JPH11140350A - Resin composition for antibacterial coating material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a coating composition having very excellent antibacterial properties and good film properties by incorporating phosphonium salt groups, hydrophilic groups, and reactive groups other than the hydrophilic groups. SOLUTION: The phosphonium salt groups are desirably in the state in which they are incorporated in the main chain of a polymeric substance or as the side chain of the substance, and a polymeric substance containing acidic groups and phosphonium salt groups ionically bonded to the acidic groups is desirable. It is desirable that at lest two hydrophilic groups are present in the molecule, and that they are contained in the composition in the form of a water-soluble or-dispersible hydrophilic substance. The reactive groups are desirable in the case where they are bonded to a polymeric substance containing phosphonium salt groups and hydrophilic groups, in the case where they are bonded to at least either of a polymeric substance containing phosphonium salt groups and a hydrophilic substance and in the case where the are bonded to another added compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin for antibacterial paint comprising a polymer substance having a phosphonium base, and is suitable as a resin composition for antibacterial paint having both excellent antibacterial properties and practical paint properties. .

[0002]

2. Description of the Related Art Many antibacterial agents are used in food-related fields such as industrial and agricultural fields. Currently used antibacterial agents include natural products such as chitin and chitosan, ultrafine particles of zinc oxide, inorganic products such as silver-containing zeolite, and various synthetic products. Natural and inorganic products have recently received attention in terms of safety. On the other hand, synthetic products generally have better antibacterial activity than natural products and inorganic products.However, surface treatment is used to impart antibacterial properties. On the contrary, they tend to be shunned. This is because the antibacterial agent is easily dissolved in water, an organic solvent, or the like, and recently, an insoluble, nontoxic, immobilized antibacterial agent has been developed.

There are the following disclosure examples of this improvement method. JP-A-54-86584 discloses an antibacterial material mainly composed of a polymer substance containing an antibacterial agent component having a quaternary ammonium base ionically bonded to an acidic group such as a carboxyl group or a sulfonic acid group. Are listed. JP-A-61-
No. 245378 describes a fiber comprising a polyester copolymer containing an antibacterial agent component having a basic group such as an amidine group or a quaternary ammonium base. JP-A-57-204286, 63-609030, 62-
114903, JP-A-1-93596, JP-A-2-24
090 and the like, like various nitrogen-containing compounds, phosphonium salt compounds are known as biologically active chemicals having a broad activity spectrum against bacteria. There is disclosed an invention in which the above phosphonium salt is immobilized on a polymer substance to attempt to expand its use.

JP-A-4-266912 discloses an antibacterial agent of a phosphonium salt-based vinyl polymer.
814365 discloses a vinylbenzylphosphonium salt-based vinyl polymer antibacterial agent. Further, JP-A-5-310820 describes an antibacterial material mainly composed of a polymer substance containing an antibacterial component having an acidic group and a phosphonium base ionically bonded to the acidic group. In that example, a polyester using a phosphonium salt of sulfoisophthalic acid is disclosed. JP-A-6-41408 does not refer to the antibacterial action at all, but it is useful for photographic supports, packaging, general industrial use, magnetic tapes, and the like for copolyesters of phosphonium sulfonates and alkylene glycols. A modified polyester and film consisting of: The alkyl group bonded to the phosphonium salt described in the specification of the present invention is a type having a relatively short number of carbon atoms, such as a butyl group, a phenyl group and a benzyl group, unlike the above-mentioned JP-A-5-310820.

[0005] JP-A-4-266912, JP-A-4-81
4365, Japanese Patent Application Laid-Open No. 5-310820, and after studying the examples, synthesize a phosphonium base-containing vinyl polymer and a copolymerized polyester to form a structure such as a fiber or a film, and apply it to a base material. However, their antibacterial properties were examined, but the antibacterial activity was insufficient, and there was a need for improvement as an antibacterial material. Furthermore, in order to improve antibacterial properties, trinormal butyl dodecylphosphonium base is added to 5
Attempts to bond to 0% by mole or more of the polyester not only markedly reduced the mechanical properties due to the coloring of the polymer and the lowered glass transition point, but also caused a problem that sufficient antibacterial properties could not be obtained.

[0006]

When used for paints,
Silver-based antibacterial agents such as silver-containing zeolites are not preferable because they are colored black, and other known organic compounds are not able to withstand the heat during baking of the paint, in addition to the above-mentioned drawbacks, and are used due to deterioration and discoloration. I do not endure.

[0007]

Means for Solving the Problems Accordingly, the present inventors have intensively studied measures for improving the antibacterial property without unnecessarily increasing the amount of phosphonium base, which is an antibacterial component in a polymer substance, and as a result, the present invention was achieved. Was. That is, the present invention is a resin composition for an antibacterial paint, comprising a phosphonium base, a hydrophilic group and a reactive group. The resin composition for antibacterial paint of the present invention has a phosphonium base and a hydrophilic group, whereby its antibacterial activity is markedly enhanced, and contains a reactive group, so that a curing treatment such as paint baking was performed. In this case, a characteristic is that a cured film having excellent mechanical properties can be obtained. Next, the present invention will be described in detail.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The resin composition for an antibacterial coating of the present invention may be any composition as long as it contains a phosphonium base, a hydrophilic group and a reactive group. Although specific examples are shown below, the present invention is not limited to these examples. The phosphonium base of the present invention is preferably in a state of being bonded to the main chain or side chain of a polymer substance. In a preferred embodiment, it is a polymer substance containing an acidic group and a phosphonium base ionically bonded to the acidic group, and in a further preferred embodiment, a dicarboxylic acid component and a glycol component as main components, and a compound represented by the following general formula: The phosphonium base of the sulfonic acid group-containing aromatic dicarboxylic acid represented by
It is a polyester resin obtained by copolymerizing mol%, or a polyurethane resin obtained by reacting this polyester with an isocyanate compound and, if necessary, a chain extender.

