JP2000281941A - Gel coat composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a gel coat composition not suffering from long-term discoloration and exhibiting high antibacterial properties and/or antimold properties by compounding a gel coat resin with an antibacterial agent comprising a silver- containing zinc calcium phosphate and/or an antimold prepared by introducing an organic antimold into among the layers of a layered inorganic compound. SOLUTION: When the antibacterial agent or the antimold is used singly, it is used in an amount of 0.1-10 pts.wt. per 100 pts.wt. gel coat resin. When they are used in combination, the combination is used in an amount of 0.1-10 pts.wt. per 100 pts.wt. gel coat resin. The antimold may be an organic one such as at least either a triazole antimold organic compound or an isothiazoline antimold organic compound. The layered inorganic compound is desirably a clay mineral. The gel coat resin used is one based on an unsaturated polyester resin and/or a vinyl ester resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antibacterial and antifungal gel coat resin composition for use in plumbing products such as bathrooms, vanities and kitchens.

[0002]

2. Description of the Related Art A slimy deposit of pink or brown color is generated in a plumbing product such as a bathroom, a vanity table or a kitchen, and a mold of black or brown color is formed on a wall, floor or ceiling of a bathroom. And the number of cases in which discomfort is felt from the appearance and feel of these deposits and mold. All of the slimy deposits are partially generated on the surface near the discharge port where a small amount of water always stays or on the path of water, and are not easily separated by merely flowing water. In addition, mold generated on joints and walls of a bathroom often does not peel off unless a strong chlorine-based chemical is used, and the use of these chlorine-based chemicals is not preferable from the viewpoint of safety and environmental impact.

[0003] Generally, in order to impart antibacterial properties and fungicidal properties to a synthetic resin molded article, an antibacterial agent and a fungicide are blended into a resin material. Of these, the addition of an antibacterial agent is applied to many molded articles, but there are cases in which antibacterial properties are not expressed or sustainability is poor depending on the product. In addition, there is a problem that the organic fungicide deteriorates due to high temperature during molding of the resin molded product, and loses its effectiveness.

[0004] On the other hand, it is well known that certain heavy metal ions are moldy at low concentrations and have an antibacterial effect on bacteria. These metals include silver, copper, zinc, zirconium, tin, manganese, cobalt, nickel and the like, and among them, silver is known to have high antibacterial properties. Application of an inorganic powder antibacterial agent containing silver or the like having high heat resistance and excellent antibacterial durability has been disclosed (JP-A-59-133235).

However, a resin composition containing an inorganic powder-based antibacterial agent containing silver or the like is disadvantageous in that it is susceptible to changes due to the chemical reactivity of silver and changes due to energy such as light and heat. was there. In particular, among the stabilizers added to stabilize the physical properties of the resin molded product, there are sulfur compounds and phosphate compounds having high reactivity with silver. And discoloration when exposed to ultraviolet light. Of course, as a countermeasure against such discoloration, there is a method of adding an additive such as an antioxidant or an ultraviolet absorber, but it is hard to say that it is imperfect for other physical properties or discoloration.

Although antimicrobial and fungicide are easily confused, antimicrobial agents generally have little effect on fungus. Generally, an organic compound has been widely used as a fungicide. However, since it is organic, it is easily decomposed by heat and light,
In many cases, it was not usable or did not exhibit the effect depending on the application.

On the other hand, there is a gel coat method as a means for protecting the surface of a resin molded article. The gel coat composition used here is used alone or in a mixture of an unsaturated polyester resin, a vinyl ester resin, etc., with a pigment, a curing accelerator, etc. A liquid thermosetting resin composition containing, after adding a polymerization initiator thereto, spraying or applying to a mold surface with a brush, and then forming FRP and artificial marble thereon, and conversely, It is used by applying directly on the molded product of
The FRP product functions as a protective layer against water, hot water, ultraviolet rays, and the like, as well as imparting aesthetics such as gloss and coloring to the surface of the FRP product.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to focus on the gel coating method in order to improve the above-mentioned drawbacks. In the gel coating resin composition, there is no discoloration over time, and high antibacterial properties and Another object of the present invention is to provide a gel coat resin composition exhibiting mold resistance.

[0009]

A first aspect of the present invention is a gel coat composition characterized by blending an antibacterial agent comprising silver-containing zinc calcium phosphate with a gel coat resin. 0.1 to 10 parts, preferably 0.3 to 3 parts, of the above antibacterial agent is blended with each part.

A second aspect of the present invention is a gel coat composition comprising a gel coat resin and a fungicide in which an organic fungicide is carried between layers of a layered inorganic compound. 0.1 to 10 parts, preferably 0.3 to 3 parts, of the above fungicide is blended with 100 parts of gel coat resin.

A third aspect of the invention is that a gel coat resin is mixed with an antibacterial agent comprising silver-containing zinc calcium phosphate and a fungicide having an organic fungicide carried between layers of a layered inorganic compound. A gel coat composition characterized by:
Specifically, 0.1 to 10 parts, preferably 0.3 to 3 parts, of the above antibacterial agent and fungicide are added to 100 parts of the gel coat resin.

