JP3274154B2 - Cationic functional group-containing polysiloxane resin composition, coating composition using the same, and method for producing cationic functional group-containing polysiloxane resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cationic functional group-containing polysiloxane resin composition used as a heat-resistant cationic electrodeposition coating composition, a coating composition using the same, and a cationic functional group-containing polysiloxane resin composition. It relates to a manufacturing method.

[0002]

2. Description of the Related Art Heat-resistant paints are intended to prevent corrosion due to high-temperature oxidation of places where heat is used in chemical plants, refineries, power plants, automobile engines, aircraft, electric and electronic equipment, and the like. For electric and electronic devices, heat-resistant polymers having excellent electrical insulation, mechanical strength, chemical properties, dimensional stability, and the like are used as heat-resistant insulating paints. As typical heat-resistant insulating paints, silicone-based heat-resistant paints are often used. Most of these paints are of a solvent type, and the coating method is brush coating, spray coating, dip coating, roll coating, spin coating and the like.

[0003]

The above-mentioned coating methods such as brush coating have a problem that the uniformity, smoothness and edge covering property of the coating film are limited. Further, since the paint is of a solvent type, there is a problem in workability such as working environment and fire safety.

Heretofore, for the water-solubilization of organosilicone resins and silicone-modified resins, a method of dispersing them with a surfactant has been used. However, there is a problem that due to the effect of the surfactant, good coating film performance cannot be obtained, and a coating film having good uniformity, smoothness and transparency of the coating film cannot be obtained.

An example of an aqueous organosilicon-based composition in which an amino group has been introduced into polysiloxane is disclosed in JP-A-2-311581, but it is a low condensate and has no ability to form a coating film even by electrodeposition coating. It is not in line with the object of the present invention.

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems, to be excellent in various coating properties such as heat resistance, chemical resistance and water resistance, and to have a smooth surface, excellent gloss and transparency, and An object of the present invention is to provide a cationic functional group-containing polysiloxane resin composition which is safe and has high working efficiency, a coating composition using the same, and a method for producing a cationic functional group-containing polysiloxane resin composition.

[0007]

According to the present invention, at least one of the organosilicon compounds represented by the formula (1) or (2) is provided.
A component a comprising

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Embedded image (In formulas 1 and 2, R3 is an organic group having 1 to 18 carbon atoms, R4 is an organic group having 1 to 5 carbon atoms, R5 is a methyl group and a phenyl group, and R6 is a methyl group and an ethyl group. Represents.)

A component b comprising at least one kind of an organosilicon compound represented by the formula (3) or (4),

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Embedded image (In Formulas 3 and 4, R7 is an organic group having 1 to 18 carbon atoms, R8 is an organic group having 1 to 5 carbon atoms, and R9 is a methyl group or a phenyl group.)

A cationic organosilicon compound represented by the formula (5), wherein one or two of a cationic organosilicon compound c1 in which n is 0 and a cationic organosilicon compound c2 in which n is 1; In the cationic functional group-containing polysiloxane resin composition containing the component c comprising the above combination,

Embedded image (In formula 5, R1 is an organic group having 1 to 8 carbon atoms, R2 is an organic group having 1 to 5 carbon atoms, X is an organic group having 1 to 8 carbon atoms, K is an amino group, An aminoalkyl group or a diaminoalkyl group, wherein n represents an integer of 0 or 1.) Component a is added in an amount of 10 to 10 moles of components a, b and c.
A cationic functional group-containing polysiloxane resin composition comprising 80 mol%, 10 to 50 mol% of component b, and 10 to 30 mol% of component c.

[0010] The present invention also provides a cationic functional group-containing polysiloxane resin composition according to claim 1 and an acid for neutralizing the amine of the component c in the cationic functional group-containing polysiloxane resin composition. And pure water, wherein the acid is present in an amount of 0.7 to 1.4 with respect to the amine of the component c in the cationic functional group-containing polysiloxane resin composition.
The equivalent weight and pure water are 0.8 equivalent to 1.1 equivalent to the alkoxy group in the cationic functional group-containing polysiloxane resin composition.
It is a coating composition characterized by containing 2 equivalents.

