JPH10251616A - Antibacterial sealant composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an antibacterial sealant compsn. which is excellent in antibacterial properties, does not discolor even when exposed to ultraviolet rays, and is excellent also in light resistance by adding a cyclic org. phosphoric ester compd. to a sealant substrate. SOLUTION: The cyclic org. phosphoric ester comps. (A) is represented by the formula (wherein R<1> to R<3> are each 1-18C alkyl; R<4> is H or methyl; n is 1 or 2; and when n is 1, then M is H or an alkali metal atom and when n is 2, then M is an alkaline earth metal atom or Zn). As the sealant substrate (B), a resin material, such as a silicon-based sealant, exhibits excellent effects. When a resin material is used, usually used additives for the resin material are compounded together with ingredient A. A phenolic antioxidant, a plasticizer, an ultraviolet absorber, a hindered amine light stabilizer, a filler, a colorant, a pigment, a cross-linker, an antistatic agent, etc., are listed as the additives. Ingredient A is compounded in an amt. of 0.001-10wt.% of ingredient B.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to an antibacterial sealing material composition containing a cyclic organic phosphate compound.

[0002]

2. Description of the Related Art Sealing materials are filled into joints and gaps between building members such as glass-fitted portions and sashes, and various devices, to provide watertightness and airtightness. Widely used. In general, the environment in which such a sealing material is used is often humid, and molds or bacteria existing in gaps are often not completely removed during construction. In addition, these microorganisms not only grow and impair the aesthetic appearance, but also have a problem that the hyphae penetrates into the inside of the sealing to cause peeling and cracking.

In addition, antibacterial properties are imparted to the sealing material in order to prevent the occurrence of allergic symptoms due to scattering of mold spores propagated in the sealing material and infection by the propagated pathogenic bacteria and to obtain a safe hygienic environment. Is required.

In order to impart antibacterial properties to the sealing material,
It has been proposed to include inorganic and organic antibacterial agents, for example, as disclosed in JP-A-6-41516 and JP-A-6-41516.
JP-A-200238, JP-A-6-247818, JP-A-6-256755, JP-A-8-104
No. 863 and the like use an inorganic antibacterial agent using a metal having an antibacterial action such as silver.
220423, JP-A-6-227912,
JP-A-8-92545 proposes to use an organic antibacterial agent.

However, the antibacterial action of these antibacterial agents is not yet satisfactory, and those using silver have a remarkable disadvantage that discoloration due to light is remarkable, and organic antibacterial agents have poor stability. For this reason, when it comes into contact with water or oil at the time of construction or use, it not only decomposes, loses its efficacy by escaping from the product, but also generates odors and deteriorates the properties of the sealing material.

[0006] Therefore, by adding an antibacterial agent which has stability to moisture or oil, does not have coloring that impairs the value of the product, and is highly safe for the human body, and by adding such an antibacterial agent, There has been a strong demand for a sealant composition having excellent antibacterial properties.

Japanese Patent Application Laid-Open No. 58-1736 discloses that an aromatic cyclic phosphate metal salt is used as a nucleating agent for a crystalline resin, but these compounds are effective as antibacterial agents. It is not even suggested.

Accordingly, an object of the present invention is to provide a sealing material composition having an antibacterial effect over a long period of time.

[0009]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that a specific cyclic organophosphate or a metal salt thereof exhibits excellent antibacterial properties, and furthermore, has a stability against moisture or oil. Not only did not cause coloration that would impair the value of the product, but also found that it was highly safe for the human body, and found that a sealing material composition containing this compound could achieve the above object.

The present invention has been made based on the above findings, and has the following general formula (I):
The present invention provides an antibacterial sealing material composition containing a cyclic organic phosphate compound represented by the formula:

[0011]

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[0012]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the antibacterial sealing material composition of the present invention will be described in detail. The cyclic organic phosphate compound represented by the above general formula (I) used in the present invention is used as an antibacterial agent that exhibits an excellent antibacterial effect over a long period of time on a sealing material substrate described below. .

In the above general formula (I), R ¹ , R ² and
Examples of the alkyl group represented by R ³ include methyl, ethyl, propyl, isopropyl, butyl, secondary butyl, tertiary butyl, amyl, tertiary amyl, hexyl, octyl, 2-ethylhexyl, isooctyl, tertiary octyl, and nonyl. ,
Decyl, dodecyl, tridecyl, isotridecyl, tetradecyl, hexadecyl, octadecyl and the like.

