JP2002068913A - Antimicrobial agent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an antimicrobial agent composition capable of exhibiting excellent antimicrobial activities when being compounded with a synthetic resin, and hardly changing the color with time when being molded, preserved and used, and further to provide an antimicrobial artificial marble especially usable for a kitchen counter, a washstand, an article for a toilet, an article for a bath, or the like. SOLUTION: This antimicrobial agent composition comprises (a) a silver salt of a phosphorus-containing oxyacid, (b) an inorganic ion-exchanger and (c) one or more kinds of oxides selected from zinc oxide, titanium oxide and silicon oxide. The antimicrobial resin composition contains the antimicrobial agent composition in the synthetic resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an antibacterial composition containing a silver salt of a phosphorus-containing oxyacid and an antibacterial resin composition containing the above antibacterial composition in a synthetic resin. In particular, the present invention relates to an antibacterial artificial marble used for kitchen counters, washstands, toilet articles, bath articles, and the like containing the above antibacterial agent composition. More specifically, an antibacterial agent which, when compounded in a synthetic resin, is molded, shows little discoloration over time when the molded article is stored and used, exhibits a stable and good antibacterial effect, and does not impair the appearance. The present invention relates to a composition, an antibacterial resin composition provided with antibacterial properties using the antibacterial agent composition, and an antibacterial artificial marble.

[0002]

2. Description of the Related Art As an inorganic antibacterial agent, an antibacterial metal such as silver or copper supported on apatite, zeolite, glass, zirconium phosphate, silica gel or the like has been known. These are highly safe compared to organic antibacterial agents, and have a long lasting antibacterial effect because they are hardly volatilized and eluted, and have excellent heat resistance. For this reason, inorganic antibacterial agents are used in antibacterial resin molded products for various applications such as fibrous, film or various molded articles by kneading, mixing and molding various resins.

Among inorganic antibacterial agents, silver-based inorganic antibacterial agents using silver as an antibacterial metal are more safe and antibacterial than those using other antibacterial metals such as copper and zinc. It is widely used because of its excellent balance,
Most of the industrially used inorganic antibacterial agents are silver-based inorganic antibacterial agents. However, on the other hand, the silver-based inorganic antibacterial agent is affected by the action of the contained silver and the influence of heat, light, etc., when it is processed in addition to the synthetic resin, or when the molded product is used, transported, stored, etc. There is a problem of discoloration over time.

The following proposals have been made as means for solving discoloration of antibacterial resin products containing a silver-based inorganic antibacterial agent. JP-A-11-60861 proposes a vinyl chloride-based resin composition comprising a vinyl chloride-based resin, a silver-based antibacterial agent and a specific phosphorus-based compound. It is described that the stability (initial coloring, long-term thermal stability) is improved. However, the specific phosphorus compound has no effect except for the vinyl chloride resin, and the antibacterial property of the obtained antibacterial vinyl chloride resin composition is not sufficient.

Japanese Patent Application Laid-Open No. 6-263916 proposes an antibacterial agent in which an inorganic ion exchanger carrying silver ions and an inorganic ion exchanger not carrying silver ions are mixed at a specific ratio. Although the antimicrobial resin composition containing this antimicrobial agent has the effect of suppressing deterioration that occurs during storage, use, processing, etc., the effect of preventing long-term deterioration over time and stable discoloration prevention is one step away. It is.

[0006]

SUMMARY OF THE INVENTION The present invention provides an antibacterial composition which exhibits excellent antibacterial properties when blended with a synthetic resin and has excellent discoloration resistance. It is an object of the present invention to provide an antibacterial resin composition which is extremely resistant to discoloration over time during use, particularly an antibacterial artificial marble used for kitchen counters, washbasins, toilet articles, bath articles and the like.