The present invention also provides a component a comprising at least one kind of an organosilicon compound represented by the formula (1) or (2),

Embedded image

Embedded image (In formulas 1 and 2, R3 is an organic group having 1 to 18 carbon atoms, R4 is an organic group having 1 to 5 carbon atoms, R5 is a methyl group and a phenyl group, and R6 is a methyl group and an ethyl group. Represents.)

A component b comprising at least one kind of an organosilicon compound represented by the formula (3) or (4),

Embedded image

Embedded image (In Formulas 3 and 4, R7 is an organic group having 1 to 18 carbon atoms, R8 is an organic group having 1 to 5 carbon atoms, and R9 is a methyl group or a phenyl group.)

A cationic organosilicon compound represented by the formula (5), wherein one or two of a cationic organosilicon compound c1 in which n is 0 and a cationic organosilicon compound c2 in which n is 1; A component c comprising the above combination;

Embedded image (In formula 5, R1 is an organic group having 1 to 8 carbon atoms, R2 is an organic group having 1 to 5 carbon atoms, X is an organic group having 1 to 8 carbon atoms, K is an amino group, An aminoalkyl group or a diaminoalkyl group, and n represents an integer of 0 or 1.)

The pure water is mixed with a component a and a cationic organosilicon compound c1 and a component b and a cationic organosilicon compound c2 represented by Formula 1 in a molar ratio r of 1 or more,
Component a is 10 to 80 with respect to the total number of moles of components a, b and c.
Mol%, component b is 10 to 50 mol% and component c is 10
To 30 mol%, and pure water is 0.1 to 0.1 mol per alkoxy group.
A method for producing a cationic functional group-containing polysiloxane resin composition, which is obtained by mixing so as to be 8 to 1.2 equivalents, and performing hydrolysis and condensation reactions.

(Equation 1)

Further, the present invention is characterized in that the cationic functional group of the component c is obtained by an addition reaction between an isocyanate group and an activated hydrogen in a hydroxyl group of a tertiary amine amino alcohol.

The present invention is also characterized in that the cationic functional group of component c is obtained by an addition reaction between an epoxy group and activated hydrogen of a secondary amine.

[0017]

According to the present invention, the cationic functional group-containing polysiloxane resin composition contains the components a, b, and c, and the components a, b, and c are mixed with pure water, followed by hydrolysis and condensation. Obtained by: Further, a coating composition using the cationic functional group-containing polysiloxane resin composition,
It contains the above-mentioned cationic functional group-containing polysiloxane resin, a neutralizing agent and pure water.

Component a comprises one or more compounds having three alkoxy groups in one molecule.
Component a includes a trialkoxysilane monomer represented by the formula (1) (hereinafter, the monomer is referred to as a monomer) and a trialkoxysilane low condensate represented by the formula (2) (hereinafter, a low condensate) Is called an oligomer).

[0019]

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[0020]

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In the formula (1), R3 has 1 to 18 carbon atoms.
R4 is an organic group having 1 to 5 carbon atoms.
In the formula (2), R5 is a methyl group and a phenyl group, and R6 is a methyl group and an ethyl group.

The trialkoxysilane monomer has a function of promoting resinification in the reaction for forming the cationic functional group-containing polysiloxane resin composition. The trialkoxysilane monomer is preferably used in an amount of 10 to 80 mol% based on the total number of moles of the components a, b and c. Trialkoxysilane monomers include methyltrimethoxysilane, methyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-anilinopropyltrimethoxysilane, phenyltrimethoxysilane, 3-chloropropyltrimethoxysilane, hexyltrimethoxy Silane, 3-methacryloxypropyltrimethoxysilane, octadecyltriethoxysilane, octadecyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, vinylethoxysilane, trifluoropropyltrimethoxysilane, tridecafluorooctyltrimethoxysilane , Heptadecafluorodecyltrimethoxysilane, vinyltris (β-methoxy, ethoxy) silane, etc., and one or more of these To use.

