JP2001049444A - Production of metallic oxide thin film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a film forming method capable of forming an oxide thin film having tight adhesion reaching a practical level even on a polymer base material. SOLUTION: This is a method in which, on a base material immersed into an aq.soln. contg. a fluorometallic complex compd. and a fluorine capturing agent, a metallic oxide thin film derived from the above fluorometallic complex compd. is precipitated, where the above base material is composed of a high polymer material, and also, at least one part of the surface has been subjected to treatment for hydrophilicity impartment. As the treatment for hydrophilicity impartment, chemical treating methods such as treatment by an organic solvent, acid soln. treatment and alkali soln. treatment, and physical treatment such as plasma glow discharge can be given.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a metal oxide thin film. In particular, the present invention relates to a method for producing a metal oxide thin film that is well adhered to the surface of a substrate made of a polymer material that is a substrate having low surface energy.

[0002]

2. Description of the Related Art Techniques for forming an oxide thin film include a sputtering method, a CVD method, a vacuum evaporation method, a sol-gel method, and an aqueous solution deposition method. Further, as one application of the aqueous solution deposition method, T
there is iO ₂ seed aqueous solution deposition method (Reference: Anataze synth
esis from aqueous solutionand photo-catalytic acti
vity by Koji Sato in Proceedings of The Sixth Inte
rnational Symposium on New Glass).

[0003] TiO_TwoIn the seed aqueous solution deposition method, (N
H_Four)_TwoTiF₆Is dissolved in water. Dissolved (NH_Four)_TwoT
iF₆Is TiF₆ ^2-Present in aqueous solution as ions.
TiO 2 is added to this aqueous solution as a seed (seed crystal)._Twoyou
Powder, and as a fluorine scavenger B_TwoO_ThreeTo
Add. B_TwoO_ThreeIs dissolved in an aqueous solution,_Three ^3-Nana
, BO_Three ^3-Is TiF₆ ^2-F that constitutes the ion^-With ions
Reacts with TiF₆ ^2-Decomposes ions and provides stable BF_Four ^-Confusion
Form the body. TiF₆ ^2-T formed by decomposition of ions
i-ion reacts with oxygen to react with TiO_TwoGenerate TiO_Two
Formation (precipitation) of TiO _TwoProgress with anatase powder as core
TiO2 on the substrate surface immersed in the aqueous solution_TwoThin film
Generate These reactions are represented by the following chemical reaction formulas.
It is as follows. TiF₆ ^2-+ 2H_TwoO → TiO_Two↓ + 6F^-+ 4H⁺ (1) BO_Three ^3-+ 4F^-+ 6H⁺→ BF_Four ^-+ 3H_TwoO (2)

Since the above-mentioned TiO ₂ seed aqueous solution deposition method is carried out under atmospheric pressure and at least around room temperature below the boiling point of the aqueous solution, it does not matter whether the substrate on which TiO ₂ is deposited has heat resistance. Furthermore, since a TiO ₂ thin film having crystallinity can be formed, a TiO ₂ thin film having a photocatalytic action can be generated.

[0005]

A high-temperature process is required for forming a TiO ₂ film having a normal photocatalytic function, whereas the above-described seed aqueous solution deposition method forms a TiO ₂ film having a photocatalytic function at room temperature. What you can do is an important feature. Due to this feature, interest in film formation of TiO _{2 on} polymer materials having low temperature resistance using the above-described seed aqueous solution method has been attracting attention. However, when a TiO ₂ film is formed on a polymer substrate using the above-mentioned seed aqueous solution method as it is, almost no TiO ₂ film can be deposited on the polymer substrate, or
TiO ₂ film can be deposited but its adhesion is very weak.
If it was washed lightly, it would easily come off. For this reason, the range to which the TiO ₂ film formation by the seed aqueous solution method can be applied has been considerably narrow.

SUMMARY OF THE INVENTION An object of the present invention is to provide a film forming method capable of forming an oxide thin film having a good adhesion to a practical level on a polymer substrate.

[0007]

The present inventors have found SUMMARY OF THE INVENTION were investigated, poor adhesion between the TiO ₂ such as a metal oxide thin film and the substrate which is formed on a polymer material substrate by the aqueous solution method Was found to be due to the small surface energy of the polymer material surface. Therefore, in the present invention, a process of increasing the surface energy on the surface of the polymer material base material is performed,
The above problem was solved by activating and modifying those surfaces. That is, the present invention is a method for depositing a metal oxide thin film derived from the fluorometal complex compound on a substrate immersed in an aqueous solution containing a fluorometal complex compound and a fluorine scavenger, wherein the substrate is highly immersed. Made of molecular material,
The present invention also relates to a method for producing a metal oxide thin film, characterized in that at least a part of its surface has been subjected to a hydrophilic treatment.

[0008] Because the thin film is attached to the substrate, there is some interaction between the substrate and the thin film. The everyday expression of this interaction is adhesion. That is, adhesion is a state in which atoms of the thin film and the substrate interact with each other. If the adhesion is large, the thin film adheres well to the substrate. If the adhesive force is small, the thin film is easily peeled from the substrate.
Macroscopically, the problem of adhesion is thermodynamically a problem of surface energy. Generally, when the surface of an object having a large surface energy is covered with an object having a small surface energy, the adhesion is good. However, since the surface energy of most polymer objects is small, the adhesion of the thin film is not good. In order to improve the adhesion between the polymer object and the thin film, it is necessary to activate the surface of the polymer object and increase the surface energy.

