JP2002121466A - Solution for forming electrodeposition film and method for forming electrodeposition film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a solution for forming an electrodeposition film, which can be electrodeposited with low energy and can form the electrodeposition film having a high film strength and excellent solvent resistance, and to provide a method for forming the electrodeposition film, using the solution for forming the electrodeposition film. SOLUTION: This solution for forming the electrodeposition film, containing at least an acidic functional group-having polymer, a basic compound and water, characterized in that the polymer further has thermally cross-linkable functional groups and a degree of neutralization of X to (X+30)% [X is the degree of neutralization (solid phase-forming degree of neutralization) of the polymer, when the viscosity of the solution for forming the electrodeposition film is minimized at 25 deg.C]. The method for forming the electrodeposition film, characterized by forming a deposition film on the surface of a conductive substrate by an electrodeposition method using the solution for forming the electrodeposition film and then thermally treating the deposition film to form the electrodeposition film.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrodeposition film forming solution capable of electrochemically forming an electrodeposition film at low potential and low energy, and an electrodeposition film using the electrodeposition film forming solution. It relates to a forming method.

[0002]

2. Description of the Related Art An electrodeposition film for recording a pattern on a substrate is provided by:
It can be used for various display devices such as CCD cameras and liquid crystal display devices, color filters used in display panels, color image sensors, etc. Conventional methods include the dyeing method, pigment dispersion method, and printing method. , An ink jet method, an electrodeposition method and the like are known.

However, the dyeing method, the pigment dispersing method, and the printing method require a photolithography step for patterning, and there is a problem that the number of manufacturing steps increases and the manufacturing cost increases. In the inkjet method,
Although the photolithography step is not necessary,
There is a problem that the resolution and the film thickness uniformity are inferior. In addition, there is a problem that color mixing easily occurs between adjacent filter layers, resulting in poor resolution and positional accuracy.

[0004] The above-mentioned electrodeposition method uses a 70-100
In this method, a high voltage of about V is applied to form an electrodeposition film. In the electrodeposition method, when the electrodeposition potential is set to be close to 100 V, a foaming phenomenon occurs due to electrolysis of water, so that there is a problem that film surface properties are poor and performance is poor. Further, since the transparent electrode needs to be patterned in advance by photolithography, there has been a problem that the manufacturing cost is increased as a result.

[0005] Therefore, there is a need for a method capable of manufacturing a color filter excellent in high resolution and pattern accuracy at a low cost and with a simple process without passing through a photolithography process. In recent years, a demand for a display capable of displaying video information and communication information at a high resolution has been increasing, and a higher definition patterned color filter has been demanded.

In order to solve the above problem, there has been proposed a technique for manufacturing a color filter having high resolution and excellent pattern accuracy by a simple process using an electrodeposition method utilizing photovoltaic power. For example, JP-A-5-119209 and JP-A-5-157905 propose a method of manufacturing a color filter using a polymer compound used for general electrodeposition coating. JP-A-10-324994 proposes a technique using a dye that precipitates at pH 4 or lower or pH 10 or higher. Further, JP-A-11-13
JP-A-3224, JP-A-11-350193, and JP-A-2000-28821 disclose the solution p.
A technique using a polymer material that precipitates with H change has been proposed.

However, in the technique using a polymer compound used for electrodeposition coating, since the electrodeposition voltage is set to a high potential of 20 to 80 V, the color filter obtained has poor film surface properties and poor performance. was there. In addition, the technique using a dye that precipitates at a predetermined pH has a problem in that light resistance is poor because the dye is used. Furthermore, in the technique using a polymer material that precipitates with a change in the pH of the solution, the pH of the electrodeposition solution is adjusted in advance to a pH that is a condition for dissolving the polymer material.
In order to adjust the pH to any of 1 to 4 and pH 10 to 13, the energy required for electrodeposition is large, and there is a problem that the surface of the electrodeposited film generated by the foaming phenomenon due to the electrolysis of water is deteriorated.

Further, the film strength and the solvent resistance of the electrodeposited film do not reach a sufficiently satisfactory level similarly to the color filters produced by the above-mentioned respective color filter production methods, and the resolution of the displayed image is reduced. There was a problem of lowering. As described above, at present, a material provided with an electrodeposition film having high film strength and sufficient solvent resistance has not yet been provided.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems, meet various demands, and achieve the following objects. That is, the present invention provides an electrodeposition film forming liquid capable of forming an electrodeposition film with low energy, capable of forming an electrodeposition film having high film strength and excellent solvent resistance, and the electrodeposition film forming liquid. It is an object of the present invention to provide a method for forming an electrodeposition film using the same.

[0010]

Means for solving the above problems are as follows. That is, <1> at least a polymer having an acidic functional group,
An electrodeposition film-forming solution containing a basic compound and water, wherein the polymer further has a thermally crosslinkable functional group, and the neutralization rate of the polymer is X to (X + 30)% (Where X represents the neutralization rate of the polymer (solidification neutralization rate) when the viscosity of the electrodeposition film forming liquid is minimized at 25 ° C.). Forming liquid.

<2> The electrodeposition film-forming liquid according to <1>, wherein the polymer has a constituent part represented by the following chemical formula (1) having a thermally crosslinkable functional group.

Chemical formula (1)

Embedded image (Where R ₁ represents hydrogen or a methyl group; R ₂ , R ₃
Each independently represents an alkyl group having 1 to 6 carbon atoms or an aralkyl group, and n represents a positive integer. )

<3> The electrodeposition film forming liquid according to <1> or <2>, wherein the turbidity of the electrodeposition film forming liquid is 100 degrees or less. <4> The polymer contains an acrylic acid-derived constituent site and / or a methacrylic acid-derived constituent site as a copolymer component, and the polymer has an acid value of 100 to 160 <1> to <1>.
The liquid for forming an electrodeposition film according to any one of <3>.

<5> By using the electrodeposition film forming liquid according to any one of <1> to <4>, a deposition film is formed on the surface of the conductive substrate by an electrodeposition method, and then a heat treatment is performed. An electrodeposition film forming method characterized by forming an electrodeposition film.

<6> The method for forming an electrodeposited film according to <5>, wherein the potential between the electrodes when forming the electrodeposited film by the electrodeposition method is 10 V or less. <7> The method for forming an electrodeposition film according to <5> or <6>, wherein the temperature of the heat treatment is 120 to 220 ° C.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. [Electrodeposition Film Forming Solution] The electrodeposition film forming solution of the present invention contains at least a polymer, a basic compound, and water, and further contains other components as necessary.

-Neutralization rate of polymer-The neutralization rate of the polymer is X to (X + 30)%
(However, it is necessary that X represents a neutralization rate of the polymer (solidification neutralization rate) when the viscosity of the electrodeposition film forming liquid is minimum at 25 ° C.).

Here, the neutralization ratio of the polymer will be described. The polymer has acidic functional groups. The acidic functional group is formed by the following chemical formula (2) due to the presence of a basic compound.
Is partially neutralized as shown in FIG.

Chemical formula (2)

Embedded image

When the neutralization rate of the polymer is considered for one molecule of the polymer, the neutralization rate for one molecule of the polymer is the acid function neutralized by the basic compound among the acidic functional groups contained in one molecule of the polymer. It is shown as a ratio of a group (the following formula (1)).

Equation (1)

(Equation 1)

However, since the molecular weights of the polymers in the electrodeposition film forming solution are not always the same, the neutralization ratio for one polymer molecule cannot be calculated. Therefore, in the present invention, the neutralization rate of the polymer is shown as a ratio of the total acidic functional groups neutralized by the basic compound to the total acidic functional groups in all the polymers in the electrodeposition film forming liquid. (Formula (2) below).

