JP2002363488A - Coating composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a coating composition excellent in stain resistance, weather resistance, impact resistance, or the like. SOLUTION: This coating composition contains a polyamine polyalkoxylate compound which is formed by adding alkylene oxide molecules to amino groups in a polyamine compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coating composition, and more particularly to a coating composition having excellent stain resistance, weather resistance, impact resistance, and the like.

[0002]

2. Description of the Related Art Conventionally, coating compositions have been used, especially as paints, for buildings, structures, automobiles, vehicles, electrical equipment,
It is applied to the surface of precision equipment and the like, and it is required to have a beautiful appearance of the painted surface, weather resistance to external temperature, humidity and other climates, cracking of the coating film due to mechanical shock, prevention of peeling, and the like. However, a coating composition that has been conventionally used has not been obtained that satisfies all of stain resistance, weather resistance and impact resistance.

[0003]

DISCLOSURE OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and has the following effects.
An object of the present invention is to provide an excellent coating composition having both satisfactory impact resistance and mechanical strength.

[0004]

The inventors of the present invention have made intensive studies on the above problems, and as a result, a coating composition containing a specific polyamine polyalkoxylate compound is a coating composition that can solve the above problems. Thus, the present invention has been completed.

That is, the coating composition of the present invention is characterized by containing a polyamine polyalkoxylate compound in which an alkylene oxide is added to an amino group in the polyamine compound.

The polyamine polyalkoxylate compound is, for example, represented by the following general formula (1):

[0007]

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Wherein R ¹ represents an alkylene group;
X and Y are integers of 0 or more, and the sum of X and Y is 1 or more. )) Is obtained by adding an alkylene oxide to the amino group in the polyalkyleneimine.

The weight percentage of the (poly) oxyalkylene group in the polyamine polyalkoxylate compound is from 20 to
It is preferably contained within a range of 98% by weight,
More preferably, it is contained within the range of 95% by weight.

[0010] Further, a coating composition containing the above-mentioned polyamine polyalkoxylate compound and a curing agent as main components is particularly preferable.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The coating composition of the present invention contains, as an essential component, a polyamine polyalkoxylate compound obtained by adding an alkylene oxide to an amino group in a polyamine compound.

The content of the polyamine polyalkoxylate compound in the coating composition of the present invention is not particularly limited, but is usually 1 to 90% by weight, 10 to 8% by weight.
The content is preferably in the range of 0% by weight, more preferably in the range of 20 to 60% by weight.

The polyamine polyalkoxylate compound used in the present invention can be obtained by adding an alkylene oxide to an amino group in the polyamine compound in a specific number of moles. Weight% of (poly) oxyalkylene groups in the obtained polyamine polyalkoxylate compound
Is preferably contained within a range of 20 to 98% by weight, more preferably within a range of 30 to 95% by weight.

When the coating composition of the present invention is used as a coating material, a polyamine polyalkoxylate compound having a reduced content of low boiling impurities is preferred from the viewpoint of working environment, handling safety and the like. The total content of light impurities such as 2,3-butanedione, acetonitrile, dioxane, acetaldehyde and acetone in the polyamine polyalkoxylate compound is 10 pp.
m or less, more preferably 5 ppm or less.

The polyamine used as a raw material for the polyamine alkoxylate compound is not particularly limited, but is a polymer containing an amino group reactive with an alkylene oxide. For example, N-vinylformamide, N-
Alkenylcarboxylic acid amides such as vinylacetamide, polymers or copolymers such as allylamine, acrylamide and methacrylamide, ethyleneimine,
A ring-opened polymer of an alkylene imine such as methylethylene imine (polyalkylene imine); and the functional group may be modified with an amine after forming the polymer. For example,
Polyvinylamine, vinylformaldehyde and the like. Among these, polyalkyleneimine is preferable, and examples thereof include a compound represented by the general formula (1).

The polyalkyleneimine is not particularly limited, but is, for example, one obtained by adding an alkyleneimine to a compound or halide having active hydrogen. Examples of the compound having active hydrogen include water, alcohol, amine, acid and the like, and specific examples include ammonia, ethanolamine, diethyltriamine, ethylenediamine, and triethylenetetramine.
Examples of the halide include ethylene dichloride. The alkyleneimine is preferably an alkyleneimine having 2 to 4 carbon atoms, and preferably has 2 carbon atoms.
Is more preferred.