The alkali metal represented by M includes sodium, potassium, lithium and the like, and the alkaline earth metal includes calcium, magnesium, barium, strontium and the like. In particular, M is an alkali metal atom or What is a zinc atom has a large effect, and is preferable.

Accordingly, specific examples of the cyclic organic phosphate compound represented by the general formula (I) include the following compound Nos. 3 to 10: 1 to No. 8 and the like.

[0016]

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[0017]

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[0018]

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[0019]

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[0020]

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[0021]

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[0022]

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[0023]

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The content of the above-mentioned cyclic organic phosphate compound is not particularly limited, but is usually preferably 0.001 to 10 parts by weight, more preferably 0.005 to 10 parts by weight, based on 100 parts by weight of the added sealing material base material. -5 parts by weight is more preferred.
If the content is less than 0.001 part by weight, a sufficient antibacterial effect may not be obtained, and if it exceeds 10 parts by weight, the effect may not be improved so much and it may be economically disadvantageous.

Further, the above-mentioned cyclic organic phosphate compound is excellent in stability and has good dispersibility in various substrates, so that the powder can be directly blended with the sealing material substrate. Can be used by being supported on various carriers or dispersed in a solvent or a liquid additive.

In the antimicrobial sealing material composition of the present invention, a sealing material base is used as a main component, and the sealing material base may be any of an organic material, an inorganic material, and an organic / inorganic mixed material. Alternatively, the organic material may be a resin material such as a synthetic resin emulsion or a reaction curable resin, and the inorganic material may be a cement material. Among these sealing materials, a resin-based material is preferable because excellent effects can be obtained.

Further, as the resin-based material, for example,
Silicone sealing materials (including modified silicone type sealing materials), polysulfide type sealing materials, polyurethane type sealing materials, epoxy type sealing materials, butyl rubber type sealing materials, acrylic type sealing materials, etc., especially for silicon type sealing materials The effect is large and preferable when there is.

When a resin-based material is used as the sealing material base material, an additive usually added to the resin material together with the cyclic organic phosphate compound represented by the general formula (I) is used in the present invention. Can be added in an amount that does not impair the effect of the above.

Examples of the additives include phenol-based, phosphorus-based, sulfur-based antioxidants, plasticizers, ultraviolet absorbers, hindered amine light stabilizers, fillers, colorants, and the like.
Pigments, crosslinking agents, antistatic agents, flame retardants and the like.

Examples of the phenolic antioxidants include 2,6-di-tert-butyl-p-cresol, stearyl (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, thiodiethylenebis (3 , 5-di-tert-butyl-4-hydroxyphenyl) propionate, triethylene glycol-bis (3-tert-butyl-
4-hydroxy-5-methylphenyl) propionate, 3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane-bis (3 -Tert-butyl-4-hydroxy-5-methylphenyl) propionate, 4,
4'-thiobis (6-tert-butyl-m-cresol),
4,4'-butylidenebis (6-tert-butyl-m-cresol), 2,2'-methylenebis (6-tert-butyl-
p-cresol), 2-tert-butyl-4-methyl-6-
(2-acryloyloxy-3-tert-butyl-5-methylbenzyl) phenol, 2,2′-ethylidenebis (4,6-di-tert-butylphenol), 1,1,3-tris (2-methyl-4) -Hydroxy-5-tert-butylphenyl) butane, 1,3,5-tris (2,6-di-tert-butyl-4-hydroxybenzyl) isocyanurate,
1,3,5-tris (2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate,
3,5-tris (2,6-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, pentaerythritol-tetra (3,5-di-tert-butyl-4)
-Hydroxyphenyl) propionate and the like.