Equation (2)

(Equation 2)

Next, the neutralization ratio (X) for solid-phase immobilization will be described. The solidification neutralization ratio (X) is defined as
It refers to the neutralization rate of the polymer when the viscosity of the electrodeposition film forming liquid is minimized. According to the study of the present inventors, with the change of the neutralization ratio of the polymer, the viscosity of the electrodeposition film forming liquid changes, and when the neutralization ratio of the polymer is a predetermined value, the viscosity becomes a minimum value. . Although the mechanism is not clear, it is thought to be due to the interaction between molecules due to the dissociation of the acidic functional group.

FIG. 1 is a graph showing the relationship between the neutralization ratio (%) of the polymer in the electrodeposition film forming solution and the viscosity (25 ° C.) of the electrodeposition film forming solution, and the neutralization ratio of the polymer. (%) And the particle diameter (volume average particle diameter) of the fine particles when the electrodeposition film forming liquid contains fine particles (silicon oxide, volume average particle diameter = 0.015 μm). Graph. In FIG. 1, the horizontal axis represents the neutralization rate (%) of the polymer, the vertical axis represents the viscosity (mPa · s), and the particle diameter (volume average particle diameter) of the fine particles in the electrodeposition film forming liquid.

In FIG. 1, in the graph, when the neutralization ratio of the polymer is equal to or higher than a predetermined value, the ionized acidic functional groups increase as the neutralization ratio of the polymer increases. For this reason,
The polymer spreads in the electrodeposition film forming solution, the interaction between the molecules increases, and the viscosity of the electrodeposition film forming solution increases. As the neutralization rate of the polymer decreases, the number of ionized acidic functional groups decreases, so that the polymer molecules hardly spread, the interaction decreases, and the viscosity of the electrodeposition film forming solution decreases. On the other hand, when the neutralization rate of the polymer is less than the predetermined value in the graph, the polymer changes from a dissolved state to a precipitated state as the neutralization rate of the polymer decreases. For this reason, the viscosity of the electrodeposition film forming liquid increases as the neutralization rate of the polymer decreases. Therefore, in the graph, when the neutralization ratio of the polymer is the above-mentioned predetermined value, the viscosity of the electrodeposition film forming liquid is minimized.

In the graph, when the neutralization rate of the polymer is less than the predetermined value, the neutralization rate of the polymer decreases, and
With the precipitation of the polymer, the particle diameter of the fine particles in the electrodeposition film forming liquid increases.

In the present invention, the electrodeposition film-forming liquid 2
The predetermined value at which the viscosity at 5 ° C. becomes minimum is referred to as a solidification neutralization ratio (X (%)) (hereinafter sometimes simply referred to as “X (%)”).

When an electrodeposited film is formed by an electrodeposition method using the electrodeposited film forming solution, a deposited film is formed by a change from a dissolved state of the polymer in the electrodeposited film forming solution to a precipitated state. At this time, hydrogen ions are generated on the electrode surface by the electrolysis of water represented by the following chemical formula (3), and the generated hydrogen ions reduce the neutralization ratio of the polymer as shown by the following chemical formula (4). It is considered that the deposited film is formed by changing the thickness.

Chemical formula (3) H ₂ O → 1 / 2O ₂ + 2H ⁺ + 2e ⁻

Chemical formula (4)

Embedded image

The neutralization rate of the polymer is X to (X + 3
0) It needs to be%. If the neutralization rate of the polymer is less than X%, the polymer is precipitated as described above, and the particle diameter of fine particles and the like contained in the electrodeposition film forming solution is increased as described above, and the uniformity is reduced. No electrodeposition film is formed. On the other hand, the neutralization rate of the polymer is (X + 30)
%, It is difficult to form an electrodeposited film, and the electrodeposited film once formed is dissolved.

The “precipitation of the polymer” can be confirmed by measuring the turbidity of the electrodeposition film forming solution. The turbidity is preferably 100 degrees or less, more preferably 75 degrees or less. If the turbidity exceeds 100 degrees, the polymer is excessively precipitated in the electrodeposition film forming solution, and the quality of the electrodeposited film formed may be poor. here,
The term “turbidity” refers to the transmission turbidity, which is a measure of the degree of turbidity of water, and indicates the intensity of transmitted light having a wavelength of about 660 nm that has passed through a sample and the same transmission that has passed through a formazin standard solution. It can be determined by comparing with the light intensity. However, in the case of the electrodeposition film forming liquid, when there is a dispersion, such as fine particles, which absorbs and scatters light and affects turbidity, the turbidity is measured in the electrodeposition film forming liquid. This is a value measured without the dispersion.

-Constitution of Polymer- The composition of the polymer is a copolymer having an acidic functional group and having a minimum value of the viscosity of the electrodeposition film forming liquid as the neutralization rate of the polymer changes. There is no particular limitation, and examples include a block copolymer, a random copolymer, and a graft copolymer. These copolymers may be used alone or in combination of two or more.

Examples of the acidic functional group include a carboxyl group, a sulfone group, a sulfate group, a phosphate group, and the like. Among them, a carboxyl group is particularly preferred from the viewpoint of electrodeposition film deposition. . Therefore, as the constitution of the polymer, a copolymer having at least one of a constituent part derived from acrylic acid and a constituent part derived from methacrylic acid having a carboxyl group is particularly preferable. In the present invention, the term "acrylic acid-derived constituent site" refers to a constituent portion of a polymer derived from acrylic acid in a polymer obtained by copolymerizing acrylic acid as a copolymerizable monomer, and a "methacrylic acid-derived constituent site". The term "site" refers to a component of a polymer derived from methacrylic acid in a polymer obtained by copolymerizing methacrylic acid as a copolymer monomer.

The constitution of the polymer may include at least one of the above-mentioned constituent parts derived from acrylic acid and methacrylic acid, as well as constituent parts derived from other monomers.

Examples of the other monomer having no acidic functional group include olefin compounds such as ethylene and butadiene; styrene, methylstyrene, ethylstyrene, butylstyrene, methoxystyrene, phenylstyrene, chlorostyrene and the like. Styrene compounds of methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, octyl methacrylate, lauryl methacrylate, benzyl methacrylate, hydroxy methacrylate Ethyl, isobonyl acrylonitrile methacrylate, vinyl acetate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, hexyl acrylate, Cyclohexyl acrylic acid, octyl acrylate, lauryl acrylate, cetyl acrylate, stearyl acrylate, benzyl acrylate, isobornyl acrylate, carboxylic acid ester compounds such as acrylamide; and derivatives thereof. Among these, styrene, butyl methacrylate, and methacrylic acid 2- in terms of electrodeposition property, dispersibility of contained fine particles and film-forming property.
Ethylhexyl is preferred. The other monomer is
One type may be used alone, or two or more types may be used in combination.

The polymer further has a heat-crosslinkable functional group. The thermally crosslinkable functional group refers to a functional group capable of forming a three-dimensional network structure in the polymer by a heat treatment, whereby a chemical reaction occurs between the acidic functional group present in the polymer and a hydroxyl group, Examples include a methylol group, a glycidyl group, an aziridinyl group, an oxazoline group, a carbodiimide group, an isocyanate group, and a block isocyanate group. Among these, it is particularly preferable that a constituent part (structural unit) having a block isocyanate group represented by the following chemical formula (5) is present in the polymer from the viewpoint of electrodeposition properties, liquid storage stability, and pigment dispersibility.

Chemical formula (1)

Embedded image (Where R ₁ represents hydrogen or a methyl group; R ₂ , R ₃
Each independently represents an alkyl group having 1 to 6 carbon atoms or an aralkyl group, and n represents a positive integer. )

MOI-BM (manufactured by Showa Denko KK) can also be used as one of the monomers for forming the above constituent parts.