[0007]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, (a) a silver salt of a phosphorus-containing oxyacid, (b) an inorganic ion exchanger, and (c) )
An antimicrobial composition comprising one or more oxides selected from the group consisting of zinc oxide, titanium oxide and silicon oxide has been found to be excellent in solving all of the above-mentioned problems, and has been completed. Successful.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. ○ Silver salt of phosphorus-containing oxyacid Among the antibacterial agent compositions of the present invention, the silver salt of phosphorus-containing oxyacid directly exerts an antibacterial effect. The silver salt of a phosphorus-containing oxyacid can be obtained by reacting a phosphorus-containing oxyacid or a phosphorus-containing oxyacid salt with a silver compound such as silver nitrate. Silver salts of phosphorus-containing oxygen acids that can be used in the present invention are orthophosphoric acid, pyrophosphoric acid, tripolyphosphoric acid,
Silver salts such as hexametaphosphoric acid, phosphomolybdic acid, and phosphotungstic acid, in which some or all of the protons of these phosphorus-containing oxyacids have been replaced by silver ions, or replaced by several cations containing silver ions Including things. Among them, one or more silver salts selected from the group consisting of silver orthophosphate, silver pyrophosphate, silver tripolyphosphate and silver hexametaphosphate are preferred.

[0009] The mixing ratio of the silver salt of phosphorus-containing oxyacid in the antibacterial agent composition is from 0.05 to 0.05 with respect to the total amount of the antibacterial agent composition.
It is preferably 30% by mass (hereinafter simply referred to as%), and 0.1% by mass.
-10% is particularly preferred. When the compounding ratio is small, the antibacterial performance is hardly exhibited, and when the compounding ratio is large, the possibility of discoloration is increased and the cost is increased.

○ Inorganic ion exchanger As an inorganic ion exchanger which can be used in the present invention,
Layered zirconium phosphate, NASICON-type zirconium phosphate, layered titanium phosphate, NASICON-type titanium phosphate, layered tin phosphate, layered cerium phosphate, hydrous antimony pentoxide, hydrous antimony trioxide, hydrous titanium oxide, hydrous zirconium oxide, Examples thereof include hydrous silicon oxide, hydrous bismuth oxide, bismuth oxyhydroxide nitrate, hydroxyapatite, hydrotalcite compounds, and calcined products of hydrotalcite compounds. As long as it has an ion exchange capacity, it can be either crystalline or amorphous. In the present invention,
Among the above inorganic ion exchangers, 4 having a layered structure
A valent metal phosphate such as layered zirconium phosphate, layered titanium phosphate, or layered tin phosphate is preferred.

The mixing ratio of the inorganic ion exchanger in the antimicrobial composition is 0.05 to 30 with respect to the total of the antimicrobial composition.
% Is preferable, and 0.1 to 10% is particularly preferable. If the compounding ratio is small, the possibility of discoloration increases, and if the compounding ratio is large, the possibility that the antibacterial performance deteriorates increases. The possibility of discoloration increases, and the cost also increases.

Oxide selected from the group consisting of zinc oxide, titanium oxide and silicon oxide Zinc oxide, titanium oxide and silicon oxide can be used in any of crystalline and crystalline forms. It is also possible to mix two or more of these three types. The compounding ratio of one or more oxides selected from the group consisting of zinc oxide, titanium oxide and silicon oxide in the antibacterial composition of the present invention is 40 to 99.9 with respect to the total of the antibacterial composition. %, Particularly preferably 45 to 99.8%. If the compounding ratio is small, the possibility of discoloration increases, and if the compounding ratio is large, the possibility that the antibacterial performance deteriorates increases.

○ Synthetic Resin In the present invention, the synthetic resin that can be used in the antibacterial resin composition containing the antibacterial agent composition may be either a thermoplastic resin or a thermosetting resin. For example, polyethylene, polypropylene, vinyl chloride, ABS resin, AS resin, nylon resin, polyester, polyvinylidene chloride, polystyrene, polyacetal, polycarbonate, PBT, (meth) acrylic resin, fluororesin, polyurethane elastomer, polyester Elastomer, melamine, urea resin, ethylene tetrafluoride resin, unsaturated polyester resin, polyethylene, polypropylene, resin
Yeon, acetate, acrylic, polyvinyl alcohol,
Synthetic resins such as cupra, triacetate, and vinylidene can be used, and furthermore, silicone rubber, styrene butadiene rubber, ethylene propylene rubber, fluorine rubber, nitrile rubber, chlorosulfonated polyethylene rubber, butadiene rubber, synthetic natural rubber, butyl rubber, Rubbery synthetic resins such as urethane rubber and acrylic rubber can also be used.

