JPH09124996A - Antibacterial water-base coating composition and antibacterial coating film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To form a coating film with high persistence of an antibacerial effect. SOLUTION: This coating composition contains an aqueous dispersion of an acetoacetoxylated copolymer obtained by copolymerizing a monomer containing a compound having polymerizable double bonds and acetoacetoxy groups, a polyamine compound, and antibacterial agents. The antibacterial agents contain, for example, an organic nitrogen- and sulfur-base antibacterial agent and a silver-containing antibacterial agent.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aqueous coating composition and a coating film, and more particularly to an antibacterial aqueous coating composition and an antibacterial coating film.

[0002]

2. Description of the Related Art So-called nosocomial infections have become a problem in medical facilities such as hospitals. As one of the simple means for preventing such nosocomial infections, application of antibacterial paint to medical facilities has been studied. In general, the antibacterial coating used here mainly contains an aqueous dispersion of a resin and an antibacterial agent such as an organic antibacterial agent or a silver-containing antibacterial agent.

[0003]

The above-mentioned paint can impart antibacterial properties to the coating film due to the antibacterial agent contained therein, but the antibacterial effect of the coating film is difficult to last for a long time.
Therefore, in order to maintain the antibacterial effect for a long period of time using such a paint, it is necessary to reapply the paint frequently, but when it is difficult to take a leave like medical facilities or when hygiene is particularly required. There is a problem in application in the facilities that are used.

An object of the present invention is to form a coating film having a high antibacterial effect.

[0005]

The antibacterial aqueous coating composition according to the present invention comprises an acetoacetoxy group-containing copolymer obtained by copolymerizing a monomer containing a compound having a polymerizable double bond and an acetoacetoxy group. It contains an aqueous dispersion of a polymer, a polyamine compound, and an antibacterial agent.

In such an antibacterial aqueous coating composition, the antibacterial agent contains, for example, an organic nitrogen sulfur antibacterial agent and a silver-containing antibacterial agent.

The antibacterial coating film according to the present invention is an aqueous dispersion of an acetoacetoxy group-containing copolymer obtained by copolymerizing a monomer containing a compound having a polymerizable double bond and an acetoacetoxy group. And an antibacterial water-based coating composition containing a polyamine compound and an antibacterial agent.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION An aqueous dispersion of an acetoacetoxy group-containing copolymer used in the present invention comprises, for example, a compound having a polymerizable double bond and an acetoacetoxy group in one molecule and a polymerizable diamine. A carboxyl compound having a heavy bond,
It can be obtained by emulsion polymerization with other monomers.

The compound having a polymerizable double bond and an acetoacetoxy group in one molecule used herein is
Examples thereof include acrylic acid esters and methacrylic acid esters having an acetoacetoxy group. Specific examples thereof include acetoacetoxyethyl acrylate and acetoacetoxyethyl methacrylate.

On the other hand, examples of the carboxyl compound having a polymerizable double bond include acrylic acid, methacrylic acid, itaconic acid and maleic acid. Also,
Other monomers include methyl, ethyl, propyl, n-butyl, i-butyl, t-butyl, 2-ethylhexyl, lauryl, phenyl, benzyl, 2-hydroxyethyl and 2-hydroxypropyl of acrylic acid or methacrylic acid. Esters, adducts of polycaprolactone with 2-hydroxyethyl (meth) acrylate, acrylic monomers such as acrylamide, methacrylamide, and derivatives of N-methylolacrylamide, and non-functional monomers such as styrene, α-methylstyrene, and vinyl acetate. Acrylic monomers can be exemplified.

The amount of the compound having a polymerizable double bond and an acetoacetoxy group used for producing an aqueous dispersion of an acetoacetoxy group-containing copolymer is usually 0.1 to 30% by weight of all monomers. %, Preferably 0.5 to 10% by weight, more preferably 1 to 10% by weight. If it is less than 0.1% by weight, the degree of crosslinking of the coating film obtained from the coating composition of the present invention may be insufficient. Conversely, 30
If the content is more than weight%, the physical properties of the resulting coating film may be adversely affected.

On the other hand, the amount of the carboxyl compound having a polymerizable double bond is preferably set so that the acid value of the copolymer becomes 10 to 50. When the acid value is less than 10, it is difficult to obtain a stable aqueous dispersion, and when it exceeds 50, the physical properties of the resulting coating film may be adversely affected. Other monomers can be used by appropriately selecting the amounts necessary for adjusting the physical properties of the resulting coating film.

The emulsion polymerization method for producing the aqueous dispersion of the acetoacetoxy group-containing copolymer is not particularly limited, and methods generally known to those skilled in the art can be used.

