JPH0586194A - Composition of polysiloxane resin containing cationic functional group, coating composition made by using it, and production of the resin composition - Google Patents

Abstract

PURPOSE:To obtain the title resin composition which is suitable for use as a heat-resistant cationic electrodeposition coating material by mixing an organosilicon compound having three alkoxy groups, an organosilicon compound having two alkoxy groups, and a cationic organosilicon compound. CONSTITUTION:The title resin composition is obtained by mixing at least one organosilicon compound having three alkoxy groups in the molecule, an organosilicon compound having two alkoxy groups, two silanol groups, or a combination of one alkoxy group and one silanol group in the molecule, and at least one cationic organosilicon compound of the formula (wherein R<1> is a 1-8C organic group; R<2> is a 1-5C organic group; X is 1-8C organic group; K is a cationic functional group; n is 0 or 1).

Description

Detailed Description of the Invention

[0001]

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 in places where heat is used in chemical plants, refineries, power plants, automobile engine outer circumferences, aircrafts, electric and electronic equipments and the like. For electric / electronic devices, heat-resistant polymers having excellent electric insulation, mechanical strength, chemical properties, and dimensional stability are used as heat-resistant insulating coatings. As a typical heat-resistant insulating paint, a silicone-based heat-resistant paint is often used. Most of these paints are solvent-based, and the usual coating methods are brush coating, spray coating, dip coating, roll coating and spin coating.

[0003]

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

Conventionally, in order to make an organosilicone resin or a silicone-modified resin water-soluble, a method of dispersing with a surfactant has been used. However, due to the influence of the surfactant, there is a problem that good coating performance cannot be obtained and a coating having good uniformity, smoothness and transparency cannot be obtained.

An example of an aqueous organosilicon composition in which an amino group is introduced into a polysiloxane is disclosed in JP-A-2-311581, but it is a low condensation product and does not have a film-forming ability even by electrodeposition coating. , Does not meet the purpose of the present invention.

The object of the present invention is to solve the above-mentioned problems, to provide excellent coating film performance such as heat resistance, chemical resistance, and water resistance, and to have a smooth surface, excellent gloss and transparency, and to improve workability. It is intended to provide a cationic functional group-containing polysiloxane resin composition which is safe and has good working efficiency, a coating composition using the same, and a method for producing a cationic functional group-containing polysiloxane resin composition.

[0007]

The present invention provides 3 in one molecule.
Component a consisting of one or more kinds of organosilicon compounds having one alkoxy group, and two alkoxy groups or two silanol groups in one molecule, or one alkoxy group and one silanol group And at least one
And a component b consisting of one or more kinds of organosilicon compounds each having a combination including one and R, R1 is an organic group having 1 to 8 carbon atoms, and R2 is It is an organic group having 1 to 5 carbon atoms, and X is 1 carbon atom.
~ 8 organic groups, K is a cationic functional group,
Cationic organosilicon compound c1 or n in which n is 0
A cationic functional group-containing polysiloxane resin composition, characterized in that it contains one or a combination of two or more kinds of the cationic organosilicon compound c2 in which 1 is 1.

[0008]

[Chemical 1]

Further, the present invention is characterized in that the cationic functional group of the component c is selected from an amino group, a monoaminoalkyl group and a diaminoalkyl group.

The present invention also provides a component a consisting of one or more kinds of organosilicon compounds having three alkoxy groups in one molecule, and two alkoxy groups or two silanol groups in one molecule. Or a component b consisting of one or more kinds of organosilicon compounds each having a combination containing at least one alkoxy group and one silanol group, and the general formula shown in Chemical formula 1 , 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 a cationic functional group, A cationic functional group-containing polysiloxa containing one or a combination of two or more kinds of the cationic organosilicon compound c1 in which n is 0 or the cationic organosilicon compound c2 in which n is 1. And the resin composition, and a neutralizing agent, a coating composition using a cationic functional group-containing polysiloxane resin composition which comprises a pure water.