Antibacterial Resin Composition The preferred proportion of the antibacterial agent composition in the antibacterial resin composition is 0.001 as silver content per 100 parts by mass (hereinafter simply referred to as “parts”) of the antibacterial resin composition. To 1 part, more preferably 0.005 to 0.5 part. 0.
If the amount is less than 001 part, the antibacterial property of the resin composition becomes insufficient. On the other hand, if the amount exceeds 1 part, the antibacterial effect is hardly improved and the properties of the resin are rather deteriorated. When an intermediate product such as a masterbatch is produced, a preferable compounding ratio of the antibacterial agent composition is 10 to 200 parts as an antibacterial agent composition per 100 parts of the antibacterial resin composition (masterbatch), more preferably 10 to 40 parts.

O Antibacterial Artificial Marble An especially useful field for the use of the antibacterial agent composition of the present invention is artificial marble. The antibacterial artificial marble of the present invention is manufactured by mixing and dispersing an antibacterial agent composition throughout the resin composition for artificial marble and curing the mixture (hereinafter, this manufacturing method is referred to as a bulk method), and an artificial marble. There is a product manufactured by incorporating an antibacterial agent composition only in the resin composition for gel coating constituting the surface of the base material and forming a gel coat layer on the surface of the substrate (hereinafter, this manufacturing method is referred to as a gel coating method). In each case,
The antibacterial agent composition of the present invention is used by being mixed with a specific resin component suitable for producing artificial marble.

The resin component constituting the artificial marble of the present invention is a matrix resin constituting an artificial marble base material or a gel coat layer, and a (meth) acrylic resin or an unsaturated polyester resin can be used. In the present invention, “(meth) acryl” means “acryl and / or methacryl”. (Meth) acrylic resin is a resin obtained by polymerizing various (meth) acrylic monomers. Specific (meth) acrylic monomers include (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and benzyl (meth) acrylate. Acrylic ester, glycidyl (meth)
Acrylate, melamine (meth) acrylate and the like can be mentioned. If necessary, a vinyl monomer for copolymerization may be used together with the (meth) acrylic monomer. Examples of the vinyl monomer for copolymerization include styrene, α-methylstyrene, vinyl toluene, acrylonitrile, and vinyl acetate. The amount of the vinyl monomer for copolymerization is preferably 10 parts or less per 100 parts of the monomer used.

Further, as a crosslinking agent for crosslinking the (meth) acrylic resin, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di ( (Meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, polybutylene glycol di (meth) acrylate,
It is preferable to use a crosslinkable vinyl monomer having a plurality of polymerizable double bonds in a molecule such as neopentyl glycol di (meth) acrylate. The amount of the crosslinkable vinyl monomer used is usually 0.05 to 20 parts per 100 parts of the (meth) acrylic resin. Further, as the (meth) acrylic resin of the present invention, a mixture of the above-mentioned (meth) acrylic monomer and its polymer (referred to as syrup) may be used to prevent the sedimentation of a filler such as aluminum hydroxide or the like. It is preferable for shortening the curing time of the components.

The polymer having a (meth) acrylic monomer as a main constituent unit includes an acyl peroxide such as benzoyl peroxide and N, N-dimethylaniline, N, N-diethylaniline, N, N-dimethyl. It can be obtained by redox polymerization using an amine compound such as paratoluidine, or a combination of a peroxyl compound such as tertiary butyl peroxymaleic acid and a mercaptan compound such as glycol dimercaptoacetate.

On the other hand, the unsaturated polyester resin used in the present invention comprises an unsaturated polybasic acid or an acid anhydride thereof (and optionally a saturated polybasic acid or an acid anhydride thereof) and a polyhydric alcohol. Obtained by polycondensation with
In particular, an unsaturated polyester obtained by polycondensation of an α, β-unsaturated dibasic acid or an acid anhydride thereof, an aromatic saturated dibasic acid or an acid anhydride thereof, and glycols is preferable.

Α for synthesizing unsaturated polyester,
Examples of the β-unsaturated dibasic acid or its acid anhydride include maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, chlormaleic acid and esters thereof, and the glycols include ethylene glycol. ,
Propylene glycol, diethylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-
Butanediol, 2-methylpropane-1,3-diol, neopentyl glycol, triethylene glycol, tetraethylene glycol, 1,5-pentanediol, 1,6-hexanediol, bisphenol A,
And hydrogenated bisphenol A.