[0009]

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Wherein A is an aromatic group, X ₁ and X ₂ are ester-forming functional groups, and R ₁ , R ₂ , R ₃ and R ₄ are alkyl groups, at least one of which has 10 carbon atoms. And represents an alkyl group of 20 or more.

Examples of the dicarboxylic acid component used in the polyester resin include aromatic dicarboxylic acids, alicyclic dicarboxylic acids, aliphatic dicarboxylic acids, and heterocyclic dicarboxylic acids. Examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, orthophthalic acid, and 2,6-naphthalenedicarboxylic acid. 1,2-cyclohexanedicarboxylic acid as an alicyclic dicarboxylic acid, 1,3-
Cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid and the like can be mentioned. As aliphatic dicarboxylic acids, succinic acid, glutaric acid, adipic acid, sebacic acid, dodecanedicarboxylic acid, azelaic acid, eicoic acid,
Dimer acid and its derivatives are exemplified. Heterocyclic dicarboxylic acids include pyridine dicarboxylic acid and derivatives thereof. Further, an oxycarboxylic acid such as p-oxybenzoic acid and a polyvalent carboxylic acid such as trimellitic anhydride and pyromellitic anhydride may be used in combination within a range not to impair the content of the invention. Among them, it is preferable to contain an aromatic dicarboxylic acid in an amount of 70 mol% or more from the viewpoint of physical properties of the coating film. As other dicarboxylic acids, 1,4-cyclohexanedicarboxylic acid, adipic acid, sebacic acid and the like are particularly preferred.

The glycol component includes ethylene glycol, propylene glycol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,4-propanediol.
Butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 2-methyl-1,5-
Alkylene glycols such as pentanediol, 2,2-diethyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,9-nonanediol, and 1,10-decanediol; Alicyclic glycols such as 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, alkylene oxide adducts of bisphenol A or F, diethylene glycol, polyethylene glycol, neopentyl hydroxypivalic acid Glycol ester (HPN), polypropylene glycol, polytetramethylene glycol, and the like are included.
In addition, a small amount of a compound containing an amide bond, a urethane bond, an ether bond, or a carbonate bond may be contained. Preferred from the viewpoint of physical properties of the coating film are ethylene glycol, neopentyl glycol, 2-methyl-1,3-
Propanediol, 1,6-hexanediol, 1,5
-Pentaneddiol, 3-methyl-1,5-pentanediol, and 1,4-cyclohexanedimethanol.
Further, a polyhydric polyol such as trimethylolethane, trimethylolpropane, glycerin, pentaerythritol and the like may be used in combination as long as the content of the invention is not impaired.

Examples of the phosphonium salt of a sulfonic acid group-containing aromatic dicarboxylic acid include tri-n-sulfoisophthalic acid.
Butyldecylphosphonium salt, tri-n-butyloctadecylphosphonium sulfoisophthalate, tri-n-butylhexadecylphosphonium sulfoisophthalate, tri-n-butyltetradecylphosphonium sulfoisophthalate, tri-n-sulfoisophthalate Butyl dodecyl phosphonium salt, tri-n-sulfoterephthalate
-Butyldecylphosphonium salt, tri-n-butyloctadecylphosphonium sulfoterephthalate, tri-n-butylhexadecylphosphonium sulfoterephthalate, tri-n-butyltetradecylphosphonium sulfoterephthalate, tri-n sulfoterephthalate -Butyldodecylphosphonium salt, 4-sulfonaphthalene-2,
Tri-n-butyldecylphosphonium 7-dicarboxylate, tri-n-butyloctadecylphosphonium 4-sulfonaphthalene-2,7-dicarboxylate, tri-n-butylhexadecyl 4-sulfonaphthalene-2,7-dicarboxylate Phosphonium salt, 4-sulfonaphthalene-
2,7-dicarboxylic acid tri-n-butyltetradecylphosphonium salt, 4-sulfonaphthalene-2,7-dicarboxylic acid tri-n-butyldodecylphosphonium salt, and the like. From the viewpoint of antibacterial activity, sulfoisophthalic acid is used. Particularly preferred are tri-n-butylhexadecylphosphonium salt, tri-n-butyltetradecylphosphonium sulfoisophthalate and tri-n-butyldodecylphosphonium sulfoisophthalate.

The above phosphonium salts of aromatic dicarboxylic acids include aromatic dicarboxylic acids or their sodium, potassium and ammonium salts, tri-n-butylhexadecylphosphonium bromide, tri-n-butyltetradecylphosphonium bromide, tri-n -Butyl dodecylphosphonium bromide or the like, and is obtained by reacting the same. The reaction solvent is not particularly limited,
Water is most preferred. For the purpose of improving the degree of coloring and the degree of gelation, the copolymerized polyester may be made of a magnesium salt such as magnesium acetate or magnesium chloride, a Ca salt such as calcium acetate or calcium chloride, or a Mn salt such as manganese acetate manganese chloride. It is also possible to add phosphoric acid or a phosphoric acid ester derivative such as phosphoric acid trimethyl ester, phosphoric acid triethyl ester or the like in an amount of from 20 ppm to 200 ppm as P. If the metal ion exceeds 300 ppm, the coloring of the polymer becomes remarkable, and if it is less than 20 ppm, no improvement in the heat resistance of the polymer is observed. Also, in terms of heat resistance, P
It is preferable that the molar ratio between the metal ions and the metal ions is 0.4 to 1.0.

