Antibacterial coating treatment solution and antibacterial coating treatment method

Abstract

To provide an antibacterial coating treatment solution which can form an antibacterial coating with superior antibacterial capability and curing property, and with superior durability of antibacterial effect and resistance to water.SOLUTION: An antibacterial coating treatment solution containing: (A) an antibacterial polymer containing a unit (a) having an alkoxysilane as a side chain, a unit (b) having an ammonium salt as a side chain, and a unit (c) having a hydrophobic group as a side chain; (B) a silicon compound having at least one selected from the group consisting of an alkoxysilyl group, an alkoxysilylene group, and a siloxane bond; (C) an organometallic compound; (D) water; and (E) an organic solvent.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to an antibacterial film treatment liquid and an antibacterial film treatment method.

Background Art

[0002] In recent years, from the viewpoint of hygiene, methods for imparting antibacterial properties to the surface of articles have been developed. Such methods use materials having antibacterial properties. Materials having antibacterial properties are roughly classified into inorganic materials such as metals and metal compounds, and organic materials such as quaternary ammonium salts and alcohols.

[0003] For example, Patent Document 1 discloses a coating composition using photocatalytic particles such as titanium oxide and cuprous oxide particles. However, in antibacterial compositions using inorganic antibacterial components, there are problems such as metal and metal compound particles being likely to aggregate and precipitate, poor storage stability, and a decrease in the transparency of the coating film.

[0004] On the other hand, although organic antibacterial components have good stability and a transparent film can be obtained, there is a problem that the antibacterial components are easily eluted by water immersion, especially warm water, and the antibacterial property does not persist.

[0005] It has been proposed to use organic antibacterial components. For example, Patent Document 2 discloses an antibacterial paint containing an amino group-containing alkoxysilane for the purpose of coating a washing machine tub. Further, Patent Documents 3 and 4 disclose that the elution of the quaternary ammonium salt from the film is suppressed by using a polyvalent carboxylic acid or phosphoric acid together with the quaternary ammonium salt, and both show antibacterial persistence in water immersion at 25°C ± 2°C. Furthermore, Patent Document 5 shows antibacterial persistence in warm water immersion at 50 ± 5°C with an aqueous solution composed of a quaternary ammonium salt and a polyvalent carboxylic acid. However, when these organic antibacterial materials are used, there is a problem that the water resistance of the film itself is poor.

Prior Art Documents

Patent Documents

[0006] Patent Document 1 International Publication No. 2014 / 184989 Patent Document 2 Japanese Unexamined Patent Application Publication No. 2017 - 101204 Patent Document 3 Japanese Unexamined Patent Application Publication No. 2015 - 067658 Patent Document 4 Japanese Unexamined Patent Application Publication No. 2017 - 014401 Patent Document 5 Japanese Unexamined Patent Application Publication No. 2015 - 067657 SUMMARY OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION

[0007] An object of the present invention is to provide an antibacterial film treatment liquid capable of forming an antibacterial film excellent in antibacterial property, curability, antibacterial persistence, and water resistance. Another object of the present invention is to provide an antibacterial film treatment method capable of forming an antibacterial film excellent in antibacterial property, curability, antibacterial persistence, and water resistance. MEANS FOR SOLVING THE PROBLEMS

[0008] As a result of intensive studies in view of the above problems, the present inventor has found that the above object can be achieved by an antibacterial film treatment liquid containing (A) a specific antibacterial polymer containing a unit (a) having an alkoxysilane in the side chain, a unit (b) having an ammonium salt in the side chain, and a unit (c) having a hydrophobic group in the side chain, (B) a specific silicon compound, (C) an organometallic compound, (D) water, and (E) an organic solvent, and thus has completed the present invention.