The saturated dibasic acid or its anhydride used in combination, if necessary, includes aromatic acids such as phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid and tetrahydrophthalic anhydride, or anhydrides thereof, oxalic acid, and the like. Examples thereof include aliphatic acids such as malonic acid, succinic acid, adipic acid, sebacic acid, and azelaic acid, and anhydrides thereof. Examples of the unsaturated monomer for crosslinking the unsaturated polyester include styrene, vinyltoluene, α-methylstyrene, chlorostyrene, vinylnaphthalene, methylvinylketone, methyl (meth) acrylate, and ethyl (meth) acrylate. Can be

If necessary, the above (meth) acrylic resin,
It is preferable to add a curing (polymerization) catalyst, a curing (polymerization) accelerator, a filler, a pigment, a dye, a flame retardant, a release agent, a thickener, and the like to the unsaturated polyester resin. Examples of the curing catalyst include tertiary butyl peroxymaleic acid, benzoyl peroxide, methyl etoketone peroxide, cumene hydroperoxide, tertiary butyl hydroxy peroxide, dicumyl peroxide and the like. Further, examples of the curing accelerator include cobalt naphthenate.

As the filler added to the (meth) acrylic resin or unsaturated polyester resin, aluminum hydroxide, calcium hydroxide, magnesium hydroxide, talc, quartz, silica, zinc oxide, titanium oxide, clay, calcium carbonate, etc. And aluminum hydroxide is particularly preferably used.

Known methods can be used to incorporate the antimicrobial composition of the present invention into the resin composition for artificial marble in the bulk method and the resin composition for gel coating in the gel coating method. For example, it is carried out by adding a predetermined amount of the antibacterial agent composition of the present invention to an artificial marble resin composition, kneading and mixing with a kneader, a mixer, a roll mill, an extruder or the like, and sufficiently dispersing.

The preferred compounding ratio of the antibacterial agent composition of the present invention in the artificial marble resin composition by the bulk method or the gel coat layer resin composition in the gel coating method is 0.1% in terms of silver content per 100 parts of each resin composition. 001-001
1 part, more preferably 0.005 to 0.5 part. If the amount is less than 0.001 part, the antibacterial property of the artificial marble may be insufficient. On the other hand, if the amount is more than 1 part, the antibacterial effect is hardly improved.

Manufacturing method of antibacterial artificial marble The antibacterial artificial marble of the present invention by a bulk method is manufactured as follows. A matrix resin, that is, a (meth) acrylic resin monomer or an unsaturated polyester resin raw material, a curing catalyst, and the antibacterial agent composition of the present invention are mixed. As needed,
Further, it is preferable to mix and disperse an inorganic filler such as glass fiber, aluminum hydroxide, silica, and silica gel, a crosslinking agent, a curing accelerator, a pigment, and the like. The mixture is poured into a mold and cured at room temperature or by heating to obtain an antibacterial artificial marble. In addition to injection molding, other molding methods such as injection molding and press molding can be used, but injection molding is most preferable.

In the case of artificial marble having a gel coat layer on the surface of the base resin, it is generally prepared as follows. The resin composition of the gel coat layer in which the antibacterial agent composition of the present invention is dispersed in a mold for molding is applied by a spray-up method or the like and cured. Next, the composition for base resin is poured into a mold and cured. Thereafter, the laminate of the gel coat layer and the base resin is removed from the mold to obtain an antibacterial artificial marble.

Use The antibacterial resin composition containing the antibacterial agent composition of the present invention is:
It can be used in various fields where antibacterial properties are required. Specific applications include, for example, dishwashers, dish dryers, refrigerators, washing machines, pots, televisions, personal computers, C
D boombox, camera, video camera, water purifier, rice cooker,
Vegetable cutter, register, futon dryer, FAX, ventilation fan, air conditioner, etc., appliances, tableware, cutting board, push-cut, tray, chopsticks, old tea set, thermos, kitchen knife, ladle pattern, fly return, lunch box, Kitchen utensils such as rice scoops, bowls, drain baskets, triangular corners, scoops, garbage baskets, drain bags, shower curtains, futon cotton, air conditioner filters, pantyhose, socks, towels, sheets , Futon side ground,
There are textile products such as pillows, gloves, aprons, curtains, diapers, bandages, masks, and sportswear.