-Polymer Molecular Weight- The molecular weight of the polymer is from 1.0 × 10 ^{3 to} 1.0 × 10 ^{5 in} terms of number average molecular weight from the viewpoint of the film properties of the electrodeposited film.
Is preferably 5.0 × 10 ^{3 to} 5.0 × 10 ⁴ . When the number average molecular weight is less than 1.0 × 10 ³ , the electrodeposited film becomes non-uniform, and as a result, the water resistance is reduced. As a result, cracks occur in the electrodeposited film, or the electrodeposited film is powdered, May be poor in robustness. On the other hand, the number average molecular weight is
If it exceeds 1.0 × 10 ⁵ , the affinity of the electrodeposition film-forming solution with the aqueous solvent decreases, and precipitation occurs, or the viscosity of the electrodeposition film-forming solution becomes too high, and the electrodeposition film becomes uneven. It may be.

—Acid Value of Polymer— The acid value of the polymer is preferably from 100 to 160, more preferably from 110 to 150. The acid value is 10
If it is less than 0, the solubility of the polymer in water is low,
While the quality of the electrodeposited film to be formed may be inferior, when it exceeds 160, the solubility of the polymer in water becomes too high, and the minimum value of the viscosity of the electrodeposited film forming liquid may become unclear.
As a method for measuring the acid value of the polymer, a known method can be used. For example, the acid value can be determined by a method according to JIS K0070.

-Polymer Content- The content of the polymer in the electrodeposition film forming solution is preferably 0.5 to 30% by weight, and 1 to 15% by weight.
Is more preferable, and 3 to 10% by weight is further preferable. When the content is less than 0.5% by weight, the deposited film may not be sufficiently deposited. On the other hand, when the content is more than 30% by weight, the viscosity of the electrodeposition film forming solution is too high or the deposited film is not formed. In some cases, the amount of the polymer that does not contribute to the deposition increases, and the cost required for forming the deposited film increases.

-Basic Compound- Examples of the basic compound include an inorganic basic compound and an organic basic compound. Specifically, inorganic basic compounds such as sodium hydroxide, potassium hydroxide, lithium hydroxide and ammonia; organic basic compounds such as tetramethylammonium hydroxide and tetraethylammonium hydroxide; and other basic trimethylamine and diethylamine And alkylamines such as triethylamine, tripropylamine and tributylamine; and alkanolamines such as monoethanolamine, methylethanolamine, diethanolamine, diisopropanolamine, triethanolamine, dimethylaminoethanol and morpholine. These basic compounds may be used alone or in combination of two or more. In addition, the content of the basic compound in the electrodeposition film-forming liquid is, as described above in the section of “Polymerization Neutralization Rate”, that the neutralization rate of the polymer is X to (X
The value is appropriately set so as to be adjusted within the numerical range of +30)%.

-Water- As the water, distilled water, ion-exchanged water, pure water, and
Ultrapure water and the like can be mentioned.

-Other components- As the other components, for example, fine particles, acidic compounds, compounds having various buffering actions, electric conductivity adjusters,
Examples include low molecular surfactants, organic solvents, solubilizers, physical property modifiers, clathrate compounds, fungicides, and the like.

Examples of the fine particles include resin fine particles and inorganic fine particles. The resin fine particles are obtained by forming a polymer material into fine particles by a polymer polymerization method such as emulsion polymerization, suspension polymerization, or seed polymerization, a suspension aggregation method, or a method of melting a pulverized resin with hot air.

As the polymer material, for example, polyethylene, polypropylene, polystyrene, ABS resin,
Polymethyl methacrylate, polyisoprene, ethylene propylene rubber, butyl rubber, nitrile rubber, acrylic rubber, silicone rubber, fluoro rubber, nylon, polycarbonate, polyamide, polyethylene terephthalate, polybutylene terephthalate, polyphenyl sulfide, polysulfone, polyether sulfone, Polyetheretherketone, polyarylate, polyimide,
Polyamide imide, polyurethane, urea resin, phenol resin, melamine resin, polyacetal, acrylic resin, acrylic silicone resin, fluorine resin, polyester resin, vinyl acetate resin, vinyl chloride resin, styrene-butadiene polymer resin, Polyurethane resin, polystyrene resin, epoxy resin,
Examples include polyamide-based resins, silicone-based resins, and vinyl acetate-based resins.

Examples of the inorganic fine particles include oxides such as aluminum oxide, tin oxide, silicon oxide and molybdenum oxide; nitrides such as silicon nitride and titanium nitride; silicon carbide;
Examples include carbides such as tungsten carbide, and fine particles such as clay, talc, and mica. These can be formed into fine particles by a method of oxidizing, nitriding, or carbonizing a metal vapor in a gas phase, or a method such as submerged electric discharge, spray drying, and pulverization.

The resin fine particles and the inorganic fine particles may be used alone or in combination of two or more. Further, the resin fine particles and the inorganic fine particles may be obtained in a powder state in a gas phase, or may be obtained in a state of being dispersed in an aqueous continuous phase.

The particle diameter (volume average particle diameter) of the fine particles in the electrodeposition film forming solution is 0.001 to 5 μm.
m is preferable, and 0.01 μm to 3 μm is more preferable.
When the particle diameter is less than 0.001 μm, the amount of the dispersant required for dispersing the fine particles may be excessive. On the other hand, when the particle diameter is more than 5 μm, aggregation or sedimentation in the electrodeposition film forming liquid may occur. May occur.

The content of the fine particles in the electrodeposition film forming solution is preferably 30% by weight or less, more preferably 10% by weight or less. When the content exceeds 30% by weight, the viscosity of the electrodeposition film forming liquid may increase.

The acidic compound can be added for the purpose of adjusting the neutralization rate of the polymer. Hydrochloric acid, sulfuric acid, nitric acid, acetic acid, citric acid, oxalic acid, malonic acid, boric acid, phosphoric acid,
Phosphorous acid and the like. Examples of the compound having a buffering action include hydrochloride, phosphate, oxalate, amine salt,
Ammonium salts and the like.

The electric conductivity adjusting agent is an ionic dissociable salt that can be contained for the purpose of increasing the electrodeposition rate and the like. Specific examples of the ion include ammonium ion, sodium ion, Examples include potassium ion, organic cation ion, chloride ion, nitrate ion, sulfate ion, phosphate ion, perchlorate ion and the like.

The low molecular surfactant can be added for the purpose of stabilizing the dispersion state of the fine particles, and may be any of nonionic, anionic, cationic and amphoteric surfactants.

Examples of the nonionic surfactant include polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene dodecyl phenyl ether, polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, Polyoxyethylene sorbitan fatty acid esters and fatty acid alkylolamides are exemplified.

Examples of the anionic surfactant include alkyl benzene sulfonate, alkyl phenyl sulfonate, alkyl naphthalene sulfonate, higher fatty acid salt,
Sulfate of higher fatty acid ester, sulfonate of higher fatty acid ester, sulfate and sulfonate of higher alcohol ether, higher alkyl sulfosuccinate and the like.

Examples of the cationic surfactant include primary to tertiary amine salts and quaternary ammonium salts.

As the amphoteric surfactant, betaine,
Sulfobetaine, sulfate betaine, and the like.

The content of these low molecular surfactants in the electrodeposition film forming solution is preferably 10% by weight or less, more preferably 5% by weight or less, so as not to impair the electrodeposition properties.