[0009]

DESCRIPTION OF THE PREFERRED EMBODIMENTS In the production method of the present invention, a method for depositing a metal oxide thin film derived from the above-mentioned fluorometal complex compound on a substrate immersed in an aqueous solution containing a fluorometal complex compound and a fluorine scavenger has been described. Is a known method. Further, the production method of the present invention is characterized in that a base material for depositing the metal oxide thin film is made of a polymer material, and at least a part of the surface of the base material is subjected to a hydrophilic treatment.

The base material for depositing the metal oxide thin film is not particularly limited as a polymer material. In addition, the hydrophilization treatment includes a chemical treatment method and a physical treatment method, for example, a chemical treatment method such as an organic solvent treatment, an acid solution treatment, an alkali solution treatment, and a physical treatment such as a plasma glow discharge. Can be mentioned. Hydrophilic treatment is a method of activating the surface of a polymer material, and chemical treatment methods include:
In addition to the above chemical treatments and solvent treatments, there are methods such as surface grafting and surfactant treatment. In addition, physical processing methods include plasma processing,
Corona treatment, UV treatment, ion implantation, etc. are also available.
Above all, the plasma treatment can be used irrespective of the type of the base material, the effect of increasing the adhesion of the metal oxide thin film is large, and the waste liquid is harmful to the environment, as compared to the chemical treatment methods described above. It is excellent in that it does not have to be issued.

Examples of the organic solvent used for the treatment with the organic solvent include chloroform, acetone, tetrahydrofuran, DMSO (dimethyl sulfoxide), DMF
(Dimethylformamide) and the like.
Further, methanol, ethanol, water and the like can be used in combination for diluting these organic solvents. The treatment with an organic solvent is performed by immersing a base material made of a polymer material in an appropriate organic solvent. In the etching method using an organic solvent, unevenness is formed on the surface of the polymer substrate which has been smooth. When viewed as a microscopic view, when the thin film adheres to the surface, atoms of the thin film enter the substrate and exert an anchoring effect of fastening the thin film to the substrate in a manner as if driven by a nail. This anchoring effect is believed to result in increased adhesion. Also, some mechanical polishing can provide an anchoring effect. The immersion in the organic solvent is preferably performed so that the contact angle of water on the surface of the substrate subjected to the hydrophilic treatment to water is 60 degrees or less. In addition, as a substrate (polymer material) suitable for the hydrophilization treatment with an organic solvent, for example, polycarbonate, acrylic (PMMA), PET (polyethylene terephthalate), polystyrene, polyacrylonitrile, polyvinyl acetate, urethane and the like can be mentioned. Can be.

The acid used for the acid solution treatment includes, for example,
Examples include hydrochloric acid, sulfuric acid, and nitric acid. The acid solution treatment is performed by immersing a substrate made of a polymer material in an appropriate acid aqueous solution. It is preferable that the immersion is performed so that the contact angle of water on the surface of the substrate subjected to the hydrophilic treatment becomes 60 degrees or less. In addition, as a substrate (polymer material) suitable for the hydrophilization treatment with an acid aqueous solution, for example, nylon, polycarbonate, acrylic, delrin (acetal resin), P
ET (polyethylene terephthalate), polyoxymethylene and the like can be mentioned.

Examples of the alkali used for the alkali solution treatment include sodium hydroxide and potassium hydroxide. The alkali solution treatment is performed by immersing a substrate made of a polymer material in a suitable alkaline aqueous solution. It is preferable that the immersion is performed so that the contact angle of water on the surface of the substrate subjected to the hydrophilic treatment becomes 60 degrees or less.
In addition, as a substrate (polymer material) suitable for the hydrophilization treatment with an alkaline aqueous solution, for example, vinyl chloride, nylon,
Examples thereof include polycarbonate, acrylic (PMMA), polyvinyl acetate, polyimide, and urethane.

In the treatment with an acid or alkali solution, the material surfaces of the ester group and the amede group are treated with an acid or alkali to introduce another functional group or to substitute another functional group, thereby obtaining the same. The surface changes from a hydrophobic surface to a hydrophilic surface, and the adherence of the deposited thin film increases.

The plasma glow discharge can be applied irrespective of the kind of the polymer material constituting the base material, and can be limited to the processing of only the outermost surface of the base material, so that the light transmittance is not impaired. Suitable for processing substrates for optical elements. The hydrophilic treatment by plasma glow discharge is preferably performed such that the contact angle of water on the surface of the substrate subjected to the hydrophilic treatment becomes 60 degrees or less. The features of this method are:
The point is that only the surface portion can be improved without substantially affecting the bulk properties of the polymer itself. When a polymer is placed in an oxygen plasma, excited molecules, ions, and electrons present in the plasma attack the polymer surface. As a result, a direct action of the activated gas (surface oxidation action) and the generation of free radicals occur on the polymer surface. This increases the adhesion of the deposited film.

The degree of the hydrophilic treatment is preferably such that the contact angle of water on the surface of the substrate is 60 degrees or less, more preferably 55 degrees or less, more preferably 40 degrees or less. Degrees or less. The contact angle with water can be measured using, for example, a gonio-type contact angle measuring device manufactured by Elma Optical Co., Ltd.