As the above-mentioned phosphorus antioxidant, for example,
Triphenyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris (nonylphenyl) phosphite, tris (mono, di-mixed nonylphenyl) phosphite, diphenylacid phosphite, diphenyldecyl phosphite, Phenyldidecyl phosphite, tridecyl phosphite, 2,2′-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, Bis (2,4-dicumylphenyl) pentaerythritol diphosphite, bis (2,6-ditert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-
Tri (tert-butylphenyl) pentaerythritol diphosphite, tetra (C _12-15 mixed alkyl) bisphenol A-diphosphite, tetra (tridecyl) -4,
4'-butylidenebis (2-tert-butyl-5-methylphenol) diphosphite, hexa (tridecyl)-
1,1,3-tris (2-tert-butyl-5-methylphenol) triphosphite, 2-butyl-2-ethylpropylene-2,4,6-tritert-butylphenylphosphite, 9,10- And dihydro-9-oxa-10-phosphaphenanthrene-10-oxide.

The sulfur-based antioxidants include, for example,
Examples thereof include dialkylthiodipropionates such as dilauryl, dimyristyl and distearyl esters of thiodipropionic acid, and polyol esters of β-alkylmercaptopropionic acid such as pentaerythritol tetra (β-dodecylmercaptopropionate).

Examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, didecyl phthalate, trioctyl trimellitate, tetraoctyl pyromellitate, tetraoctyl biphenyl tetracarboxylate, dioctyl adipate, diisononyl adipate, dioctyl sebacate, Dioctyl azelate,
Alkyl esters of aliphatic or aromatic polycarboxylic acids such as trioctyl citrate: Phosphate esters such as triphenyl phosphate, tricresyl phosphate, trixylyl phosphate; aliphatic or aromatic polycarboxylic acids and glycols Polyester obtained by condensation and, if necessary, terminal-terminated with a monohydric alcohol and / or a monocarboxylic acid; epoxidized natural oil such as epoxidized soybean oil; chlorinated paraffin;

As the above-mentioned ultraviolet absorber, for example, 2-
(2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-3
-Tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3,5-di-tert-butylphenyl) -5-chlorobenzotriazole,
2,2'-methylenebis (4-tert-octyl-6-benzotriazolylphenol), 2- (2-hydroxy-
Benzotriazole ultraviolet absorbers such as octyl alcohol or polyethylene glycol ester of 3-tert-butyl-5-carboxyphenyl) benzotriazole, 2-hydroxy-4-methoxybenzophenone, 2
-Hydroxy-4-octoxybenzophenone, 5,
Benzophenone-based ultraviolet absorbers such as 5'-methylenebis (2-hydroxy-4-methoxybenzophenone); 2
And triazine-based ultraviolet absorbers such as-(2-hydroxy-4-hexyloxy) -4,6-diphenyltriazine and 2- (2-hydroxy-4-octoxy) -4,6-dixylyltriazine.

Examples of the hindered amine light stabilizer include bis (2,2,6,6-tetramethyl-4).
-Piperidinyl) sebacate, bis (1,2,2,6,
6-pentamethyl-4-piperidinyl) sebacate, tetrakis (2,2,6,6-tetramethyl-4-piperidinyl) butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidinyl) Butanetetracarboxylate, bis (2,2,
6,6-tetramethyl-4-piperidinyl) ditridecylbutanetetracarboxylate, bis (1,2,2
2,6,6-pentamethyl-4-piperidinyl) ditridecylbutanetetracarboxylate, butanetetracarboxylic acid and 3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8,10 -Tetraoxaspiro [5.5] undecane and 2,2,6,6-tetramethyl-4-piperidinol or 1,2,2,6,6-
Polycondensate with pentamethyl-4-piperidinol, 1-
Polycondensate of (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol and diethyl succinate, 1,6-bis (2,2,6,6-tetramethyl-4
Polycondensation product of -piperidinylamino) hexane and dibromoethane, 1,6-bis (2,2,6,6-tetramethyl-4-piperidinylamino) hexane and 2,4-dichloro-6- Polycondensate with tertiary octylaminotriazine, 1,6-bis (2,2,6,6-tetramethyl-4
-Piperidinylamino) hexane and 2,4-dichloro-
Polycondensates with 6-morpholinotriazine, 1,5,8,
12-tetrakis [2,4-bis (N-butyl-N-
(2,2,6,6-tetramethyl-4-piperidinyl)
Amino) -s-triazin-6-yl] -1,5,8,
12-tetraazadodecane, 1,5,8,12-tetrakis [2,4-bis (N-butyl-N- (1,2,2,
6,6-pentamethyl-4-piperidinyl) amino)-
[s-triazin-6-yl] -1,5,8,12-tetraazadodecane and the like.