The polyamine compound used in the present invention is
For example, it has a plurality of primary or secondary amino groups in one molecule like 1,6-hexanediamine. As the polyamine compound, a polyoxyalkyleneamine compound, for example, Jeffamine D-230 and D-400 manufactured by Texaco Chemical Company,
The same ED-600 and the same ED-900 can also be used.

The antibacterial agent used in the present invention is an organic nitrogen-sulfur antibacterial agent or a silver-containing antibacterial agent. In general, when an organic antibacterial agent is used, a rapid antibacterial effect can be expected, and when a silver-containing antibacterial agent is used, a sustained antibacterial effect can be expected.
Therefore, in the present invention, it is preferable to use the organic nitrogen-sulfur antibacterial agent belonging to the organic antibacterial agent and the silver-containing antibacterial agent together.

The organic nitrogen-sulfur antibacterial agent used in the present invention is not particularly limited, and various commercially available ones can be used. Specific examples of the organic nitrogen-sulfur antibacterial agent include Slaoff series (trade name) manufactured by Takeda Pharmaceutical Co., Ltd. and KB-9 manufactured by Nippon Applied Chemistry Co., Ltd.
(Product name).

On the other hand, the silver-containing antibacterial agent used in the present invention is not particularly limited, and various commercially available antibacterial agents can be used. Specific examples of the silver-containing antibacterial agent include Amteclean Z manufactured by Matsushita Amtec Co., Ltd.
MK series (trade name), Ion Pure (trade name) made by Ishizuka Glass Co., Ltd., Bactekiller (trade name) made by Kanebo Co., Ltd., Apacider (trade name) made by Sanki Co., Ltd., Zeomic (made by Shinagawa Fuel Co., Ltd.) (Trade name), ice (trade name) manufactured by Catalyst Kasei Kogyo Co., Ltd., antibacterial ceramics (trade name) manufactured by Shinto V Cerax Co., Ltd., Novalon (trade name) manufactured by Toagosei Co., Ltd., Fuji Silysia Chemical Co., Ltd. Siriwell (trade name), Ameni Top (trade name) manufactured by Matsushita Electric Industrial Co., Ltd., Rentover (trade name) manufactured by Rengo Co., Ltd., and the like.

In the antibacterial aqueous coating composition of the present invention, the mixing ratio of the above-mentioned aqueous dispersion of the acetoacetoxy group-containing copolymer and the above-mentioned polyamine compound is based on the acetoacetoxy group of the acetoacetoxy group-containing copolymer. Therefore, the amino group of the polyamine compound is preferably set to 0.5 to 1.0 equivalent, and more preferably set to 0.6 to 0.8 equivalent. If the proportion of the polyamine compound is outside this range, the curability and water resistance of the coating film obtained from the composition of the present invention may be insufficient.

The proportion of the antibacterial agent in the composition of the present invention is 0.1 to the total weight of the solid content of the aqueous dispersion of the acetoacetoxy group-containing copolymer and the polyamine compound.
It is preferably set to 2.0% by weight. Also,
When the organic nitrogen-sulfur antibacterial agent and the silver-containing antibacterial agent are used in combination, it is preferable to add each antibacterial agent in the range of 0.05 to 1.0% by weight. When the proportion of the antibacterial agent is out of the above range, the coating film obtained by the composition of the present invention may not show sufficient antibacterial properties, and when the appearance characteristics of the coating film are impaired, for example, The color may change.

The antibacterial aqueous coating composition of the present invention usually contains other components such as an aqueous dispersion of the above-mentioned acetoacetoxy group-containing copolymer, a polyamine compound, an antibacterial agent and, if necessary, a pigment and various additives. It is obtained by mixing by the method of.

The antibacterial aqueous coating composition of the present invention is used for coating the inner wall, ceiling or floor of a building such as a medical facility. When forming a coating film from this composition, various methods such as brush coating and spray coating can be adopted. Since the coating film thus obtained exhibits antibacterial properties, it can effectively suppress nosocomial infection when used in medical facilities. Further, the coating film has a long-lasting antibacterial property, and the antibacterial property does not easily decrease even when exposed to water or a solvent. Therefore, this coating film is economical because it does not need to be repainted frequently to maintain antibacterial properties.

The coating film of the composition of the present invention exhibits the above-mentioned highly durable antibacterial property because the acetoacetoxy group of the acetoacetoxy group-containing copolymer contained in the coating film and the antibacterial agent are contained in the coating film. It is considered that this is because the silver ions contained in the above interact with each other and the elution of the silver ions hardly occurs.

[0023]

Example 1 (Production of antibacterial water-based coating composition) A 1-liter five-necked round equipped with a stirrer, a thermometer, a cooling tube, a dropping funnel and a glass tube for nitrogen gas flow as a reactor. A bottom separable flask was prepared. 160 g of deionized water and 1.2 g of Rebenol WZ (an emulsifier manufactured by Kao Co., Ltd.) were charged into this reaction vessel, and the mixture was stirred at a temperature of 80 ° C. while flowing nitrogen gas.