Hereinafter, a method for depositing a metal oxide thin film derived from the fluorometal complex compound on a substrate immersed in an aqueous solution containing a fluorometal complex compound and a fluorine scavenger will be described. Examples of the fluorometal complex compound to be contained in the aqueous solution containing the fluorometal complex compound include a compound represented by the following general formula (I). AaMbFc (I) In the formula, A is one or two or more atoms selected from the group consisting of a hydrogen atom, an alkali metal atom, an ammonium group and coordinating water, and M is a metal; c is
This is a number that makes the complex compound electrically neutral. To form this fluorometal complex compound, an acid or salt soluble in water is used. A includes, in addition to a hydrogen atom, an alkali metal atom such as lithium, sodium, potassium, rubidium, and cesium; and an ammonium group and coordinating water. Examples of M (metal) include titanium, silicon, zirconium, niobium, germanium, aluminum, indium, tin, zinc, and copper. However, it is not limited to these metals. When b is 1, c is usually 6, and then a
Is 2 or 3 depending on the valence of. Typically, it can be represented by A ₃ MF ₆ or A ₂ MF ₆ . However, a polynuclear complex compound having a plurality of metal atoms (M) may be used.

The aqueous solution containing the fluorometal complex compound can be prepared by dissolving the target metal oxide in hydrofluoric acid. Alternatively, the hydroxide or oxyhydroxide of the desired metal is dissolved in an aqueous solution of an alkali metal hydrogen difluoride such as ammonium hydrogen difluoride or sodium hydrogen difluoride, and the corresponding fluorometal complex is dissolved. Compounds can also be synthesized.
The fluorometal complex compound is usually 10 ^-9 to 10 as a metal amount.
mol / L, preferably 10 ^-6 to 10 ^-1 mol / L. Here, the aqueous solution may be an aqueous solution containing excess hydrogen fluoride used for synthesizing the metal complex compound.

The fluoride ion scavenger used in the present invention may be any as long as it can capture fluorine ions from an aqueous solution containing a fluorometal complex compound and deposit a metal oxide thin film. Generally, a fluoride ion scavenger includes a homogeneous system used by being dissolved in a liquid phase and a heterogeneous system which is a solid. Depending on the purpose, either one of these two may be used or both may be used. The homogeneous fluoride ion scavenger reacts with hydrogen fluoride to form a stable fluoro complex compound and / or fluoride,
This is to shift the equilibrium of fluorine ions so as to deposit a metal oxide thin film. Besides boric acid such as orthoboric acid and metaboric acid, examples thereof include aluminum chloride, sodium hydroxide, and aqueous ammonia. Such a capture agent is usually used in the form of an aqueous solution, but may be added in the form of a powder and dissolved in the system. Such addition of the scavenger may be performed once or several times intermittently, or may be performed continuously at a controlled feed rate, for example, at a constant rate.

In the production method of the present invention, a seed crystal of a metal oxide to be precipitated can be added to an aqueous solution. By using a seed crystal, any of the precipitated metal oxides becomes a stable phase. The seed crystal is in the range of 0.001 to 10 μm, preferably in the range of 0.001 to 1 μm, more preferably about 0.001 to 0.15 μm,
The addition amount can be appropriately determined in consideration of the amount of the oxide to be precipitated and the like. In the method of the present invention, a precipitate can be obtained as a stable phase by using a seed crystal of a target metal oxide as a seed crystal. Further, the precipitation rate can be controlled by selecting the particle diameter and the amount of the seed crystal. If necessary, seed crystals can be replenished during the precipitation.

Filtration of the aqueous solution for precipitation can be carried out using a filter having a pore size that allows the seed crystal to pass through but captures precipitated particles having a particle size larger than the seed crystal.
This is preferable from the viewpoint of maintaining the effect of adding the seed crystal and generating an oxide thin film having a uniform thickness. In particular,
From the viewpoint of generating an oxide thin film having a uniform thickness, it is preferable to use a filter having a pore size of 150 nm or less. The pore size of the filter is more preferably 100 nm or less, and even more preferably 50 nm or less.

The filtration can be performed by continuously or intermittently circulating an aqueous solution for precipitation through a filter. Specifically, a part of the aqueous solution for precipitation is extracted and removed. This can be performed by passing through a filter and returning the obtained aqueous solution to an aqueous solution for precipitation again. In the production method of the present invention, deposition of a metal oxide thin film is performed while continuously or intermittently or temporarily applying sound waves and / or ultrasonic waves to an aqueous solution containing a fluorometal complex compound and a fluorine scavenger. Therefore, the fine particles can be more uniformly dispersed in the thin film. A sound wave has a frequency of 10
A wave shorter than 1 kHz
Hz to 100 kHz. From the viewpoint that the effects of the present invention can be effectively obtained, the frequency is 20 kHz to 100 kHz.
It is preferable to use sound waves and ultrasonic waves in the range of kHz.
Also, using sound waves or ultrasonic waves of a single frequency,
Also, a plurality of sound waves and / or ultrasonic waves having different frequencies can be used. The amount (output) of sound waves and / or ultrasonic waves given to the aqueous solution is represented by sound waves or ultrasonic density (output / bottom area of the reaction vessel) and is, for example, 0.0%.
It can be in the range of 1 to ¹ W / cm ² . However, the sound wave or ultrasonic density can be appropriately determined in consideration of the shape and volume of the reaction vessel, the amount of the reaction solution, and the like.

The sound waves and / or ultrasonic waves can be given continuously, intermittently or temporarily. When sound waves and / or ultrasonic waves are applied to an aqueous solution, the temperature of the aqueous solution tends to increase. Therefore, in consideration of the temperature of the aqueous solution and the effects of the present invention, the time and timing for applying the sound waves and / or ultrasonic waves are It can be determined appropriately. The reaction temperature can be arbitrarily set within a range in which the system maintains an aqueous solution.
C., but is preferably in the range of 10 to 80C, more preferably in the range of 30C to 70C. The reaction time is also arbitrary. For example, when the target precipitate is large, the reaction time can be lengthened accordingly.