[0015]

(Equation 1)

When the above molar ratio is less than 0.4 or more than 1.0, the coloring of the polymer and the generation of coarse particles become remarkable, and the application to coating materials becomes unfavorable.

Examples of the method for producing the polyester include a so-called direct polymerization method in which an aromatic dicarboxylic acid and a glycol are directly reacted, and a so-called transesterification method in which a dimethyl ester of an aromatic carboxylic acid is transesterified with a glycol. Can be applied. The timing of adding the metal ion, phosphoric acid and its derivative is not particularly limited, but it is preferable that the metal ion is added at the time of charging the raw materials and that the phosphoric acid is added before the polymerization reaction.

In addition, one preferred embodiment of the phosphonium base of the present invention is a phosphonium salt-based vinyl polymer having a compound represented by the following general formula as one of the constituent units.

[0019]

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(Wherein R ₁ , R ₂ , and R ₃ are a hydrogen atom, a linear or branched alkyl group having 1 to 18 carbon atoms, an aryl group, a hydroxy group, or an alkyl group substituted with an alkoxy group. group, an aryl group or an aralkyl group, X ^- is an anion, n represents methyl specific examples of R _1, R _2, R ₃ are shown) of 2 a natural number, ethyl, propyl, butyl, pentyl, hexyl, heptyl , Octyl, dodecyl and the like, aryl groups such as phenyl, tolyl and xylyl, aralkyl groups such as benzyl and phenyl, hydroxyl group, alkoxy group and the like, and an alkyl group and an aryl group are particularly preferable. R ₁ , R ₂ and R ₃ may be the same group or different groups. X ^- is an anion, for example, fluorine, chlorine,
Examples thereof include a halogen ion such as bromine or iodine, a sulfate ion, a phosphate ion, and a perchlorate ion, and a halogen ion is preferable. n is not particularly limited, but is 2 to 500,
Preferably it is 10-300.

The hydrophilic group of the present invention is, for example, a hydroxyl group, an amino group, a carboxyl group, a sulfonic acid group or a derivative thereof, a metal base, an ether group, and the like. One of the preferred embodiments is that the resin composition is contained in the resin composition for antibacterial coating in the form of a hydrophilic substance that can be contained and dissolved or dispersed in water.
Further, this hydrophilic substance may be mixed in the resin composition for antibacterial coating as a compound different from the polymer substance containing a phosphonium base, or may be chemically bonded to the polymer substance containing a phosphonium base. It doesn't matter. The antibacterial coating resin of the present invention has significantly improved antibacterial properties due to the presence of both a polymer substance containing a phosphonium base and a hydrophilic substance.

Specific examples of the hydrophilic substance in the present invention include alkylene glycols such as polyvinyl alcohol, starch, polyvinyl pyrrolidone, polyacrylic acid, polystyrene sulfonic acid, polyethylene glycol, polypropylene glycol, and polytetramethylene glycol.
Glycerin, polyglycerin, and water-soluble modified cellulose include hydroxyethyl cellulose, methyl cellulose, methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl methyl cellulose, sodium carboxymethyl cellulose, cellulose nitrate carboxymethyl ether, and 5-sulfoisophthalic acid. No. Further, as another hydrophilic substance, a metal salt such as 4-sulfonaphthalene-2,7-dicarboxylic acid, 5 (4-sulfophenoxy) isophthalic acid, or 2-sulfo-1,4-butanediol, 2,5- A hydrophilic polyester obtained by copolymerizing a dicarboxylic acid or a glycol containing a metal salt of a sulfonic acid such as a metal salt such as dimethyl-3-sulfo-2,5-hexanediol or the like, or a polyethylene glycol or the like, Polyurethane reacted with an isocyanate compound is exemplified. These can be used as a mixture with a polymer substance containing the phosphonium base. Among these, polyalkylene oxides such as polyethylene glycol and polyalkylene oxide derivatives, partially saponified polyvinyl alcohol, dicarboxylic acids or glycols containing sulfonic acid metal bases, and hydrophilic polyesters copolymerized with polyethylene glycol and the like, A polyurethane obtained by reacting this hydrophilic polyester with an isocyanate compound is particularly preferred.

The molecular weight of the hydrophilic substance is not particularly limited, but is preferably from 200 to 30,000, more preferably from 1,000 to 15,000 in number average molecular weight. The preferable addition amount of the hydrophilic substance is 0.1 to 2 with respect to the polymer substance.
0% by weight, preferably 0.5 to 10% by weight, more preferably 1 to 5% by weight. 0.1% by weight of hydrophilic substance
If the amount is less than 20%, the effect of increasing the antibacterial activity is insufficient.

The method of mixing the polymer substance and the hydrophilic substance, which are important for the expression of antibacterial properties, is not particularly limited, and any method may be adopted depending on the production method, chemical properties, and physical properties of the polymer substance. it can. For example, a method in which both are heated and melt-mixed using an extruder or the like, a method in which a hydrophilic substance is added into a reaction system during or after the completion of the reaction, during the production of a polymer substance, in a monomer before a polymerization reaction, Further, a method of mixing and dissolving or dispersing a polymer substance and a hydrophilic substance in an appropriate solvent, for example, water, a mixed solvent of water / alcohol, an organic solvent such as acetone, methyl ethyl ketone, and cyclohexanone, and then drying the solvent. There is.