[0009] That is, the present invention relates to the following antibacterial film treatment liquid and antibacterial film treatment method. 1. An antibacterial polymer containing (A) a unit (a) having an alkoxysilane in the side chain, a unit (b) having an ammonium salt in the side chain, and a unit (c) having a hydrophobic group in the side chain, (B) A silicon compound having at least one selected from the group consisting of an alkoxysilyl group, an alkoxysilylene group, and a siloxane bond, (C) An organometallic compound, (D) Water, and (E) An organic solvent An antibacterial film treatment liquid containing the same. 2. The (A) antibacterial polymer is represented by the following general formula (A-1) [Chemical formula] (In the general formula (A-1), n represents a natural number of 1 or more. R A-1 and R A-2 are the same or different and represent H, a functional group derived from a radical initiator, or a functional group derived from a chain transfer agent. R A-3 ~R A-5 are the same or different and represent an alkyl group having 1 to 6 carbon atoms. A + represents an ammonium ion, and X - represents a halogen ion. R A-6 represents a linear or branched alkyl group having 1 to 20 carbon atoms, a cyclohexyl group, or a phenyl group. f and g represent decimals. The units (a), (b), and (c) may be randomly polymerized.) The antibacterial film treatment liquid according to item 1, which is an antibacterial polymer represented by the formula. 3. The ratio of each unit number to the total unit number in the (A) antibacterial polymer is such that, taking the total unit number as 100%, the unit (a) is 10 to 30%, the unit (b) is 20 to 40%, and the unit (c) is 40 to 60%. The antibacterial film treatment liquid according to item 1 or 2. 4. The weight average molecular weight of the (A) antibacterial polymer is 20,000 to 40,000, the side chain of the unit (a) is an alkoxysilane, and the hydrophobic group of the side chain of the unit (c) is a linear or branched alkyl group having 1 to 20 carbon atoms, a cyclohexyl group, or a phenyl group. The antibacterial film treatment liquid according to any one of items 1 to 3. 5. The content of the (A) antibacterial polymer is 30 to 90% by mass or more, taking the antibacterial film treatment liquid as 100% by mass. The antibacterial film treatment liquid according to any one of items 1 to 4. 6. The antibacterial film treatment liquid according to any one of items 1 to 5, wherein the (C) organometallic compound is an aluminum chelate compound. 7. The antibacterial film treatment liquid according to any one of items 1 to 6, wherein the (E) organic solvent is a polar solvent. 8. An antibacterial film treatment method having a step 1 of attaching the antibacterial film treatment liquid to a surface to be treated and a step 2 of performing a heat treatment, wherein the antibacterial film treatment liquid is (A) An antibacterial polymer containing a unit (a) having an alkoxysilane in the side chain, a unit (b) having an ammonium salt in the side chain, and a unit (c) having a hydrophobic group in the side chain, (B) A silicon compound having at least one selected from the group consisting of an alkoxysilyl group, an alkoxysilylene group, and a siloxane bond, (C) An organometallic compound, (D) Water, and (E) An organic solvent and is an antibacterial film treatment liquid containing the above components. 9. An article formed by forming a film with the antibacterial film treatment liquid according to any one of items 1 to 7.

Advantages of the Invention

[0010] The antibacterial film treatment liquid of the present invention is excellent in antibacterial properties and curability, and can form an antibacterial film excellent in antibacterial persistence and water resistance. Further, the antibacterial film treatment method of the present invention is excellent in antibacterial properties and curability, and can form an antibacterial film excellent in antibacterial persistence and water resistance.

Embodiments for Carrying Out the Invention

[0011] In this specification, expressions such as "containing" and "comprising" include concepts such as "containing", "comprising", "substantially consisting of", and "consisting only of".

[0012] 1. Antibacterial film treatment liquid The antibacterial film treatment liquid of the present invention contains (A) an antibacterial polymer containing a unit (a) having an alkoxysilane in the side chain, a unit (b) having an ammonium salt in the side chain, and a unit (c) having a hydrophobic group in the side chain, (B) a silicon compound having at least one selected from the group consisting of an alkoxysilyl group, an alkoxysilylene group, and a siloxane bond, (C) an organometallic compound, (D) water, and (E) an organic solvent. Hereinafter, each component contained in the antibacterial film treatment liquid will be described in detail.

[0013] ((A) Antibacterial polymer) The antibacterial film treatment liquid of the present invention contains (A) an antibacterial polymer containing a unit (a) having an alkoxysilane in the side chain, a unit (b) having an ammonium salt in the side chain, and a unit (c) having a hydrophobic group in the side chain (hereinafter, also referred to as the “component (A)”). If the antibacterial film treatment liquid of the present invention does not contain the component (A), the antibacterial property, curability, antibacterial persistence, and water resistance of the antibacterial film formed by the antibacterial film treatment liquid of the present invention will decrease.

[0014] The unit (a) is a unit having an alkoxysilane in the side chain. Examples of the alkoxy group contained in the alkoxysilane which is the side chain of the unit (a) include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an i-butoxy group, a sec-butoxy group, a t-butoxy group, an n-pentyloxy group, an n-hexyloxy group, a cyclopentyloxy group, a cyclohexyloxy group, and the like. Among these, a methoxy group and an ethoxy group are more preferable, and an ethoxy group is even more preferable. When the alkoxysilane is an ethoxy group, the compatibility with the diluting solvent is further improved, so that the precipitation of the component (A) is suppressed, and the appearance defect of the formed antibacterial film is further suppressed.