The polyalkyleneimine may be linear or branched. For example, the polyalkyleneimine may be polyethyleneimine “Epomin SP-018” (manufactured by Nippon Shokubai Co., Ltd.). Primary amine 35%, secondary amine 35%, tertiary amine 30%),
BASF's polyethylene imine "Lupasol G3"
5 "(typical branching degree 38%, secondary amine 36%, tertiary amine 26%) and the like. The average molecular weight of the polyalkyleneimine is 100 to 15
Although the range of 100,000 is preferable, the stain resistance of the coating film,
In consideration of weather resistance and impact resistance, it is preferably 300 to 1
It is in the range of 10,000, more preferably in the range of 300 to 50,000.

The polyamine polyalkoxylate compound is obtained, for example, by adding an alkylene oxide to the amino group in the polyalkyleneimine represented by the general formula (1) in a specific addition mole number.

The alkylene oxide used is not particularly limited, but ethylene oxide having 2 to 4 carbon atoms, propylene oxide and butylene oxide are preferred, and ethylene oxide is particularly preferred. These may be used alone or in combination,
Blocks or random combinations may be alternately combined.

The (poly) oxyalkylene group in the above-mentioned polyamine polyalkoxylate compound can be contained in a range that does not substantially hinder the performance. However, the performance of the coating film such as stain resistance, weather resistance, impact resistance and the like can be improved. In order to sufficiently exhibit the effect, the content is preferably in the range of 20 to 98% by weight, and more preferably in the range of 30 to 95% by weight.

The reaction conditions for the reaction (alkoxylation) between the polyalkyleneimine and the alkylene oxide are not particularly limited. For example, the polyalkyleneimine and the alkylene oxide are preferably used as they are or, if necessary, diluted with a solvent. Can be synthesized by reacting at a temperature of 0 to 200 ° C, more preferably 120 to 180 ° C. At this time, an alkaline catalyst such as potassium hydroxide or sodium hydroxide may be used as the catalyst. Preferably, it is 0.8 to 1.1 mol or less, more preferably 0.9 to 1.1 mol based on the amino group of the polyalkyleneimine.
The addition reaction at 0 mol or less is carried out in the absence of a catalyst, and when adding an alkylene oxide in a molar amount greater than 0 mol, it is preferable to carry out the reaction using an alkali catalyst.

After the above-mentioned reaction, water is added to the mixture for 120 to 20 minutes.
It is preferable to perform deaeration at a temperature of 0 ° C, more preferably 140 to 180 ° C, to remove light impurities such as 2,3-butadione contained in the polyamine polyalkoxylate compound.

In the coating composition of the present invention, those containing the above-mentioned polyamine polyalkoxylate compound and a curing agent reactive with the polyamine polyalkoxylate as the main components are preferred. The total content of the polyamine polyalkoxylate compound and the curing agent in the coating composition of the present invention varies depending on the type of the curing agent, but is usually in the range of 10 to 100% by weight, and 50 to 100% by weight. It is preferably contained in the range, more preferably in the range of 60 to 100% by weight.

As the curing agent, polyisocyanate, blocked polyisocyanate, amino resin, polyaziridine, polyoxazoline, polyepoxy compound and the like are preferable.

Examples of the polyisocyanate include hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate and the like.

Examples of the blocked isocyanate include compounds obtained by blocking the above polyisocyanate with methyl ethyl ketoxime, acetoxime, caprolactam and the like. The amount of the polyisocyanate or the blocked isocyanate used is determined by the amount of the hydroxyl group and the amine group (NH group) in the polyamine polyalkoxylate compound.
It is 0.8 to 1.2 equivalent, preferably equivalent to the amount.

Examples of the amino resin include alkyl etherified melamine resins such as methyl etherified and butyl etherified, alkyl etherified urea resins, alkyl etherified benzoguanamine, and the like. The amount of the amino resin used is preferably 5 to 80 parts by weight as the solid content of the amino resin based on 100 parts by weight of the polyamine polyalkoxylate.

Examples of the polyepoxy compound include diglycidyl ether, ethylene glycol diglycidyl ether, bisphenol A diglycidyl ether, resorcinol diglycidyl ether, triglycidyl isocyanurate and the like. The amount of the polyepoxy compound used is 0.8 to 0.8 with respect to the amount of hydroxyl groups and amine groups (NH groups) in the polyamine polyalkoxylate compound.
1.2 equivalents, preferably equivalent.

