JP2003253197A - Antifouling agent for aqueous coating material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antifouling agent for an aqueous coating material, which is added to the aqueous coating material, is excellent in stability after added, and prevents a surface coated with the aqueous coating material from rain streaks or blackishness, maintaining the luster of the coated surface. <P>SOLUTION: This antifouling agent contains a cross-linked polymer formed by the ring-opening addition polymerization of an epoxy compound selected from the group consisting of monool glycidyl ethers and polyol glycidyl ethers with a hydroxylated compound selected from the group consisting of monools, polyols, and polyoxyalkylene compound formed by substituting a monool or a polyol with a polyoxyalkylene group. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is added to a water-based paint used for coating building materials, structures, etc., and it is an antifouling agent that prevents the paint surface of the water-based paint from being contaminated with rain marks and dust. It is related to agents.

[0002]

2. Description of the Related Art Conventionally, oil-based paints have been widely used as paints for coating beautiful building materials and exteriors of buildings, and improving weather resistance and water resistance. Instead, water-based paints have been used that do not damage the health of painters.

The exposed surface of the water-based paint, when exposed to light rain,
Rain flows on the surface and dries to form rain marks, and since the adsorbed hydrophobic dust is infiltrated due to the low hardness of the coating film on the surface of the paint, it is easier to stain than the surface of the oil paint. Therefore, in order to make it difficult to adsorb dust and make it easier to wash with rainwater, an antifouling agent such as an alcosoxysilane-modified condensate that imparts hydrophilicity to the coated surface is added in advance to the water-based paint. There is.

[0004] The alkoxyxylan-modified condensate undergoes a hydrolytic condensation reaction when mixed with an aqueous paint, causing an increase in viscosity during storage of the paint, resulting in difficulty in coating the paint or in the paint. It may cause aggregates. Therefore, the gloss of the surface of the coating film becomes poor. Further, the coated surface is easily absorbed by the adsorbed hydrophobic dust and becomes dark.

[0005]

The present invention has been made in order to solve the above-mentioned problems, and is used by adding it to a water-based paint, which is excellent in stability after addition, It is an object of the present invention to provide an antifouling agent for water-based paints that does not cause rain marks or darkening on the painted surface and does not reduce the glossiness of the painted surface.

[0006]

The antifouling agent for water-based paints of the present invention made to achieve the above object is an epoxy group-containing compound selected from glycidyl ethers of monools and glycidyl ethers of polyols. And a hydroxyl group-containing compound selected from the group consisting of monools and polyols, and polyoxyalkylenes substituted with polyoxyalkylene groups.

The epoxy group-containing compound preferably has an epoxy equivalent of up to 3,000. The epoxy equivalent is the molecular weight of the epoxy group-containing compound divided by the number of epoxy groups in one molecule. Epoxy equivalent is 3,
If it exceeds 000, the antifouling property and the dust penetration resistance of the coating film formed by coating the water-based paint containing the antifouling agent for water-based paint deteriorates. Epoxy equivalent is 100 ~
More preferably, it is 1,000.

Examples of the epoxy group-containing compound include monool glycidyl ethers such as butyl glycidyl ether and ethylhexyl glycidyl ether. Also, as glycidyl ethers of polyols,
Specifically, alkylene diglycidyl ether having 4 to 18 carbon atoms, glycerin diglycidyl ether, polyoxyethylene glycol diglycidyl ether, polyalkylene glycol diglycidyl ether, for example, diglycidyl ether such as polypropylene glycol diglycidyl ether; trimethylol Triglycidyl ethers such as propane triglycidyl ether and glycerol triglycidyl ether; and polyglycidyl ethers such as sorbitol polyglycidyl ether. These epoxy group-containing compounds may be used alone or in combination.