As a method for chemically bonding a hydrophilic substance to a polymer substance containing a phosphonium base, a hydroxyl group, an amino group,
Examples include a method of copolymerizing a compound having a hydrophilic group such as a carboxyl group, a sulfonic acid metal base, or an ether group into a main chain or a side chain. By copolymerizing hydrophilic substances,
The compatibility is improved, and the appearance, storage stability, and physical properties of the coating are improved. Also, the water resistance is improved.

Preferred methods for copolymerizing these hydrophilic substances include metal salts such as 5-sulfoisophthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid, and 5 (4-sulfophenoxy) isophthalic acid. -Sulfo-
A dicarboxylic acid or a glycol containing a metal salt of a sulfonic acid such as a metal salt such as 1,4-butanediol or 2,5-dimethyl-3-sulfo-2,5-hexanediol is contained in the above phosphonium base. A method in which a sulfonic acid or a sulfonic acid group is bonded to a polyester resin by copolymerizing with an aromatic dicarboxylic acid, and an alkylene glycol such as polyethylene glycol, polypropylene glycol, or polytetramethylene glycol is copolymerized with a phosphonium group-containing aromatic dicarboxylic acid to form a polyester. A method of bonding an ether group to a resin, or reacting the above-mentioned phosphonium base and ether group-containing polyester resin with an isocyanate compound, or isocyanate compound of a phosphonium base-containing polyester resin with alkylene glycol A method of reacting a polyester resin containing a phosphonium base with an isocyanate compound by using a carboxyl group-containing diol or polyol such as dimethylolpropionic acid as a chain extender. Examples include a method of bonding a group or a salt thereof, and a method of graft-polymerizing a vinyl-based monomer containing a hydrophilic group onto a phosphonium base-containing polyester resin to bond various hydrophilic groups.

Examples of the vinyl monomer having a hydrophilic group that can be grafted onto the polymer substance in the present invention include those containing a carboxyl group, a hydroxyl group, a sulfonic acid group, an amide group, and the like, and a group that can be converted into a hydrophilic group. Examples thereof include those containing an acid anhydride group, a glycidyl group, a chloro group and the like. Among them, those having a carboxyl group are most preferred. For example, it is a monomer containing a carboxyl group or a salt thereof such as acrylic acid, methacrylic acid and salts thereof. As other vinyl monomers having a hydrophilic group, for example, epoxy group-containing monomers such as allyl glycidyl ether, styrene sulfonic acid,
Monomers containing sulfonic acid groups or salts thereof, such as vinylsulfonic acid and salts thereof, crotonic acid, itaconic acid,
Monomers containing a carboxyl group or a salt thereof such as maleic acid, fumaric acid and salts thereof, and monomers containing an acid anhydride such as maleic anhydride and itaconic anhydride are exemplified.

These can be used in combination with other vinyl monomers. As other vinyl monomers, for example, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-
Alkyl acrylates such as butyl acrylate and t-butyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate and t-butyl methacrylate;
Hydroxy-containing monomers such as hydroxyethyl acrylate and 2-hydroxyethyl methacrylate, acrylamide, methacrylamide, N-methylacrylamide, N-methylmethacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, N-methoxymethylacrylamide, N- Methoxymethyl methacrylamide, N, N-dimethylolacrylamide,
Amide group-containing monomers such as N-phenylacrylamide, styrene, vinyl methyl ether, vinyl ethyl ether, acrylonitrile, methacrylonitrile, vinylidene chloride, vinyl acetate, vinyl chloride, and the like. One or more of these are included. Can be used for copolymerization.

The ratio between the vinyl monomer having a hydrophilic group and the other vinyl monomer is 30/70 in molar ratio.
The range of 範 囲 100/0 is preferred. If the ratio of the monomer having a hydrophilic group is less than 30 mol%, the effect of enhancing the antibacterial property is not sufficiently exhibited. As a method for grafting a vinyl-based monomer having a hydrophilic group to a polymer substance, a known graft polymerization method can be used. The following method is mentioned as a typical example. For example, a radical polymerization method in which radicals are generated in a main chain polymer substance by light, heat, radiation, or the like, and then a vinyl monomer is graft-polymerized, or a cation that generates cations using a catalyst such as AlCl ₃ or TiCl ₄ Polymerization method or metal Na,
There is an anion polymerization method of generating an anion using metal Li or the like.

Further, there is a method in which a polymerizable unsaturated double bond is previously introduced into a main chain polymer substance and a vinyl monomer is reacted with the polymerizable unsaturated double bond. Examples of the compound capable of forming an ester bond having a polymerizable unsaturated double bond include fumaric acid, maleic acid, maleic anhydride, itaconic acid, citraconic acid, 2,5-norbornene dicarboxylic anhydride, and tetrahydrophthalic anhydride. Acids and the like can be mentioned. The most preferred of these are fumaric acid, maleic acid, and 2,5-norbornene dicarboxylic acid.

Further, there is a method in which a main chain high molecular substance having a functional group introduced into a side chain is reacted with a branch polymer having a group which reacts with the above functional group at the terminal. For example, -OH group, -SH group, -NH2 group, -COOH group, -C
A polymer substance having a hydrogen donating group such as an ONH ₂ group, and one end having a —N ＝ C ＝ O group, a —C ＝ C ＝ O group,

[0032]

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[0033]

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And a method of reacting with a vinyl polymer which is a hydrogen-accepting group, and a reverse combination thereof. The preferred weight ratio of the polymer material serving as the main chain of the present invention to the vinyl monomer grafted is 95/5.
-40/60, more preferably 93/7.
~ 55/45, most preferably 90 / 10-60 / 40
Range. When the weight ratio of the main chain polymer substance is less than 40%, the heat resistance of the conventional polymer substance because the graft polymerizable vinyl monomer remains without completely reacting,
Properties such as processability and water resistance are impaired. On the other hand, when the weight ratio of the main chain polymer substance exceeds 95%, the effect of improving antibacterial properties, which is the object of the present invention, cannot be sufficiently exhibited. There is no significant difference in the antibacterial effect between the case where the hydrophilic substance is mixed with the polymer substance and the case where the hydrophilic substance is copolymerized, and good antibacterial properties are obtained.