Specific examples of the organic fungicide used in the present invention are a triazole-based fungicide and / or an isothiazoline-based fungicide.

[0013] The gel coat resin used in the present invention is mainly composed of an unsaturated polyester resin and / or a vinyl ester resin as a main component. It is a waterproof pan.
In addition, all of the compounding parts referred to in the present invention are parts by weight.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The antibacterial agent composed of silver-containing zinc calcium phosphate used in the present invention is mainly a silver / phosphate ceramic in which silver ions are supported on a phosphate ceramic in which calcium and zinc are combined. The specific chemical formula has the following hydroapatite composition. Ag-CaαZnβAl ₇ (PO ₄ ) γ (OH)
_Two

The method for producing the antibacterial agent comprising the silver-containing zinc calcium phosphate includes, for example, calcium hydroxide, zinc oxide,
A reaction for synthesizing phosphate ceramics is performed using aluminum hydroxide and phosphoric acid as starting materials. Next, silver nitrate is added, and silver ions are supported at the acid sites of the phosphate by a mechanochemical reaction using a ball mill or the like, followed by washing / filtration, drying and crushing, followed by crushing. Get. Here, the amount of silver carried can be up to about 20% by weight of the whole antibacterial agent, but is preferably 1 to 5% by weight.

The antibacterial agent comprising silver-containing zinc calcium phosphate has a fine white powder, is non-crystalline, and usually has a particle size of 0.1 μm to 50 μm. ５5 μm is preferred.

On the other hand, a fungicide in which an organic fungicide is supported between layers of a layered inorganic compound, wherein the layered inorganic compound is a silicate having a layered structure in which crystal layer units are stacked on each other. And may be any of natural products and synthetic products. Preferable layered silicates include clay minerals, and specific examples thereof include the following. That is, smectites such as montmorillonite, beidellite, hectorite and saponite; mica such as muscovite and biotite; kaolinite such as kaolinite and halosite; serpentine group such as antigorite. The average particle diameter of the layered inorganic compound in the present invention is preferably 10 μm or less, more preferably 0.1 to 7 μm. In order to exhibit a sufficient effect as a fungicide, the cation exchange capacity of the layered silicate is preferably 0.1 meq / g or more. Only one kind of these layered silicates may be used, but two or more kinds can be used in combination for controlling the sustained release and the like.

In the present invention, the organic fungicide is a triazole-based fungicide and / or an isothiazoline-based fungicide. Preferred specific examples of the triazole-based antifungal organic compound include α- [2- (4-chlorophenyl) ethyl] -α- (1,1-dimethylethyl) -1H-1,2,4-triazol-1-yl-ethanol, (4-Chlorophenoxy) -3,3-1-dimethyl-1- (1H-1,2,4-triazo-1-yl-2-butanone, β- (4-chlorophenoxy) -α- (1,1-dimethyl-ethyl) -1H
-1,2,4-triazole-1-ethanol and the like, and the isoliazoline-based antifungal organic compound is 2-n-octyl-4-isothiazoline-3-one, 5-chloro-2-methyl-4-isothiazoline-3-one, 2-methyl-4-isothiazoline- 3-one, 1,2-benzisothiazolone-3, Nn-butyl-1,2-benzisothiazolone-3 and the like. In the present invention, only one kind of the fungicidal organic compound may be used, or two or more kinds may be used in combination. The lower limit of the preferred amount of the organic fungicide to be supported on the layered inorganic compound in the present invention is 0.1 part per 100 parts of the layered inorganic compound,
It is more preferably at least 1 part, particularly preferably at least 5 parts. If the amount is too small, the antifungal effect is reduced.

The method for producing the fungicide in the present invention is not particularly limited as to the method of supporting the fungicide organic compound on the layered inorganic compound. It can be introduced regardless of whether the fungicidal organic compound is in a solid, liquid, or gas state. For example, in the case where the mold-proof organic compound is a liquid, the mold-proof organic compound is mixed with the layered silicate and stirred, and then dried and pulverized, or the mold-proof organic compound is dissolved in a highly soluble solvent. Mix and stir the dissolved solution with the layered silicate,
Thereafter, filtration, washing, and drying and pulverization are performed to obtain a fungicide in which a fungicidal organic compound is supported on a layered silicate.

Since the fungicide of the present invention has a fungicidal organic compound carried between layers of the layered inorganic compound, the heat-resistant temperature and the volatilization temperature of the fungicidal organic compound are increased, for example, when the resin is formed or when the resin is formed. Despite the rise in heat during use, the decomposition of the fungicidal organic compound can be prevented or minimized.
Further, since the fungicide in the present invention, since the fungicide organic compound is carried between the layers of the layered inorganic compound, the bleeding speed from the resin of the fungicide organic compound is slow, and , The long-term sustainability is superior to the case where it is blended. In the present invention, the antibacterial agent and / or fungicide are added in an amount of 0.1 part per 100 parts of the unsaturated polyester resin component.
1 to 10 parts are blended, and particularly preferably each is 0.3 to 10 parts.
It is three parts. If the added amount is too large, the physical properties are reduced, and
If the amount is too small, the desired antibacterial effect and fungicide effect may not be obtained.