The hydroxyl group-containing compound has a maximum hydroxyl group equivalent of 3,
It is preferably 000. The hydroxyl equivalent is the molecular weight of the hydroxyl group-containing compound divided by the number of hydroxyl groups in one molecule. When the hydroxyl group equivalent exceeds 3,000, the antifouling property and the dust permeation resistance of the coating film formed by coating the aqueous paint containing the antifouling agent for the aqueous paint are deteriorated. The hydroxyl equivalent is more preferably 80 to 1,000.

The hydroxyl group-containing compound is a monool such as a saturated lower monoalcohol such as hexanol; a saturated higher monoalcohol such as stearyl alcohol; and an unsaturated monoalcohol such as 3-methyl-1-butyn-3-ol. Examples include alcohol. Examples of polyols include saturated diols such as ethylene glycol and butanediol; 2,4,7,9-tetramethyl-5-
Unsaturated diols such as decyne-4,7-diol; trimethylolpropane, triols such as glycerin; sorbitol, polyols such as cellulose derivatives. As polyoxyalkylenes in which these are substituted with a polyoxyalkylene group, alkylene oxide adducts such as polyethylene glycol; alkoxy polyoxyalkylene alkyl ethers; polyoxyalkylene fatty acid esters such as polyoxyethylene oleate; polyoxy Alkylene alkyl ethers; polyoxyalkylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monooleate. These hydroxyl group-containing compounds may be used alone or in combination.

The number of epoxy groups in the epoxy group-containing compound,
The ratio with the number of hydroxyl groups of the hydroxyl group-containing compound is 2: 1 to 1: 2.
Is preferred.

The ring-opening addition polymer is added to the epoxy group of the epoxy group-containing compound while the hydroxyl group of the hydroxyl group-containing compound is ring-opening, and is sequentially ring-opened and added to another epoxy group-containing compound to form a network. It is a crosslinked polymer. This ring-opening addition reaction is preferably carried out by heating in the presence of a catalyst such as dimethylbenzylamine.

The antifouling agent for water-based paint may contain a solvent such as isopropyl alcohol.

The antifouling agent is added in an amount of 0.5 to 10 in the water-based paint.
It is preferably contained in a weight percentage.

The water-based paint of the present invention contains the above-described antifouling agent for water-based paint. The antifouling agent is preferably contained in the water-based paint in an amount of 0.2 to 5% by weight in terms of solid content. More preferably about 5% by weight.

Since the antifouling agent is stable and does not decompose in the water-based paint containing the antifouling agent, the viscosity does not increase during storage. The surface of the coating film formed by applying this paint has no rain mark or darkening and has excellent gloss.

[0017]

EXAMPLES Examples of the antifouling agent for water-based paints of the present invention will be described in detail below.

Examples of preparation of antifouling agents for water-based paints to which the present invention is applied are shown in Examples 1 to 6, and examples of preparations of antifouling agents for aqueous paints to which the present invention is not applied are shown in Comparative Examples 1 to 3. Show.

Example 1 100.0 parts by weight of Epolite 200E (trade name of Kyoeisha Chemical Co., Ltd.), which is a polyoxyethylene glycol # 200 diglycidyl ether as an epoxy group-containing compound, and polyoxyethylene olein as a hydroxyl group-containing compound. 100.0 parts by weight of acid ester Noniolite O-30 (trade name of Kyoeisha Chemical Co., Ltd.) was mixed. After adding 1.0 part by weight of dimethylbenzylamine as a catalyst thereto, the mixture was stirred at 105 ° C. for 8 hours to ring-open the addition of the epoxy group-containing compound and the hydroxyl group-containing compound to obtain a crosslinked polymer. After the reaction, the mixture was cooled to 70 ° C. and diluted with 200 parts by weight of isopropyl alcohol to obtain an antifouling agent for water-based paint.

