KR101266728B1 - Method for producing coating liquid for film formation - Google Patents

Abstract

Provided is a method for producing a coating liquid for forming a film, which can form a film that is sufficiently cured under low-temperature curing conditions, and can form an alignment film with fine pores and pin holes suppressed on the film.

[Process 1] which obtains the solution containing the condensate produced by hydrolyzing and condensing a metal alkoxide (A) in the solvent (B), and the solution which substituted the solution obtained by said [step 1] with the solvent (C) [Process 2] which obtains the process, The manufacturing method of the coating liquid for film formation characterized by the above-mentioned.

However, a metal alkoxide (A) is at least 1 sort (s) of metal alkoxide chosen from the compound represented by Formula (1) (In formula, R <^1> represents a C1-C5 alkyl group);

The solvent (B) is at least one organic solvent selected from the group consisting of alcohols of 1 to 10 carbon atoms, esters of 2 to 5 carbon atoms, tetrahydrofuran and ethers of 2 to 5 carbon atoms; The solvent (C) is at least one organic solvent selected from glycols having 2 to 10 carbon atoms.

Description

Manufacturing method of coating liquid for film formation {METHOD FOR PRODUCING COATING LIQUID FOR FILM FORMATION}

This invention relates to the manufacturing method of the coating liquid for film formation. In detail, it is a manufacturing method of the coating liquid for film formation which forms the film containing a titanium atom.

In accordance with the enlargement of the liquid crystal display element, the oxide film is formed for the purpose of insulation and protection of the transparent electrode. As a formation method of an oxide film, the vapor deposition method represented by the vapor deposition method, the sputtering method, etc., and the coating method using the coating liquid for oxide film formation are known. Among these, many coating methods are used for productivity and the ease of film formation on a large sized substrate. As a coating liquid, the complex of the hydrolyzate of tetraalkoxysilane, another metal alkoxide, and a metal chelate is known.

When a coating liquid is prepared using an alkoxide compound, generally used alkoxide compounds have a high hydrolysis rate except for silicon alkoxide. For this reason, it is attempted to make chelating agents, such as acetylacetone, act on the purpose of adjusting the hydrolysis rate of an alkoxide compound. However, in general, chelated compounds have a high thermal decomposition temperature, and it is considered that firing at 450 ° C or higher is preferable (see Patent Document 1, for example).

As another method, in a silica-titania-based coating liquid, a photoacid is added to the hydrolyzate of silicon alkoxide and titanium alkoxide to attempt to make a transparent coating agent without using stabilization means such as chelation. Also in this case, baking at least 300 degreeC or more is required (for example, refer patent document 2).

In recent years, as the thinning of liquid crystal display devices progresses, it is desirable to lower the formation temperature of the insulating film (oxide film) due to problems such as resistance value change of the transparent electrode film used for the liquid crystal display device, thinning of the substrate glass, and heat resistance of the color filter. It is requested. Furthermore, the demand for the insulating film (oxide film) which hardens especially at 250 degrees C or less is increasing from the situation of reducing the manufacturing cost of a liquid crystal display element, or energy saving orientation.

At the same time, the high resolution of the liquid crystal display device is required to improve the insulating film as fine holes, pinholes, etc. of the liquid crystal alignment film derived from the insulating film greatly influence the display characteristics of the liquid crystal display device. It is becoming. Moreover, according to said improvement, the improvement of the productivity in the manufacturing process of a liquid crystal display element is also calculated | required.

Patent Document 1: Japanese Patent Application Laid-Open No. 63-258959

Patent Document 2: Japanese Patent Application Laid-open No. 55-25487

DISCLOSURE OF INVENTION

Problems to be solved by the invention

An object of the present invention is to form a coating film that is sufficiently cured under a curing condition of 150 to 250 ° C., and a method for producing a coating liquid for forming a coating film capable of forming an alignment film with fine pores and pinholes suppressed on the coating film. Is to provide.

Means for solving the problem

MEANS TO SOLVE THE PROBLEM The present inventors came to complete this invention as a result of earnestly researching in view of said situation.

That is, the gist of the present invention is as follows.

1. [Step 1] of obtaining a solution containing a condensate produced by hydrolysis and condensation of a metal alkoxide (A) in a solvent (B);

It has a [process 2] which obtains the solution which substituted the solution obtained by said [step 1] with the solvent (C), The manufacturing method of the coating liquid for film formation characterized by the above-mentioned.

However, a metal alkoxide (A) is at least 1 sort (s) of metal alkoxide chosen from the compound represented by Formula (1) (In formula, R <^1> represents a C1-C5 alkyl group.);

The solvent (B) is at least one organic solvent selected from the group consisting of alcohols of 1 to 10 carbon atoms, esters of 2 to 5 carbon atoms, tetrahydrofuran and ethers of 2 to 5 carbon atoms; The solvent (C) is at least one organic solvent selected from glycols having 2 to 10 carbon atoms.

2. The manufacturing method of 1 in which a metal alkoxide (A) contains the at least 1 sort (s) of alkoxysilane further chosen from the compound represented by Formula (2).

In which R ² Represents an alkyl group, an alkenyl group, or an aryl group, R ³ Represents an alkyl group having 1 to 5 carbon atoms, n represents an integer of 0 to 2)

3. The said 2 manufacturing method whose alkoxysilane is at least 1 sort (s) of silicon compound chosen from the compound whose n of Formula (2) is 0.

4. The manufacturing method of the coating liquid for film formation in any one of 1-3 whose metal alkoxide (A) contains 0.05-4 mol of alkoxysilanes with respect to 1 mol of alkoxy titanium.

5. The production method according to any one of 1 to 4 above, wherein one or more kinds of catalysts selected from metal salts are used in [Step 1].

6. The manufacturing method in any one of said 1-5 which has [step 3] which adds the solvent (D) compatible with this solution with respect to the solution obtained in [process 2].

7. Coating liquid for film formation obtained by the manufacturing method in any one of said 1-5.

8. The film obtained using the coating liquid for film formation of 7 said.

9. Insulation film obtained using the coating liquid for film formation of 7 said.

10. The board | substrate for liquid crystal display elements which has a film formed using the coating liquid for film formation of said 7.

11. The liquid crystal display element which has a film formed using the coating liquid for film formation of 7 said.

Effects of the Invention

The coating liquid for film formation obtained by the manufacturing method of this invention fully hardens on 150-250 degreeC low temperature hardening conditions, and can form the liquid crystal aligning film which suppressed the fine hole and pinhole on the film. For this reason, it is useful for manufacture of the liquid crystal display element excellent in display characteristics.