Further, decorative materials, wallpaper, floorboards, window films, handles, carpets, mats, handrails, joints, tiles, wax and other housing / building material products, toilet seats, bathtubs, tiles, pots, dirt, Toilet brush, bath lid, pumice stone,
Toiletries such as soap containers, bath chairs, clothes baskets, showers, wash basins, etc., paper products such as medicine packing paper, medicine boxes, sketchbooks, medical records, origami, toys such as dolls, stuffed animals, paper clay, blocks, puzzles, etc., shoes , Bags, belts, watch bands, interior goods, chairs, gloves, leather products such as hanging leather, ball pens, sharp pens, pencils, erasers, crayon, paper, notebooks, floppy disks, rulers, post-it,
Stationery such as stapler, and other items such as insoles, makeup containers, scrubbers, makeup puffs, hearing aids, musical instruments, cigarette filters, cleaning adhesive paper sheets, hanging leather grips, sponges, kitchen towels, cards, microphones , Barber supplies, vending machines, razors, telephones, thermometers, stethoscopes, slippers, costumes
, Toothbrush, sandbox sand, food packaging film, spray
There are products such as.

The antibacterial artificial marble of the present invention can be used for products such as kitchen countertops, kitchen tops, wash basins, bathtubs, sanitary products, furniture, stationery accessories, and other interior products.

[0031]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. Reference Example (Synthesis of Silver Salt of Phosphorus-Containing Oxygen Acid) To an aqueous solution of the four types of phosphates a to d shown in Table 1, an equivalent amount of an aqueous silver nitrate solution was added, and the mixture was stirred at room temperature for 24 hours while shielding light. . The precipitate obtained by filtering the reaction solution was washed with water, dried and pulverized to obtain a silver salt of a phosphorus-containing oxyacid.

[0032]

[Table 1]

[Examples] Preparation of antibacterial agent composition In the four kinds of silver salts of phosphorus-containing oxyacids obtained above, inorganic ion exchangers and oxides such as zinc oxide are shown in Table 2. (% By mass) to obtain seven kinds of antibacterial agent compositions.

[0034]

[Table 2]

Comparative Example For comparison with the antimicrobial composition of the present invention, an antimicrobial composition having the composition shown in Table 3 (% represents% by mass) was prepared.

[0036]

[Table 3]

Test Example 1 Polymethyl methacrylate /
Mixture of methyl methacrylate (mass ratio 2: 8) 10
Resin composition for artificial marble obtained by adding 150 parts of aluminum hydroxide to 0 parts by weight and further adding 0.6 parts of tertiary butyl peroxymaleic acid and 0.3 parts of ethylene glycol dimercaptoacetate as a redox polymerization catalyst. To 100 parts, the antibacterial agent compositions prepared in Examples and Comparative Examples were added and mixed in the number shown in Table 4. This composition was poured into a mold, cured at room temperature, and then removed from the mold to obtain an artificial marble molded product (Sample Nos. 1 to 5).
10).

For comparison, without adding the antimicrobial composition,
It was similarly manufactured (prototype No. 11). As appearance evaluation,
The color of the molded body produced above was visually confirmed, and the results are shown in Table 4.

The antibacterial activity of the formed antibacterial artificial marble was evaluated by the following method. The results are shown in Table 4. Staphylococcus aureus was used as a test bacterium, and an antibacterial artificial marble molded body was cut into 5 cm x 5 cm, and the surface of the marble 1
The bacterial solution is 0.5 so that the number of bacteria per sheet is 10 ⁵ to 10 ^6.
ml on the surface, and 4.5 cm x 4.5 cm from above
And kept in contact with the surface uniformly at a temperature of 35 ° C. and a humidity of 95 RH% for 24 hours.
After 0 hour from the start of storage (the number of theoretically added bacteria) and after storage for 24 hours, the surviving bacteria on the test piece were washed out with a culture medium for measuring the number of bacteria (SCDLP liquid medium). The number of viable cells was measured by the pour plate method (37 ° C. for 2 days) used, and 5 cm × 5 c
It was converted to the number of viable bacteria per m. The initial number of bacteria was 1.9 ×
The number of cells of the control, which was subjected to the same operation without using the sample after 10 ⁵ and 24 hours, was 3.0 × 10 ⁵ .