Thus, a metal oxide thin film can be formed on the substrate surface. The precipitate thus formed is:
In particular, a metal oxide thin film crystallized according to conditions can be obtained as a precipitate without a heating step such as firing. However, a heating step may be provided according to the purpose. Metal oxide thin film obtained by the method of the present invention, depending on the type of fluorometal complex compound used, for example, titanium,
Silicon, zirconium, niobium, germanium,
The thin film contains one or more kinds of oxides of aluminum, indium, tin, zinc, and copper. Further, the metal oxide thin film includes a metal oxide thin film doped with metal ions.

The method for producing a metal oxide thin film of the present invention can be divided into, for example, the following three modes. A first aspect is a method for forming a thin film made of a metal oxide derived from a fluorometal complex compound. When forming a thin film made of a single metal oxide, an aqueous solution containing one type of fluorometal complex compound is used. When a thin film composed of a plurality of metal oxides is to be formed, an aqueous solution containing two or more fluorometal complex compounds is used. In this case, two kinds of metal oxides derived from two or more fluorometal complex compounds are used. It is preferable to carry out the reaction in the presence of the above seed crystal. This is because the use of a seed crystal of a metal oxide to be deposited causes any deposited metal oxide to be a stable phase.

The second aspect of the present invention is a method for producing a metal oxide thin film derived from a fluorometal complex compound doped with metal ions. In this embodiment, the formed thin film is a metal ion-doped metal oxide. As metal ions to be doped into the metal oxide, for example, silver ions, copper ions,
Platinum ion, vanadium ion, chromium ion, manganese ion, iron ion, cobalt ion and the like can be mentioned. However, any metal ion derived from a compound soluble in an aqueous solution containing the fluorometal complex compound can be doped.

Examples of the water-soluble metal compound include, for example, Ag
F xH_TwoO, AgNO_Three, Rh (NO_Three)_Three・ 2H_TwoO, C
u (NO_Three)_Two・ 3H_TwoO, Cr (NO_Three)_Three・ XH_TwoO, Cu
F_Two・ 2H_TwoO, CuCl_Two・ 2H_TwoO, PtCl_Four・ 5H_Two
O, VOSiO_Four・ 2H_TwoO, VOCl_Three, Cr_Two(S
O_Four)_Three・ 18H_TwoO, CrCl_Three・ XH_TwoO, MnCl_Two・
4H_TwoO, MnCl_Two, Mn (NO_Three)_Two・ 6H_TwoO, MnS
O_Four・ 6H_TwoO, MnF _Two, MnF_Three・ 3H_TwoO, FeCl_Two
・ 4H_TwoO, FeCl_Two, FeCl_Three・ 6H_TwoO, FeCl
_Three, Fe (NO_Three)_Three・ 9H_TwoO, FeSO_Four・ 7H_TwoO, F
eSO_Four, (NH _Four) Fe (SO_Four)_Three・ XH_TwoO, Co (N
O_Three)_Two・ 6H_TwoO, CoSO_Four・ 7H_TwoO, NiCl_Two・ 6
H_TwoO, Ni (NO_Three)_Two・ 6H_TwoO, NiSO_Four, Cu (N
O_Three)_Two・ 3H_TwoO, CuSO_Four・ 5H_TwoO, CuSO_Four, C
uCl_Two・ 2H_TwoO, CuF_Two・ 2H_TwoO, CuCl, Sc
(SO_Four)_Three・ XH_TwoO and the like are exemplified. Water-soluble metallization
The concentration of the compound is determined in consideration of the solubility and the doping amount to the thin film.
For example, 10 liters per liter of treatment liquid^-Four-10 mol
In the range. In addition, water-soluble metal compounds
Replenishment can be performed during the reaction.

The third embodiment is a method for producing a thin film containing fine particles in a metal oxide derived from a fluorometal complex compound.
This thin film can be formed by adding and dispersing fine particles in an aqueous solution containing a fluorometal complex compound, and depositing the thin film from the aqueous solution. Examples of the fine particles include metal colloid particles, metal oxide colloid particles, and organic particles. Examples of the metal colloid particles include Cu, Ag, and Pt. As metal oxide colloid particles, for example, Fe ₂
O ₃ , Cu ₂ O, CuO and the like can be mentioned. Examples of the organic particles include polystyrene, polyethylene terephthalate, acrylic, and polycarbonate.

The particle size of the fine particles and the amount added to the aqueous solution are as follows:
It can be changed as appropriate depending on the intended thin film. However, in consideration of the dispersibility of the fine particles in the aqueous solution and the state of existence in the thin film, the particle diameter can be, for example, in the range of 10 ^{−3 to 1} μm. In addition, the amount of the fine particles added to the aqueous solution is determined, for example, in consideration of the concentration of the fine particles in the thin film, for example, in the treatment liquid
It can range from 10 ^-2 to 10 ² g relative to liters. Fine particles can be added and replenished during the reaction in the same manner as the seed crystal. In the production method of the present invention, since the sound waves and / or the ultrasonic waves are used, the fine particles can be more uniformly dispersed.