1 is a result of measuring the weight loss ratio of the dry powder (Example) of the coating liquid for film formation (Z2) and the dry powder (Comparative Example) of the coating liquid T1.

2 is a differential thermal measurement result of the dry powder (Example) of the coating liquid (Z2) for film formation and the dry powder (Comparative Example) of the coating liquid (T1).

Carrying out the invention  Best form for

This invention is a manufacturing method of the coating liquid for film formation, Selected from the group which consists of a solvent (B), ie, a C1-C10 alcohol, a C2-C5 ester, tetrahydrofuran, and a C2-C5 ether It is the biggest feature to have a solvent substitution process with at least 1 type of organic solvent from solvent (C), ie, glycol. The coating liquid for film formation obtained by the manufacturing method of this invention can provide the film which fully hardens at 150-250 degreeC low temperature. And when using this film as an electrode protective film (insulating film) of a liquid crystal display element, the liquid crystal aligning film can be printed on this film, and also the outstanding effect which can form the alignment film which suppressed the fine hole and the pinhole was carried out. Indicates.

Conventionally, hydrolysis-condensation reaction using an alkoxy titanium is performed in presence of stabilizers, such as acetylacetone and glycol, in order to adjust the hydrolysis rate of alkoxy titanium in solvents, such as alcohol. This is hydrolyzed and condensed in the state which stabilized the alkoxy titanium, and produces | generates a condensate. In contrast, in the present invention, the metal alkoxide containing the alkoxy titanium is hydrolyzed and condensed to produce a condensate, followed by solvent substitution with glycol.

Here, conventionally, the alkoxy titanium coordinated by stabilizers, such as glycol, or the metal alkoxide containing it hydrolyzes and condenses, and produces a condensate. In the latter (this invention), glycol coordinates after alkoxy titanium or the metal alkoxide containing it hydrolyzes and condenses and produces a condensate.

In view of the remarkable effects obtained by the present invention, it is assumed that the coordination state of the condensate produced by the reaction conventionally carried out and the stabilizer glycol and the coordination state of the condensate produced by the present invention and glycol are very different states. do.

In particular, in the coordination state of the titanium atom and the glycol of the condensate, the present invention is inferred to be a state in which the glycol is more easily detachable.

And since this coordination state is hold | maintained also in the coating liquid and the coating film obtained from this, it is guessed to express the effect of this invention.

In other words, in the latter (invention), since the desorption of glycol is relatively easy with respect to the former, it can be said that a coating film is easy to harden at low temperature.

In addition, when using a coating film as an electrode protective film (insulating film) of a liquid crystal display element, when there is little glycol coordinated to the titanium atom in a coating film, it will lead to suppression of the fine hole and pinhole of a liquid crystal aligning film. That is, this invention exhibits the very outstanding effect which improves the printability of a liquid crystal aligning film also when using a coating film as an electrode protective film (insulating film) of a liquid crystal display element.

EMBODIMENT OF THE INVENTION Below, this invention is demonstrated concretely.

About [Step 1]:

In this step 1, the metal alkoxide (A) is hydrolyzed and condensed in the solvent (B).

As the metal alkoxide (A) used in this step 1, at least one alkoxy titanium selected from the compounds represented by formula (1) is used.

In formula, R <^1> is C1-C5, Preferably it is an alkyl group of 2-4.

Specific examples of the tetraalkoxy titanium represented by the formula (1) include tetramethoxytitanium, tetraethoxytitanium, tetraisopropoxytitanium, tetran-propoxytitanium, tetran-butoxytitanium, tetraisobutoxytitanium and tetra t-butoxy titanium, tetrapentoxy titanium, etc. are mentioned. Preferably, it is tetraethoxy titanium, tetraisopropoxy citrate, or tetra n-butoxy titanium.

The component (A) to be used in Step 1 is not particularly limited as long as at least one of the alkoxy titanium represented by Formula (1) is an essential component. Therefore, for example, metal alkoxides (hereinafter, referred to as other alkoxides) other than the alkoxytitanium represented by the formula (1) can also be used in combination. As another alkoxide, alkoxides, such as Si, Al, Sn, In, Bi, Zn, Pb, Ti, Ta, Mn, Zr, are mentioned. These other alkoxides can be suitably selected and used out of the compound which has one or more alkoxy groups as needed, and can also use multiple types together.

Among these, silicone alkoxides (hereinafter referred to as alkoxysilanes) are also easy to use because they are rich in type and are easily available on the market. In particular, when applying the coating liquid for film obtained by the manufacturing method of this invention to a liquid crystal display element, since the refractive index of the film obtained from the coating liquid for film is easy to adjust, it is preferable.

The alkoxysilane used at this time can use not only a monomer but also condensate of methyl silicate and ethyl silicate, and can use 1 type (s) or multiple types chosen from these.

Specific examples of the condensate of methyl silicate and ethyl silicate include ethyl silicate 40 (trade name, manufactured by Tama Chemical Industries, Ltd.), ethyl silicate 48 (trade name, manufactured by Nippon Colcot, Inc.), MKC silicate (trade name, manufactured by Mitsubishi Chemical Corporation), Torre Dow The silicone resin from Corning Corporation, the silicone resin from GE TOSHIBA Silicone Corporation, the silicone resin from Shin-Etsu Chemical Co., Ltd., the hydroxyl group containing polydimethylsiloxane by Dow Corning Asia Co., the silicone oligomer by Nippon Unicar Co., etc. are mentioned.

In this invention, especially the alkoxysilane represented by Formula (2) is used preferably, 1 type or multiple types selected from these can be used.

In the formula, R ² Represents an alkyl group, an alkenyl group, or an aryl group, R ³ Represents a C1-C5 alkyl group, n represents the integer of 0-2.

Although the specific example of the alkoxysilane represented by the said Formula (2) is shown below, it is not limited to this.

Tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane and tetrabutoxysilane; Methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, pentyl Limethoxysilane, pentyltriethoxysilane, heptyltrimethoxysilane, heptyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, hexadecyl Trimethoxysilane, hexadecyltriethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-aminopropyltrimethoxy silane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyl tree Oxysilane, γ-methacryloxyproyl trimethoxysilane, γ-methacryloxypropytriethoxysilane, γ-ureidopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, trifluoro Propyltrimethoxysilane, trifluoropropyltriethoxysilane, tridecafluorooctyltrimethoxysilane, tridecafluorooctyltriethoxysilane, heptadecafluorodecyltrimethoxysilane, heptadecafluorodecyl Trialkoxysilanes such as triethoxysilane; And dialkoxysilanes such as dimethyldimethoxysilane and dimethyldiethoxysilane.

Among the alkoxysilanes described above, tetraalkoxysilanes having n of 0 are most readily available and inexpensive, and therefore easy to use.