The trialkoxysilane oligomer is effective for accelerating the formation of a polymer in the condensation reaction and for accelerating the ability to form a coating film for electrodeposition coating. Further, the trialkoxysilane oligomer functions to enhance the flexibility and leveling property of the coating film as compared with the trialkoxysilane monomer. The amount of the trialkoxysilane oligomer is preferably 80 mol% or less based on the total number of moles of the components a, b, and c.

As the trialkoxysilane oligomer, for example, TSR-650 manufactured by Toray Silicon Co., Ltd. is used. When R5 in the formula (2) is a phenyl group,
Compared with the case where 5 is a methyl group, the hardness and heat resistance of the electrodeposition coating film are improved, but the dispersibility and water solubility of the paint tend to decrease. However, the dispersibility and water solubility of the coating can be improved by using it in combination with a monomer such as a trialkoxysilane monomer.

Component (b) is one or two kinds each having two alkoxy groups or two silanol groups or a combination containing at least one alkoxy group and one silanol group in one molecule. It consists of more than one kind of organosilicon compound. The component b includes a dialkoxysilane monomer represented by the formula (3) and a bifunctional reactive silicone oligomer represented by the formula (4).

[0026]

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[0027]

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In the formula (3), R7 has 1 to 18 carbon atoms.
R8 is an organic group having 1 to 5 carbon atoms,
In the formula (4), R9 represents a methyl group and a phenyl group.

The dialkoxysilane monomer comprises component a,
It is preferable to use 50 mol% or less based on the total number of moles of b and c. If the dialkoxysilane monomer is used in an amount greater than 50 mol%, resinification is alienated in the condensation reaction, and the hardness of the electrodeposition coating film further decreases. Further, at the time of baking after the formation of the coating film, the fluidity of the coating film becomes excessive, and a uniform and smooth good appearance cannot be obtained.

As the dialkoxysilane monomer, dimethyldimethoxysilane, dimethyldiethoxysilane,
Diphenyldiethoxysilane, diphenyldimethoxysilane, 3-chloropropylmethyldiethoxysilane, 3
-Chloropropylmethyldimethoxysilane, heptadecafluorodecylmethyldimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, dimethyldiethoxysilane, methylvinyldimethoxysilane, octadecylmethyldimethoxysilane, etc., and one or more of these Use As the component b, a dialkoxysilane monomer and the aforementioned bifunctional reactive silicone oligomer may be used in combination.

The component c comprises one or more cationic organosilicon compounds represented by the formula (5). In the formula (5), R1 is an organic group having 1 to 8 carbon atoms, R2 is an organic group having 1 to 5 carbon atoms, X is an organic group having 1 to 8 carbon atoms, and K is a cationic functional group. And n is 0 or 1. When n = 0, it is a cationic organosilicon compound c1 which is a trialkoxysilane, and when n = 1, it is a cationic organosilicon compound c2 which is a dialkoxysilane.

Component c is preferably from 10 to 30 mol%, more preferably from 1 to 30 mol%, based on the total moles of components a, b and c.
5 to 25 mol%. When the amount is less than 10 mol%, the water solubility of the cationic functional group-containing polysiloxane resin composition having an ability to form an electrodeposition coating film is reduced. When the amount exceeds 30 mol%, re-dissolution or detachment of the electrodeposition coating film may occur. It occurs during the work from the deposition step to the water washing step, and if used in excess, there is a problem that the ability to form an electrodeposition coating film is reduced and the electrodeposition coating film is not formed.

The cationic functional group of the component c is an amino group,
It is selected from a monoaminoalkyl group and a diaminoalkyl group. The cationic functional group may be obtained by an addition reaction between an isocyanate group and an activated hydrogen in a hydroxyl group of a tertiary amine amino alcohol as shown in the formula (6). The functional group may be obtained by an addition reaction between an epoxy group and an activated hydrogen of a secondary amine as shown in formula (7).

[0034]

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[0035]

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In the formula (6), R10 is an organic group,
In the formula (7), R11 is an organic group, and R12 is an organic group.