To this, a mixed solution of 20 g of deionized water and 0.8 g of ammonium persulfate was added, and after 10 minutes, a pre-emulsion having the following composition was added dropwise over 3 hours. 30 minutes after the start of dropping the pre-emulsion, deionized water 8
A mixed solution of 0 g and 0.6 g of ammonium persulfate was further added dropwise over 3 hours.

[Pre-emulsion] Acetoacetoxyethyl methacrylate 20 g Acrylic acid 12 g Methyl methacrylate 123 g 2-Ethylhexyl acrylate 123 g Styrene 122 g Rebenol WZ 14.8 g Deionized water 400 g

After all the dropping was completed, stirring was further continued at 80 ° C. for 2 hours, then cooled to 40 ° C., and the pH was adjusted to 8-9 with aqueous ammonia. Thereby, an acrylic emulsion was obtained.

Next, the obtained acrylic emulsion 50
Parts by weight, 0.4 parts by weight of 1,6-hexanediamine, 20 parts by weight of titanium dioxide, 3 parts by weight of SMA1440H (pigment dispersant manufactured by Fujii Yoshitsusho Co., Ltd.), 1620 dehydrane.
(Antifoam manufactured by San Nopco Co., Ltd.) 0.5 parts by weight, CS
-12 (5% by weight of Chisso Corporation film forming aid), KB
-9 parts (organic nitrogen-sulfur antibacterial agent manufactured by Nippon Kagaku Kabushiki Kaisha) 1 part by weight, Amteclean Z MK-10 (zinc oxide / silver / hydroxyapatite antibacterial agent manufactured by Matsushita Amtec Co., Ltd.) 1 part by weight and tap water 5 parts by weight were mixed to obtain a desired antibacterial aqueous coating composition.

Comparative Example 1 (Production of Antibacterial Aqueous Coating Composition) An antibacterial aqueous coating composition was prepared in the same manner as in Example 1 except that 20 g of methyl methacrylate was used instead of acetoacetoxyethyl methacrylate used in Example 1. I got a thing.

Example 2 and Comparative Example 2 (Production of antibacterial coating film)
Ltd.) immersed for 1 week in distilled water and washed 30 × 30 × 5 mm calcium silicate plate (JIS-A-5418: the bulk specific gravity = 1.0) on, NIPPE permeability manufactured by Nippon Paint Co., Ltd. as a primer coating Apply 0.5 part by weight of sealer to 1
Dried for weeks. After that, the antibacterial water-based coating composition obtained in Example 1 or Comparative Example 1 was applied onto the obtained undercoat coating film.
2 parts by weight was applied and dried for 1 week to obtain a coating film for antibacterial effect test. The antibacterial property of the obtained coating film for antibacterial effect test was measured before and after the weather resistance test. The antibacterial evaluation method and the weather resistance test method are as follows. Table 1 shows the results.

(Antibacterial property) Test bacterium Escherichia
On the GB agar medium to which E. coli was added, the antibacterial effect test coating film was applied with the lower surface. The inhibition zone (unit: mm) formed after culturing this at 33 ° C. for 18 hours was measured.

(Weather resistance test) JIS K5400 9.
An accelerated weather resistance test was conducted for 1,000 hours by the method specified in 8.1. As a tester, a long life weather meter WEL-SUN-HC manufactured by Suga Test Instruments Co., Ltd.
Was used.

[0032]

[Table 1]

[0033]

The antibacterial aqueous coating composition according to the present invention comprises
An aqueous dispersion of an acetoacetoxy group-containing copolymer obtained by copolymerizing a monomer containing a compound having a polymerizable double bond and an acetoacetoxy group is used as an aqueous dispersion, and it is mixed with an antibacterial agent. Therefore, a coating film having a high antibacterial effect can be formed.

Further, since the antibacterial coating film according to the present invention comprises the above antibacterial aqueous coating composition, the antibacterial effect is highly durable.

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Claims (3)

[Claims] 1. An aqueous dispersion of an acetoacetoxy group-containing copolymer obtained by copolymerizing a monomer containing a compound having a polymerizable double bond and an acetoacetoxy group, a polyamine compound, and an antibacterial agent, An antibacterial aqueous coating composition containing: 2. The antibacterial aqueous coating composition according to claim 1, wherein the antibacterial agent contains an organic nitrogen-sulfur antibacterial agent and a silver-containing antibacterial agent. 3. An aqueous dispersion of an acetoacetoxy group-containing copolymer obtained by copolymerizing a monomer containing a compound having a polymerizable double bond and an acetoacetoxy group,
An antibacterial coating film formed of an antibacterial aqueous coating composition containing a polyamine compound and an antibacterial agent.