When using the alkoxysilane represented by Formula (2) as (A) component, it is 150-250 by making alkoxysilane into 0.05-4 mol, especially preferably 0.25-4 mol with respect to 1 mol of alkoxy titanium. The effect which can harden | cure sufficiently at low temperature of ° C and can form the coating film with favorable printability of a liquid crystal aligning material is easy to be acquired.

This effect depends on the coordination state of the titanium atom in the condensate produced in Step 1 and the glycol as the component (C). For this reason, when there are more than 4 mol of alkoxysilanes, since the quantity of the glycol in said coordination and bonding state becomes comparatively small, it becomes difficult to obtain the effect of this invention.

Moreover, by using the above-mentioned amount of alkoxysilane, it becomes easy to arbitrarily adjust the refractive index of a cured film in the range of 1.50-2.1.

The solvent (B) used in the step 1 is 1 to 10, preferably 1 to 8, particularly preferably 1 to 4 alcohols, esters of 2 to 5 carbon atoms, tetrahydrofuran and ethers of 2 to 5 carbon atoms. It is at least 1 sort (s) of organic solvent chosen from the group which consists of. Therefore, it is also possible to use multiple types in solvent (B) together.

And this solvent (B) will not be specifically limited if it melt | dissolves (A) component. The specific example is illustrated below.

For example, methanol, ethanol, 1-propanol (n-propanol), 2-propanol (isopropanol), 1-butanol, 2-butanol, 2-methyl-1-propanol, hexanol, octanol, diacetone alcohol, Alcohols such as 1-methoxy-2-ethanol, 1-ethoxy-2-ethanol and 1-methoxy-2-propanol; Esters such as ethyl acetate, ethyl lactate and butyl acetate; Ethers such as tetrahydrofuran, diethyl ether, 1,4-dioxane, and the like.

Among these solvents (B), it is difficult to azeotrope with the solvent (C) described later, and it is preferable to select a solvent having a higher vapor pressure at atmospheric pressure than the solvent (C). By selecting such a solvent (B), substitution from the solvent (B) to the solvent (C) can be performed with high efficiency.

In terms of economics, methanol, ethanol, propanol, butanol and the like are easy to use.

In step 1, the component (A) is subjected to a hydrolysis and condensation reaction in the solvent (B). Preferably, a catalyst is used to promote the condensation of the component (A). It is preferable that the usage-amount of a catalyst is 0.005-0.5 mol with respect to 1 mol of metal atoms in an alkoxide.

As a catalyst, an acid, an alkali, a metal inorganic acid salt, an organometallic compound, etc. are used. Generally, an acid or a metal inorganic acid salt is used preferably. Although the specific example of this catalyst is illustrated below, it is not limited to this.

Examples of the inorganic acid in the acid include hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, and the like. As an organic acid, Monocarboxylic acids, such as formic acid, acetic acid, and malic acid; And polyhydric carboxylic acids such as hydroxyl, citric acid, propionic acid and succinic acid. As an alkali, Inorganic alkalis, such as ammonia, caustic soda, and potassium hydroxide; Monoethanolamine; Diethanolamine; Triethanolamine; Pyridine etc. are mentioned.

The metal inorganic acid salt used as a catalyst is an inorganic acid salt, such as hydrochloric acid, nitric acid, and sulfuric acid which are metals or transition metals of group IIIa, IVa, and Va, their basic salts, or their hydrates.

Examples of the metals of Groups IIIa, IVa, and Va include Al, In, Sn, Sb, Pb, Bi, and the like. Examples of the transition metals include Ti, Mn, Fe, Ni, Zn, Y, Zr, Mo, Cu, W, and Ce.

Specific examples of such metal inorganic salts include aluminum chloride, aluminum nitrate, aluminum sulfate, basic aluminum chloride, indium chloride, indium nitrate, tin chloride, antimony chloride, lead chloride, lead nitrate, lead sulfate, bismuth chloride, bismuth nitrate, and iron chloride. , Iron nitrate, iron sulfate, nickel chloride, nickel nitrate, zinc chloride, zinc nitrate, zinc sulfate, yttrium chloride, yttrium nitrate, zirconium chloride, zirconium nitrate, zirconium sulfate, basic zirconium chloride, basic zirconium nitrate, molybdenum chloride, copper chloride Copper nitrate, copper sulfate, tungsten chloride, tungsten nitrate, cerium chloride, cerium nitrate, and the like and hydrates thereof.

Specific examples of the organometallic compound include aluminum acetate, zinc acetate, dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, octylate tin, naphthenic acid tin, dibutyltin diacetylacetonato, Tri-i-propoxy aluminum, di-i-propoxy ethylacetoacetate aluminum, di-i-propoxy acetylacetonato aluminum, i-propoxy bis (ethylacetoacetate) aluminum, i-propoxy Bis (acetoacetonatoaluminum, tris (ethylacetoacetate) aluminum, tris (acetylacetonato) aluminum, monoacetylacetonatobisbis (ethylacetoacetate) aluminum, tetra-n-butoxyzirconium, tri-n-butoxy Ethylacetoacetic zirconium, di-n-butoxybis (ethylacetoacetate) zirconium, n-butoxytris (ethylacetoacetate) zirconium, te Lakis (n-propylacetoacetate) zirconium, tetrakis (acetylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium and the like, and partial hydrolyzates of these compounds.

The metal inorganic acid salt and the organometallic compound described above are not particularly limited as long as they are dissolved in the solvent (B), and can be appropriately selected and used as necessary. At this time, you may use together 1 type (s) or multiple types.

In the case of use in the field of electronic materials, metal nitrate, its basic salt or its hydrate or organometallic compound is preferable. More preferably, it is a nitrate of Al, In, Zn, Zr, Ce, Sn, its basic salt or its hydrate or organometallic compound.

In addition, in the process 1, you may use together the said metal inorganic salt and organometallic compound with another catalyst, unless the effect of this invention is impaired.

The hydrolysis and condensation reaction in step 1 may be any of partial hydrolysis and / or complete hydrolysis. In the case of complete hydrolysis, theoretically, 0.5 times mole of water of all the alkoxide groups in (A) component may be added, but an excess amount of water is usually added more than 0.5 times mole. In the case of partial hydrolysis, 0.2-0.5 times mole of water may be added.

In this invention, although the quantity of the water used for the said reaction can be suitably selected as desired, it is 0.2-2.5 times mole of all the alkoxide groups in (A) component. When the metal salt is a hydrous salt, its moisture is also introduced into the amount of water used for the hydrolysis.