As described above, there are various cases in which the combination of the phosphonium base-containing polymer substance and the hydrophilic substance of the present invention, the presence or absence of a chemical bond, and the state of the bond are all used as embodiments of the present invention. To summarize as a preferred example, the phosphonium base-containing polymer substance is obtained by copolymerizing the phosphonium base of the sulfonic acid group-containing aromatic dicarboxylic acid represented by the general formula (1) with 1 to 50 mol% based on all acid components. When the obtained polyester resin or the polyurethane resin obtained by reacting the polyester with an isocyanate compound and a chain extender as necessary, the hydrophilic substance is a polyalkylene oxide or a partially saponified polyvinyl alcohol and a phosphonium base-containing polymer substance. When it is compounded as a compound different from When the hydrophilic base is a graft of a vinyl polymer having a hydrophilic group in the side chain, particularly preferably a phosphonium base-containing base, In the case of the combination wherein is a polyester, a polymer material obtained by copolymerizing a main chain with a compound capable of forming an ester containing a metal salt of sulfonic acid, and a phosphonium base-containing polymer material in the main chain or side chain In the case where the phosphonium base-containing polymer is a polyester, the hydrophilic substance is a carboxyl group-containing diol or polyol, and the chain extender is a phosphonium base-containing. A polyurethane resin obtained by reacting a polymer material with an isocyanate compound. If, particularly preferably among this a phosphonium-containing polymeric material is the polyester in the reaction of isocyanate compounds include the combination is a polyurethane resin obtained by adding a chain extender as needed.

The resin composition for an antibacterial coating of the present invention must contain a reactive group different from a hydrophilic group in order to obtain good film properties. The reactive group is a functional group capable of chemically reacting with a hydroxy group, a carboxyl group, a polymerizable unsaturated double bond group or the like in a polymer substance or a hydrophilic substance, and specifically, an epoxy group, an isocyanate group. Polymerizable unsaturated double bond groups such as vinyl, allyl and N, N-
Bis (alkoxymethyl) amino group, N, N-bis (hydroxymethyl) amino group, N-alkoxymethyl-N
An alkylol-modified amino group such as a -hydroxymethylamino group or a hydroxymethylamino group or a group of an alkyl etherified product thereof.

When these reactive groups are bonded to a polymer substance containing both a phosphonium base and a hydrophilic group, when they are bonded to one or both of a polymer substance containing a phosphonium base and a hydrophilic substance, When the compound is bonded to a compound added separately from the phosphonium base-containing polymer substance and the hydrophilic substance as a curing agent, any of them can be suitably used.

As a method for bonding an epoxy group to a polymer substance containing a phosphonium base or a hydrophilic substance, a method of using an epoxy group-containing vinyl monomer such as glycidyl acrylate or glycidyl methacrylate when polymerizing or grafting a hydrophilic substance. To carboxy groups contained in already synthesized hydrophilic substances or polyesters containing phosphonium bases, or to carboxy groups obtained by reacting hydroxy groups with phthalic anhydride or trimellitic anhydride, for example bisphenol A type epoxy Resin, bisphenol F type epoxy resin, novolak type epoxy resin, phenolic compound modified epoxy resin or other epoxy compound containing two or more epoxy groups in one molecule so that the epoxy group is in excess amount to the carboxy group. One who reacts Etc. The.

As a method of bonding an isocyanate group to a polymer substance containing a phosphonium base or a hydrophilic substance, a method of using an isocyanate group-containing monomer such as vinyl isocyanate or allyl isocyanate at the time of polymerizing or graft-polymerizing a hydrophilic substance, An isocyanate compound containing two or more isocyanate groups such as hexamethylene diisocyanate, diphenylmethane diisocyanate, toluene diisocyanate, etc. in a molecule of a previously synthesized hydrophilic substance or polyester containing a phosphonium base is reacted with the isocyanate group. A method in which the reaction is carried out so as to be in excess with respect to the functional group, and the like can be given.

As a method for bonding the polymerizable unsaturated double bond group to a polymer substance or a hydrophilic substance containing a phosphonium base, a hydrophilic substance or a polyester containing a phosphonium base bonded to an isocyanate group by the above-mentioned method can be used. Examples thereof include a method of reacting hydroxyl group-containing acrylates such as 2-hydroxymethyl acrylate and 2-hydroxymethyl methacrylate.

The method of adding a compound containing a reactive group as a curing agent separately from a phosphonium base-containing polymer substance and a hydrophilic substance is to adjust the physical properties of the cured coating film according to the type and amount of the curing agent. And is one of the most preferred embodiments of the present invention. The preferred compounding amount of the curing agent is 5 to 35% by weight, more preferably 10 to 25% by weight, based on the total of the polymer substance and the hydrophilic substance. As a curing agent containing an alkylol-modified amino group or an alkyl etherified group thereof, an alkyl etherified amino formaldehyde resin is used. As a curing agent containing an epoxy group, various epoxy compounds are used. As a curing agent containing an isocyanate group, various isocyanates are used. Examples of the compound and the like and the curing agent containing a polymerizable unsaturated double bond group include various vinyl group-containing monomers.