Also in the second and third embodiments, the aqueous solution containing the fluorometal complex compound may contain a seed crystal composed of a metal oxide formed by the fluorometal complex compound. By using such a seed crystal,
A metal oxide can be deposited as a stable phase.
Note that two or more of the above three aspects can be combined to simultaneously form a thin film containing two or more types of substances.

[0031]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. still,
In the examples, the contact angle with water was measured using a gonio-type contact angle measuring device manufactured by Elma Optical Co., Ltd.

Example 1 First, as a film forming substrate, the contact angle with water was about 63 degrees.
Acrylic plate with plasma glow discharge on its surface
Pretreatment. As a plasma processing apparatus, Sam
Co.'s Plasma Deposition system
tem, Model PD-10 was used. Plasma
The processing time is 30 sce, in an oxygen atmosphere, the pressure of oxygen is
It was set to 1.2 to 1.5 Torr. After plasma treatment,
The contact angle with water on the surface of the rill plate is about 40 degrees, and it is hydrophobic
The acrylic plate surface became hydrophilic. After that, the film formation process
went inside. Ammonium as a fluoro complex metal compound
Hexafluorotitanate (NH _Four)_TwoTiF₆Using
After dissolving 2.8 g of this in 400 ml of water and stirring,
TiO_TwoA solution in which anatase microparticles are suspended in pure water in advance.
The solution was allowed to stand overnight, and 10 ml of the supernatant obtained was added.
The mixture was homogenized with stirring. The treatment solution prepared in this way is
Transfer to a 500ml cylindrical container and keep at 35 ℃
It was immersed in a sonic bath. Quickly before 10g of boron oxide
It was added to the above-mentioned treatment solution and stirred. Then, 50 × 60 × 2
Acrylic substrate of mm size is immersed in this treatment liquid for 3 hours
(See FIG. 1). 30 minutes during the film formation process
Ultrasound was applied for 30 seconds every time (frequency multiplication, output
100W, ultrasonic density 0.3W / cm^Two). During film formation
After a lapse of time, the substrate was taken out of the processing solution and washed lightly.
After that, air dry and TiO_TwoObtain a substrate on which a thin film is deposited
Was. The resulting thin film shows uniform interference reflected light,
The film was highly transparent without light scattering. The thin film obtained
Was not peeled off by washing with water. In addition, cello
The peeling test using Tape (trademark)
There was no separation. Using the method of Example 1,
Titanium oxide film with good adhesion and photocatalytic performance is formed
did it.

Comparative Example 1 An acrylic plate made of the same material as in Example 1 was used, and the process of forming a TiO ₂ thin film was started directly without performing any pretreatment on the surface. The preparation of the film forming solution and the film forming conditions were the same as in Example 1. After the elapse of the film forming process time, the substrate was taken out of the processing solution, but no TiO ₂ thin film was deposited on the substrate.

Comparative Example 2 An acrylic plate of the same material as in Example 1 was used, and the process of depositing and depositing a TiO ₂ thin film was started directly without performing any pretreatment on the surface. The preparation of the film forming solution was the same as in Example 1, and the film forming conditions were the same as in Example 1 except that no ultrasonic wave was applied. After the elapse of the film formation processing time, the substrate was removed from the processing solution, and deposition of a TiO ₂ thin film on the substrate was observed. But,
Since no ultrasonic wave was applied, the uniformity of the film was not good. After the film forming process, the film was easily removed from the substrate by gently washing with water.

Example 2 First, a P film having a contact angle with water of 72 degrees was used as a film forming substrate.
Preliminary surface by plasma glow discharge using C plate
Processed. As a plasma processing apparatus, Samco
Plasma Deposition System,
 Model PD-10 was used. Plasma processing time
Is 15 seconds and the oxygen pressure is 1.0 to
1.5 Torr. After plasma treatment,
The contact angle with water becomes about 30 degrees, and the hydrophobic PC surface becomes
It became hydrophilic. Thereafter, a film formation process was started. Fluoro
As a complex metal compound, ammonium hexafluorotitanium
Nate (NH _Four)_TwoTiF₆Using 400 ml of water
2.8 g dissolved in_TwoO_FiveAnd add 0.06 g.
After stirring, TiO_TwoPreliminarily suspend anatase microparticles in pure water.
The turbid solution was allowed to stand overnight, and the supernatant obtained was 10 m
and the mixture was stirred and homogenized. Prepared as above
Transfer the treated solution to a 500 ml cylindrical container,
Immersed in an ultrasonic water bath held in a water bath. 10 g of boron oxide
It was quickly added to the above-mentioned treatment solution and stirred. As a deposition substrate,
Size 70mm × 5 after the above plasma glow discharge treatment
A 0 mm PC substrate was used. Place the substrate in the processing solution described above.
To form a film for 3 hours. Every 30 minutes during the film formation process
30 seconds ultrasonic (frequency multi, output 10
0 W, ultrasonic density 0.3 W / cm^Two). Processing time elapsed
After that, remove the substrate from the processing solution and wash it lightly.
Dry and vanadium doped TiO_TwoDeposit a thin film of
The obtained substrate was obtained. The resulting thin film has uniform interference reflected light
This is a highly transparent film without light scattering.
Was. The obtained thin film does not peel off by washing with water
Was. Furthermore, a peel test using Cellotape (trademark)
However, the thin film did not peel off. Example 2
Method, uniform, good adhesion and photocatalytic acid
A titanium oxide film was formed.