Step 1 performs the hydrolysis and condensation reaction of the component (A) in the solvent (B), but the addition order of the component (A) and the solvent (B) is not particularly limited. Generally, the method of adding components, such as water and a catalyst, to the solution which mixed the alkoxy titanium and a solvent (B) in (A) component in advance is often used. When using another alkoxide together, you may mix with alkoxy titanium and a solvent (B) simultaneously, and may add later. In that case, another alkoxide may be previously diluted with the solvent (B).

In addition, in order to suppress the hydrolysis of the alkoxy titanium, you may cool beforehand and perform a hydrolysis and a condensation reaction. And you may cool in hydrolysis and condensation reaction, and you may cool after hydrolysis and condensation reaction.

Water and a catalyst may be mixed and added, and may be added separately. Usually, it is common to add water and a catalyst in the solution diluted with the solvent (B).

And the mixed solution of (A) component and a solvent (B) can also be heated in order to accelerate the hydrolysis-condensation reaction of (A) component. The heating temperature and the heating time can be appropriately selected as desired. For example, methods, such as heating and stirring at 50 degreeC for 24 hours, or heating and stirring for 8 hours under reflux, are mentioned.

Moreover, water and a catalyst can also be added during the heating of the mixed solution of (A) component and the solvent (B).

As for the solution obtained after such a process 1, it is preferable to make the density | concentration (metal oxide solid content conversion concentration) which converted all the metal atoms in this solution into the oxide 20 mass% or less, especially 15 mass% or less. By selecting an arbitrary concentration in this concentration range, the formation of a gel can be suppressed to obtain a homogeneous solution. As described so far, a solution (hereinafter referred to as a pre-substitution solution) containing a condensate obtained by hydrolyzing and condensing the component (A) in the solvent (B) can be obtained by passing through step 1.

About [Step 2]:

Process 2 is a process mainly performing solvent substitution of the solvent (B) of the solution before substitution obtained in the said process 1 by the solvent (C).

Here, the solvent (C) is at least one organic solvent selected from glycols having 2 to 10 carbon atoms, preferably 2 to 6 carbon atoms, and may use multiple types selected from the solvent (C) in combination.

Although the specific example of a solvent (C) is given to the following, it is not limited to this.

Ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 2- Methyl-2,4-pentanediol (hexylene glycol), 3-methyl-1,5-pentanediol, 1,6-hexanediol, 2-ethyl-1,3-hexanediol, and the like.

Among these, hexylene glycol is preferable because of its good wettability with respect to the substrate.

In process 2, the method of substituting the solution before substitution with a solvent (C) is not specifically limited.

As a simple method, the method of distilling off the solvent which mainly makes solvent (B) from the solution which mixed the solvent (C) with the solution before substitution is mentioned. Moreover, the method etc. which add the solvent (C), while distilling off the solvent which mainly makes solvent (B) from the solution before substitution, are mentioned.

In order to improve the substitution efficiency of a solvent, the conditions at the time of substituting a solvent are normally implemented under reduced pressure, but may be normal pressure. That is, solvent substitution is preferably carried out under the conditions of preferably 0.1 mmHg (13.3 Pa) to 760 mmHg (101.3 kPa), and particularly preferably 5 mmHg (666.6 Pa) to 200 mmHg (26.7 KPa). At this time, you may heat in order to improve the substitution efficiency of a solvent further. It is preferable to make heating temperature into the temperature of 100 degrees C or less in consideration of cost, but what is necessary is just temperature lower than the boiling point of a solvent (C).

In this invention, it is not necessary to completely substitute the organic solvent in the solution before substitution with the solvent (C), It is preferable that 80 mass% or more of all the organic solvents in the solution before substitution are substituted by the solvent (C), In particular, 85 mass% or more is preferable. By doing in this way, favorable coating property is easy to be obtained in the coating liquid for film formation mentioned later, and coating formation in flexographic printing becomes easy. And although it is not certain, at the time of solvent substitution of the process 2, a part of water is azeotropically removed with the organic solvent of the solution before substitution, and the amount of water in the solution obtained after the process 2 (henceforth a substitution solution) decreases, The storage stability of a substitution solution and the coating liquid for film formation obtained using the same improves remarkably.

In addition, in process 2, the metal oxide solid content conversion concentration of a substitution solution can also be adjusted by adjusting the quantity of a solvent (C). At this time, metal oxide solid content conversion density | concentration becomes like this. Preferably it is 20 mass% or less, Especially preferably, it is 15 mass% or less. In addition, a desired concentration can be selected as required.

Thus, by passing through the said process 1 and the process 2, the solution (pre-substitution solution) containing the condensate which hydrolyzed and condensed the (A) component in the solvent (B) was substituted by the solvent (C), The solution obtained, ie, a substitution solution, can be obtained.

About [Step 3]:

Process 3 is a process of manufacturing the coating liquid for film formation, However, when making the substitution solution obtained above as a coating liquid for film formation, this process can also be skipped.

Usually, the coating liquid for film formation is manufactured by adding a solvent (D) further for the purpose of adjustment of the oxide solid content conversion density | concentration of coating liquid for film formation, and coating property improvement.

Moreover, other components, such as inorganic fine particles, surfactant, a leveling agent, can also be added as needed, unless the effect of this invention is impaired.

In this invention, metal oxide conversion density | concentration of the coating liquid for film formation becomes like this. Preferably it is 0.5-20 mass%, Especially preferably, it is 1-15 mass%. When using an inorganic fine particle, it is preferable to make the density | concentration which carried out oxide conversion the total amount of the metal atom in a substitution solution, and the metal atom in an inorganic fine particle into 0.5-20 mass%.

The method of adding the said solvent (D) and another component is not specifically limited as long as a homogeneous solution is obtained.

As a solvent (D), the solvent compatible with a substitution solution is used, It does not specifically limit to this, You may use multiple types together.

Specific examples thereof include methanol, ethanol, 1-propanol (n-propanol), 2-propanol (isopropanol), 1-butanol, 2-butanol, 2-methyl-1-propanol, 1,1-dimethylethanol, hexa Alcohols such as phenol, octanol and diacetone alcohol, esters such as ethyl acetate, ethyl lactate, butyl acetate and γ-butyl lactone; Ethers such as tetrahydrofuran, diethyl ether and 1,4-dioxane; Ketones such as acetone, 2-butanone, 3-methyl-2-butanone, and 4-methyl-2-pentanone; Ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 2- Glycols such as methyl-2,4-pentanediol (hexylene glycol), 3-methyl-1,5-pentanediol, 1,6-hexanediol and 2-ethyl-1,3-hexanediol; Ketones such as acetone, 2-butanone, 3-methyl-2-butanone, and 4-methyl-2-pentanone; 1-methoxy-2-ethanol, 1-ethoxy-2-ethanol, 1-propoxy-2-ethanol, 1-butoxy-2-ethanol, 1-methoxy-2-propanol, 1-ethoxy- 2-propanol, 1-butoxy-2-propanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol Dibutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono butyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dibutyl ether, ethyl carbitol, butyl Glycol ethers such as carbitol and diethylcarbitol; N-methylpyrrolidone; Amides, such as dimethylformamide and dimethylacetamide, etc. are mentioned.