Alkyl etherified aminoformaldehyde resins include, for example, formaldehyde or paraformaldehyde alkyletherified with an alcohol having 1 to 4 carbon atoms such as methanol, ethanol, n-propanol, isopropanol, n-butanol and urea; Condensation products with N, N-ethylene urea, dicyandiamide, aminotriazine, etc., methoxylated methylol-N, N-ethyleneurea, methoxylated methylol dicyandiamide, methoxylated methylol benzoguanamine, butoxylated methylol benzoguanamine, methoxylated methylol melamine Butoxylated methylol melamine, mixed methoxylated / butoxylated methylol melamine, butoxylated methylol benzoguanamine, and the like. Preferred from sexual surfaces, methoxylated methylolmelamine, butoxy methylol melamine or methoxylated / butoxylated mixed melamine, it may be used alone, or in combination.

As the epoxy compound, bisphenol A
Diglycidyl ethers and oligomers thereof, diglycidyl ethers of hydrogenated bisphenol A and oligomers thereof, diglycidyl orthophthalate, diglycidyl isophthalate, diglycidyl terephthalate, diglycidyl p-oxybenzoate, tetrahydrophthalate Acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, succinic acid diglycidyl ester, adipic acid diglycidyl ester, sebacic acid diglycidyl ester, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol di Glycidyl ether, 1,6-hexanediol diglycidyl ether and polyalkylene glycol diglycidyl ethers, trime Triglycidyl citrate, triglycidyl isocyanurate, 1,4-diglycidyloxybenzene, diglycidyl propylene urea, glycerol triglycidyl ether, trimethylol ethane triglycidyl ether, trimethylol propane triglycidyl ether, pentaerythritol tetraglycidyl ether And glycerol alkylene oxide adduct triglycidyl ether.

Further, as the isocyanate compound, there are aromatic and aliphatic diisocyanates, and polyisocyanates having a valency of 3 or more. Either a low molecular compound or a high molecular compound may be used. For example, tetramethylene diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate or trimers of these isocyanate compounds, and excess of these isocyanate compounds Amount and, for example, ethylene glycol, propylene glycol, trimethylolpropane, glycerin, sorbitol, ethylenediamine, monoethanolamine, diethanolamine, low molecular weight active hydrogen compounds such as triethanolamine or various polyester polyols, polyether polyols, polyamides Reacts with polymer active hydrogen compounds, etc. Terminal isocyanate group-containing compounds obtained Te are exemplified.

The isocyanate compound may be a blocked isocyanate. As the isocyanate blocking agent, for example, phenol, thiophenol,
Phenols such as methylthiophenol, ethylthiophenol, cresol, xylenol, resorcinol, nitrophenol, chlorophenol, acetoxime, methylethylketoxime, cyclohexanone oxime and its oximes, alcohols such as methanol, ethanol, propanol and butanol, ethylene chlorohydroxide Phosphorus, halogen-substituted alcohols such as 1,3-dichloro-2-propanol, t-butanol, t-
Tertiary alcohols such as pentanol, ε-caprolactam, δ-valerolactam, γ-butyrolactam,
lactams such as β-propyrolactam; and other active methylene compounds such as aromatic amines, imides, acetylacetone, acetoacetate, and malonic acid ethyl ester; mercaptans, imines, ureas, and diaryls. Compounds such as sodium bisulfite are also included. The blocked isocyanate can be obtained by subjecting the above isocyanate compound to an isocyanate blocking agent to undergo an addition reaction by a conventionally known appropriate method.

Examples of the vinyl group-containing monomers include, in addition to the above-mentioned vinyl monomers that can be used in the graft reaction, ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, ethylene glycol diacrylate, trimethylolpropane triacrylate, and the like. A polyfunctional monomer containing two or more vinyl groups in one molecule is exemplified. When a polymer substance or a hydrophilic substance containing a phosphonium base having a polymerizable unsaturated double bond bonded thereto is used as the resin composition for an antibacterial coating of the present invention, this vinyl is used in order to efficiently perform a curing reaction. It is preferred to add group-containing monomers. These reactive groups and curing agents may be used in combination of two or more as needed.

The resin composition for an antibacterial coating of the present invention may use a known curing reaction initiator or accelerator selected according to the type of the reactive group as a catalyst. In addition, the resin composition for an antibacterial coating of the present invention can be used by dispersing inorganic pigments such as titanium oxide, red iron oxide, calcium carbonate, barium sulfate, and zinc oxide, carbon black, various organic coloring pigments, various lubricants, and the like. Moreover, you may apply | coat as a clear paint directly on a base material or on an existing coating film.

The resin composition for antibacterial coating of the present invention contains silver / zeolite particles, silver / zirconium phosphate particles, zinc oxide fine particles, and titanium oxide having a photooxidation catalytic function for the purpose of further improving antibacterial properties. It is also possible to add inorganic particles such as fine particles. Further, for the purpose of imparting antibacterial properties, the antibacterial paint resin of the present invention can be used by being blended with an ordinary paint resin. The resin composition for an antibacterial coating of the present invention is applied to an object to be coated such as a metal plate, a resin plate, a wood block, a molded product, and then heated, left naturally, irradiated with radiation, and the like. The curing reaction can be performed by a known method according to the catalyst and the catalyst.

[0049]

Next, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples. In the examples, “part (s)” means “part (s) by weight”. Each measurement item followed the following method.