Example 3 First, as a film forming substrate, the contact angle with water was about 90 degrees.
Using a polyethylene (PE) plate with a plasma
A preliminary treatment by glow discharge was performed. Plasma processing equipment and
And then Samco's Plasma Depositi
on system, using Model PD-10
Was. Plasma treatment time is 30 seconds, in oxygen atmosphere,
The pressure of oxygen was set to 1.2 to 1.5 Torr. plasma
After treatment, the contact angle of the polyethylene plate surface with water is about 50 degrees
And the hydrophobic polyethylene surface becomes hydrophilic
Was. Thereafter, a film formation process was started. Fluoro complex metal compound
As ammonium hexafluorotitanate (NH
_Four)_TwoTiF₆2.8 g in 400 ml water
After dissolving and stirring, TiO_TwoAnatase fine particles in advance
Supernatant obtained by leaving the solution suspended in pure water overnight
10 ml of the liquid was added, and the mixture was similarly stirred and homogenized. As above
Transfer the processing solution prepared in the above to a 500 ml cylindrical container
Then, it was immersed in an ultrasonic cleaning bath maintained at 35 ° C. Oxidation
10 g of boron was quickly added to the above-mentioned treatment solution and stirred.
Then, a polyethylene substrate of 30 × 30 × 1 mm size
Was immersed in this treatment solution for 3 hours to form a film (see FIG. 1).
). Ultrasonic wave for 30 sec every 30 min during the film formation process
(Frequency multi, output 100W, ultrasonic density
0.3W / cm^Two). After the elapse of the film formation processing time, the substrate is processed.
Remove from the solution, lightly wash, air dry,
iO_TwoA substrate on which a thin film was deposited was obtained. The resulting thin film is
Shows uniform interference reflected light, no light scattering and transparency
Was high. The obtained thin film is peeled off by washing with water
I never did. In addition, using Cellotape (trademark)
No peeling of the thin film by the peel test
Was. Using the method of Example 3, uniform, good adhesion, and light
A titanium oxide film having catalytic performance was formed.

COMPARATIVE EXAMPLE 3 Polyethylene (PE) made of the same material as in Example 3 was used, and the process of forming a TiO ₂ thin film was started directly without performing any pretreatment on its surface. The preparation of the film forming solution and the film forming conditions were the same as in Example 3. After the elapse of the film formation time, the substrate was taken out of the processing solution, and no TiO ₂ thin film was deposited on the substrate.

Example 4 First, as a film formation substrate, the contact angle with water was about 90 degrees.
Using a polypropylene (PP) plate
Preliminary treatment was carried out by muggle discharge. Plasma processing equipment
As the Plasma Deposit of Samco
Use ion system, Model PD-10
Was. Plasma treatment time is 30 seconds, oxygen atmosphere
The oxygen pressure was set to 1.0 to 1.5 Torr. Plastic
After the zuma treatment, the contact angle of the polypropylene plate surface with water is 5
About 9 degrees, hydrophobic polypropylene (PP) surface
Became hydrophilic. Thereafter, a film formation process was started. Fluo
As a complex metal compound, ammonium hexafluorothi
Tanate (NH _Four)_TwoTiF₆Using 400ml
After dissolving 2.8 g in water and stirring, TiO_TwoAnata
The solution in which fine particles are suspended in pure water is left overnight.
10 ml of the obtained supernatant was added, and the mixture was stirred and homogenized in the same manner.
Was. The treatment solution prepared as described above was used for a 500 ml circle.
Transfer to a cylindrical container and maintain an ultrasonic cleaner tank at 35 ° C
Dipped in. 10 g of boron oxide quickly into the above-mentioned processing solution
Added and stirred. Then, a 40 × 40 × 1 mm size port
A polyethylene substrate is immersed in this processing solution for 3 hours to form a film.
(Shown in FIG. 1). 30 s every 30 min during the film formation process
ec ultrasonic waves (frequency multi, output 100W,
Ultrasonic density 0.3W / cm^Two). Of the film formation processing time
After that, remove the substrate from the processing solution and wash it lightly.
Dried, TiO_TwoA substrate on which a thin film was deposited was obtained. Get
The thin film shows uniform interference reflected light and reduces light scattering.
It was not shown and was a highly transparent film. The obtained thin film is washed with water
Therefore, it did not peel off. In addition, scotch tape
The thin film peels off even by a peeling test using (trademark)
I never did. Uniform, adhesive force using the method of Example 4
Titanium oxide film with good and photocatalytic performance can be formed
Was.

Comparative Example 4 Using the same material as in Example 4, polypropylene (PP) was used.
The TiO ₂ thin film was directly formed without performing any pretreatment on its surface. The preparation of the film forming solution and the film forming conditions were the same as in Example 4. After the elapse of the film forming time, the substrate was taken out of the processing solution, and no TiO ₂ thin film was deposited on the substrate.