The composition of the present invention may be used in combination with known inorganic and / or organic antibacterial agents and fungicides to enhance its effect and / or broaden the antibacterial spectrum. You can also.

As the above-mentioned inorganic antibacterial agents and fungicides,
For example, a metal capable of imparting antibacterial and / or antifungal properties, such as silver and copper, or an oxide, hydroxide, phosphate thereof,
Examples include thiosulfate salts, silicates and inorganic compounds supporting them, and more specifically, silver or copper zeolites, silver zirconium phosphate, silver hydroxyapatite, silver phosphate glass, silver phosphate Ceramics, silver calcium phosphate and the like are commercially available.

Examples of the above-mentioned organic antibacterial agents include organic nitrogen sulfur-based antibacterial agents, organic bromide-based antibacterial agents, organic nitrogen-based antibacterial agents, and other antibacterial agents.
Examples of the organic nitrogen sulfur-based antibacterial agent include alkylene bisthiocyanate compounds such as methylene bisthiocyanate, and 5
-Chloro-2-methyl-4-isothiazolin-3-one, 2-octyl-4-isothiazolin-3-one,
Isothiazoline compounds such as 4,5-dichloro-2-octyl-4-isothiazolin-3-one, chloramine T,
Sulfonamide compounds such as N, N-dimethyl-N ′-(fluorodichloromethylthio) -N′-phenylsulfamide, thiazole compounds such as 2- (4-thiocyanomethylthio) benzothiazole 2-mercaptobenzothiazole, 2-pyridinethiol-1-oxide and its metal salt, 2- (4-thiazolyl) benzimidazole, 3,5-dimethyl-1,3,5-2H-tetrahydrothiadiazine-2-thione, N- (fluoro Dichloromethylthio) phthalimide, dithio-2,2'-bis (benzmethylamide) and the like. Examples of the above-mentioned organic bromide antibacterial agent include 2-bromo-2-nitropropane-1,3-diol, , 1-Dibromo-1-nitro-2-propanol, 2,2-dibromo-2-nitroethanol, 2-bromo-2 Organic bromonitro compounds such as nitro-1,3-diacetoxypropane, β-bromo-β-nitrostyrene 5-bromo-5-nitro-1,3-dioxane, and 2,2-dibromo-3-cyanopropionamide Organic bromocyano compounds, bromoacetic acid compounds such as 1,2-bis (bromoacetoxy) ethane, 1,4-bis (bromoacetoxy) -2-butene and bromoacetamide, and organic bromosulfone compounds such as bistribromomethylsulfone. Hexahydro-1,3,5-triethenyl-s-triazine, hexahydro-1,3,5-
S-triazine compounds such as tris (2-hydroxyethyl) -s-triazine, halogenated oxime compounds such as N, 4-dihydroxy-α-oxobenzeneethaneimidoyl chloride, α-chloro-O-acetoxybenzaldoxime, Chlorinated isocyanuric acid compounds such as trichloroisocyanurate and sodium sodium dichloroiisocyanurate; quaternary ammonium compounds such as benzalkonium chloride and decalinium chloride; carbamic acid compounds such as 2-methylcarbonylaminobenzimidazole;
[2- (2,4-dichlorophenyl)]-2′-
[(2,4-dichlorophenyl) methoxy] ethyl-3
Imidazole compounds such as-(2-phenylethyl) -1H-imidazolium chloride; amide compounds such as 2-chloroacetamide; N- (2-hydroxypropyl)
Amino alcohol compounds such as aminomethanol and 2- (hydroxymethylamino) ethanol; 2,4,5,6
And nitrile compounds such as tetrachloroisophthalonitrile.

The antimicrobial sealing material composition of the present invention is prepared by a generally known method by adding the above-mentioned additives to the above-mentioned sealing material base material together with the above-mentioned cyclic organic phosphate compound as needed.

The antibacterial sealing material composition of the present invention is filled into, for example, joints and gaps of building members such as a glass-fitted portion, a sash periphery and the like, and various devices to provide watertightness,
It provides airtightness and exhibits an excellent antibacterial effect.

[0041]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited by the following examples. In addition, Compound No. used below. 1 to N
o. 8 is a compound exemplified as the cyclic organic phosphate compound.