The present invention also provides a component a consisting of one or more kinds of organosilicon compounds having three alkoxy groups in one molecule, and two alkoxy groups or two silanol groups in one molecule. Or a component b consisting of one or more kinds of organosilicon compounds each having a combination containing at least one alkoxy group and one silanol group, and the general formula shown in Chemical formula 1 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. , A component c comprising one or a combination of two or more of the cationic organosilicon compound c1 in which n is 0 or the cationic organosilicon compound c2 in which n is 1,

[0012]

[Chemical 1]

Molar ratio r of the component a and the cationic organosilicon compound c1 and the component b and the cationic organosilicon compound c2 represented by the formula 1 is 1 or more.
The component c is 10 to 30 with respect to the total number of moles of the components a, b and c.
The cationic functional group-containing polysiloxane resin composition is obtained by mixing in a molar ratio of 0.8% or more of pure water with respect to an alkoxy group, and performing a hydrolysis and condensation reaction. Is a manufacturing method.

[0014]

[Equation 1]

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

The present invention is also characterized in that the cationic functional group of the component c is obtained by an addition reaction between an epoxy group and an 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 to cause hydrolysis and condensation reaction. Obtained by Further, the 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.

The component a is composed of one kind or two or more kinds of compounds having three alkoxy groups in one molecule.
As the component a, a trialkoxysilane monomer shown in Chemical formula 2 (hereinafter, the monomer is referred to as a monomer) and a trialkoxysilane low condensate shown in Chemical formula 3 (hereinafter, the low condensate is referred to as an oligomer) ) There is.

[0019]

[Chemical 2]

[0020]

[Chemical 3]

In the chemical formula 2, R3 is an organic group having 1 to 18 carbon atoms, and R4 is an organic group having 1 to 5 carbon atoms. Further, in Chemical Formula 3, 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 10 to 80 mol% based on the total number of moles of the components a, b and c. Examples of the trialkoxysilane monomer include methyltrimethoxysilane, methyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-anilinopropyltrimethoxysilane, phenyltrimethoxysilane, 3-chloropropyltrimethoxysilane, and hexyltrimethoxy. Silane, 3-methacryloxypropyltrimethoxysilane, octadecyltriethoxysilane, octadecyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, vinylethoxysilane, trifluoropropyltrimethoxysilane, tridecafluorooctyltrimethoxysilane , Heptadecafluorodecyltrimethoxysilane, vinyltris (β-methoxy, ethoxy) silane, etc., and one or more of these are available. To use.

The trialkoxysilane oligomer is effective in accelerating the polymerization in the condensation reaction and accelerating the film forming ability of electrodeposition coating. Further, the trialkoxysilane oligomer has a function of improving the flexibility and leveling property of the coating film, as compared with the trialkoxysilane monomer. The trialkoxysilane oligomer is preferably 80 mol% or less with respect to 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. is used. When R5 in Chemical Formula 3 is a phenyl group, the hardness and heat resistance of the electrodeposition coating film are improved, but the dispersibility and water solubility of the coating tend to be lower than when R5 is a methyl group. .. 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.

The component b is one kind or two kinds each having a combination containing at least one of two alkoxy groups or two silanol groups or one alkoxy group and one silanol group in one molecule. It consists of more than one type of organosilicon compound. Examples of the component b include the dialkoxysilane monomer shown in Chemical formula 4 and the bifunctional reactive silicone oligomer shown in Chemical formula 5.

[0026]

[Chemical 4]

[0027]

[Chemical 5]

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

The dialkoxysilane monomer is composed of the components a,
It is preferably used in an amount of 50 mol% or less based on the total number of mols of b and c. If the dialkoxysilane monomer is used in an amount of more than 50 mol%, resinification is excluded in the condensation reaction and the hardness of the electrodeposition coating film is further reduced. Further, the fluidity of the coating film becomes excessive at the time of baking after forming the coating film, and it becomes impossible to obtain a good appearance that is uniform and smooth.

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 To use. As the component b, a dialkoxysilane monomer and the above-mentioned bifunctional reactive silicone oligomer may be used in combination.

The component c is composed of one kind or two or more kinds of cationic organosilicon compounds shown in Chemical formula 1. In Chemical formula 1, R1 is an organic group having 1 to 8 carbon atoms, and R2
Is an organic group having 1 to 5 carbon atoms, X is an organic group having 1 to 8 carbon atoms, 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 n = 1.
In this case, the cationic organosilicon compound c2 is dialkoxysilane.