Example 5 First, PE having a contact angle with water of 65 degrees as a film-forming substrate was used.
Using T, the surface was pre-treated with an acid. Prepare 400 ml of 1M HCl solution, and adjust the temperature of the solution.
Is maintained at 20 ° C. and 50 × 60 mm size in the acid solution.
The PET sample was immersed for 3 minutes and processed. So
Thereafter, the mixture was appropriately flushed with distilled water and dried at room temperature. processing
Later, the contact angle of the PET surface with water becomes about 40 degrees,
After that, a titanium oxide film formation process was started. Ammonium hexaflur as a fluoro complex metal compound
Orotitanate (NH _Four)_TwoTiF₆Using 40
After dissolving 2.8 g in 0 ml water and stirring, TiO 2_TwoA
Release a solution of previously suspended natase microparticles in pure water overnight
10 ml of the supernatant liquid obtained by the
Quality. 500 m of the treatment liquid prepared as described above
Transfer to a 1 l cylindrical container and ultrasonic cleaning maintained at 35 ° C
It was immersed in a water tank. 10 g of boron oxide quickly treated as described above
The solution was added and stirred. After that, the sump treated with the above acid
Was immersed in this treatment solution for 3 hours to form a film (see FIG. 1).
). Ultrasonic wave for 30 sec every 30 min during the film formation process
(Frequency 45kHz, output 100W, ultrasonic density
Degree 0.3W / cm^Two). After the elapse of the film formation time, the sump
Remove from the processing solution, lightly wash, air dry
And TiO_TwoA substrate on which a thin film was deposited was obtained. Thin obtained
The film shows uniform interference reflected light and no light scattering
It was a highly transparent film. The obtained thin film is washed with water
There was no peeling. In addition, Cellotape ™
The peeling test using
won. Using the method of Example 5, uniform and good adhesion
A titanium oxide film having photocatalytic performance was formed.

Example 6 First, Ny having a contact angle with water of 67 degrees as a film-forming substrate was used.
lon6, and the surface is pre-treated with alkali
Was. Prepare 400 ml of a 5 M NaOH solution and heat the solution.
The temperature is maintained at 20 ° C. and 50 × 40 in the alkaline solution.
Immersion of Nylon6 sample of 10 mm in 10 mm
And processed. After that, pour slowly with distilled water and at room temperature
Dried. After treatment, the contact angle of Nylon 6 surface with water is
It reaches about 45 degrees, and then enters the titanium oxide film formation process
Was. Ammonium hexa as a fluoro complex metal compound
Fluorotitanate (NH _Four)_TwoTiF₆And use this
After dissolving 2.8 g in 400 ml water and stirring, TiO 2
_TwoA solution of anatase microparticles suspended in pure water in advance
Add 10 ml of the supernatant obtained by standing overnight, and stir similarly.
The mixture was homogenized. The treatment solution prepared as described above was
Ultrasonic transferred to a 0 ml cylindrical container and kept at 35 ° C
It was immersed in a washing tank. 10 g of boron oxide quickly
It was added to the treatment liquid and stirred. After that, treatment with the above alkali
The sample thus obtained was immersed in this treatment solution for 3 hours to form a film.
(Shown in FIG. 1). 30 seconds every 30 minutes during the film formation process
c was applied (frequency 45 kHz, output 100
W, ultrasonic density 0.3W / cm^Two). Elapsed time of deposition process
After, remove the sample from the processing solution and wash it gently
After that, air dry and TiO_TwoObtain a substrate on which a thin film is deposited
Was. The resulting thin film shows uniform interference reflected light,
The film was highly transparent without light scattering. The thin film obtained
Was not peeled off by washing with water. In addition, cello
The peeling test using Tape (trademark)
There was no separation. Using the method of Example 6, uniform
Titanium oxide film with good adhesion and photocatalytic performance is formed
did it.

Example 7 First, as a film-forming substrate, P having a contact angle with water of 72 degrees was used.
Preparing the surface by organic solvent etching using a C plate
Processed. As an etchant, the organic solvent chloropho
Lum and ethanol (chloroform) 1: (Ethanor
4) prepared in a ratio of 4. PC in the etching solution
The plate was immersed for 5 seconds and etched. By that
Thus, the PC surface became rougher. Then, enter the film formation process.
You. Ammonium hexa as a fluoro complex metal compound
Fluorotitanate (NH _Four)_TwoTiF₆And use this
After dissolving 2.8 g in 400 ml water and stirring, TiO 2
_TwoA solution of anatase microparticles suspended in pure water in advance
Add 10 ml of the supernatant obtained by standing overnight, and stir similarly.
The mixture was homogenized. The treatment solution prepared as described above was
Ultrasonic transferred to a 0 ml cylindrical container and kept at 40 ° C
It was immersed in a washing tank. 10 g of boron oxide quickly
It was added to the treatment liquid and stirred. Then, 50 × 70 × 1mm
PC board of size is immersed in this processing solution for 3 hours to form a film
(Shown in FIG. 1). 30 every 20 min during the deposition process
seconds of ultrasonic waves (frequency 45 kHz, output 10
0 W, ultrasonic density 0.3 W / cm^Two). Deposition time
After passing, remove the substrate from the processing solution, wash it lightly,
Air dried, TiO_TwoA substrate on which a thin film was deposited was obtained.
The resulting thin film shows uniform interference reflected light,
The film was highly transparent without any disturbance. The resulting thin film is made of water
It was not peeled off by washing. In addition,
The peeling test using the
I never did. Uniform and adhere using the method of Example 7.
A powerful and photocatalytic titanium oxide film can be formed.
Was.

Comparative Example 5 Using a PC board made of the same material as in Example 7, the process of forming a TiO ₂ thin film was started directly without performing any pretreatment on the surface. Preparation of a film forming solution, film forming conditions, and the like were performed in the same manner as in Example 1. After the elapse of the film formation time, the substrate was taken out of the processing solution, and no TiO ₂ thin film was deposited on the substrate.