As described above, the component c is classified into a cationic organosilicon compound c1 which is a trialkoxysilane and a cationic organosilicon compound c2 which is a dialkoxysilane.
The cationic organosilicon compound c2 has the same number of alkoxy groups as the component b. Component a and cationic organosilicon compound c1 represented by Formula 1, component b and cationic organosilicon compound c
The molar ratio r to 2 is preferably 1.0 or more.

[0038]

(Equation 1)

If r is less than 1.0, resinification is reduced during the condensation reaction. In addition, there is a problem that the hardness of the electrodeposition coating film is reduced. Further, at the time of baking after the formation of the coating film, the fluidity of the coating film becomes excessive, and a uniform and smooth good appearance cannot be obtained.

Examples of the cationic organosilicon compound in which the cationic functional group of component c is an amino group, a monoaminoalkyl group or a diaminoalkyl group include γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, and N-aminopropyltrimethoxysilane. β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, N-phenyl-
γ-aminopropyltrimethoxysilane, 3- [N-allyl-N (2-aminoethyl)] aminopropyltrimethoxysilane, p- [N- (2-aminoethyl) aminomethyl] phenethyltrimethoxysilane, N- 3-trimethoxysilylpropyl-m-phenylenediamine, γ
-Aminopropylmethyldiethoxysilane, γ-aminopropylethyldiethoxysilane and the like.
Use two or more types.

When the cationic functional group of the component c is obtained by the addition reaction between the activated hydrogen of the hydroxyl group of the tertiary amine amino alcohol represented by the formula (6) and the isocyanate group, the tertiary amine amino alcohol As N,
N-dimethylethanolamine, N, N-diethylethanolamine and the like are used. As the substance having an isocyanate group, an alkoxysilane represented by the formula (8) is used.

[0042]

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In the formula (8), R13 represents an organic group,
R14 represents an alkyl group. Examples of the alkoxysilane having an isocyanate group include γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatopropyltrimethoxysilane, and the like.

When the cationic functional group of the component c is obtained by the addition reaction between the epoxy group represented by the formula (7) and the activated hydrogen of the secondary amine, the secondary amine is diethylamine, diethanolamine, di-diamine. Examples include n-propanolamine, di-iso-propanolamine, N-methylethanolamine, N-ethylethanolamine and the like. The epoxy group is preferably used as an epoxy-functional alkoxysilane. Examples of the epoxy-functional alkoxysilane include γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, and 2-glycidoxyethyl. Trimethoxysilane,
2-glycidoxyethyltriethoxysilane, β-
(3,4-epoxycyclohexyl) ethyl-trimethoxysilane, β- (3,4-epoxycyclohexyl)
Ethyl-methyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-methyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-
And triethoxysilane.

The above components a, b, c and pure water are hydrolyzed and condensed in a solvent system comprising one or more water-soluble solvents such as alcohol, glycol and cellosolve to form a cation. A polysiloxane resin composition having a functional functional group is produced. At this time, the pure water is selected so as to be 0.8 equivalent or more, preferably 0.9 equivalent or more with respect to the alkoxy group contained in the components a, b and c. If the amount of water is less than 0.8 equivalents relative to the alkoxy group, the resinization and electrodeposition coating film-forming ability in the condensation reaction are reduced. Therefore, a good electrodeposition coating film cannot be obtained.

The hydrolysis and condensation reaction comprises the components a, b,
c, pure water and a solvent of 10 to 1 at 80 to 100 ° C.
Performed for 5 hours. At this time, no catalyst is required. By performing a multi-step reaction, the resulting cationic functional group-containing polysiloxane resin composition can be polymerized.

If the reaction time is less than 10 hours, the cationic functional group-containing polysiloxane resin composition will be insufficiently polymerized, and the ability to form an electrodeposition coating film will be impaired. There is a problem that the polymerization of the polysiloxane resin composition becomes excessive and the water solubility decreases.