Examples of the inorganic fine particles include silica fine particles and metal oxide fine particles such as alumina, titania and zeolites; Composite oxide fine particles such as antimony-tin oxide (ATO), indium-tin oxide (ITO), and indium-zinc oxide (IZO) are preferable. In particular, the colloidal solution is preferable. This colloidal solution may disperse | distribute inorganic fine particle powder in a dispersion medium, and may be a commercially available colloidal solution.

In this invention, by containing an inorganic fine particle, the surface shape of the cured film formed and other function can be provided. As inorganic microparticles | fine-particles, it is preferable that the average particle diameter is 0.001-0.2 micrometer, More preferably, it is 0.001-0.1 micrometer. When the average particle diameter of an inorganic fine particle exceeds 0.2 micrometer, transparency of the hardened film formed with the coating liquid manufactured may fall.

The dispersion medium of the inorganic fine particles is preferably an organic solvent in order to maintain the storage stability of the coating liquid for film formation satisfactorily. As a colloidal solution, it is preferable that pH or pKa is adjusted to 2-10, especially 3-7 from a viewpoint of the stability of the coating liquid for film formation.

As an organic solvent used for the dispersion medium of a colloidal solution, Alcohol, such as methanol, ethanol, isopropanol (2-propanol), 1-butanol; Glycols such as ethylene glycol, propylene glycol, hexylene glycol, and ethylene glycol monopropyl ether; Ketones such as acetone, methyl ethyl ketone (2-butanone), methyl isobutyl ketone (3-methyl-2-butanone), and 4-methyl-2-pentanone; Aromatic hydrocarbons such as toluene and xylene; Amides such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone; Ester, such as ethyl acetate, butyl acetate, (gamma)-butyrolactone; Ethers, such as tetrahydrofuran and a 1, 4- dioxane, Furthermore, the solvent illustrated above is mentioned as a solvent (B), a solvent (C), and a solvent (D), respectively. Among these, alcohols or glycols are preferable. These organic solvents can be used individually or in mixture of 2 or more types as a dispersion medium.

In addition, a leveling agent, surfactant, etc. can use a well-known thing, Especially since a commercial item is easy to obtain, it is preferable.

As mentioned above, the coating liquid for film formation obtained by this invention is manufactured by the manufacturing method containing [step 1] and [step 2], and can also be manufactured by the method containing [step 3] as needed. have.

[Formation of film]

The coating liquid for film formation obtained by the manufacturing method of this invention is apply | coated to a base material, and a desired cured film can be obtained by thermosetting. As a coating method, a well-known or well-known method can be employ | adopted. For example, the dip method, the flow coat method, the spray method, the bar coat method, the gravure coat method, the roll coat method, the blade coat method, the air knife coat method, the flexographic printing method, the ink jet method, and the like can be adopted. Among these, a favorable coating film can be formed by the flexographic printing method.

At this time, the base material to be used is plastic; Glass ; Glass with transparent electrodes, such as ATO, FTO (fluorine-doped tin oxide), ITO, IZO, etc .; Base materials, such as a ceramic, are mentioned. Examples of the plastic include polycarbonate, poly (meth) acrylate, polyether sulfone, polyarylate, polyurethane, polysulfone, polyether, polyether ketone, polyolefin, polyethylene terephthalate, polyacrylonitrile, triacetyl cellulose, di Acetyl cellulose, acetate butyrate cellulose, etc. are mentioned. Examples of the shape include a plate or a film.

It is common for the coating liquid for film formation to filter using a filter etc. before application | coating.

After the coating film formed in the base material is dried at the temperature of room temperature-120 degreeC, it thermosets at the temperature of 150-250 degreeC preferably. At this time, the time required for drying may be 30 seconds or more, but 10 minutes or less is sufficient.

Although it can select suitably according to the time required for thermosetting and the desired cured film characteristic, it is good if it is 10 minutes or more. When selecting a low hardening temperature, the hardened film which has sufficient hardness is easy to be obtained by lengthening hardening time.

Moreover, the coating liquid for film formation of this invention can obtain the cured film which has sufficient hardness even at the curing temperature exceeding 250 degreeC of temperature.

Moreover, it is also effective to irradiate an energy ray (ultraviolet rays etc.) using a mercury lamp, a metal halide lamp, a xenon lamp, an excimer lamp, etc., before thermosetting. By irradiating an energy ray to a dried coating film, hardening temperature can be reduced further, hardness of a film, or a refractive index can be raised. Although the irradiation amount of an energy ray can be suitably selected as needed, normally several hundred-thousands mJ / cm <2> is suitable.

The coating liquid for film formation obtained by this invention is excellent in coating-film formation ability in flexographic printing, and can form the film which can fully harden at low temperature.

And since the printability of the liquid crystal aligning material with respect to this film is favorable, the liquid crystal aligning film which suppressed the fine hole and the pinhole can be formed.

Therefore, since the coating liquid for film formation obtained by this invention can form the film which has the above characteristics, it is very useful for the improvement of the display characteristic of a liquid crystal display element.

Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not limited to the following Example.

Explanation of the abbreviation in a present Example is as follows.

TEOS: tetraethoxysilane

MTES: methyltriethoxysilane

TET: tetraethoxytitanium

TIPT: tetraisopropoxytitanium

HG: Hexylene Glycol (alias 2-methyl-2,4-pentanediol)

THF: tetrahydrofuran

PG: Propylene glycol (alias: 1,2-propanediol)

EG: ethylene glycol

PGME: propylene glycol monomethyl ether (alias name: 1-methoxy-2-propanol)

BCS: Butyl cellosolve (alias 1-butoxy-2-ethanol)

PB: Propylene glycol monobutyl ether (alias name: 1-butoxy-2-propanol)

AN: Aluminum Nitrate Heptahydrate

CN: Cerium Nitrate Heptahydrate

IN: Indium Nitrate Trihydrate

The measuring method in the following example is shown below.

[Measurement Method of Residual Solvent (B)]

Using diethylene glycol dibutyl ether as a diluting solvent and diethylene glycol diethyl ether as an internal standard material, the sample of mass ratio 97.5 / 0.5 / 2.0 of dilution solvent / internal standard substance / coating-forming liquid was prepared, The amount of solvent (B) remaining in the coating liquid for film formation was measured by the internal standard method using gas chromatography (henceforth called GC). The measurement conditions of GC are as follows.