(Example 2) 100.0 parts by weight of Epiol EH (trade name of NOF Corporation), which is 2-ethylhexyl glycidyl ether as an epoxy group-containing compound,
As the hydroxyl group-containing compound, 100.0 parts by weight of polyoxyethylene glycol # 200 (trade name of Sanyo Kasei Co., Ltd.) was mixed. After adding 1.0 part by weight of dimethylbenzylamine as a catalyst thereto, the mixture was stirred at 105 ° C. for 8 hours to ring-open the addition of the epoxy group-containing compound and the hydroxyl group-containing compound to obtain a crosslinked polymer. After the reaction, the mixture was cooled to 70 ° C. and diluted with 200 parts by weight of isopropyl alcohol to obtain an antifouling agent for water-based paint.

Example 3 100.0 parts by weight of Epolite 200E (trade name of Kyoeisha Chemical Co., Ltd.), which is polyoxyethylene glycol # 200 diglycidyl ether as an epoxy group-containing compound, and polyoxyethylene glycol as a hydroxyl group-containing compound. 100.0 parts by weight of # 400 (trade name of Sanyo Kasei Co., Ltd.) was mixed. After adding 1.0 part by weight of dimethylbenzylamine as a catalyst to this, 1
The mixture was stirred at 05 ° C. for 8 hours, and the epoxy group-containing compound and the hydroxyl group-containing compound were ring-opened to give a crosslinked polymer. After the reaction, the mixture was cooled to 70 ° C. and diluted with 200 parts by weight of isopropyl alcohol to obtain an antifouling agent for water-based paint.

Example 4 Epolite 80, which is glycerin diglycidyl ether as an epoxy group-containing compound
80.0 parts by weight of MF (trade name of Kyoeisha Chemical Co., Ltd.) and 100.0 parts by weight of noniolite SPO-1 (trade name of Kyoeisha Chemical Co., Ltd.), which is a polyoxyethylene sorbitan monooleate as a hydroxyl group-containing compound. Mixed. After adding 1.0 part by weight of dimethylbenzylamine as a catalyst thereto, the mixture was stirred at 105 ° C. for 8 hours to ring-open the addition of the epoxy group-containing compound and the hydroxyl group-containing compound to obtain a crosslinked polymer. After the reaction, cool to 70 ° C. and isopropyl alcohol 1
80 parts by weight was added and diluted to obtain an antifouling agent for water-based paint.

(Embodiment 5) Epolite 100MF (trade name of Kyoeisha Chemical Co., Ltd.) which is trimethylolpropane triglycidyl ether as an epoxy group-containing compound 5
0.0 parts by weight and noniolite O-30, which is a polyoxyethylene oleate as a hydroxyl group-containing compound
(Trade name of Kyoeisha Chemical Co., Ltd.) 100.0 parts by weight were mixed. Dimethylbenzylamine 1.0 which is a catalyst for this
After adding parts by weight, the mixture was stirred at 105 ° C. for 8 hours, and the epoxy group-containing compound and the hydroxyl group-containing compound were subjected to ring opening addition to obtain a crosslinked polymer. After the reaction, the mixture was cooled to 70 ° C. and diluted with 150 parts by weight of isopropyl alcohol to obtain an antifouling agent for water-based paint.

Example 6 100.0 parts by weight of Epolite 200E (trade name of Kyoeisha Chemical Co., Ltd.), which is polyoxyethylene glycol # 200 diglycidyl ether as an epoxy group-containing compound, and 2,4 as a hydroxyl group-containing compound. 7,9-Tetramethyl-5-decyne-4,7-
100.0 parts by weight of Surfynol 420 (trade name, manufactured by Nisshin Chemical Co., Ltd.), which is an ethylene oxide adduct of diol, was mixed. After adding 1.0 part by weight of dimethylbenzylamine as a catalyst thereto, the mixture was stirred at 105 ° C. for 8 hours to ring-open the addition of the epoxy group-containing compound and the hydroxyl group-containing compound to obtain a crosslinked polymer. After the reaction, the mixture was cooled to 70 ° C. and diluted with 200 parts by weight of isopropyl alcohol to obtain an antifouling agent for water-based paint.