After the components a, b, c and pure water are reacted in a solvent, the amino resin, the fluorine resin, the polyimide resin, A thermosetting / heat-resistant isocyanate oligomer, a silicone-based polycyclic oligomer, or the like may be added. When the amount of the resin to be added exceeds 20% by weight, the effect of the cationic functional group-containing polysiloxane resin composition decreases.

The cationic functional group-containing polysiloxane resin composition obtained by the above reaction is used as a cationic electrodeposition paint. After the reaction, the cationic functional group-containing polysiloxane resin composition, 0.7 to the amino group in the cationic functional group-containing polysiloxane resin composition
Neutralize with one or more organic acids and mineral acids to 1.4 equivalents. Formic acid as an organic acid,
Those having 3 or less carbon atoms such as acetic acid, lactic acid, i-propionic acid, and n-propionic acid are used.
Hydrochloric acid and phosphoric acid are used.

When a neutralized product of the cationic functional group-containing polysiloxane resin composition is diluted with pure water, a cationic electrodeposition paint is obtained. An inorganic filler such as rutile-type titanium white, mica, or clay, a fluororesin powder, silica, alumina oxide, or the like is dispersed in the above-described cationic electrodeposition coating composition to obtain a cationic electrodeposition coating composition suitable for the purpose.

After the electrodeposition coating, the resulting coating film has a curing temperature of 20
Cured above 0 ° C. The baking process includes the components a, b, c
In addition, when a curable resin such as an amino resin, a polyimide resin, a thermosetting / heat-resistant isocyanate oligomer and a silicone-based polycyclic oligomer is used, the curing is performed at a baking temperature of 200 ° C. for about 1 hour to remove the curable resin. If not used, baking is performed at a baking temperature of 250 to 300 ° C. for about 1 hour.

[0052]

The present invention will be described in more detail with reference to the following examples. The present inventor performed Examples 1 to 8 as shown in Table 1. In these examples, the materials are different, but the manufacturing conditions are the same. Hereinafter, the manufacturing conditions will be described.

Examples 1 to 8 (1) Production of cationic functional group-containing polysiloxane resin Components a, b, and c (provided that components a, b, and c were added to a 1-liter four-necked flask equipped with a stirrer, a thermometer, and a reflux condenser) As component c,
When γ-isocyanatopropyltriethoxysilane and dimethylethanolamine are used, they are reacted to obtain component c), pure water and 3/4 of the solvent.
, And the mixture was reacted at a reflux temperature of 85 to 100 ° C. for 6 hours. Then, the remaining 1/4 was charged and the reaction was further performed for 4 hours.
Then, it cooled to 30 degreeC or less, and neutralized using lactic acid as a neutralizing agent after 12 to 16 hours. The amount of the neutralizing agent was 1 equivalent relative to the amino group-containing alkoxysilane.

Table 1 shows the composition of each component of Examples 1 to 8 and the reaction conditions.

[0055]

[Table 1]

(2) Manufacture of cationic electrodeposition paint, preparation of test sample, and performance test of paint The neutralized cationic functional group-containing polysiloxane resin composition obtained by the above-mentioned method was used. weight%
Was diluted to 1 liter with pure water to obtain a crude cationic electrodeposition paint. The crude cationic electrodeposition paint was subjected to a performance test as described below, and the test results in Table 2 were obtained.

(A) Water-solubilizing ability of cationic functional group-containing polysiloxane resin composition The water-solubilizing ability of the cationic functional group-containing polysiloxane resin composition when diluted to prepare a crude cationic electrodeposition coating composition is approximately as follows. Was visually determined based on the water-solubilizing ability of an acrylic-melamine-based anion electrodeposition coating composition for use. Thus, the degree of dissolution of the composition in pure water was determined. The symbols of the test items in Table 2 represent the following meanings.

◎ Equal or better, ○ Equal, △ Slightly inferior, × Inferior (b) Dispersion stability of electrodeposition paint The crude cationic electrodeposition paint is allowed to stand for 2 to 3 days, and a conventional acrylic-melamine anion electrodeposition paint Based on the dispersion stability of the dispersion, the dispersion stability was visually determined. The symbols of the test items in Table 2 represent the following meanings.