GC measurement conditions:

Device: Shimadzu GC-14B

Column: Capital Column, CBP1-W25-100 (25mm × 0.53mmΦ × 1㎛)

Column Temperature: The column temperature was controlled using an elevated temperature program. After holding at the start temperature of 40 degreeC for 4 minutes, it heated up at 15 degreeC / min and hold | maintained for 3 minutes at 300 degreeC of arrival temperature.

Sample injection volume: 1µl

Injection temperature: 270 ℃

Detector temperature: 320 ℃

Carrier gas: nitrogen (flow rate 30 mL / min)

Detection method: FID method

[Production Example 1]

2.70 g of pure water, 62.53 g of ethanol as a solvent (B) and 2.96 g of AN as a catalyst were injected into a 300 ml flask, and it stirred, and obtained the uniform solution. 24.98g of TEOS was added to this solution as another metal alkoxide, and it stirred at room temperature for 30 minutes. Then, 6.84g of TET was added and it stirred at room temperature for 30 minutes. This solution was made into solution (P1) before substitution.

Production Examples 2 to 11

With the composition shown in Table 1, the pre-substitution solutions (P2-P11) were manufactured by the method similar to the manufacture example 1.

However, in Production Example 4, no other alkoxide was used.

In addition, nitric acid in Table 1 means a 60 mass% nitric acid aqueous solution.

Example 1

In a 300 ml flask, 24.00 g of the pre-substitution solution (P1) obtained in the manufacture example 1, and 25.87 g of HG as a solvent (C) were mixed. Subsequently, the solvent was distilled off under reduced pressure to 60 mmHg (2.67 kPa) at 60 degreeC by the NEW rotary steam evaporator (NE-1 by Tokyo Rica Machinery Co., Ltd.), and 28.91 g of substitution solution (Q1) was obtained. Then, PGME 11.09g was mixed as 28.91g of substitution solutions (Q1) as a solvent (D), and the coating liquid (Z1) for film formation was manufactured. It was 5.7 mass% when the residual amount of the solvent (B) was measured by GC with respect to this coating liquid (Z1).

Moreover, about the obtained coating liquid for film formation (Z1), pencil hardness, refractive index, printability, and liquid crystal aligning film printability were evaluated using the method mentioned later. The results are shown in Table 3.

[Examples 2 to 15]

In the composition shown in Table 2, the pre-substitution solutions (P2-P11) were substituted by the method similar to Example 1 with the solvent (C), and the substitution solutions (Q2-Q15) were obtained. And the solvent (D) was added to substitution solution (Q2-Q15) by the composition shown in Table 2, and the coating liquid for film formation (Z2-Z15) was manufactured. The amount of the residual solvent (B) in this coating liquid (Z2-Z15) was measured by GC.

Moreover, pencil hardness, refractive index, printability, and liquid crystal aligning film printability were evaluated about the obtained coating liquid for film formation (Z2-Z15) using the method mentioned later. The results are shown in Table 3.

[Example 16]

To a solution obtained by mixing TEOS 20.8 g with ethanol, 0.6 g of a 28 mass% aqueous ammonia solution in 23.2 g of ethanol as a water 5.4 g and an alkali catalyst was mixed while stirring at room temperature. After 30 minutes, the liquid began to show a colloidal color, and a particulate product was confirmed. Then, to obtain a silica colloid dispersed in a solution of 6% by mass of ethanol in terms of SiO ₂ concentration to proceed 24 hours at room temperature gyobanreul. The particle size of the colloidal particles of the obtained solution was measured using DLS-7000 (manufactured by Otsuka Electronics Co., Ltd.), and the average particle diameter by the dynamic light scattering method was 20 nm.

Next, 40.0 g of silica colloidal solution obtained in a 300 ml flask and 22.8 g of HG were mixed. Subsequently, the solvent was distilled off under reduced pressure to 60 mmHg (2.67 kPa) at 60 degreeC by NEW rotary steam evaporator (NE-1, Tokyo Rika Machinery Co., Ltd.), and the silica colloid solution disperse | distributed to 25.3 g of HG was carried out. Got it. Thereafter, 14.7 g of PGME was added to the silica colloid solution dispersed in the obtained HG to prepare a particle dispersion solution K.

10.00 g of coating liquid (Z2) for forming a film shown in Table 2 and 10.00 g of particle dispersion solution K were mixed to prepare a coating liquid for forming a film (Z16).

Moreover, about the obtained coating liquid for film formation (Z16), pencil hardness, refractive index, printability, and liquid crystal aligning film printability were evaluated using the method mentioned later. The results are shown in Table 3.

Comparative Example 1

In a 300 ml flask, a solution in which 1.63 g of AN was dissolved in 1.49 g of pure water, and 23.66 g of PGME and 26.94 g of HG were mixed. TEOS 8.60g was added here and it stirred at room temperature for 30 minutes. Then, the solution which mixed TET 9.42g and HG28.26g previously was added, and it stirred at room temperature for 30 minutes, and obtained coating liquid (T1).

Moreover, about the obtained coating liquid (T1), pencil hardness, refractive index, printability, and liquid crystal aligning film printability were evaluated using the method mentioned later. The results are shown in Table 3.

Comparative Example 2

In a 300 ml flask, a solution in which 1.43 g of AN was dissolved in 1.31 g of pure water, and 24.20 g of PGME and 6.74 g of HG were mixed. The solution which mixed 16.58 g of TET and 49.74g of HG previously was added here, it stirred at room temperature for 30 minutes, and obtained coating liquid (T2).

Moreover, about the obtained coating liquid (T2), pencil hardness, refractive index, printability, and liquid crystal aligning film printability were evaluated using the method mentioned later. The results are shown in Table 3.

[Comparative Example 3]

In a 300 ml flask, a solution in which 1.63 g of AN was dissolved in 1.49 g of pure water, and 23.66 g of PGME, 7.89 g of EG, and 19.07 g of HG were mixed. TEOS 8.60g was added to this, and it stirred at room temperature for 30 minutes. Then, the solution which mixed TET 9.42g and HG28.25g previously was added, and it stirred at room temperature for 30 minutes, and obtained coating liquid (T3).

Moreover, about the obtained coating liquid (T3), pencil hardness, refractive index, printability, and liquid crystal aligning film printability were evaluated using the method mentioned later. The results are shown in Table 3.