The coating composition of the present invention may contain, as auxiliary components, pigments, dyes, antioxidants, viscosity modifiers, fillers, and other various additives which are usually added as necessary.

The coating composition of the present invention can be used as a coating solution dissolved or dispersed in an organic solvent, water or the like. The polyamine polyalkoxylate compound in the coating composition is usually in the range of 1 to 90% by weight, preferably in the range of 10 to 80% by weight, and more preferably in the range of 20 to 60% by weight. Is more preferred.

When the coating composition of the present invention is applied to the surface of an object to be coated, a coating excellent in stain resistance, weather resistance and impact resistance can be easily formed. Therefore, the coating composition of the present invention is a stain-resistant paint, a weather-resistant paint,
It is suitable for applications such as antistatic paint.

As a method for applying the coating composition of the present invention, any method such as spray coating, dip coating, roll coater coating, and electrodeposition coating can be employed.

Examples of articles to be painted include vehicles such as automobiles and trains, buildings, building materials, and electric devices.

[0034]

The present invention will be described below with reference to examples of the present invention.
The present invention is not limited to these examples. In addition, the numerical values shown in the tables of the examples indicate% by weight.

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples.
In addition, the numerical values shown in the tables of the examples indicate% by weight.

Synthesis Example of Compound (1 ) 344.6 g of polyethyleneimine having an average molecular weight of 1800 (trade name "SP-018" manufactured by Nippon Shokubai Co., Ltd.)
It was charged into a 1.2 L autoclave and heated to 150 ° C. Thereafter, 176.2 g of ethylene oxide was fed to add ethylene oxide to polyethylene imine.

Then, the mixture was cooled to 80 ° C., adjusted to pH 7 by adding acetic acid, pure water was added at 10% by weight based on the total amount of the polyethyleneimine polyethoxylate compound, and nitrogen bubbling was performed at a flow rate of 20 ml / min. The pressure was reduced to 0.005 MPa while degassing was performed for 5 hours to remove light impurities, thereby obtaining the target compound (1). As a result of analyzing light impurities in the obtained compound (1) by gas chromatography (GC), the concentration of acetaldehyde was 1.
Each concentration of 2 ppm, acetonitrile, acetone, 2,3-butanedione, and dioxane was 1 ppm or less.
The polyethoxylate group in the compound (1) is 3
It was 3.8% by weight.

Synthesis Example of Compound (2 ) 172.3 g of polyethyleneimine having an average molecular weight of 1800 (trade name “SP-018” manufactured by Nippon Shokubai Co., Ltd.)
It was charged into a 1.2 L autoclave and heated to 150 ° C. Thereafter, ethylene oxide was added to polyethyleneimine by feeding 167.4 g of ethylene oxide.

Then, the mixture was cooled to 80 ° C., 2.5 g of a 49% KOH aqueous solution was charged, and the temperature was raised to 165 ° C.
The pressure was reduced to 0.05 MPa while bubbling nitrogen at a flow rate of 1 minute, and after dehydration, 361.0 g of ethylene oxide was added.
Feeding added ethylene oxide to the polyethylene imine.

After cooling to 80 ° C. and adjusting the pH to 7 by adding acetic acid, pure water was added at 10% to the total amount of polyethyleneimine polyethoxylate, and the water was added while bubbling with nitrogen at a flow rate of 20 ml / min. The pressure was reduced to 0.005 MPa, degassing was performed for 5 hours, and light impurities were removed to obtain the target compound (2). As a result of analyzing light impurities in the obtained compound (2) by gas chromatography,
The acetaldehyde concentration was 2.1 ppm, and the concentrations of acetonitrile, acetone, 2,3-butanedione, and dioxane were 1 ppm or less. Incidentally, the polyethoxylate group in the compound (2) was 75.4% by weight.

Synthesis Example of Compound (3) In the synthesis example of compound (1), propylene oxide 23 was used instead of 176.2 g of ethylene oxide.
Except that 2.2 g was used, the target compound (3) was obtained in the same manner as the compound (1). As a result of analyzing light impurities in the obtained compound (3) by gas chromatography, the concentration of acetaldehyde was 1.5 ppm, and the concentrations of acetonitrile, acetone, 2,3-butanedione, and dioxane were 1 ppm or less. The compound (3)
The content of polypropoxylate groups therein was 40.3% by weight.