◎ Equal or better, ○ Equal, ΔSlightly inferior, × Inferior The above-mentioned crude cationic electrodeposition paint was purified using Diaion SA-10AP (manufactured by Mitsubishi Kasei Co., Ltd.), which is an anion exchange resin, to obtain a cationic electrodeposition paint. I got

The above-mentioned cationic electrodeposition paint was electrodeposited on an aluminum plate (JIS A-10501 × 70 × 70 mm ³ ) by applying a voltage of 50 V for 2 minutes at a liquid temperature of 25 ° C.
After pre-drying at 00 to 120 ° C. for 15 minutes, 250
A baking treatment was performed at 1 ° C. for 1 hour to prepare a sample, and a test of an electrodeposition coating type performance, which is a performance test described later, was performed.

(C) Ability to form electrodeposited coating film The ability to form an electrodeposited coating film obtained by electrodeposition was visually determined based on the electrodeposited coating film obtained from a general acrylic-melamine anion electrodeposition coating material. . The symbols of the test items in Table 2 represent the following meanings.

◎ Equal or better, ○ Equivalent, △ Slightly poor, × Poor (3) Coating performance test of sample The present inventor carried out the following tests on the performance of the electrodeposition paint and the electrodeposition coating film. The test results shown in Table 2 below were obtained. In the table below, for water resistance, solvent resistance, and chemical resistance, the state of the sample before the test is compared with the state of the sample after the test. When a change such as whitening occurs, a symbol of △ is attached.

(A) Appearance of coating film (uniformity / smoothness, gloss) A visual judgment was made on the basis of the appearance of a general acrylic-melamine-based anion electrodeposition coating film. The symbols of the test items in Table 2 represent the following meanings.

◎ Equal or better, ○ Equal, × Poor (b) Adhesion of coating film (crosscut taping test) Cut 100 squares of 1 × 1 mm ^{2 with} a cutter, tap the coating film with cellophane tape, It is indicated by the number of squares that do not peel off when the tape is peeled off.

(C) Pencil hardness The scratch hardness was measured with Mitsubishi Pencil Uni.

(D) Heat resistance (i) Heat resistance Temperature is the temperature at which the coating film does not fall off or peel off after heating for 1 hour.

(Ii) Under the following heating conditions, the presence or absence of peeling or peeling of the coating film is determined visually and by a grid taping test.
Those that have not changed from the state before the test are regarded as good.

250 ° C. × 120 hours 300 ° C. × 24 hours (e) Water resistance The sample was immersed in boiling pure water for 8 hours a day, and this test was performed for 3 days. The secondary adhesiveness is examined using.

(F) Solvent resistance The sample is immersed in a thinner for 24 hours, and the coating is examined for changes in appearance such as dissolution, blistering, and whitening.

(G) Chemical Resistance A sample is immersed in each chemical solution (5% hydrochloric acid, 50% sulfuric acid, 50% sodium hydroxide) for 24 hours, and the appearance change such as corrosion of metal and swelling of the coating film is tested.

Table 2 shows the test results.

[0072]

[Table 2]

Comparative Examples 1 to 7 Comparative Examples 1 to 7 were carried out using the component compositions and reaction conditions shown in Table 3 based on the production methods of the examples. When the reaction time was 4 hours or less, all the materials were charged at once, and the reaction was performed for a predetermined time. When the reaction time exceeds 10 hours, 3/4 of the material is reacted for 4 hours, and the remaining 1/4 is reacted.
The reaction was continued until a predetermined time was reached.
For the comparative example, a test sample was prepared, and the same items as in the example were tested. Table 4 shows the test results of Comparative Examples 1 to 7.

[0074]

[Table 3]

[0075]

[Table 4]

Comparative Example 1 is disclosed in Japanese Unexamined Patent Application Publication No.
No. 11581 is reproduced. In Comparative Example 1, components a and b were not used, and only component c having a cationic functional group was used, so that the water-solubility and the dispersion stability of the electrodeposition paint were excellent. On the other hand, pure water was not used during the reaction, the reaction time was short, and the reaction temperature was low, so that no polymerization occurred and no electrodeposition coating film could be formed.