(Comparative Example 1) Ethyl silicate condensate which is a condensate of tetraethoxysilane (average molecular weight 750,
100.0 parts by weight of silica residual amount ratio (40% by weight) and 106.7 parts by weight of polyoxyethylene glycol # 200 (trade name of Sanyo Chemical Co., Ltd.) were mixed. After adding 0.02 part by weight of dibutyltin dilaurate as a catalyst to this, 75
The ethanol removal reaction was carried out at 8 ° C. for 8 hours to obtain an alkoxysilane-modified condensate as an antifouling agent.

Comparative Example 2 Ethyl silicate condensate (average molecular weight 750, silica residual ratio 40% by weight) 100.
0 parts by weight and 81.7 parts by weight of polyoxyethylene glycol monocetyl ether Noniolite AC-10 (trade name of Kyoeisha Chemical Co., Ltd.) were mixed. After adding 0.02 part by weight of dibutyltin dilaurate as a catalyst to this, a deethanolation reaction was carried out at 75 ° C. for 8 hours to obtain an alkoxysilane-modified condensate as an antifouling agent.

(Comparative Example 3) Ethyl silicate condensate (average molecular weight 900, silica residual ratio 45% by weight) 100.
0 parts by weight and polyoxyethylene lauryl ether Noniolite AL-20 (trade name of Kyoeisha Chemical Co., Ltd.)
385.4 parts by weight were mixed. After adding 0.02 part by weight of dibutyltin dilaurate as a catalyst to this, a deethanolation reaction was carried out at 75 ° C. for 8 hours to obtain an alkoxysilane-modified condensate as an antifouling agent.

After adding the antifouling agents obtained in Examples 1 to 6 and Comparative Examples 1 to 3 to the water-based paint, a viscosity stability test and a compatibility test were conducted. Further, this paint was applied to form a coating film, and a 60-degree specular gloss test, a water resistance test, a rain line trace antifouling test, and a dust penetration resistance test were conducted.

Aqueous paints were prepared prior to these tests.

45.22 parts by weight of water, 23.90 parts by weight of dispersant Floren TG-750W (trade name of Kyoeisha Chemical Co., Ltd.), and preservative ACTICIDE MV-4 (trade name of So Chemicals Co., Ltd.) 53 parts by weight and titanium oxide JR-600A (trade name of Teikoku Kako Co., Ltd.) 257.17
Parts by weight and thickener 3% CELLOSIZEQP-440
OH (trade name of Union Carbide Co.) 6.98 parts by weight. 300 parts by weight of glass beads having a diameter of 2.0 to 2.5 mm were added to this, and 2 at 1810 rpm.
It was dispersed by a time batch type sand grinder. After dispersion, filter the glass beads, then ethylene glycol 1
8.45 parts by weight, 59.12 parts by weight of Boncoat EC-853 (trade name of Dainippon Ink and Chemicals, Inc.), which is an acrylic-styrene emulsion resin, and a thickener Ticuzole K
-130B (Kyoeisha Chemical Co., Ltd. trade name) 30.59 parts by weight, film-forming aid Texanol (Eastman Co. trade name) 38.24 parts by weight, and water 47.80 parts by weight are added, and paint is added. The mixture was mixed with a shaker for 20 minutes to obtain an acrylic-styrene emulsion paint which is a water-based paint.

(Viscosity stability test) 100.0 parts by weight of the water-based paint was mixed with 5% by weight of the antifouling agent of Examples 1 to 6 and Comparative Examples 1 to 3 in terms of solid content. A water-based paint was prepared. Immediately, the viscosity was measured with a B-type viscometer (manufactured by Shibaura System Co., Ltd.). Next, temperature 25 ℃ relative humidity 6
After storing at 5% for 48 hours, the viscosity was measured again. The case where the increase in viscosity after storage was less than 0.5 Pa · s was evaluated as ◯, and the case where the increase in viscosity after storage was 0.5 Pa · s or more was evaluated as x. The results are shown in Table 1.