Further, the test piece was immersed in hot water at 90 ° C. for 16 hours, and the antibacterial activity was evaluated.
The appearance after immersion for 0 hours is shown in Table 4.

[0041]

[Table 4]

Test Example 2 Various antibacterial agent compositions prepared in Examples and Comparative Examples were added in predetermined amounts to 100 parts of an isophthalic acid-based unsaturated polyester resin composition whose viscosity was adjusted to 20 poise with fine-particle silica. Added and mixed. Predetermined amounts of methyl ethyl ketone peroxide as a curing agent and cobalt naphthenate as a curing accelerator were added to obtain a coating composition for a gel coat layer. The coating composition was applied to the inside of a mold by a spray gun so as to have a thickness of about 0.5 mm, and cured at room temperature. Subsequently, a base resin composition mainly composed of an isophthalic unsaturated polyester resin containing 50% by mass of aluminum hydroxide is poured into a mold, cured at room temperature, and then demolded to obtain an antibacterial artificial marble. Was.

For comparison, an antibacterial agent was not added (prototype N
o.22), and produced similarly. As an appearance evaluation, the color of the formed molded body was visually checked, and the results are shown in Table 5. The antibacterial activity of the molded article was evaluated in the same manner as in Test Example 1, and is shown in Table 5. The initial bacterial count was 2.5 × 10 ⁵ , and the control bacterial count obtained by performing the same operation without using the sample after 24 hours was 3.0 × 10 ⁵ .

[0044]

[Table 5]

[0045]

The antibacterial agent of the present invention has excellent antibacterial properties and resistance to discoloration, and is extremely useful as an antibacterial agent capable of maintaining the antibacterial effect for a long time. In addition, the antibacterial resin composition and the antibacterial artificial marble of the present invention have excellent antibacterial properties, which show very little deterioration in appearance such as discoloration over time during processing, storage and use, and exhibit a stable antibacterial effect. are doing. The antibacterial artificial marble of the present invention also has warm water resistance and is extremely useful as an artificial marble mainly used for kitchen counters, wash basins, toilet articles, bath articles and the like used around water.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08K 3/00 C08K 3/00 3/22 3/22 3/32 3/32 3/36 3/36 C08L 101/00 C08L 101/00 // C04B 103: 67 C04B 103: 67 111: 54 111: 54 F term (reference) 4H011 AA02 BB18 BC19 DA02 DA23 DD05 DH02 DH04 4J002 AB021 AC001 BB021 BB121 BC031 BC061 BD031 BD101 BD121 BE021 BG021 BN151 CB001 CF001 CF071 CF101 CG001 CK021 CL001 CP031 DE108 DE127 DE137 DE138 DE287 DH036 DH037 DH046 DH056 DJ017

Claims (6)

[Claims] 1. It comprises (a) a silver salt of a phosphorus-containing oxyacid, (b) an inorganic ion exchanger, and (c) one or more oxides selected from the group consisting of zinc oxide, titanium oxide and silicon oxide. Antimicrobial composition. 2. The antibacterial agent according to claim 1, wherein the silver salt of the phosphorus-containing oxyacid is at least one silver salt selected from the group consisting of silver orthophosphate, silver pyrophosphate, silver tripolyphosphate and silver hexametaphosphate. Composition. 3. The antibacterial agent composition according to claim 1, wherein the inorganic ion exchanger is a tetravalent metal phosphate having a layered structure. 4. A silver salt of a phosphorus-containing oxyacid, from 0.05 to 0.05.
30% by mass, (b) 0.05 to 30% by mass of an inorganic ion exchanger, and (c) one or more oxides selected from the group consisting of zinc oxide, titanium oxide and silicon oxide.
An antimicrobial composition comprising 9% by mass. 5. An antibacterial resin composition comprising the antibacterial agent composition according to claim 1, 2 or 3 in a synthetic resin. 6. An antibacterial artificial marble comprising the antibacterial agent composition according to claim 1, 2, 3 or 4, and a (meth) acrylic resin or an unsaturated polyester resin.