[0021]

The present invention will be described below in more detail with reference to examples. Example 1 An organic antibacterial agent was present between 0.5 part of an antibacterial agent having silver ions supported on zinc calcium phosphate and 100 parts of a gel coat composition based on an unsaturated polyester resin, and a layered inorganic compound. 0.5 parts of a fungicide loaded with 2-n-octyl-4-isothiazolin-3-one as a fungicide was blended to prepare an antibacterial and antifungal gel coat composition. After adding and mixing 1.0 part of a polymerization initiator methyl ethyl ketone peroxide to the gel coat composition, a 0.3 mm-thick sprayed FRP mold coated with a release agent in advance was dried at 40 ° C. for 40 minutes, and then dried. After spraying a FRP resin composition comprising a glass mat, an unsaturated polyester resin, and a polymerization initiator methyl ethyl ketone from above to a thickness of about 3 mm, curing at 80 ° C. for 3 hours, taking out from the mold, and applying a gel coat film FRP
I got a board.

[Examples 2 to 3] A gel coat film was formed in the same manner as in Example 1, but in Examples 2 to 3, only an antibacterial agent having silver ions carried on zinc calcium phosphate was an unsaturated polyester. 0.5 part and 1 part of each were mixed with 100 parts of the resin to obtain a gel coat composition.

[Examples 4 and 5] A gel coat film was formed in the same manner as in Example 1, but in Examples 4 and 5, 2-n-octyl-4 was used as an organic fungicide between inorganic compound layers.
Only 0.5 part and 1 part of the fungicide alone carrying -isothiazolin-3-one were mixed with 100 parts of the unsaturated polyester resin to prepare a gel coat composition.

Comparative Example 1 A gel coat film was prepared in the same manner as in the example, except that no antibacterial agent and fungicide were added.

Comparative Example 2 A gel coat film was prepared in the same manner as in the Example, except that 2- (4-thiazolyl) benzimidazole was used as the fungicide in the unsaturated polyester resin 1.
0.5 part was added to 00 parts.

[Evaluation of antibacterial activity] The antibacterial activity was evaluated according to the "Self-Assessment Standard for Silver and Other Inorganic Antibacterial Agents and the Antibacterial Testing Method for Antibacterial Activity of Antibacterial Processed Products / One Film Adhesion". The difference between the increase and decrease in the antibacterial test was calculated by the following equation. Increase / decrease value difference = logC−logD C: Average value of the number of viable bacteria after 24 hours of the sample not containing the antibacterial agent D: Average value of the number of viable bacteria after 24 hours of the sample containing the antibacterial agent

[Evaluation of antifungal property] ASTM-G21-19
90. The numerical values in the fungicide test have the following meanings. 4: Vigorous growth (60% or more) 3: Intermediate growth (30-60%) 2: Slight growth (10-30%) 1: Slight growth (10% or less) 0: No growth at all

[Evaluation of Boiling Test] The gel coat surface of the test piece was boiled at 90 ° C. for 150 hours, and the color difference ΔE between before and after the test was determined with a spectrophotometer.

The evaluation results are shown in Table 1. Examples 1 to 3 show high antibacterial properties, and Examples 1, 4 and 5 show superior fungicidal properties as compared with Comparative Examples 1 and 2. Is shown.
In Examples 1 to 5, even when the boiling test was performed, there was almost no change in the color difference.

[0030]

According to the present invention, it is possible to provide a gel coat resin composition having no discoloration with time and exhibiting high antibacterial and / or antifungal properties.

[Table 1]

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09D 7/12 C09D 7/12 Z 133/04 133/04 167/06 167/06

Claims (9)

[Claims] 1. A gel coat composition comprising a gel coat resin mixed with an antibacterial agent comprising silver-containing zinc calcium phosphate. 2. The gel coat composition according to claim 1, wherein the antibacterial agent is added in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the gel coat resin. 3. A gel coat composition comprising a gel coat resin and a fungicide having an organic fungicide supported between layers of a layered inorganic compound. 4. The gel coat composition according to claim 3, wherein the fungicide is incorporated in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the gel coat resin. 5. A gel coat composition comprising a gel coat resin and an antibacterial agent comprising silver-containing zinc calcium phosphate and a fungicide having an organic fungicide supported between layers of a layered inorganic compound. . 6. The gel coat composition according to claim 5, wherein the antibacterial agent and the fungicide are combined in a total amount of 0.1 to 10 parts by weight with respect to 100 parts by weight of the gel coat resin. 7. The gel coat composition according to claim 3, wherein the organic fungicide is a triazole organic fungicide and / or an isothiazoline organic fungicide. 8. The gel coat composition according to claim 1, wherein the gel coat resin contains an unsaturated polyester resin and / or a vinyl ester resin as a main component. 9. The gel coat composition according to claim 1, wherein the resin member to be applied is a waterproof pan for a unit bath.