(Compatibility test) 100.0 parts by weight of the water-based paint was mixed with 5% by weight of the antifouling agent of Examples 1 to 6 and Comparative Examples 1 to 3 in terms of solid content, and each was mixed with an antifouling agent. A water-based paint was prepared. After storing at a temperature of 25 ° C. and a relative humidity of 65% for 48 hours, the presence or absence of foreign matter was visually observed. The case where the foreign matter was excellent and the foreign matter was not recognized at all was marked with ○, and the case where a lump of foreign matter was recognized even slightly was marked with 2
The grade was evaluated. The results are shown in Table 1.

(60-degree specular gloss test) Water-based paint 10
0.0 parts by weight and 5% by weight in terms of solid content of the antifouling agents of Examples 1 to 6 and Comparative Examples 1 to 3 were mixed to prepare antifouling agent-containing aqueous coatings. A blank consisting of only water-based paint and water-based paint containing each antifouling agent were applied to a transparent glass plate having a length of 200 mm, a width of 100 mm and a thickness of 1 mm, and a film thickness of 150.
It was coated with an applicator so that it had a thickness of μm, and dried and cured at a temperature of 25 ° C. and a relative humidity of 65% for 7 days.
According to Z 8741 (1997) specular gloss, the gloss value at an angle of 60 degrees was measured. The results are shown in Table 1.

(Water resistance test) First, Epicoat 1001
-X-70 (trade name of Yuka Shell Epoxy Co., Ltd.) 27.
0 parts by weight, titanium oxide R-820 (trade name of Ishihara Sangyo Co., Ltd.) 20.0 parts by weight, talc ND (trade name of Nippon Talc Co., Ltd.) 13.0 parts by weight, precipitated barium sulfate 13.0 parts by weight Part, xylene 22 parts by weight and methyl isobutyl ketone 5 parts by weight, 27.0 parts by weight, a curing agent Versamide 115 (trade name of Henkel Hakusui Co., Ltd.) and the above-mentioned thinner in a mixture of 70:30 by weight 25. Parts by weight,
The mixture was uniformly mixed to prepare an epoxy resin base paint. Vertical 1
This epoxy resin base paint is spray coated on a flexible plate 50 mm wide, 70 mm wide and 3 mm thick so that the dry film thickness is about 30 μm, and the temperature is 25 ° C. and the relative humidity is 65%.
Allowed to dry for hours. Next, each of 100.0 parts by weight of the above-mentioned water-based coating and 5 weight% of the antifouling agent of Examples 1 to 6 and Comparative Examples 1 to 3 in terms of solid content is mixed with each of the water-based coatings containing an antifouling agent. Was spray-coated so that the dry film thickness was 40 μm. This was dried and cured at a temperature of 25 ° C. and a relative humidity of 65% for 7 days, and then JIS K 5660 (1995) 4.1.
In accordance with 0, the gloss retention after dipping in water at 20 ° C. for 96 hours was calculated. When the gloss retention rate was 90% or more, it was ⊚, and when it was 80% or more and less than 90%, it was ◯.
The evaluation was made in 3 grades with x being less than%. The results are shown in Table 1.