Example 1 A sealant was prepared by thoroughly mixing the following ingredients, and was cured at 20 ° C. and 65% RH for 14 days to form a sheet having a thickness of 3 mm. A 40 mm test piece was prepared. Using this test piece, the antibacterial properties of bacteria (Bacteria 1 to 4 in Table 1 below) and fungi (Bacteria 5 to 7 in Table 1 below) were evaluated by the following methods. The results are shown in Table 1 below. Bacteria: A bacterial culture solution was applied on a test piece, a polyethylene wrap film was adhered thereto, and the number of bacteria after culturing at 35 ° C. for 2 days was measured and evaluated according to the following criteria. ◎: Only less than 0.1% of the number of bacteria before the test survived. Good: 0.1% or more and less than 1% of the number of bacteria before the test are alive. B: 1% or more and less than 10% of the number of bacteria before the test are alive. X: 10% or more of the number of bacteria before the test is alive. Fungi: Place a test piece in the center of a petri dish, pour a normal agar medium so that the test piece is covered thinly, apply a culture solution of the fungus on the agar medium, and culture at 35 ° C for 2 weeks to grow the fungus The situation was observed and the results were evaluated according to the following criteria. ◎: No growth of bacteria on the upper part of the test piece. ：: Bacteria that grew on the test piece had less than 30% of the surface area. Δ: Bacteria grown on the test piece were 30% or more and 70% of the surface area
What is less than. ×: Bacteria that grew on the test piece accounted for 70% or more of the surface area.

[Blending] Parts by weight Methyldimethoxysilyl-terminal-modified polypropylene oxide 100 (Kaneka MS Polymer, manufactured by Kaneka Chemical Industry Co., Ltd.) Vinyl trimethoxysilane 2 N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane 2 dibutyltin dilaurate 2 dioctyl phthalate 40 calcium carbonate 100 titanium dioxide 30 test compound (see [Table 1] below) 2

[0044]

[Table 1]

Example 2 2 parts by weight of a test compound (see Table 2 below) were added to 100 parts by weight of a sealing material containing polyorganosiloxane as a main component (Tosseal # 388, manufactured by Toshiba Silicone Co., Ltd.), followed by roll kneading. Then, the same test as in Example 1 was performed using this test piece. The results are shown in Table 2 below.

[0046]

[Table 2]

Example 3 100 parts by weight of an aqueous acrylic resin-based sealing material (manufactured by Cemedine Co., Ltd.) was mixed with 3 parts by weight of a test compound (see Table 3 below) based on the solid content to form a sealing material. A composition was prepared, which was 50 mm × 50
A test piece was prepared by filling a mold of mm × 0.5 mm, and the same test as in Example 1 was performed using this test piece. Further, a test piece obtained by applying a sealing material composition containing the above-described test compound to Kent paper was put into a weathering tester having a cycle of ultraviolet irradiation (60 ° C. × 1 hour) and humidification (40 ° C. × 1 hour). Discoloration after the time was measured by a Hunter colorimeter and indicated by a color difference (ΔE) before and after irradiation.

[0048]

[Table 3]

As shown in the above tables, when a conventionally used silver inorganic antibacterial agent was contained (Comparative Example 1-
2, 3-2) not only have insufficient antibacterial properties, but also have significantly large discoloration when irradiated with ultraviolet rays. On the other hand, when a cyclic phosphate compound represented by the general formula (I) according to the present invention is contained (see Examples in each table).
Shows excellent antibacterial properties, has an extremely broad antibacterial spectrum, does not discolor even when irradiated with ultraviolet light, and is clearly excellent in stability.

[0050]

The sealing material composition of the present invention has excellent antibacterial properties, does not discolor even when exposed to ultraviolet rays, and has excellent light resistance.

Claims (4)

[Claims] An antibacterial sealing material composition containing a cyclic organic phosphate compound represented by the following general formula (I): Embedded image 2. The antibacterial sealing material composition according to claim 1, wherein in the general formula (I), M is an alkali metal atom or a zinc atom. 3. The antibacterial sealing material composition according to claim 1, wherein the resinous material is a sealing material base material. 4. The antibacterial sealing material composition according to claim 3, wherein the resin material is a silicone sealing material.