Component c is preferably 10 to 30 mol%, more preferably 1 to 30 mol% with respect to the total number of moles of components a, b and c.
It is 5 to 25 mol%. If it is 10 mol% or less, the water-solubility of the cationic functional group-containing polysiloxane resin composition having the ability to form an electrodeposition coating film will decrease, and if it exceeds 30 mol%, re-dissolution of the electrodeposition coating film or peeling-off will occur. It occurs during the work from the coating process to the water washing process, and if it is used in excess, it causes a problem that the ability to form an electrodeposition coating film is lowered and the electrodeposition coating film is not formed.

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

[0034]

[Chemical 6]

[0035]

[Chemical 7]

In the chemical formula 6, R10 is an organic group,
In, R11 is an organic group and R12 is an organic group.

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

[0038]

[Equation 1]

When r is less than 1.0, resinification is lowered during the condensation reaction. In addition, there is a problem that the hardness of the electrodeposition coating film decreases. Further, the fluidity of the coating film becomes excessive at the time of baking after forming the coating film, and it becomes impossible to obtain a good appearance that is uniform and smooth.

As the cationic organosilicon compound in which the cationic functional group of the component c is an amino group, a monoaminoalkyl group or a diaminoalkyl group, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N- 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, etc.
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-based amino alcohol represented by the chemical formula 6 and the isocyanate group, the tertiary amine-based amino alcohol is , N, N
-Dimethylethanolamine, N, N-diethylethanolamine and the like are used. As the substance having an isocyanate group, an alkoxysilane represented by Chemical formula 8 is used.

[0042]

[Chemical 8]

In the chemical formula 8, R13 represents an organic group, and R1
4 represents an alkyl group. Examples of the alkoxysilane having an isocyanate group include γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, and γ-isocyanatopropyltrimethoxysilane.

When the cationic functional group of the component c is obtained by the addition reaction of the epoxy group represented by the chemical formula 7 and the activated hydrogen of the secondary amine, the secondary amine may be diethylamine, diethanolamine or di-n-. There are propanolamine, di-iso-propanolamine, N-methylethanolamine, N-ethylethanolamine and the like.
The epoxy group is preferably used as an epoxy-functional alkoxysilane, and 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-triethoxysilane and the like.

The above components a, b and c and pure water are hydrolyzed and condensed in a solvent system containing one or more water-soluble solvents such as alcohol, glycol and cellosolve as main components, and cations are added. A polysiloxane resin composition containing a 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 equivalent to the alkoxy group, the resinification and electrodeposition coating film forming ability in the condensation reaction will be reduced. Therefore, a good electrodeposition coating film cannot be obtained.

The hydrolysis and condensation reactions are carried out by the components a, b,
c, pure water and solvent 10 to 1 under the condition of 80 to 100 ° C
It will be held for 5 hours. At this time, no catalyst is required. By carrying out a multi-step reaction, the obtained cationic functional group-containing polysiloxane resin composition can be polymerized.

When the reaction time is less than 10 hours, the cationic functional group-containing polysiloxane resin composition is insufficiently polymerized to impair the ability to form an electrodeposition coating film, and when it exceeds 15 hours, it contains a cationic functional group. There is a problem that the polysiloxane resin composition becomes excessively polymerized and the water solubility thereof is lowered.

After reacting the components a, b, and c with pure water in a solvent, 20% by weight or less of the cationic functional group-containing polysiloxane resin composition is amino resin, fluorine resin, polyimide resin, A thermosetting / heat-resistant isocyanate oligomer, a silicone-based polycyclic oligomer, etc. may be added. If the amount of the resin added is more than 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 coating composition. The cationic functional group-containing polysiloxane resin composition after the reaction is added to the cationic functional group-containing polysiloxane resin composition in an amount of 0.7 to
The organic acid and the mineral acid are neutralized with one kind or two or more kinds so that the amount becomes 1.4 equivalents. Formic acid as organic acid,
Acetic acid, lactic acid, i-propionic acid, n-propionic acid, or the like having a carbon number of 3 or less is used, and the mineral acid is sulfuric acid,
Hydrochloric acid and phosphoric acid are used.