[Pencil hardness]

The coating liquid for film formation of an Example and the coating liquid of the comparative example were filtered using the chromatographic disc (The Kurashiki Spinning company make, pore diameter 0.45 micrometer). Then, it was dripped on the glass substrate with ITO (ITO film thickness 0.7mm), and pre-rotated for 5 second at 300 rpm by using a spin coater (1H-DX2 by the Mikasa company), and then rotated at 4000 rpm Was rotated for 20 seconds to form a coating film. Subsequently, after drying for 3 minutes on the hotplate of the temperature of 80 degreeC, it heated at the curing temperature of 180 degreeC on the hotplate for 15 minutes, and obtained the hardened film. The pencil hardness of the obtained hardened film was measured based on the test method (JIS K5400).

However, in Example 3, Example 14, and the comparative example 3, hardening temperature was 200 degreeC, and in Example 4 and comparative example 2, hardening temperature was 250 degreeC.

[Refractive index]

Except having changed the board | substrate into the silicon substrate 100 from the glass substrate with ITO, the hardened film was formed by the method similar to said [pencil hardness] evaluation. The refractive index in wavelength 633nm was measured with the ellipsometer (The DVA-36L type, manufactured by Mizo Gei optical industry company).

[Printability]

The coating liquid for film formation of an Example and the coating liquid of the comparative example were filtered using the chromatographic disc (The Kurashiki Spinning company make, pore diameter 0.45 micrometer). Subsequently, a coating film was formed on a glass substrate (ITO film thickness of 0.7 mm) with an ITO using a DR type printing machine (manufactured by Nippon Photo Printer, Anilox Roll (360 #), a convex plate (400L 30% 70 ° of dots)). did. After drying this coating film for 3 minutes on the hotplate of temperature 80 degreeC, on the hotplate, hardening temperature was 180 degreeC, and it heated for 15 minutes, and obtained the hardened film. The obtained cured film was visually observed, and (circle) and the case where pinhole smear generate | occur | produced the favorable case where a cured film does not have pinhole stain were made into (triangle | delta), and the state which was not fully formed into a film on the board | substrate was made into x.

However, in Example 3, Example 14, and the comparative example 3, hardening temperature was 200 degreeC, and in Example 4 and comparative example 2, hardening temperature was 250 degreeC.

[Liquid crystal aligning film printability]

On the cured film formed by the method similar to the above-mentioned [printability], liquid crystal orientation using DR-type printing machine (made by Nippon Photographic Co., Ltd., anilox roll (360 #), convex plate (40OL 30% of 70 degree)). Ash (manufactured by Nissan Chemical Co., Ltd., Sun Ever (registered trademark) SE-5291 032B (trade name)) was applied. Then, it dried on the hotplate of temperature 80 degreeC for 3 minutes, and formed the liquid crystal aligning film. The liquid crystal aligning film formed was visually observed, and in the liquid crystal aligning film, a good case without fine pores, pinholes and stains was formed in a case where ○, pinholes or unevenness occurred, △, fine pores were generated and the film was not sufficiently formed on the substrate. Was ×.

Example 17

About the coating liquid for film formation (Z1) obtained in Example 1, pencil hardness (with UV irradiation), refractive index (with UV irradiation), and liquid crystal aligning film printability (with UV irradiation) were evaluated by the method shown below. . The results are shown in Table 4.

[Example 18]

About the coating liquid for film formation (Z2) obtained in Example 2, pencil hardness (with UV irradiation), refractive index (with UV irradiation), and liquid crystal aligning film printability (with UV irradiation) were evaluated by the method shown below. . The results are shown in Table 4.

[Pencil hardness (UV irradiation);

The coating liquid for film formation was filtered using a chromatographic disc (Kurashiki Spinning Co., Ltd., pore diameter 0.45 μm), and then added dropwise onto a glass substrate with ITO, using a spin coater (1H-DX2 manufactured by Mikasa Co., Ltd.), After preliminary rotation for 5 seconds at a rotational speed of 300 rpm, the coating film was formed by rotating for 20 seconds at a rotational speed of 4000 rpm. Then, it dried for 3 minutes on the hotplate of temperature 80 degreeC. Then, it irradiated for 2 minutes at 50mW / cm <2> (wavelength 350nm conversion) using the ultraviolet irradiation device (Igfix Corporation make, UB 011-3A type | mold) and a high pressure mercury lamp (input power supply 1000W), 6000mJ / cm <2> accumulated, It heated at 150 degreeC of hardening temperature on a hotplate for 15 minutes, and obtained the hardened film. The pencil hardness of the obtained hardened film was measured based on the test method (JIS K5400).

[Refractive index (with UV irradiation)]

Except having changed the board | substrate into the silicon substrate 100 from the glass substrate with ITO, the cured film was formed by the method similar to said [pencil hardness (UV irradiation)] evaluation. The refractive index in wavelength 633nm was measured with the ellipsometer (The DVA-36L type | mold by the MIZOJI OPTICAL INDUSTRY CO., LTD.).

[Liquid crystal aligning film printability]

On the cured film formed by the same method as the above-mentioned [pencil hardness (with UV irradiation)] evaluation, a DR type printing machine (made by Nippon Photo Printer, Anilox Roll (360 #), a convex plate (dot dot 400L 30% 70 °)) Using the liquid crystal, a liquid crystal aligning material (manufactured by Nissan Chemical Co., Ltd., Sun EVA (registered trademark) SE-5291 032B (trade name)) was applied. Then, it dried on the hotplate of temperature 80 degreeC for 3 minutes, and formed the liquid crystal aligning film. The formed liquid crystal aligning film was visually observed, and the liquid crystal aligning film showed a good case without fine holes, pin holes, and unevenness. It was set as ×.

[Referential Example 1]

About the coating liquid (Z1) for film formation obtained in Example 1, pencil hardness (with UV irradiation) and refractive index (with UV irradiation) by the same method as Example 17 except having changed hardening temperature from 150 degreeC to 300 degreeC ) And liquid crystal aligning film printability (with UV irradiation) were evaluated. The results are shown in Table 5.

[Reference Example 2]

About the coating liquid (Z2) for film formation obtained in Example 2, pencil hardness (with UV irradiation) and refractive index (with UV irradiation) by the same method as Example 18 except having changed hardening temperature from 150 degreeC to 300 degreeC. ) And liquid crystal aligning film printability (with UV irradiation) were evaluated. The results are shown in Table 5.

[Example 19]

1g of the coating liquid (Z2) for film formation of Example 2 was weighed in the weighing bottle, and it dried at the temperature of 120 degreeC in oven for 1 hour, and baked at the temperature of 180 degreeC for 2 hours. The mass of the calcined residue was measured, and the residual organic component amount was calculated using the following formula. At this time, the value which computed all the metal atoms contained in the coating liquid for film formation as an oxide was made into the metal oxide solid amount. The results are shown in Table 6.