In Comparative Example 2, since the content of the component c was as low as 5 mol% with respect to the total number of moles of the components a, b and c, the water-solubilizing ability was low.
The electrodeposition paint could not be obtained. Therefore component c
It is understood that the concentration is preferably more than 5 mol%, for example, 10 mol% or more, more preferably 15 mol% or more, based on the total number of moles of the components a, b and c.

In Comparative Example 3, since the component c was as high as 40 mol% with respect to the total number of moles of the components a, b and c, the performance of the electrodeposition coating film was low, and no electrodeposition coating film could be obtained. Was. Therefore, the component c is 40% based on the total number of moles of the components a, b and c.
It is understood that the content is preferably less than mol%, for example, 30 mol% or less, and more preferably 25 mol% or less.

Therefore, as can be seen from Comparative Examples 2 and 3, component c is 10% based on the total number of moles of components a, b and c.
It is understood that the content is preferably from 30 to 30 mol%, more preferably from 15 to 25 mol%.

In Comparative Example 4, the molar ratio r between the trialkoxysilane and the dialkoxysilane represented by Formula 1 was 1.0.
Since it was less than 1, the resinification was reduced, the hardness of the electrodeposition coating film was reduced, and the pencil hardness was F. Therefore, the molar ratio r is 1.
It is understood that 0 or more is preferable.

In Comparative Example 5, the reaction time was as short as 3 hours, the polymerization was insufficient, the ability to form an electrodeposition coating film was impaired, and an electrodeposition coating film could not be obtained. Therefore, it is understood that the reaction time is preferably longer than 3 hours, for example, 10 hours or longer.

In Comparative Example 6, the reaction time was as long as 21 hours, and the polymerization was excessive, so that the cationic functional group-containing polysiloxane resin composition had a low water-solubility and was uniform, smooth and glossy. No coating film was obtained. Therefore, it is understood that the reaction time is preferably less than 21 hours, for example, 15 hours or less.

Therefore, it is understood from Comparative Examples 5 and 6 that the reaction time is preferably 10 to 15 hours.

In Comparative Example 7, since the amount of pure water with respect to the alkoxy group was as low as 0.6 equivalent, the polymerization was reduced, the ability to form an electrodeposition coating film was reduced, and an electrodeposition coating film having uniformity and smoothness was obtained. I couldn't. Therefore, it can be seen that the amount of pure water exceeds 0.6 equivalents relative to the alkoxy group, for example, preferably 0.8 equivalents or more, and more preferably 0.9 equivalents or more.

As compared with the comparative example, in Examples 1 to 8, an electrodeposition coating film having excellent heat resistance, water resistance, solvent resistance, and chemical resistance, and having a smooth surface, gloss, and high hardness was obtained. Obtained. In addition, a coating composition using a cationic functional group-containing polysiloxane resin composition having higher water-solubility and dispersion stability than a conventional acrylic-melamine-based anion electrodeposition coating was obtained.

As described above, according to this embodiment, a water-soluble cationic functional group-containing polysiloxane resin composition is manufactured and used as an electrodeposition coating material. Safety and work efficiency are improved. In addition, since electrodeposition coating can be performed, a coating film having a uniform and smooth surface, excellent heat resistance, water resistance, chemical resistance, and the like and high hardness can be obtained.

[0087]

According to the present invention, an organosilicon compound having three alkoxy groups in one molecule, two alkoxy groups or two silanol groups or one alkoxy group in one molecule, A cationic functional group-containing polysiloxane resin composition containing an organosilicon compound having at least one combination with at least one silanol group and a cationic organosilicon compound is produced and used as a coating composition. Since the cationic functional group-containing polysiloxane resin composition has water solubility, work safety during painting is improved.

Further, the work efficiency was improved because of the electrodeposition coating. Further, a coating film having excellent heat resistance, water resistance, chemical resistance, etc., and high hardness can be obtained, and the coating film has a uniform thickness and can have a smooth surface.