A cationic electrodeposition coating composition can be obtained by diluting a neutralized product of a cationic functional group-containing polysiloxane resin composition with pure water. Inorganic fillers such as rutile-type titanium white, mica, and clay, fluororesin powder, silica, alumina oxide, and the like can be dispersed in the above-mentioned cationic electrodeposition coating material to prepare a cationic electrodeposition coating material according to the purpose.

After electrodeposition coating, the obtained coating film has a curing temperature of 20.
It is cured at 0 ° C or higher. The baking process is performed with components a, b, c
In addition to the above, when a curable resin such as an amino resin, a polyimide resin, a thermosetting / heat-resistant isocyanate oligomer, and a silicone polycyclic oligomer is used, the baking is carried out at a baking temperature of 200 ° C. for about 1 hour. When not used, the baking temperature is 250 to 300 ° C. and the baking is performed for about 1 hour.

[0052]

The present invention will be described in more detail by the following examples. The inventor of the present case carried out Examples 1 to 8 as shown in Table 1. These examples have different materials but the same manufacturing conditions. The manufacturing conditions will be described below.

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

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

[0055]

[Table 1]

(2) Production of cationic electrodeposition coating, preparation of test sample and performance test of coating The neutralized cationic functional group-containing polysiloxane resin composition obtained by the above-mentioned method has a solid content of 10 weight%
Was diluted to 1 liter with pure water to obtain a crude cationic electrodeposition coating composition. The crude cation electrodeposition coating composition was subjected to the performance test as described below, and the test results shown in Table 2 were obtained.

(A) Water-Solubilizing Ability of Cationic Functional Group-Containing Polysiloxane Resin Composition The water-solubilizing ability when diluting the cationic functional group-containing polysiloxane resin composition to prepare a crude cationic electrodeposition coating is The water-solubilizing ability of the acrylic-melamine-based anion electrodeposition coating composition for water was used as a reference to make a visual determination. From this, the degree of dissolution of the above composition in pure water was determined. The symbols of this test item in Table 2 have the following meanings.

◎ Equivalent or better, ○ Equivalent, △ Slightly inferior, × Inferior (b) Dispersion stability of electrodeposition coating A crude cation electrodeposition coating is allowed to stand for 2 to 3 days, and a general acrylic-melamine-based anion electrodeposition coating Based on the dispersion stability of No. 1, the dispersion stability was visually evaluated. The symbols of this test item in Table 2 have the following meanings.

◎ Equivalent or better, ○ Equivalent, △ Slightly inferior, × Inferior The above-mentioned crude cationic electrodeposition coating was purified using anion exchange resin Diaion SA-10AP (manufactured by Mitsubishi Kasei) Got

The above-mentioned cationic electrodeposition coating was applied to 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
Baking treatment was performed at 1 ° C. for 1 hour to prepare a sample, and an electrodeposition coating film type performance test, which is a performance test described later, was performed and the test results shown in Table 2 were obtained.

(C) Electrodeposition coating film forming ability The formation ability of the coating film obtained by electrodeposition was visually judged on the basis of the electrodeposition coating film obtained by the conventional acrylic-melamine anion electrodeposition coating composition. .. The symbols of this test item in Table 2 have the following meanings.

◎ Equal or better, ○ Equivalent, △ Slightly inferior, × Inferior (3) Coating film performance test of sample 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, and when there is no change, a symbol of ○ is given. When changes such as whitening occur, the symbol Δ is attached.

(A) Appearance of coating film (uniformity / smoothness / gloss) A visual judgment was made based on the appearance of a conventional acrylic-melamine-based anion electrodeposition coating film as a reference. The symbols of this test item in Table 2 have the following meanings.

◎ Equal or better, ○ Equal, poorer inferior (b) Adhesion of coating film (cross-cut taping test) 100 squares of 1 × 1 mm ² are cut with a cutter, and the coating film is taped with cellophane tape. It is indicated by the number of squares that cannot be peeled off when the tape is peeled off.