The organic solvent is not particularly limited as long as it has an affinity for water and does not impair the effects of the present invention.
For example, monoalcohols such as methanol, ethanol, propanol and butanol; ethylene glycol, diethylene glycol, propylene glycol, polyethylene glycol, triethylene glycol, glycerin, trimethylolpropane, 1,2,6-hexanetriol, 1,5-pentane Polyhydric alcohols such as diols and dipropylene glycol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether , Triethylene glycol mo Glycol ethers such as butyl ether; ketones such as acetone, methyl ethyl ketone, methyl butyl ketone, cyclohexanone, and isophorone; ethers such as diethyl ether, methyl ethyl ether, dibutyl ether, dioxane, and tetrahydrofuran; thiodiethanol, 2-mercaptoethanol, and thiol Sulfur-containing solvents such as glycerol, sulfolane, and dimethyl sulfoxide; 2-pyrrolidone, N-methyl-
Nitrogen-containing solvents such as 2-pyrrolidone, cyclohexylpyrrolidone, triethanolamine and diethanolamine; and the like. These organic solvents may be used alone or in combination of two or more.

The content of the organic solvent in the electrodeposition film forming solution is preferably 60% by weight or less, more preferably 40% by weight or less. When the content is increased, the viscosity of the electrodeposition film forming solution is too high, or the film properties of the obtained deposited film may be deteriorated, or a problem that the deposited film to be deposited may be dissolved may occur. .

Examples of the solubilizer include urea and acetamide. Examples of the physical property modifier include polyethyleneimine, polyamines, polyvinylpyrrolidone, polyethylene glycol, and cellulose derivatives. Examples of the clathrate include cyclodextrin, macrocyclic amines, crown ethers and the like.

<Method for Preparing Electrodeposition Film Forming Solution> A method for preparing the electrodeposition film forming solution of the present invention will be described below, but the present invention is not limited thereto.

First, a monomer-containing liquid containing at least a monomer having an acidic functional group and a monomer having a thermally crosslinkable functional group is heated at 40 to 100 ° C. in a nitrogen atmosphere or an inert gas atmosphere such as argon. 3 to 24 hours,
The reaction is carried out with stirring in the presence of a polymerization initiator. This reaction may be carried out in an organic solvent or may be carried out by suspending in water. Thereafter, purification is performed to prepare a polymer.

The content of the monomer having an acidic functional group in the monomer-containing liquid is 10 to 10
60 mol% is preferable, and 15 to 50 mol% is more preferable. The content of the monomer having a thermally crosslinkable functional group in the monomer-containing liquid is determined by the balance between electrodeposition characteristics and solvent resistance.
ol% is preferable, and 6 to 40 mol% is more preferable.
If it is less than 4 mol%, sufficient solvent resistance may not be obtained, and if it exceeds 60 mol%, sufficient electrodeposition properties may not be obtained. In addition, when a polymerization initiator is added, the content of the polymerization initiator in the above-mentioned liquid is (all monomers +
0.1 to 10 mol% is preferable with respect to the polymerization initiator).

The polymer obtained as described above, water, and a basic compound are weighed so as to obtain a desired polymer neutralization ratio, and sufficiently mixed and dissolved. Thereafter, coarse particles and dust are removed by filtration or the like to prepare a polymer solution (electrodeposition film forming solution).

For the mixing and dissolution, a magnetic stirrer, a homogenizer, an ultrasonic homogenizer, a ball mill, a paint shaker and the like are appropriately used. These may be used alone or in combination of two or more. During the mixing and dissolving, the electrodeposition film forming liquid may be heated as desired. However, the heating temperature is preferably a temperature at which the components of the electrodeposition film forming solution are not decomposed.

For filtration, a membrane filter or the like is appropriately used, and the filtration can be performed by pressure filtration, suction filtration, or the like.
The membrane filter is preferably made of a hydrophilic material, and has an appropriate pore size in the range of 0.1 to 20 μm.

<Physical Properties of Electrodeposition Film Forming Solution> The viscosity of the electrodeposition film forming solution at 25 ° C. is 1 to 500 mPa · s.
Is preferable, and 1 to 100 mPa · s is more preferable. If the viscosity exceeds 500 mPa · s, the uniformity of the electrodeposited film may be impaired.

The electric conductivity of the electrodeposition film forming liquid is as follows.
1-50 mS / cm is preferable, and 3-12 mS / cm is more preferable. When the electric conductivity is less than 1 mS / cm, the components of the electrodeposition film-forming liquid may not be sufficiently added. On the other hand, when the electric conductivity exceeds 50 mS / cm, the viscosity of the electrodeposition film-forming liquid may be too high. In some cases, the electrodeposition film forming solution may gel. In addition, the electric conductivity of the electrodeposition film forming liquid is suitably adjusted by adding the electric conductivity adjusting agent described above.

According to the electrodeposition film forming solution of the present invention, an electrodeposition film having low energy, uniformity, and excellent solvent resistance can be formed.

[Method of Forming Electrodeposited Film] In the method of forming an electrodeposited film of the present invention, an electrodeposited film is finally formed on the surface of a conductive substrate using the electrodeposited film forming liquid of the present invention by an electrodeposition method. How to In the method for forming an electrodeposited film of the present invention, a potential is generated between electrodes, an electrodeposited material is electrochemically deposited on a conductive substrate surface, a deposited film is formed, and the obtained deposited film is subjected to heat treatment. There is no particular limitation as long as it is a method for forming an electrodeposited film by applying a low voltage between electrodes to form an electrodeposited film. Examples include “photoelectrodeposition” in which an electrodeposition film is formed using a film.

The potential between the electrodes is preferably 10 V or less, more preferably 5 V or less. The potential is 10
If the voltage exceeds V, bubbles may be generated due to hydrogen gas at the time of energization, and the formed electrodeposition film may be uneven.

-Low-potential electrodeposition- In the case of the "low-potential electrodeposition", the method for forming an electrodeposition film of the present invention includes at least a step of bringing a conductive substrate into contact with the electrodeposition film forming liquid (hereinafter, referred to as " A contact step), and a step of electrochemically depositing a polymer in an electrodeposition film forming solution on the conductive substrate surface to selectively form a deposited film (hereinafter, referred to as a “deposited film”). A forming step), a step of cleaning an excessive electrodeposition film forming solution adhering to the formed deposited film (hereinafter, sometimes referred to as a “cleaning step”), and a step of cleaning the obtained deposited film. Heat treatment to cause a cross-linking reaction in the polymer to form an electrodeposited film (hereinafter referred to as
"Heat treatment step").

--Contacting Step-- The contacting step is a step of bringing the conductive substrate into contact with an electrodeposition film forming liquid. The method for bringing the conductive substrate into contact with the electrodeposition film forming liquid is not particularly limited.For example, the entire conductive substrate may be immersed in the electrodeposition film forming liquid, and a part of the conductive substrate may be It may be brought into contact with an electrodeposition film forming liquid.

--Deposited film forming step-- In the deposited film forming step, after the contacting step, a voltage is applied, hydrogen ions are generated by electrolysis of water, and the polymer in the electrodeposited film forming liquid is deposited. This is a step of electrochemically forming a deposited film on the surface of the conductive substrate.

In forming the deposited film, the applied voltage (inter-electrode potential) is preferably 10 V or less, and 4 V or less.
The following is more preferred. The voltage (potential between electrodes) is 10
If it exceeds V, the generation of bubbles due to the electrolysis of water becomes severe, and the uniformity and quality of the finally formed electrodeposited film may be poor.

The current density when the voltage is applied is preferably 0.3 to 50 mA / cm ² , and 0.3 to 1 mA / cm ^2.
0 mA / cm ² is more preferable. The energization time when the voltage is applied is proportional to the intensity of the applied current value,
0.01 second to 1 hour is preferable, and 0.1 second to 10 minutes is more preferable.