Synthesis Example of Compound (4) After the ethylene oxide addition reaction in the compound (1),
The target compound (4) was obtained by omitting the degassing step. As a result of analyzing light impurities in the obtained compound (4) by gas chromatography, the concentration of acetaldehyde was 19.3.
ppm, the concentration of acetone is 4.4 ppm, the concentration of 2,3-butanedione is 11 ppm, and the concentration of dioxane is 8 ppm.
1.7 ppm and the concentration of acetonitrile were 1 ppm or less. The polyethoxylate group in the compound (4) was 33.8% by weight.

Synthesis Example of Compound (5) Polyethyleneimine having an average molecular weight of 1800 (trade name “SP-018” manufactured by Nippon Shokubai Co., Ltd.) was used as Compound (5). As a result of analyzing light impurities in the obtained compound (5) by gas chromatography (GC), the concentration of acetonitrile was 51 ppm, acetaldehyde, acetone,
Each concentration of 2,3-butanedione and dioxane is 1 ppm
It was below. Examples 1 to 4 Polyamine polyalkosylates of compounds (1) to (4) and an oxime block of hexamethylene diisocyanate, and dibutyl dilaurate as a curing catalyst were mixed, and coating compositions (1) to (4) were prepared. I got The oxime block of hexamethylene diisocyanate is obtained by reacting hydroxyl groups and NH in polyamine polyalkoxylate.
It mixed so that the total molar amount of the group and the molar amount of the isocyanate group might be equivalent. The amount of dibutyl dilaurate added was 250 pp based on polyamine polyalkylate.
m.

Next, each coating composition was applied to a chromated hot-dip galvanized steel sheet so that the thickness of the coating film became 30 μm, and baked at 230 ° C. to obtain coated steel sheets 1 to 3 according to the present invention. Obtained.

Example 5 A polyamine polyalkoxylate of the compound (1) and ethylene glycol diglycidyl ether were mixed in methanol to obtain a coating composition (5). Ethylene glycol diglycidyl ether is the total molar amount of hydroxyl groups and NH groups in the polyamine polyalkoxylate,
Mixing was performed so that the molar amount of the epoxy group became equal.

Then, the coated steel sheet was applied to the chromate-treated galvanized steel sheet and dried at 100 ° C. to obtain a coated steel sheet 4 having a coating thickness of 30 μm.

Comparative Example 1 The polyamine polyalkoxylate of Compound 5 was prepared in Example 1.
3 to obtain a coated steel sheet 5 . (Performance test of coated steel sheet) Stain resistance test Actual exposure was performed outdoors (south direction, 30 ° inclination) for 3 months, and stain on the coated surface was observed. ○ is clean,
Δ indicates that there is slight dirt, and X indicates that there is dirt. Chipping Resistance Test (Impact Resistance Test) After spraying 50 g of No. 7 crushed stone at an angle of 45 degrees with respect to the coated surface at an air pressure of 4 kg / cm 2, the coated surface was observed. ○ indicates that there was no abnormality in the coating surface, △ indicates that cracks occurred, and X indicates that peeling occurred.

As a test for accelerating the weather resistance test , measurement was carried out for 1000 hours with a weather meter, and the coated surface was observed. ○ indicates that no abnormality was observed, △ indicates that discoloration was slightly observed, and X indicates that discoloration was observed.

[0049]

[Table 1]

[0050]

The coating composition of the present invention has the effect of improving the properties of the coating film, such as stain resistance, weather resistance, impact resistance and mechanical strength. Although the cause is not clear, the dispersibility is increased by the polyamine polyalkoxylate compound obtained by adding an alkylene oxide to the amino group in the polyamine compound contained in the coating composition of the present invention, and the polyamine polyalkoxy compound has a higher dispersibility. It is presumed that the composition will be more excellent due to the resistance of the alkoxylate itself to acidic substances due to amines, the ability to release stains derived from polyoxyalkylene groups, and the flexibility of the coating film.

Accordingly, the coating composition of the present invention is useful as a coating composition for buildings, building materials, structures, vehicles such as automobiles and trains, electric equipment, precision equipment and the like.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J038 DA112 DB002 DG101 DG261 DG301 DJ002 DJ011 GA09 KA03 NA03 NA05 NA11 PB05 PB06 PB07 PB09

Claims (2)

[Claims] 1. A coating composition containing a polyamine polyalkoxylate compound obtained by adding an alkylene oxide to an amino group in the polyamine compound. 2. The coating composition according to claim 1, comprising the polyamine polyalkoxylate compound and a curing agent as main components.