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

(D) Heat resistance (i) Heat resistance temperature The temperature at which the coating film does not fall off or peel off within 1 hour of heating.

(Ii) Under the following heating conditions, the presence or absence of peeling or peeling of the coating film is judged visually and by a cross-cut taping test.
Those that do not change from the state before the test are considered good.

250 ° C. × 120 hours 300 ° C. × 24 hours (e) Water resistance After dipping the sample in boiling pure water for 8 hours a day and conducting this test for 3 days, the coating film was whitened and the cross-cut taping test was conducted. To check the secondary adhesion.

(F) Solvent resistance The sample is immersed in thinner for 24 hours, and the appearance change such as dissolution, swelling and whitening of the coating film is tested.

(G) Chemical resistance A sample is dipped in each chemical solution (5% hydrochloric acid, 50% sulfuric acid, 50% sodium hydroxide) for 24 hours, and changes in appearance such as metal corrosion and coating film swelling are tested.

Table 2 shows the above test results.

[0072]

[Table 2]

Comparative Examples 1 to 7 Comparative Examples 1 to 7 were carried out based on the production methods of Examples using the component compositions and reaction conditions shown in Table 3. When the reaction time was 4 hours or less, all the materials were charged at once and reacted for a predetermined time. If the reaction time exceeds 10 hours, 3/4 of the material is allowed to react for 4 hours and then the remaining 1/4
The above materials were added and the reaction was carried out until a predetermined time was reached.
Also in the comparative example, a test sample was prepared and the same items as those 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 Japanese Patent Laid-Open No. 2-3 shown in the prior art.
It is a reproduction of No. 11581. In Comparative Example 1, components a and b are not used, and only component c having a cationic functional group is used, so that the water-solubilizing ability and the dispersion stability of the electrodeposition coating are excellent. On the other hand, since pure water was not used during the reaction, the reaction time was short, and the reaction temperature was low, polymerization did not occur and an electrodeposition coating film could not be formed.

In Comparative Example 2, since 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,
It was not possible to obtain an electrodeposition paint. Therefore component c
It can be seen that is preferably a concentration of more than 5 mol%, for example 10 mol% or more, and more preferably 15 mol% or more with respect to 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 an electrodeposition coating film could not be obtained. It was Therefore, the component c is 40 with respect to the total number of moles of the components a, b and c.
It can be seen that it is preferably less than 30 mol%, for example, 30 mol% or less, and more preferably 25 mol% or less.

Therefore, as can be seen in Comparative Examples 2 and 3, the component c is 10 relative to the total number of moles of the components a, b and c.
It can be seen that -30 mol% is preferable, and 15-25 mol% is more preferable.

In Comparative Example 4, the molar ratio r of the trialkoxysilane and the dialkoxysilane represented by the formula 1 was 1.0.
Since it was less than the above, resinification was lowered, the hardness of the electrodeposition coating film was lowered, and the pencil hardness was F. Therefore, the molar ratio r is 1.
It can be seen 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-solubilizing ability, and the electrodeposition 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 groups was as low as 0.6 equivalent, the polymerization was lowered and the ability to form an electrodeposition coating film was lowered, and an electrodeposition coating film having a uniform and smooth surface was obtained. I couldn't do it. Therefore, it is understood that the amount of pure water is more than 0.6 equivalent to the alkoxy group, for example, 0.8 equivalent or more is preferable, and 0.9 equivalent or more is more preferable.

Compared to the comparative example, in Examples 1 to 8, excellent heat resistance, water resistance, solvent resistance, chemical resistance, smooth surface, gloss, and high hardness of electrodeposition coating films were obtained. Was obtained. Further, a coating composition using a cationic functional group-containing polysiloxane resin composition having high water-solubilizing ability and dispersion stability as compared with the conventional acrylic-melamine-based anionic electrodeposition coating composition was obtained.

As described above, according to this example, since a water-soluble cationic functional group-containing polysiloxane resin composition is produced and used as an electrodeposition coating, a large amount of solvent is not required for coating, The safety and work efficiency of are improved. Further, since the electrodeposition coating can be performed, a coating film having a uniform and smooth surface, excellent heat resistance, water resistance, chemical resistance, etc. and high hardness can be obtained.