--Washing Step-- The washing step is a step of removing, after the deposition film forming step, an excess electrodeposition film forming solution adhering to the deposited film with a washing solution. As the cleaning liquid, it is preferable to use a transparent liquid that is safe and inert to the formed deposited film, and more preferably a cleaning liquid that promotes solidification of the deposited film. As the cleaning solution that promotes solidification of the electrodeposited film, an acidic aqueous solution having a lower pH than a solution in which the neutralization rate of the polymer in the electrodeposition film forming solution is less than the solidification neutralization rate (X%) is used. preferable. By using the cleaning solution, the robustness of the deposited film can be improved.

--Heat Treatment Step-- The heat treatment step is a step of heating the deposited film to cause a cross-linking reaction in the polymer forming the film to form an electrodeposited film. Heating temperature is 120
-220 ° C is preferred, and 140-200 ° C is more preferred. Since sufficient solvent resistance can be obtained even at 220 ° C. or less,
As a substrate material, not only a rigid inorganic material such as glass and metal but also a flexible material such as a heat-resistant polymer film can be used. Therefore, processing can be performed at a high temperature for a short time or at a low temperature for a long time, depending on the substrate material. The heat treatment in the heat treatment step can be performed in air, in an inert gas, or in a vacuum.

FIG. 2 is a schematic diagram illustrating a state during the deposition film forming step by the “low potential electrodeposition”. 2, an electrodeposition film forming apparatus 100 includes an electrodeposition film forming liquid 1.
7, an electrodeposition tank 22 containing the electrode 7, a counter electrode 18,
Potentiostat 19, salt bridge 23, reference electrode 21
And The conductive substrate 15 in which the conductive layer 12 is provided on the surface of the light transmitting substrate 11 has a surface 1 on which a deposited film is formed.
2 ″ is disposed so as to contact the electrodeposition film forming liquid 17. A voltage is applied by the potentiostat 19,
The polymer in the electrodeposition film forming liquid 17 is deposited on the surface of the conductive substrate 15 (the surface 12 ″ on the side where the deposited film is formed) and the deposited film 14 is formed.
Is formed.

-Electrodeposition- The electrodeposition film forming method of the present invention by the photoelectric deposition includes at least a contact step, a deposition film formation step, a cleaning step, and a heat treatment, as in the case of the "low potential electrodeposition". And step are sequentially provided.

FIG. 3 is a diagram showing the structure of a conductive substrate used for the above-mentioned “photoelectrodeposition”. In FIG. 3, the conductive substrate 15 '
Is a light-transmitting conductive layer 1 on the surface of the light-transmitting substrate 11 '.
2 ′ and a light-transmitting semiconductor layer 13 ′ are provided in this order.

--Contacting Step-- The contacting step is a step of bringing the conductive substrate into contact with an electrodeposition film forming liquid in the same manner as described in the section of "Low potential electrodeposition".

In the contacting step, the surface of the conductive substrate on which the electrodeposited film is formed comes into contact with the electrodeposited film forming solution, and the surface of the conductive substrate on which the deposited film is not formed (ie, the light-transmitting semiconductor layer) Is preferably not in contact with the electrodeposition film forming liquid.

--Deposited Film Forming Step-- In the deposited film forming step, after the contacting step, the conductive substrate is irradiated with light to selectively generate a photoelectromotive force in a light irradiated portion of the semiconductor layer. This is a step of generating hydrogen ions, electrochemically depositing the polymer in the electrodeposition film forming solution, and forming a deposited film on the surface of the conductive substrate.

As a method of forming an image pattern by irradiating the surface of the conductive substrate with light, a photomask and a semiconductor layer surface of the conductive substrate are brought into close contact with each other, and parallel light is irradiated from above the photomask by a known light source. And a method in which a photomask is closely attached to the conductive substrate surface on which the semiconductor layer is not provided, and light irradiation is performed from above the photomask so that irradiation light does not pass through the electrodeposition film forming liquid. . In order to improve the resolution of the image pattern, it is preferable to use a second imaging optical member or a mirror reflecting optical member.
In this case, from the surface of the conductive substrate on which the electrodeposition film is not formed, the second imaging optical member, the mirror reflection optical member, the photomask, the first imaging optical member, and the light source are arranged in this order. Using the device, an image is formed on the photomask from the light source via the first imaging optical member, and the image-patterned light emitted through the photomask is further passed through the second imaging optical member and the mirror reflection optical member. Light can be imaged on the exposed surface.

In forming the deposited film, it is necessary to apply a voltage equal to or higher than a predetermined threshold value. By applying a bias voltage, the deposited film can be controlled by controlling the input voltage level even if the voltage level is small. Can be formed.
The bias voltage is preferably 5 V or less as an inter-electrode potential, more preferably 2 V or less. The potential between the electrodes,
When the voltage exceeds 5 V, the Schottky barrier between the semiconductor layer and the electrodeposition film forming liquid is broken, so that the electrodeposition film may not be formed.

--Washing Step-- The washing step is, as described in the section of "low potential electrodeposition", after the electrodeposition film forming step, an excessive electrodeposition film adhering to the deposited film. This is a step of removing the forming liquid with a cleaning liquid or the like.
The cleaning liquid and the like are the same as those described in the section of “Low potential electrodeposition”.

--- Heat Treatment Step-- In the heat treatment step, as described in the section of "Low potential electrodeposition", the deposited film is formed by heating the deposited film after the cleaning step. This is a step of forming an electrodeposition film by causing a cross-linking reaction in the polymer being formed. The heating temperature and the like are the same as those described in the section of “Low potential electrodeposition”.

FIG. 4 is a schematic structural view for explaining a state during the step of forming an electrodeposition film by the “photoelectrodeposition”. In FIG. 4, an electrodeposition film forming apparatus 200 includes an electrodeposition tank 22 'containing an electrodeposition film forming liquid 17', a counter electrode 18 ', a potentiostat 19', and a salt bridge 23 '. Electrode 2
1 ′ and a light source 16. In FIG. 4, a conductive substrate 15 'in which a light-transmitting conductive layer 12' and a light-transmitting semiconductor layer 13 'are provided in this order on the surface of a light-transmitting substrate 11' forms a deposited film. The surface 13 ″ on the side to be coated (the side on which the semiconductor layer is provided) is arranged to be in contact with the electrodeposition film forming liquid 17 ′. A photomask 20 is in close contact with the conductive substrate 15 ′ on the side where the semiconductor layer 13 ′ is not provided, and parallel light is irradiated from above the photomask 20 by the light source 16, and a portion irradiated with the light is selected. The configuration is such that photovoltaic power is generated. A voltage is applied by the potentiostat 19 ', and the electrodeposition film forming liquid 17'
The polymer therein is deposited on the surface of the conductive substrate 15 ′ (the surface 13 ″ on the side where a deposited film is formed) to form a deposited film 14 ′.

The electrodeposition method as described above mainly comprises an undercoat layer,
It is suitable for forming a rust prevention layer and a dielectric layer.

[0094]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be specifically described below with reference to embodiments. However, the present invention is not limited at all by these examples. The "part" used in the examples
Indicates "parts by weight" unless otherwise specified.