[0015] Unit (b) is a unit having an ammonium salt in the side chain. As the ammonium salt, a quaternary ammonium salt is preferred. Specifically, ammonium chloride, benzethonium chloride, ethylbenzylammonium chloride, ethylbenzethonium chloride, myristyltrimethylammonium chloride, methylbenzethonium chloride, cetalkonium chloride, cetrimonium chloride (CTAB), carnitine, dofanium chloride, tetraethylammonium bromide (TEAB), domiphen bromide, benzododecinium bromide, benzoxonium chloride, choline, denatonium, and mixtures thereof can be mentioned. Among these, ammonium chloride is preferred in terms of more excellent antibacterial properties.

[0016] Unit (c) is a unit having a hydrophobic group in the side chain. Examples of the hydrophobic group include a linear or branched alkyl group having 1 to 20 carbon atoms, a cyclohexyl group, and a phenyl group. Among these, an alkyl group having 1 to 10 carbon atoms is preferred, more preferably an alkyl group having 2 to 8 carbon atoms, still more preferably an alkyl group having 3 to 6 carbon atoms, and particularly preferably an alkyl group having 4 carbon atoms. By setting the range of the carbon number of the alkyl group within the above range, the antibacterial persistence of the antibacterial film can be further improved.

[0017] The ratio of each unit number to the total unit number in component (A) is preferably such that, taking the total unit number as 100%, the unit (a) is 10 to 40%, the unit (b) is 20 to 40%, and the unit (c) is 30 to 60%, and more preferably the unit (a) is 20%, the unit (b) is 30%, and the unit (c) is 50%. By setting the ratio of each unit number within the above range, the antibacterial film can exhibit antibacterial properties, sclerosis, antibacterial persistence, and water resistance in a well-balanced manner, and these properties can be more fully exerted.

[0018] In addition to the above units (a), (b), and (c), component (A) may contain other units other than these.

[0019] Component (A) is preferably an antibacterial polymer represented by the following general formula (A-1).

[0020]

Chemical formula

[0021] In general formula (A-1), n represents a natural number of 1 or more. Preferably, n represents a natural number from 1 to 300, and more preferably, n represents a natural number from 100 to 200.

[0022] In general formula (A-1), R A-1 and R A-2 are the same or different and represent H, a functional group derived from a radical initiator, or a functional group derived from a chain transfer agent.

[0023] As the above radical initiator, general ones can be used. From the viewpoints of simplicity of polymerization control and ease of availability, for example, azobisisobutyronitrile is preferable. In that case, in general formula (A-1), R A-1 and R A-2 are (CH3)3C- or H.

[0024] As the above chain transfer agent, various thiol compounds can be used. From the viewpoints of simplicity of polymerization control and ease of availability, methyl 3-mercaptopropionate is preferable. In that case, in general formula (A-1), R A-1 and R A-2 become (CH3)-O-C=O-(CH2)2-S- and H, respectively.

[0025] In general formula (1), R A-3 ~R A-5 are the same or different and represent an alkyl group having 1 to 6 carbon atoms. Among them, an alkyl group having 1 to 4 carbon atoms is preferable, an alkyl group having 2 to 4 carbon atoms is more preferable, and an alkyl group having 2 carbon atoms is still more preferable.

[0026] In general formula (1), A + represents an ammonium ion, and X -represents a halogen ion. That is, in the general formula (1), A + X - represents an ammonium salt.

[0027] A + is not particularly limited as long as it is an ammonium ion, and specifically, groups represented by the following general formula (Ab-1) can be mentioned.

[0028] [Chemical formula]

[0029] In the general formula (Ab-1), R Ab-1 and ~R Ab-3 are the same or different and represent alkyl groups having 1 to 6 carbon atoms. Among them, alkyl groups having 1 to 4 carbon atoms are preferred, alkyl groups having 1 to 2 carbon atoms are more preferred, and alkyl groups having 1 carbon atom are even more preferred.

[0030] X - is not particularly limited as long as it is a halogen ion, and specifically, Cl - , Br - , I - , F - can be mentioned, and among these, Cl - , Br - are preferred, and Cl - is more preferred.

