a composition Ic. The molar ratio of the feed amount of the raw material used is shown in Table 4. Gelation of the obtained composition Ic rapidly proceeded after preparation.

A substrate coated with a transparent film Ic-1 was produced in the same procedure as in Example 1 except that the composition Ic was used. Further, a transparent-film-attached substrate Ic-2 was produced in the same procedure as in Example 1 except that Composition Ic was used and spin coating was performed at 2000 rpm. Further, a transparent-film-attached substrate Ic-3 was produced in the same procedure as in Example 1 except that Composition Ic was used and spin coating was carried out at 5500 rpm.

[Comparative Example 2]

1.00 g of tetrabutyl orthotitanate and 15.3 g of 2-propanol were mixed and stirred for 1 hour to obtain a mixed solution 3. Further, ultrasonic agitation was carried out for 10 minutes using an ultrasonic agitator (USK-1R manufactured by Asuwa Corporation) while maintaining 0.076 g of hydrazine monohydrochloride and 1.00 g of distilled water at 10 to 30 占 폚, 25.0 g of 2-propanol was added, and ultrasonic agitation was carried out for 10 minutes while maintaining the temperature at 20 to 50 캜 to obtain a mixed solution 4. Next, a mixed solution 4 obtained by mixing 2.76 g of the mixed solution 4 was added to the mixed solution 3, and the mixture was stirred at a temperature of 25 DEG C and a rotation speed of 550 rpm for 6 hours to obtain a composition IIc. The molar ratio of the feed amount of the raw material used is shown in Table 4. A transparent film-attached substrate IIc was prepared in the same procedure as in Example 1 except that the composition IIc was used.

[Table 3]

[Table 4]

[Table 5]

[Table 6]

Details of components in Tables 3 to 4 and Table 6 are as follows. Metal alkoxide (A), ortho-titanic acid-tetra-butyl (Tokyo Chemical Industry Co., Ltd.) salt (D), mono-methyl-amine hydrochloride (Tokyo Chemical Industry Co., Ltd.), aniline hydrochloride (Showa Chemical Co., Ltd.) ( D ' ) other than the salt ( D ) of benzylamine hydrochloride (manufactured by Tokyo Chemical Industry Co., Ltd.), and the salt (D) of the benzyl amine hydrochloride (manufactured by Tokyo Chemical Industry Co., Ltd. ) Hydrazine monohydrochloride (manufactured by Tokyo Chemical Industry Co., Ltd.)

For example, Examples 1 to 3, Example 9, and Example 11 and Comparative Example 1 are prepared. The composition of Comparative Example 1 had low storage stability. The compositions of Examples 1 to 3, Examples 9 and 11 were excellent in storage stability. In Comparative Example 1, the haze value of the obtained transparent film was high, the refractive index was not measurable, and the heat resistance was low under the condition of low spin speed during spin coating, that is, under a thick film formation condition. In Examples 1 to 3, Examples 9 and 11, a transparent film having a low haze value, a high refractive index and a high heat resistance was obtained even under the above-described conditions. In Comparative Example 1, the haze of the obtained transparent film was high under the condition that the number of revolutions during spin coating was high, that is, under the condition of thin film formation. In Examples 3 and 11, a transparent film having a low haze value was obtained under the above-described conditions.

For example, the examples 6 and 8 and the comparative example 2 are prepared. In Comparative Example 2, the haze value of the obtained transparent film was high and the heat resistance was low. In Examples 6 and 8, a transparent film having a low haze value, a high refractive index and a high heat resistance was obtained.

Further, in Example 3 and Example 11, a transparent film having characteristics substantially equivalent to firing at 230 캜 was obtained even at 80 캜. In Examples 3, 5, and 6, a transparent film having a wide range of film thickness could be formed by suitably changing the amount of 2-propanol and the number of rotations during spin coating. In Example 11, a transparent film having a wide range of film thickness could be formed by suitably changing the number of rotations during spin coating. Further, in Example 3 and Example 11, a transparent film having substantially the same properties as alcohol with 1-methoxy-2-propanol and 2-propanol was obtained.

For example, Examples 6 and 8 and Comparative Example 3 are prepared. The composition of Comparative Example 3 was opaque due to a white precipitate. In Comparative Example 3, the haze value of the obtained transparent film was high, and the refractive index could not be measured. In Examples 6 and 8, a transparent film having a low haze value and a high refractive index could be obtained.

The composition of the present invention can be used, for example, in the production of device elements such as liquid crystal display elements, organic electroluminescent elements, electronic paper, touch panel elements, and solar cell elements. The composition of the present invention is excellent in storage stability, and the temperature required for film formation is low. The film that can be prepared from the composition of the present invention has high transparency, low haze, high refractive index, and high heat resistance.