(Synthesis of Polymer A) Toluene (manufactured by Wako Pure Chemical Industries): 2000 parts Methyl ethyl ketone (manufactured by Wako Pure Chemical Industries): 500 parts Styrene (manufactured by Wako Pure Chemical Industries): 420 Part (38 mol% based on all monomers) ・ n-butyl methacrylate (manufactured by Wako Pure Chemical Industries) ・ ・ ・ 370
Acrylic acid (manufactured by Wako Pure Chemical Industries, Ltd.): 220 parts (29 mol% based on all monomers) MOI-BM (manufactured by Showa Denko KK): 200 parts (all monomers) V-601 (manufactured by Wako Pure Chemical Industries, Ltd.): 47 parts (2 mol% based on (all monomers + polymerization initiator))

The composition having the above composition was charged into a 5 liter reactor equipped with a stirrer, a condenser, and a thermometer.
Heated to 65 ° C. under a nitrogen atmosphere. After reacting for 20 hours, purification was performed to obtain “Polymer A”. The molecular weight of “Polymer A” was determined by gel filtration chromatography (GP
C) (LC-10A manufactured by Shimadzu Corporation) was 28,000 in number average molecular weight. Further, the acid value of the polymer was measured with a KOH ethanol solution according to JIS K 0070, and was 132 mgKOH / g.

(Synthesis of Polymers B, C, D and E)
In "Synthesis of polymer A", polymers B to E were synthesized in the same manner as in "Synthesis of polymer A", except that the monomer composition was changed to the composition shown in each section of polymers B to E in Table 1. Molecular weight and acid value. Table 2 shows the results.

(Measurement of Neutralization Ratio for Solidification) For the obtained polymers A to E, a solution having a polymer concentration of 30% by weight was prepared using distilled water, and tetramethylammonium hydroxide (manufactured by Kanto Chemical Co., Ltd.) was prepared. The solution was added to prepare various solutions having different polymer neutralization rates. The viscosity of the obtained solution at 25 ° C. was measured using a B-type viscometer (VS-A1 manufactured by Shibaura System Co., Ltd.).
The solidification neutralization ratio (X) of each of E was determined. Table 2 shows the results.

[0099]

[Table 1]

[0100]

[Table 2]

(Example 1) -Preparation of electrodeposition film forming solution- 100 parts of polymer A25 wt% of tetramethylammonium hydroxide (2.7
N) Aqueous solution (manufactured by Kanto Chemical Co.): 52 partsDistilled water: 2110 parts

The solution having the above composition was stirred and dissolved in a water bath at 80 ° C. using a magnetic stirrer to obtain an electrodeposition film forming solution.

<Calculation of Polymer Neutralization Ratio> For the obtained electrodeposition film forming solution, the molar equivalents of all acidic functional groups in all the polymers were determined by the following formula (3) according to the following formula (3). The molar equivalent of the acidic functional group is derived from the following formula (4),
When the neutralization ratio of the polymer was calculated according to the formula (2), it was 60%.

Equation (3)

(Equation 3)

Equation (4)

(Equation 4) In equation (4), the normality (N) is determined according to JIS K
0211 refers to a value calculated according to 1503 (1997 version).

<Measurement of turbidity of polymer solution> The absorbance of the obtained solution at a wavelength of 660 nm was measured using an absorptiometer (U-3210, manufactured by Hitachi, Ltd.). The turbidity of the polymer solution was determined to be 33.

<Low Potential Electrodeposition> --Formation of Electrodeposited Film-- An ITO film (thickness: 0.1 μm) was formed on a quartz glass substrate (thickness: 0.5 mm) by a sputtering method to form a conductive substrate. Was prepared. Electrodeposition film forming apparatus 1 shown in FIG.
00, the electrodeposition film forming liquid 17 was stored in the electrodeposition tank 22,
The conductive substrate was arranged so that the ITO film was in contact with the liquid surface of the electrodeposition film forming liquid 17. Thereafter, a voltage was applied using the potentiostat 19 so that the potential between the electrodes became a potential difference of +2.4 V, and a deposited film was formed on the surface of the conductive substrate.

Thereafter, the conductive substrate was removed from the electrodeposition film forming apparatus 100, washed sufficiently with a 1 × 10 ⁻² mol / l ammonium chloride solution, further washed with ultrapure water, and washed with an ultrapure water. Dried in a dryer at 5 ° C. for 5 minutes. afterwards,
Heat treatment was performed at 170 ° C. for 30 minutes in air to form an electrodeposited film.

--Evaluation of Electrodeposited Film-- The quality of the obtained electrodeposited film, focusing on the uniformity of the electrodeposited film (roughness of the electrodeposited film), was obtained from an image magnified 40 times with an optical microscope. It was confirmed. The resulting electrodeposited film was uniform and of high quality. When the electrodeposited film was immersed in acetone for 30 minutes, no dissolution or peeling of the film occurred at all, and the film was excellent in solvent resistance.

<Electrodeposition> --Formation of Electrodeposited Film-- An ITO film (thickness: 0.1 μm) was formed on a quartz glass substrate (thickness: 0.5 mm) by a sputtering method, and further, the ITO film surface was formed. TiO2 by sputtering method
After forming _two films (thickness: 0.2 μm), a reduction treatment was performed in a nitrogen gas mixed with 4% hydrogen gas at 360 ° C. for 10 minutes to produce a conductive substrate.

Using the electrodeposition film forming apparatus 200 shown in FIG. 4, an electrodeposition film forming liquid 17 ′ is accommodated in an electrodeposition tank 22 ′, and Ti is deposited.
The O ₂ film was disposed so as to be in contact with the liquid surface of the electrodeposition film forming liquid 17 ′. Thereafter, the photomask 20 is brought into close contact with the surface of the conductive substrate which is not in contact with the electrodeposition film forming solution 17 ', and a mercury xenon lamp (Yamashita Denso: wavelength 365n) is applied from above.
m: Exposure was performed at a light intensity of 50 mW / cm ² ) for 4 seconds. At this time, the TiO ₂ film is +1.7 with respect to the saturated calomel electrode.
A voltage is applied so that a bias potential difference of V
Electrodeposited films were formed only on the light irradiation areas on the _two surfaces. afterwards,
After removing the conductive substrate from the electrodeposition film forming apparatus 200, 1 × 10
After sufficiently washing with a ⁻² mol / l ammonium chloride solution, the substrate was further washed with ultrapure water and dried in a dryer at 70 ° C. for 5 minutes. Then, at 170 ℃ for 30 minutes,
Heat treatment was performed in a nitrogen atmosphere to produce a deposited film.

-Evaluation of Electrodeposited Film- The quality of the obtained deposited film was confirmed in the same manner as in "Evaluation of the electrodeposited film" in the above "Low potential electrodeposition", centering on the sharpness of the edge. The resulting electrodeposited film was of high quality with sharp edges and no deviation. The electrodeposition film is N-
When the film was immersed in methylpyrrolidone for 5 minutes, no dissolution or peeling of the film occurred, and the film was excellent in solvent resistance.

(Example 2) -Preparation of electrodeposition film-forming solution--100 parts of polymer B-25% by weight of tetramethylammonium hydroxide (2.7)
N) Aqueous solution (manufactured by Kanto Chemical Co., Ltd.): 30 parts Distilled water: 1750 parts In "Preparation of polymer solution" in "Example 1," the composition of the solution was changed to the above composition. An electrodeposition film forming solution was prepared in the same manner as in "Example 1", and "calculation of the neutralization rate of the polymer" and "measurement of turbidity" were performed in the same manner as in "Example 1". The neutralization ratio of the polymer was 38%, and the “turbidity” was 47.

-Evaluation of low potential electrodeposition / photoelectrodeposition / electrodeposition film- After performing low potential electrodeposition and photoelectrodeposition in the same manner as "low potential electrodeposition" and "photoelectrodeposition" of "Example 1""Evaluation of electrodeposited film" was performed in the same manner. The electrodeposited film obtained by "low potential electrodeposition" was uniform and of high quality without unevenness.
The electrodeposited film obtained by "photoelectrodeposition" had high quality without sharp edges and no deviation. In addition, when the solvent resistance was evaluated in the same manner as in Example 1, none of the electrodeposited films obtained by “low potential electrodeposition” and “electrodeposition” caused any dissolution or peeling of the film. Excellent solvent properties.