Example 8 First, an ABS plate was used as a film-forming substrate,
Preliminary treatment was performed by solvent etching. Etching liquid
As the organic solvent chloroform and ethanol
(Formol) 1: 8 (ethanol). So
The PC board is immersed in the etching solution of
Ching. As a result, the surface of the ABS substrate becomes rougher.
It's gone. Thereafter, a film formation process was started. Fluoro complex metal
As a compound, ammonium hexafluorotitanate
(NH _Four)_TwoTiF₆And put it in 400ml water
Dissolve 2.8 g, and_TwoO_FiveWas added and stirred.
After the TiO_TwoAnatase microparticles are suspended in pure water in advance.
Let the solution stand overnight and add 10 ml of the supernatant obtained.
Then, the mixture was stirred and homogenized. Prepared as above
Transfer the processing solution to a 500 ml cylindrical container and keep it at 30 ° C.
It was immersed in an ultrasonic water tank. 10 g of boron oxide quickly
It was added to the above-mentioned treatment solution and stirred. As the film forming substrate,
40mm x 50mm size etched with organic solution
An ABS plate is used. The substrate is immersed in the above-mentioned film formation processing solution.
It was immersed and formed into a film in 4 hours. Every 30 minutes during the film formation process
30 seconds of ultrasonic waves (frequency multi, output 100
W, ultrasonic density 0.3W / cm^Two). Processing time elapsed
After that, remove the substrate from the processing solution and wash it lightly.
Dry, vanadium doped TiO_TwoOf thin film
The ejected substrate was obtained. The resulting thin film has uniform interference reflection
Shows light. The obtained thin film is peeled off by washing with water
I never did. In addition, using Cellotape (trademark)
Even in the peeling test, the thin film did not peel.
Using the method of Example 8, uniform vanadium with good adhesion
Doped TiO_TwoWas formed.

COMPARATIVE EXAMPLE 6 An ABS plate of the same material as in Example 8 was used, and the process of depositing and depositing a vanadium-doped TiO ₂ thin film directly was performed without any pretreatment on the surface. Preparation of a film forming solution, film forming conditions, and the like were performed in the same manner as in Example 2. After the elapse of the film formation time, the substrate was taken out of the processing solution, and no deposition of a TiO ₂ thin film doped with vanadium was observed on the substrate.

[0046] Using the ABS plate of the same material as in Comparative Example 7 Example 8, it enters the deposition film forming process of directly TiO ₂ thin film doped with vanadium without pretreatment to the surface. Preparation of film forming solution was performed in Example 8.
In the same manner as in Example 8, the film was formed under the same conditions as in Example 8 except that no ultrasonic wave was applied. After the elapse of the film formation time, the substrate was taken out of the processing solution, and deposition of a TiO ₂ thin film doped with vanadium was observed on the substrate. However, the uniformity of the film was not good because no ultrasonic wave was applied. After the film formation process, the film was easily separated from the substrate by lightly washing with water.

As a method for modifying the surface of the polymer material in the formation of the oxide thin film on the polymer material using the dispersed seed aqueous solution method, the organic solvent, the acid solution described in the above-mentioned embodiment,
Chemical surface treatment method of alkaline solution, and not limited to physical surface treatment method with plasma glow discharge, other surface modification means,
For example, solvent treatment of wet treatment, chemical treatment; surface polishing of dry treatment, surface etching, plasma corona discharge, light, ultraviolet, and radiation irradiation method, ion treatment, mechanochemical treatment;
Coating with a coating modifier, vacuum deposition,
Appropriate methods such as chemical vapor deposition, physical vapor deposition, multilayer polymerization, graft polymerization, and film alignment may be performed. Further, the reaction gas for the plasma treatment is not limited to the above-described oxygen gas, but may be nitrogen gas, argon gas, air, or the like.

[0048]

According to the present invention, the oxide thin film and the composite thin film cannot be deposited by the aqueous dispersion seed method, or a practically acceptable coating can be obtained on the surface of the polymer base material having a weak adhesion even if it can be deposited. An oxide thin film and a composite thin film having good adhesion can be formed.

[Brief description of the drawings]

FIG. 1 is a schematic explanatory view of an apparatus for producing a thin film.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4F006 AA04 AA12 AA15 AA22 AA35 AA36 AA38 AA58 AB68 AB74 BA00 BA10 CA00 DA00 EA01 EA03 4G047 CA02 CB05 CC03 CD02 CD07 4K022 AA14 AA15 AA16 AA19 AA23 CA12 BA15 CA16 CA22

Claims (8)

[Claims] 1. A method of depositing a metal oxide thin film derived from a fluorometal complex compound on a substrate immersed in an aqueous solution containing a fluorometal complex compound and a fluorine scavenger, wherein the substrate is a polymer A method for producing a metal oxide thin film, comprising a material and at least a part of its surface is subjected to a hydrophilic treatment. 2. The aqueous solution containing the fluorometal complex compound and the fluorine scavenger further contains a water-soluble metal compound, and the metal oxide thin film is doped with metal ions derived from the water-soluble metal compound. 2. The production method according to 1. 3. The method according to claim 1, wherein the fluorometal complex compound is a fluorotitanium complex compound, and the metal oxide is TiO ₂ . 4. The production method according to claim 1, wherein the hydrophilic treatment is performed such that the contact angle of the surface of the substrate subjected to the hydrophilic treatment to water becomes 60 degrees or less. 5. The production method according to claim 1, wherein the hydrophilic treatment of the substrate is a plasma treatment. 6. The method according to claim 1, wherein the hydrophilic treatment of the substrate is etching with an organic solvent. 7. The method according to claim 1, wherein the hydrophilic treatment of the substrate is a treatment with an acid solution. 8. The method according to claim 1, wherein the hydrophilic treatment of the substrate is a treatment with an alkaline solution.