[0087]

According to the present invention, an organosilicon compound having three alkoxy groups in one molecule and 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 of individual silanol groups and a cationic organosilicon compound is produced and used as a coating composition. Since the cationic functional group-containing polysiloxane resin composition is water-soluble, work safety during coating is improved.

Further, since the electrodeposition coating is performed, the work efficiency is improved. Further, a coating film having excellent heat resistance, water resistance, chemical resistance and the like and having high hardness can be obtained, the coating film thickness is uniform, and the surface can be smoothed.

Claims (6)

[Claims] 1. A component a consisting of one or two or more kinds of organosilicon compounds having three alkoxy groups in one molecule, and two alkoxy groups or two silanol groups in one molecule, or 1 1 each having a combination comprising at least one alkoxy group and one silanol group
Having a component b consisting of two or more kinds of organosilicon compounds and the general formula shown in Chemical formula 1, R1 is an organic group having 1 to 8 carbon atoms, and R2 is an organic group having 1 to 5 carbon atoms. And X is an organic group having 1 to 8 carbon atoms, K is a cationic functional group, and n is 0, a cationic organosilicon compound c1
Alternatively, a cationic functional group-containing polysiloxane resin composition comprising a cationic organosilicon compound c2 in which n is 1 and a component c comprising a combination of two or more types. [Chemical 1] 2. The cationic functional group of component c is an amino group,
The cationic functional group-containing polysiloxane resin composition according to claim 1, which is selected from a monoaminoalkyl group and a diaminoalkyl group. 3. A component a consisting of one or more kinds of organic silicon compounds having three alkoxy groups in one molecule, and two alkoxy groups or two silanol groups or one in one molecule. The component b consisting of one or more kinds of organosilicon compounds each having a combination containing at least one of the alkoxy group and one silanol group, and R 1 having the general formula shown in Chemical formula 1, R2 is an organic group having 1 to 5 carbon atoms, X is an organic group having 1 to 8 carbon atoms, K is a cationic functional group, and n is 0. A cationic functional group-containing polysiloxane resin composition containing one or a combination of two or more kinds of the cationic organosilicon compound c1 in which n is 1 or the cationic organosilicon compound c2 in which n is 1. A coating composition using a cationic functional group-containing polysiloxane resin composition, which comprises a neutralizing agent and pure water. 4. A component a consisting of one or more kinds of organosilicon compounds having three alkoxy groups in one molecule, and two alkoxy groups or two silanol groups in one molecule, or 1 1 each having a combination comprising at least one alkoxy group and one silanol group
Having a component b consisting of two or more kinds of organosilicon compounds and the general formula shown in Chemical formula 1, R1 is an organic group having 1 to 8 carbon atoms, and R2 is an organic group having 1 to 5 carbon atoms. And X is an organic group having 1 to 8 carbon atoms, K is a cationic functional group, and n is 0, a cationic organosilicon compound c1
Or a component c consisting of one kind or a combination of two or more kinds of the cationic organosilicon compound c2 in which n is 1.
And, Pure water and components a and b, which have a molar ratio r of the component a and the cationic organosilicon compound c1 and the component b and the cationic organosilicon compound c2 represented by the formula 1 are 1 or more,
Component c is 10 to 30 mol% with respect to the total number of moles of c, and pure water is mixed in an amount of 0.8 equivalent or more with respect to the alkoxy group, and hydrolysis and condensation reaction are performed to obtain A method for producing a cationic functional group-containing polysiloxane resin composition, comprising: [Equation 1] 5. The cationic functional group according to claim 4, wherein the cationic functional group of the component c is obtained by an addition reaction between an isocyanate group and activated hydrogen in a hydroxyl group of a tertiary amine amino alcohol. A method for producing a functional group-containing polysiloxane resin composition. 6. The cationic functional group-containing polysiloxane resin according to claim 4, wherein the cationic functional group of the component c is obtained by an addition reaction of an epoxy group and activated hydrogen of a secondary amine. A method for producing a composition.