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int.Cl. ⁷ , DB name) C08G 77/26

Claims (5)

(57) [Claims] 1. A component a comprising at least one kind of an organosilicon compound represented by the formula (1) or (2), and Embedded image (In formulas 1 and 2, R3 is an organic group having 1 to 18 carbon atoms, R4 is an organic group having 1 to 5 carbon atoms, R5 is a methyl group and a phenyl group, and R6 is a methyl group and an ethyl group. And a component b comprising at least one kind of an organosilicon compound represented by the formula (3) or the formula (4); Embedded image (In Formulas 3 and 4, R7 is an organic group having 1 to 18 carbon atoms, R8 is an organic group having 1 to 5 carbon atoms, and R9 represents a methyl group and a phenyl group.) Formula (5) A component c comprising one or a combination of a cationic organosilicon compound c1 wherein n is 0 and a cationic organosilicon compound c2 wherein n is 1; A cationic functional group-containing polysiloxane resin composition containing: (In formula 5, R1 is an organic group having 1 to 8 carbon atoms, R2 is an organic group having 1 to 5 carbon atoms, X is an organic group having 1 to 8 carbon atoms, K is an amino group, An aminoalkyl group or a diaminoalkyl group, wherein n represents an integer of 0 or 1.) Component a is added in an amount of 10 to 10 moles of components a, b and c.
A cationic functional group-containing polysiloxane resin composition comprising 80 mol%, 10 to 50 mol% of component b, and 10 to 30 mol% of component c. 2. The cationic functional group-containing polysiloxane resin composition according to claim 1, an acid for neutralizing the amine of the component c in the cationic functional group-containing polysiloxane resin composition, and pure water. Wherein the acid is 0.7 to 1.4 equivalents to the amine of the component c in the cationic functional group-containing polysiloxane resin composition, and pure water is the cationic functional group. A coating composition comprising 0.8 to 1.2 equivalents based on the alkoxy groups in the polysiloxane resin composition. 3. A component a comprising at least one kind of an organosilicon compound represented by the formula (1) or (2), and Embedded image (In formulas 1 and 2, R3 is an organic group having 1 to 18 carbon atoms, R4 is an organic group having 1 to 5 carbon atoms, R5 is a methyl group and a phenyl group, and R6 is a methyl group and an ethyl group. And a component b comprising at least one kind of an organosilicon compound represented by the formula (3) or the formula (4); Embedded image (In Formulas 3 and 4, R7 is an organic group having 1 to 18 carbon atoms, R8 is an organic group having 1 to 5 carbon atoms, and R9 represents a methyl group and a phenyl group.) Formula (5) A component c comprising one or a combination of two or more of a cationic organosilicon compound c1 in which n is 0 and a cationic organosilicon compound c2 in which n is 1
And (In formula 5, R1 is an organic group having 1 to 8 carbon atoms, R2 is an organic group having 1 to 5 carbon atoms, X is an organic group having 1 to 8 carbon atoms, K is an amino group, An aminoalkyl group or a diaminoalkyl group, and n represents an integer of 0 or 1.) Pure water is combined with a component a and a cationic organosilicon compound c1 and a component b and a cationic organosilicon compound represented by Formula 1. the molar ratio r to c2 is 1 or more, and the components a, b,
Component a is 10 to 80% by mole, component b is 10 to 50% by mole, and component c is 10 to 30% by mole based on the total number of moles of c.
A cationic functional group-containing polysiloxane resin composition obtained by mixing pure water with an alkoxy group in an amount of 0.8 to 1.2 equivalents and performing a hydrolysis and condensation reaction. Method of manufacturing a product. (Equation 1) 4. The cationic functional group according to claim 3, wherein the cationic functional group of component c is obtained by an addition reaction between an isocyanate group and an activated hydrogen in a hydroxyl group of a tertiary amine amino alcohol. A method for producing a functional group-containing polysiloxane resin composition. 5. The cationic functional group-containing polysiloxane resin according to claim 3, wherein the cationic functional group of component c is obtained by an addition reaction between an epoxy group and an activated hydrogen of a secondary amine. A method for producing the composition.