(i) Residual organic component amount (mass%) = {(mass of calcined residue-solid amount of metal oxide) / (mass of calcined residue)} x 100

(ii) Solid content concentration (mass%) = {(mass of plastic residue) / (mass of coating liquid for film formation)} x 100

(Iii) Metal oxide equivalent concentration (mass%) = {(metal oxide solid amount) / (mass of coating liquid for coating)} × 100

[Comparative Example 4]

About the coating liquid T1 of the comparative example 1, the amount of residual organic components was computed similarly to Example 19 except having changed the coating liquid Z2 for film formation of Example 19 into the coating liquid T1. The results are shown in Table 6.

[Example 20]

To the coating liquid Z2 for film formation of Example 2, Z2 was added dropwise onto the glass substrate, and preliminarily rotated at a rotational speed of 300 rpm for 5 seconds using a spin coater (manufactured by Mikasa, 1H-DX2), It formed into a film by rotating for 20 second at the rotation speed 4000rpm. Subsequently, the film-formed glass substrate was dried on a hot plate for 3 minutes at a temperature of 80 ° C. This coating film was carved and the dry powder of Z2 was extract | collected. The sampled powder was heated up to 5 ° C. per minute from room temperature to 500 ° C. using a thermogravimetric differential thermal analysis device (manufactured by McScience, Model WS 002) to obtain TG (weight loss ratio) and DTA (differential heat) of the powder. Measured. The measurement results are shown in FIGS. 1 and 2.

From this result, the weight reduction accompanying an endotherm near 140 degreeC, and the weight reduction accompanying an exotherm after endotherm around 200 degreeC were confirmed.

[Comparative Example 5]

In Example 20, the weight loss rate and the differential heat of the dry powder of T1 were measured like Example 20 except having changed the coating liquid for film formation (Z2) into the coating liquid of the comparative example 1. The measurement results are shown in FIGS. 1 and 2.

As a result, a weight reduction with endothermic at around 160 ° C, a weight reduction with endotherm at around 230 ° C, and a weight reduction with exotherm at around 270 ° C were confirmed.

[result]

From the result of Example 1-Example 16 (refer Table 3), the coating liquid for film formation obtained by this invention generally uses this film as an electrode protective film (insulating film) of a liquid crystal display element at low-temperature hardening temperature. It showed a pencil hardness of 5H or more, which is sufficient hardness.

And it was confirmed to form the liquid crystal aligning film which suppressed the fine hole and the pinhole on this film.

Moreover, by irradiating an ultraviolet-ray to a dry coating film prior to thermosetting, hardening temperature can be further reduced and the hardness and refractive index of a film can be raised at 150 degreeC, and the liquid crystal aligning film formed on this film is a minute hole and a pinhole. It showed excellent film formation without.

Furthermore, the film which can adjust arbitrarily in the range of 1.5-2.1 was formed.

Furthermore, even when the substitution solution (Q1-Q16) and the coating liquid (Z1-Z16) for film formation in Example 1-Example 16 were preserve | saved for 1 month at 25 degreeC humidity 50% RH, no precipitate generate | occur | produced. It was confirmed that the storage stability was very excellent.

From the result of Example 19 and the comparative example 4 (refer Table 6), it was confirmed that the coating liquid for film formation obtained by this invention has few organic components (carbon component) which remain in the film hardened | cured at low temperature. From this point, it is estimated that desorption and decomposition of the organic component (mainly glycol) occur under low temperature curing conditions.

From the results of thermogravimetric differential thermal analysis of Examples 20 and Comparative Example 5 (FIGS. 1 and 2), the remaining organic components of the coating film formed by using the coating liquid for film formation obtained by the present invention are more desorbed and decomposed. It is assumed to be an easy state. It is thought that this accelerates hardening of the coating film and is easy to harden at low temperature.

The coating liquid for film formation obtained by this invention is excellent in the coating film formation ability in flexographic printing, and can form the film which can fully harden at low temperature. Furthermore, the liquid crystal aligning film which suppressed fine hole and pinhole can be formed on this film. Therefore, it is useful for various electronic components and display devices, especially liquid crystal display devices. And the whole content of the JP Patent application 2005-239057, the claim, drawing, and the abstract for which it applied on August 19, 2005 is referred here, and it is referred as an indication of the specification of this invention.

Claims (11)

[Process 1] which obtains the solution containing the condensate produced by hydrolyzing and condensing a metal alkoxide (A) in a solvent (B), It has a [process 2] which obtains the solution which substituted the solution obtained by said [step 1] with the solvent (C), The manufacturing method of the coating liquid for film formation characterized by the above-mentioned. However, the metal alkoxide (A), the formula (1) compound (in the formula represented by, R ¹ Is an at least 1 type of metal alkoxide selected from C1-C5 alkyl group; [Formula 1]

The solvent (B) is at least one organic solvent selected from the group consisting of alcohols of 1 to 10 carbon atoms, esters of 2 to 5 carbon atoms, tetrahydrofuran and ethers of 2 to 5 carbon atoms; The solvent (C) is at least one organic solvent selected from glycols having 2 to 10 carbon atoms. The method of claim 1, The manufacturing method of the coating liquid for film formation containing the metal alkoxide (A) further containing at least 1 sort (s) of alkoxysilane chosen from the compound represented by Formula (2). [Formula 2]

In which R ² Represents an alkyl group, an alkenyl group, or an aryl group, R ³ Represents an alkyl group having 1 to 5 carbon atoms, n represents an integer of 0 to 2) The method of claim 2, The manufacturing method of the coating liquid for film formation whose alkoxysilane is at least 1 sort (s) of silicon compound chosen from the compound whose n of Formula (2) is 0. 4. The method according to any one of claims 1 to 3, The manufacturing method of the coating liquid for film formation in which a metal alkoxide (A) contains 0.05-4 mol of alkoxysilane with respect to 1 mol of alkoxy titanium. 4. The method according to any one of claims 1 to 3, The manufacturing method of the coating liquid for film formation which uses the 1 type (s) or several types of catalyst chosen from metal salts in [Step 1]. 4. The method according to any one of claims 1 to 3, The manufacturing method of the coating liquid for film formation which has the [step 3] which adds the solvent (D) compatible with this solution with respect to the solution obtained in [process 2]. The coating liquid for film formation obtained by the manufacturing method in any one of Claims 1-3. The film obtained using the coating liquid for film formation of Claim 7. The insulating film obtained using the coating liquid for film formation of Claim 7. The board | substrate for liquid crystal display elements which has a film formed using the coating liquid for film formation of Claim 7. The liquid crystal display element which has a film formed using the coating liquid for film formation of Claim 7.

Images