Example 3 Preparation of Electrodeposition Film Forming Solution Polymer 100: 100 parts Tetramethylammonium hydroxide 25 wt% (2.7
N) Aqueous solution (manufactured by Kanto Chemical Co., Ltd.): 40 parts Distilled water: 2125 parts In "Preparation of polymer solution" in "Example 1," the composition of the solution was changed to the above composition. An electrodeposition film forming solution was prepared in the same manner as in "Example 1", and "calculation of the neutralization rate of the polymer" and "measurement of turbidity" were performed in the same manner as in "Example 1". The neutralization ratio of the polymer was 50%, and the “turbidity” was 16.

-Evaluation of low potential electrodeposition / photoelectrodeposition / electrodeposition film- After performing low potential electrodeposition and photoelectrodeposition in the same manner as "low potential electrodeposition" and "photoelectrodeposition" in "Example 1". "Evaluation of electrodeposited film" was performed in the same manner. The electrodeposited film obtained by "low potential electrodeposition" was uniform and of high quality without unevenness.
The electrodeposited film obtained by "photoelectrodeposition" had high quality without sharp edges and no deviation. In addition, when the solvent resistance was evaluated in the same manner as in Example 1, none of the electrodeposited films obtained by “low potential electrodeposition” and “electrodeposition” caused any dissolution or peeling of the film. Excellent solvent properties.

Example 4 Preparation of Electrodeposition Film Forming Solution Preparation of Polymer Solution Polymer D: 100 parts Tetramethylammonium hydroxide 25% by weight (2.7
N) Aqueous solution (manufactured by Kanto Chemical Co., Ltd.): 48 parts Distilled water: 2120 parts In "Preparation of electrodeposition film forming liquid" of "Example 1," the composition of the solution was changed to the above composition. The above polymer solution was prepared in the same manner, and "calculation of the neutralization rate of the polymer" and "measurement of turbidity" were performed in the same manner as in "Example 1". The “polymer neutralization ratio” was 63%, and the “turbidity” was 2. -Preparation of Electrodeposition Film Forming Solution-93.8 parts of the obtained polymer solution, 5.8 parts of silicon oxide fine particles (volume average particle diameter: 14 nm) (manufactured by Nippon Aerosil Co., Ltd.), and sodium chloride ( (A product of Wako Pure Chemical Industries, Ltd.) and a ball mill using zirconia beads for 72 hours, and then pressurized and filtered through a membrane filter having a pore size of 0.45 μm to obtain an electrodeposition film forming solution. Prepared.

-Evaluation of low potential electrodeposition / photoelectrodeposition / electrodeposition film- After performing low potential electrodeposition and photoelectrodeposition in the same manner as in "low potential electrodeposition" and "photoelectrodeposition" of "Example 1". "Evaluation of electrodeposited film" was performed in the same manner. The electrodeposited film obtained by "low potential electrodeposition" was uniform and of high quality without unevenness.
The electrodeposited film obtained by "photoelectrodeposition" had high quality without sharp edges and no deviation. In addition, when the solvent resistance was evaluated in the same manner as in Example 1, none of the electrodeposited films obtained by “low potential electrodeposition” and “electrodeposition” caused any dissolution or peeling of the film. Excellent solvent properties.

(Comparative Example 1) -Preparation of electrodeposition film forming solution--Polymer A ... 100 parts-Tetramethylammonium hydroxide 25 wt% (2.7
N) Aqueous solution (manufactured by Kanto Chemical Co., Ltd.): 65 parts ・ Sodium chloride (manufactured by Wako Pure Chemical Industries): 10 parts ・ Distilled water: 2030 parts In “Preparation of polymer solution” in “Example 1” A polymer solution was prepared in the same manner as in "Example 1" except that the composition of the solution was changed to the above composition, and "calculation of the neutralization ratio of the polymer" and "turbidity" were performed in the same manner as in "Example 1." Measurement ". The neutralization ratio of the polymer was 75%, and the “turbidity” was 9.

-Evaluation of Low Potential Electrodeposition / Photodeposition / Electrodeposition Film- Low potential electrodeposition and photodeposition were performed in the same manner as in "Low potential electrodeposition" and "photodeposition" of "Example 1". In "low potential electrodeposition", no electrodeposition was performed and no electrodeposition film was formed. Similarly, the electrodeposition film was not formed in “photoelectrodeposition”.

Comparative Example 2 Preparation of Electrodeposition Film Forming Solution Polymer 100: 100 parts Tetramethylammonium hydroxide 25 wt% (2.7
N) Aqueous solution (manufactured by Kanto Chemical Co., Ltd.): 25 parts Distilled water: 1755 parts In "Preparation of polymer solution" in "Example 1," the composition of the solution was changed to the above composition. A polymer solution was prepared in the same manner as in "Example 1", and "calculation of the neutralization rate of the polymer" and "measurement of turbidity" were performed in the same manner as in "Example 1". The neutralization ratio of the polymer was 28%, and the “turbidity” was 168.

-Evaluation of Low Potential Electrodeposition / Photodeposition / Electrodeposition Film- Low potential electrodeposition and photodeposition were performed in the same manner as in "Low potential electrodeposition" and "photodeposition" of "Example 1". In the “low potential electrodeposition”, the obtained electrodeposited film was nonuniform and of low quality. In the case of “photo-electrodeposition”, the obtained electrodeposited film was of low quality with conspicuous unevenness with no clear edge.

(Comparative Example 3)-Preparation of electrodeposition film forming solution-Polymer C ... 100 parts-Tetramethylammonium hydroxide 25 wt% (2.7
N) Aqueous solution (manufactured by Kanto Chemical Co., Ltd.): 48 parts Distilled water: 2120 parts In "Preparation of polymer solution" of "Example 1," the composition of the solution was changed to the above composition. A polymer solution was prepared in the same manner as in "Example 1", and "calculation of the neutralization rate of the polymer" and "measurement of turbidity" were performed in the same manner as in "Example 1". The “polymer neutralization ratio” was 65%, and the “turbidity” was 6.

-Evaluation of Low Potential Electrodeposition / Photodeposition / Electrodeposition Film- Low potential electrodeposition and photodeposition were carried out in the same manner as in "Low potential electrodeposition" and "photodeposition" of "Example 1". In "low potential electrodeposition", it was observed that an electrodeposited film was formed immediately after the application of electricity, but the film was dissolved during cleaning and the film was peeled off, so that the electrodeposited film was not finally formed. In "photoelectric deposition",
Immediately after energization, it appeared that an electrodeposited film was formed, but it was dissolved during washing and the film was peeled off, leaving a slight deposit partially, but no electrodeposited film was formed .

Comparative Example 4 Preparation of Electrodeposition Film Forming Solution Preparation of Polymer Solution Polymer 100: 100 parts Tetramethylammonium hydroxide 25% by weight (2.7)
N) Aqueous solution (manufactured by Kanto Chemical Co., Ltd.): 46 parts Distilled water: 2120 parts In “Preparation of electrodeposition film forming liquid” in “Example 1,” the composition of the solution was changed to the above composition. The above polymer solution was prepared in the same manner, and "calculation of the neutralization rate of the polymer" and "measurement of turbidity" were performed in the same manner as in "Example 1". The “polymer neutralization ratio” was 62%, and the “turbidity” was 2. --Preparation of Electrodeposition Film Forming Solution-- 93.8 parts of the obtained polymer solution, 5.8 parts of silicon oxide (volume average particle diameter: 14 nm) (manufactured by Nippon Aerosil Co., Ltd.), and sodium chloride (sum) 0.4 of Kojun Pharmaceutical)
And a composition composed of the above-mentioned components and a zirconia bead were dispersed in a ball mill for 72 hours, followed by pressure and filtration through a membrane filter having a pore size of 0.45 μm to prepare an electrodeposition film forming solution.