(Rain mark trace stain resistance test) Height 300 mm Width 1
An aluminum plate having a thickness of 50 mm and a thickness of 3.0 mm was erected, and was bent into a mountain fold at a height of ⅔ from the lower end so that the internal angle was 135 degrees. The epoxy resin undercoat prepared in the water resistance test was spray-coated on the mountain fold surface of the aluminum plate so that the dry film thickness was about 30 μm, and dried at a temperature of 25 ° C. and a relative humidity of 65% for 8 hours. . To this, 100.0 parts by weight of the above-mentioned water-based paint, and
6 and 5% by weight in terms of solid content of the antifouling agents of Comparative Examples 1 to 3.
Each of the antifouling water-based paints mixed with and was spray-painted so that the dry film thickness was about 40 μm, and the temperature was 25 ° C.
It was dried at 65% relative humidity for 7 days. The mountain fold was turned to the south and exposed to the rain for 3 months outdoors. Then, the presence or absence of rain streaks on the surface of the coating film was visually observed. The case where no rain streak was observed was rated as ⊚, the case where extremely slight rain streak was recognized was rated as ◯, and the case where a clear rain streak was recognized was rated as x. The results are shown in Table 1.

(Dust Staining Resistance Test) An epoxy resin undercoat prepared in the above water resistance test was dried to a film thickness of 3 on an aluminum plate having a length of 150 mm, a width of 75 mm and a thickness of 0.8 mm.
Spray coating was performed so as to have a thickness of 0 μm, and drying was performed for 8 hours at a temperature of 25 ° C. and a relative humidity of 65%. In addition, 100.0 parts by weight of the above-mentioned water-based paint, Examples 1 to 6 and Comparative Examples 1 to 1
Each of the antifouling agent-containing water-based paints mixed with 5% by weight of the antifouling agent of 3 in terms of solid content was spray-coated so that the dry film thickness was 40 μm. This is the temperature 25 ℃ relative humidity 65
% Of JIS K 5400 (1
990) According to the stain resistance test of 8.10, a 15% by weight carbon black aqueous dispersion paste solution was dropped onto the surface of the coating film so as to have a diameter of 20 mm and a height of 5 mm, and stored in a thermostatic chamber at 50 ° C. for 2 hours. did. Then, the surface was washed with running water, and the extent to which carbon black, which was dust, had permeated the surface of the coating film was visually observed. The case where no trace of carbon black was observed on the surface of the coating film was marked with ⊚, the one with a slight amount was marked with ○, and the one clearly recognized was marked with ×.
It was evaluated in three stages. The results are shown in Table 1.

[0037]

[Table 1]

As is clear from Table 1, the water-based paints containing the antifouling agents of Examples 1 to 6 have viscosity stability, compatibility, glossiness, water resistance and rain mark antifouling property, and dust resistance. The dyeability was excellent. On the other hand, the water-based paints containing Comparative Examples 1 to 3 had antifouling properties, viscosity stability, compatibility, glossiness,
It was inferior in rain trace stain resistance and dust stain resistance.

[0039]

As described above in detail, the antifouling agent for water-based paints of the present invention can be easily produced at low cost. The water-based paint containing the antifouling agent has a low viscosity, does not generate lumpy foreign matter as a by-product, and is easy to handle. A paint film formed by applying an antifouling agent-containing water-based paint has excellent gloss and water resistance. The coating film has no traces of rain, and dust is hard to be absorbed so that it is not dyed. Furthermore, even if it is added to a highly glossy paint such as gloss paint, it does not affect the gloss value of the coating film formed by applying it.

Claims (4)

[Claims] 1. A glycidyl ether of monool,
And ring-opening addition of an epoxy group-containing compound selected from glycidyl ethers of polyols, and a hydroxyl group-containing compound selected from any of monools and polyols, and polyoxyalkylenes substituted with polyoxyalkylene groups An antifouling agent for water-based paints, which comprises the cross-linked polymer as described above. 2. An antifouling agent for water-based paints, wherein the epoxy group-containing compound has an epoxy equivalent of 3,000 at maximum and the hydroxyl group-containing compound has a hydroxyl equivalent of 3,000 at maximum. 3. The ratio of the number of epoxy groups of the epoxy group-containing compound to the number of hydroxyl groups of the hydroxyl group-containing compound is
The antifouling agent for water-based paints according to claim 1, which is 2: 1 to 1: 2. 4. An aqueous paint comprising the antifouling agent for an aqueous paint according to claim 1.