10: transparent substrate
20: Transparent conductive film pattern
30: A laminated film including a high refractive index transparent film

Claims (15)

A salt obtained by reacting at least one compound selected from the group consisting of (A) a metal alkoxide, (B) an alcohol, (C) water, and (D) A method for preparing a coating composition for forming a transparent film,
[Chemical Formula 1]

[In the formula (D1), R ¹ ~R ³ is each independently an aromatic group of hydrogen, an aliphatic group having 4 to 20 carbon atoms or of 1 to 20 carbon atoms, and at least one of R ¹ ~R ³ is a carbon number of 1 to An aliphatic group having 20 to 20 carbon atoms or an aromatic group having 4 to 20 carbon atoms]. The method according to claim 1,
Wherein the salt (D) is a salt obtained by reacting a strong acid with a compound represented by the formula (D1), and in the formula (D1), R ¹ to R ³ are each independently hydrogen or an aliphatic hydrocarbon group having 1 to 20 carbon atoms , And at least one of R ¹ to R ³ is the aliphatic hydrocarbon group, or R ¹ to R ² are hydrogen and R ³ is an aromatic hydrocarbon group having 6 to 20 carbon atoms. The method according to claim 1,
Wherein the salt (D) is a salt obtained by reacting a strong acid with a nitrogen-containing heterocyclic compound, and the nitrogen-containing heterocyclic compound is at least one selected from compounds represented by the following formulas (D2) to (D6) Method for preparing composition for forming coating type transparent film:
(2)

[In the formula (D2), X is a group represented by -C (R ⁷ ) = or a nitrogen atom;
In the formula (D3), Y is a group represented by -C (H) (R ⁶ ) - or a group represented by -N (H) -;
In the formula (D4), X is a group represented by -C (R &lt; ¹¹ &gt;) = or a nitrogen atom;
In the above formula (D5), Y is a group represented by -C (H) (R ¹¹ ) - or a group represented by -N (H) -;
In the formulas (D2) to (D6), R ⁴ to R ¹² are each independently hydrogen, an aliphatic group having 1 to 20 carbon atoms or an aromatic group having ^{4 to} 20 carbon atoms, and R ⁴ to R ⁸ Any two groups may combine with each other to form a ring, and any two groups selected from R ⁹ to R ¹² may be bonded to each other to form a ring]. The method according to claim 1,
(B), 0.5 to 5 mol of water (C) and 0.01 to 0.1 mol of a salt (D) per mol of the metal alkoxide (A) A method for producing a composition for forming a coating type transparent film. The method according to claim 1,
Wherein the alcohol-soluble polymer is further mixed in the step of mixing the metal alkoxide (A), the alcohol (B), the water (C) and the salt (D). A coating type transparent film-forming composition obtained by the method for producing a coating type transparent film-forming composition according to any one of claims 1 to 5. The method according to claim 6,
And a viscosity of 1 to 20 mPa.s at 25 DEG C and a shear rate of 383 s &lt; ^{-1 &} gt ;. (1) a step of applying on the substrate a composition for forming a coating type transparent film according to any one of claims 6 to 7, and
(2) Subsequent to the step (1), a step of heating the substrate at 50 to 270 캜
Of the transparent film. A transparent film obtained by the method for producing a transparent film according to claim 8. 10. The method of claim 9,
A transparent film having a film thickness of 1 to 400 nm. A laminate comprising a substrate and the transparent film according to claim 9 or 10, wherein the refractive index of the transparent film at a wavelength of 550 nm is 1.6 or more, the total light transmittance of the laminate is 82% or more, haze value H ₁ and haze value of the substrate, only the difference between the H ₂ | H ₁ -H ₂ | is less than 1.5%, the layered product. A substrate, and a transparent film according to claim 9 or 10. A transparent conductive film according to any one of claims 9 to 10, wherein the transparent conductive film is formed on the upper or lower layer of the patterned transparent conductive film, Wherein a difference in reflectance is 1% or less. A salt obtained by reacting at least one compound selected from the group consisting of (A) a metal alkoxide, (B) an alcohol, (C) water, and (D) : &Lt; tb &gt;&lt; TABLE &gt;
(3)

[In the formula (D1), R ¹ ~R ³ is each independently an aromatic group of hydrogen, an aliphatic group having 4 to 20 carbon atoms or of 1 to 20 carbon atoms, and at least one of R ¹ ~R ³ is a carbon number of 1 to An aliphatic group having 20 to 20 carbon atoms or an aromatic group having 4 to 20 carbon atoms]. 15. The method of claim 14,
Wherein the salt (D) is a salt obtained by reacting a strong acid with at least one member selected from aniline and pyridine.

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