-Evaluation of low potential electrodeposition / photoelectrodeposition / electrodeposition film- Low potential electrodeposition and photoelectrodeposition were performed in the same manner as in "low potential electrodeposition" and "photoelectrodeposition" of "Example 1". The electrodeposited film obtained by "low potential electrodeposition" was uniform and of high quality without unevenness. The electrodeposited film obtained by "photoelectrodeposition" had high quality without sharp edges and no deviation. However, the solvent resistance was evaluated in the same manner as in Example 1 (“low potential electrodeposition”).
In the case of (1), the immersion test with acetone for 30 minutes, and in the case of "photoelectrodeposition", the immersion test with N-methylpyrrolidone for 30 minutes), all the electrodeposited films were dissolved, and the solvent resistance was poor. . Examples 1 to 4 and Comparative Example 1
Tables 3 and 4 show the results.

[0127]

[Table 3]

In Table 3, in the evaluation of low potential electrodeposition and photoelectric deposition, “着” indicates that a high quality electrodeposited film was formed, and “△” indicates that the electrodeposited film was formed. “×” indicates that the electrodeposition film was not formed, that is, the electrodeposition film was not formed.

According to Table 3, in "Example 1", the neutralization ratio (60%) of the polymer falls within the numerical range of X to (X + 30)% (35 to 65%). It can be seen that the electrodeposition film was formed. On the other hand, in Comparative Example 1 in which the neutralization ratio of the polymer (75%) exceeds the above numerical range, no electrodeposition film was formed.

In Example 2, the neutralization rate of the polymer (3
8%) is in the numerical range (30 to 60) of X to (X + 30)%.
%), Which indicates that a good electrodeposited film was formed by electrodeposition. In comparison, the neutralization rate of the polymer (28
%) Is less than the above numerical range, the obtained electrodeposited film is of low quality.

In “Example 3,” the neutralization ratio of the polymer (5
0%) is in the numerical range (32 to 62) of X to (X + 30)%.
%), Which indicates that a good electrodeposited film was formed by electrodeposition. In comparison, the neutralization rate of the polymer (65
%) Exceeds the above numerical range, no electrodeposition film is formed.

In Example 4, the neutralization rate of the polymer (6
4%) is in the numerical range (36 to 66) of X to (X + 30)%.
%), Which indicates that a good electrodeposited film was formed by electrodeposition. In Example 4, rutile-type titanium oxide fine particles were included in the electrodeposited film, but a good electrodeposited film was formed as in the other examples. On the other hand, in Comparative Example 4, the neutralization ratio was substantially the same as that of Example 4, and the solidification neutralization ratio X〜
Since it was within the numerical range (35 to 65%) of (X + 30)%, an electrodepositable and good electrodeposition film was formed, but the polymer E contained a thermally crosslinkable component (MOI-BM). However, the solvent resistance of the electrodeposited film after the heat treatment was inferior.

As described above, according to the electrodeposition film forming solution of the present invention described in the examples, an electrodeposition film having good electrodeposition properties, high quality and excellent solvent resistance can be obtained. Further, even when the electrodeposition film is manufactured by patterning using a photomask, an electrodeposition film having good electrodeposition properties, sharp edges, high quality, and excellent solvent resistance can be obtained.

[0134]

As described above, according to the present invention, an electrodeposition film forming solution capable of stably forming an electrodeposited film with a low energy and a uniform surface, and the use of the electrodeposition film forming solution, It is possible to provide a method for forming a high-quality electrodeposited film having no generation and having excellent solvent resistance. Furthermore, the method for forming an electrodeposited film of the present invention can provide a low-cost and stable method for forming an electrodeposited film that can be patterned without a photolithography step.

[Brief description of the drawings]

FIG. 1 is a graph showing the relationship between the neutralization ratio (%) of a polymer in an electrodeposition film forming solution and the viscosity (25 ° C.) of the electrodeposition film forming solution, and the neutralization ratio (%) of the polymer. FIG. 6 is a graph showing a relationship between the particle diameter (volume average particle diameter) of the fine particles when the fine particles (silicon oxide) are contained in the electrodeposition film forming liquid.

FIG. 2 is a schematic configuration diagram of an electrodeposition film forming apparatus for forming an electrodeposition film by low potential electrodeposition.

FIG. 3 is a configuration diagram of a conductive substrate used for photoelectric deposition.

FIG. 4 is a schematic configuration diagram of an electrodeposition film forming apparatus for forming an electrodeposition film by a photoelectric deposition method.

[Explanation of symbols]

 11, 11 ': light-transmitting substrate 12, 12': conductive layer 12 '': surface on which a deposited film is formed 13 ': semiconductor layer 13' ': surface on which a deposited film is formed 14, 14': Electrodeposition film 15, 15 ': conductive substrate 16: light source 17, 17': electrodeposition film forming liquid 18, 18 ': counter electrode 19, 19': potentiostat 20: photomask 21, 21 ': reference electrode 22, 22 ': electrodeposition tank 23, 23': salt bridge 100, 200: electrodeposition film forming apparatus

 ──────────────────────────────────────────────────の Continued on the front page (72) Inventor Satoshi Hiraoka 1600 Takematsu, Minamiashigara-shi, Kanagawa Prefecture Inside Fuji Xerox Co., Ltd. (72) Inventor Eiichi Akutsu 430 Green Tech Nakai, Nakai-cho, Ashigara-gun, Kanagawa Prefecture F-term in Fuji Xerox Co., Ltd. GA07 GA09 GA11 GA12 HA176 HA316 JB01 JB03 JB09 JB39 KA02 MA08 MA10 MA14 NA04 NA11 PA04 PA19

Claims (7)

[Claims] 1. An electrodeposition film forming liquid containing at least a polymer having an acidic functional group, a basic compound, and water, wherein the polymer further has a thermally crosslinkable functional group, and ,
The neutralization rate of the polymer is X to (X + 30)% (where X is the neutralization rate of the polymer when the viscosity of the electrodeposition film forming liquid is minimum at 25 ° C. (solidification neutralization rate) The electrodeposited film forming liquid is characterized in that: 2. The electrodeposition film forming liquid according to claim 1, wherein the polymer has a constituent part having a thermally crosslinkable functional group and represented by the following chemical formula (1). Chemical formula (1) (Where R ₁ represents hydrogen or a methyl group; R ₂ , R ₃
Each independently represents an alkyl group having 1 to 6 carbon atoms or an aralkyl group, and n represents a positive integer. ) 3. The electrodeposition film forming liquid according to claim 1, wherein the turbidity of the electrodeposition film forming liquid is 100 degrees or less. 4. The polymer according to claim 1, wherein the polymer contains a constituent part derived from acrylic acid and / or a constituent part derived from methacrylic acid as a copolymer component, and the polymer has an acid value of 100 to 160. Electrodeposition film forming liquid. 5. An electrodeposition film by using the electrodeposition film forming liquid according to claim 1 to form a deposition film on the surface of a conductive substrate by an electrodeposition method, and then performing a heat treatment. Forming an electrodeposition film. 6. The method for forming an electrodeposited film according to claim 5, wherein a potential between electrodes when forming an electrodeposited film by the electrodeposition method is 10 V or less. 7. The temperature of the heat treatment is set to 120 to 220.
The method for forming an electrodeposited film according to claim 5 or 6, wherein the temperature is set to ° C.