1. Reduced viscosity ηsp / c (dl / g) 0.10 g of polyester resin or polyurethane resin
Was dissolved in 25 cc of a mixed solvent of phenol / tetrachloroethane (volume ratio: 6/4) and measured at 30 ° C.

2. Glass transition temperature Measured at a heating rate of 20 ° C./min using a differential scanning calorimeter (DSC). The sample was prepared by placing 5 mg of the sample in an aluminum holding lid type container and crimping it.

3. Acid value 0.2 g of sample was precisely weighed and dissolved in 20 ml of chloroform. Then, it was determined by titration with 0.01 N potassium hydroxide (ethanol solution). Phenolphthalein was used as the indicator.

5. Magic stain resistance Draw a line on the painted surface with red magic ink and leave it for 2 hours.
Traces of the magic ink after wiping with ethanol were evaluated on a five-point scale. (5: no trace, 1: complete trace)

6. Hardness The coated surface of the steel plate was measured using a high-grade pencil specified in JIS S-6006 in accordance with JIS K-5400, and judged by the presence or absence of scratches.

7. Workability The coated steel sheet was bent at 180 degrees, and cracks generated at the bent portions were observed and judged with a 10-fold loupe. 3T refers to a case where three sheets of the same thickness are sandwiched in the bent portion, and 0T refers to a case where the sheet is folded 180 degrees without sandwiching the board.

8. Gloss A 60 degree reflectance was measured.

9. Antibacterial test S. diluted with 1/50 broth aureus (Staphylococcus aureus), or E. coli. 0.1 ml of a coli solution (concentration: 107 cells / ml) of Coli (Escherichia coli) was dropped onto a sample-coated plate cut to a size of 5 cm × 6 cm which had been sterilized with high pressure steam in advance, and polyvinylidene chloride sterilized with high pressure steam thereon. The film was brought into close contact. The test piece was transferred to a sterile petri dish and cultured at 37 ° C. (Staphylococcus aureus) or 30 ° C. (Escherichia coli) for 24 hours. Then, the bacteria on the sample coated plate and the film were washed with 10 ml of SCDLP medium, diluted 10-fold, and spread on an ordinary agar plate. After 24 hours, the number of bacteria was counted.

The following were used as phosphonium salt-containing dicarboxylic acids. C-12: Tri-n-butyl, dodecylphosphonium salt of 5-sulfoisophthalic acid dimethyl ester C-16: Tri-n-butyl, hexadecylphosphonium salt of 5-sulfoisophthalic acid dimethyl ester

Preparation of sample coated plate 1) In the case of clear paint A commercially available primer and a top coat (white) were coated in advance with a clear paint prepared on a 2T coated steel sheet so as to have a film thickness of 10 μm. After setting at 10 ° C. for 10 minutes, what was baked at 240 ° C. for 1 minute was used. 2) White paint A white paint prepared on a primer steel plate to which a commercially available primer was previously applied was applied so that the film thickness became 15 μm, and setting and baking were performed in the same manner as the clear.

Production Example of Polymeric Substance (A-1) In a stainless steel autoclave equipped with a stirrer, a thermometer and a partial reflux condenser, 485 parts of dimethyl terephthalate, 437 parts of dimethyl isophthalate, C-12
Was charged with 161 parts of ethylene glycol, 409 parts of ethylene glycol, 354 parts of neopentyl glycol, and 0.52 part of tetra-n-butyl titanate, and a transesterification reaction was performed at 160 to 220 ° C. for 4 hours. Then, 200-2
The temperature was raised to 20 ° C., and the pressure of the reaction system was gradually reduced.
Reaction under a reduced pressure of 0.2 mmHg for 1.5 hours.
A polyester resin (A) was obtained. The reduced viscosity of the polyester resin (A) was 0.45 dl / g, and the acid value was 10 equivalents / 106 g. Analysis by NMR spectrum or the like revealed that the composition was such that the acid component was 50 mol% of terephthalic acid and 45 mol% of isophthalic acid. , C-12 was 5 mol%, the glycol component was ethylene glycol 48 mol%, and neopentyl glycol 52 mol%. The results are shown in Table 1.

Production Examples of Polymeric Substances (A-2) to (A-5) Synthesis was performed in the same manner as for the polymeric substance (A-1). Table 1 shows the results.
Shown in

Production Example of Polymeric Substance (A-6) 437 parts of dimethyl terephthalate, 437 parts of dimethyl isophthalate and C-12 were placed in a stainless steel autoclave equipped with a stirrer, a thermometer and a partial reflux condenser.
Was charged with 161 parts of ethylene glycol, 512 parts of ethylene glycol, 237 parts of neopentyl glycol, and 0.52 part of tetra-n-butyl titanate, and a transesterification reaction was performed at 160 to 220 ° C. for 4 hours. Then fumaric acid 29
Part, and the temperature is raised to 200 to 220 ° C. over 1 hour,
After gradually reducing the pressure of the reaction system, the reaction was carried out at a reduced pressure of 0.2 mmHg for 1 hour and 30 minutes to obtain a polyester (A-5). The results are shown in Table 1.

Comparative Production Example of Polymeric Substance (A-7) As a comparison, a polyester resin (A-7) containing no phosphonium salt was synthesized as in the case of the polymeric substance (A-1). The results are shown in Table 1.

Production Example of Polyurethane Polymer (A-8) 100 parts of the polymer (A-5) was placed in a reactor equipped with a stirrer, a thermometer and a cooling pipe, and a carboxyl group-containing glycol as a chain extender was used. Of dimethylolbutanoic acid was dissolved in cyclohexanone under a nitrogen stream and heated to 60 ° C. Then, isophorone diisocyanate 32.6
And slowly heated to 80 ° C. After the reaction for 1 hour, 0.01 part of dibutyltin dilaurate was added, and the mixture was further reacted for 2 hours to obtain a polyurethane resin (A-8). The resulting polyurethane resin has a reduced viscosity of 0.82 d.
1 / g and the acid value was 690 eq / 106 g.

Production Example of Graft Polymer Type Polymeric Substance (A-9) 300 parts of polyester (A-5), 360 parts of methyl ethyl ketone, and 120 parts of isopropyl alcohol were placed in a reactor equipped with a stirrer, thermometer, reflux device and fixed-rate dropping device. Then, the resin was dissolved in a refluxed state by heating and stirring. After the resin was completely dissolved, a mixture of 35 parts of acrylic acid and 65 parts of ethyl acrylate and 1.5 parts of octyl mercaptan, and 6 parts of azobisisobutyronitrile were added to 90 parts of methyl ethyl ketone.
And a solution dissolved in a mixture of 30 parts of isopropyl alcohol were added dropwise to the polyester solution over 1.5 hours, and the mixture was further reacted for 3 hours to obtain a graft polymer solution. After the graft polymer solution was cooled to room temperature, 59 parts of triethylamine was added and neutralized, and then 800 parts of ion-exchanged water was added and stirred for 30 minutes. Thereafter, the solvent remaining in the solvent was distilled off by heating to obtain an aqueous dispersion. This aqueous dispersion was transparent milky white and had good stability. The results are shown in Table-3.

Example 1 97 parts of the polymer substance (A-1) and 3 parts of polyethylene glycol having a molecular weight of 5,000 as a hydrophilic substance were dissolved by heating in a mixed solvent of 106 parts of methyl ethyl ketone and 27 parts of isopropyl alcohol. After cooling, 25 parts of methylated melamine Cymel 303 (Mitsui Cytec Co., Ltd.) and 0.25 part of paratoluenesulfonic acid as a curing catalyst were blended to obtain a clear coating. This paint was stable even after storage for several months, and when evaluated by the above-described method, good coating appearance and physical properties with good gloss were obtained, and the antibacterial property was very good. The results are shown in Table-2.

Example 2 97 parts of a polymer substance (A-2), partially saponified polyvinyl alcohol as a hydrophilic substance, trade name PVA205
(Kuraray Co., Ltd.) 3 parts, methyl ethyl ketone 106 parts,
It was dissolved by heating in a mixed solvent of 27 parts of isopropyl alcohol. Cymel 303, a methylated melamine after cooling
25 parts of (Mitsui Cytec Co., Ltd.), 0.25 part of paratoluenesulfonic acid as a curing catalyst, and 125 of titanium oxide were mixed and dispersed with a glass bead-type high-speed shaker for 5 hours to obtain a white paint. When this paint was evaluated by the above-described method, a good glossy and good coating film appearance was obtained, and the antibacterial property was very good. The results are shown in Table-2.

Examples 2 to 6 A paint was prepared and evaluated in the same manner as in Example 1 or 2. Table 2 shows the results.

Comparative Examples 1 to 4 Paints were prepared and evaluated in the same manner as in the examples. The results are shown in Table-3.

[0070]

Industrial Applicability The resin composition for antibacterial paint of the present invention has remarkably excellent antibacterial properties and has good coating film properties, and is suitable as a material for antibacterial paints and coatings.

[0071]

[Table 1]

[0072]

[Table 2]

[0073]

[Table 3]

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Hideto Ohashi 2-1-1 Katata, Otsu City, Shiga Prefecture Inside Toyobo Co., Ltd. (72) Inventor Satoshi Hayakawa 2-1-1 Katata, Otsu City, Shiga Prefecture No. Toyobo Co., Ltd.

Claims (9)

[Claims] 1. A resin composition for an antibacterial paint, comprising a phosphonium base, a hydrophilic group and a reactive group other than the hydrophilic group. 2. A resin composition for an antibacterial coating, wherein the phosphonium base according to claim 1 is bonded to a main chain or a side chain of a polymer substance. 3. A resin composition for an antibacterial paint, wherein the phosphonium base, hydrophilic group and reactive group according to claim 2 are contained in the same compound. 4. The method according to claim 2, wherein the phosphonium base and the hydrophilic group according to claim 2 are contained in the same compound, and the reactive group according to claim 2 is contained in a different compound. And a resin composition for an antibacterial paint. 5. The compound according to claim 2, wherein the phosphonium base and the hydrophilic group are contained in different compounds, and the reactive group according to claim 2 is contained in a compound containing the phosphonium base, or the compound contains a hydrophilic group. A resin composition for an antibacterial paint, which is contained in any of the compounds. 6. The compound according to claim 2, wherein the phosphonium base and the hydrophilic group are contained in different compounds, and the reactive group according to claim 2 is contained in a compound containing a phosphonium base, or the compound contains a hydrophilic group. A resin composition for an antibacterial paint, which is contained in both compounds. 7. A resin composition for an antibacterial paint, wherein the phosphonium base, hydrophilic group and reactive group according to claim 2 are contained in different compounds. 8. A resin composition for antibacterial paint, wherein at least two or more of the resin compositions for antibacterial paint according to claim 3, 4, 5, 6, or 7 are mixed. 9. The method of claim 2, 3, 4, 5, 6, 7, or 8.
A resin composition for an antibacterial coating, wherein the polymer substance according to any one of the above, comprises an acidic group and a phosphonium base ionically bonded to the acidic group.