[0031] In the general formula (1), R A-6 represents a linear or branched alkyl group having 1 to 20 carbon atoms, a cyclohexyl group, or a phenyl group. Among these, from the viewpoint of more excellent antibacterial properties, a linear or branched alkyl group having 1 to 20 carbon atoms is preferred.

[0032] The number of carbon atoms of the above alkyl group is preferably 1 to 10, more preferably 2 to 8, even more preferably 3 to 6, and particularly preferably 4. Also, the above alkyl group is preferably linear.

[0033] In the general formula (A-1) above, f and g represent decimals. That is, in the general formula (A-1), f, g, and 1-(f + g) respectively represent the ratio of the number of units of unit (a), unit (b), and unit (c) in component (A). The ratio of the number of units of unit (a):unit (b):unit (c) is f:g:1-(f + g). Also, f, g, and 1-(f + g) represent the ratio of the number of units of only unit (a), unit (b), and unit (c) in component (A). Even when component (A) contains other units, these ratios do not change. That is, the fact that the ratio of the number of units of unit (a):unit (b):unit (c) is f:g:1-(f + g) is not limited to the case where the units constituting component (A) consist only of unit (a), unit (b), and unit (c), and other units may be included.

[0034] In the general formula (A-1) above, f and g represent decimals. It is preferable that f is 0.1 to 0.4, g is 0.2 to 0.4, and 1-(f + g) is 0.3 to 0.6, and it is more preferable that f is 0.2, g is 0.3, and 1-(f + g) is 0.5. By setting f, g, and 1-(f + g) within the above ranges, the antibacterial film can exhibit antibacterial properties, hardening properties, antibacterial persistence, and water resistance in a well-balanced manner, and these properties can be more fully exerted.

[0035] In the general formula (A-1) above, for unit (a), unit (b), and unit (c), each unit may be randomly polymerized.

[0036] Component (A) may be contained in a dispersion medium and used as a dispersion. Examples of the dispersion medium include alcohols such as methanol, ethanol, and isopropanol; ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether and propylene glycol monoethyl ether, and the like. Among these, ethanol and propylene glycol monomethyl ether are preferable, and ethanol is more preferable from the viewpoint of better dispersion stability.

[0037] The content of component (A) in the antibacterial film treatment liquid is preferably 30 to 90% by mass, more preferably 40 to 80% by mass, and still more preferably 50 to 70% by mass, with the antibacterial film treatment liquid being 100% by mass. When the lower limit of the content of component (A) is within the above range, the antibacterial property and antibacterial persistence of the antibacterial film are further improved. When the upper limit of the content of component (A) is within the above range, the curability and water resistance of the antibacterial film are further improved.

[0038] (A) The weight average molecular weight of the antibacterial polymer is preferably 20,000 to 40,000. When the weight average molecular weight is within the above range, the curability and water resistance of the antibacterial film are further improved.

[0039] Component (A) preferably has a weight average molecular weight of 20,000 to 40,000, the side chain of unit (a) is an alkoxysilane, and the hydrophobic group of the side chain of unit (c) is a linear or branched alkyl group having 1 to 20 carbon atoms, a cyclohexyl group, or a phenyl group. When component (A) has the above characteristics, the antibacterial property and curability of the antibacterial film are further improved, and the antibacterial persistence and water resistance are further improved.

[0040] ((B) Silicon compound) The antibacterial film treatment liquid of the present invention contains a silicon compound having at least one selected from the group consisting of an alkoxysilyl group, an alkoxysilylene group, and a siloxane bond (hereinafter, also referred to as "(B) component").

[0041] As the alkoxysilyl group, an alkoxysilyl group having at least one alkoxy group is preferable. Examples of the alkoxysilyl group include a group represented by the general formula: (R B-1 ) m (R B-2 O) 3-m Si- (wherein R B-1 is a functional group, R B-2 is a lower alkyl group, and m is an integer of 0 to 2).

[0042] RB-1 Examples of the functional group represented by include methyl, dimethyl, phenyl, diphenyl, hexyl, decyl, 1,6-bis(trimethoxysilyl), trifluoropropyl, vinyl, 3-glycidoxypropyl, 3-glycidoxypropylmethyl, 2-(3,4-epoxycyclohexyl)ethyl, p-styryl, 3-methacryloxypropyl, 3-methacryloxypropylmethyl, 3-acryloxypropyl, 3-aminopropyl, N-2-(aminoethyl)-3-aminopropyl, N-2-(aminoethyl)-3-aminopropylmethyl, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyl, N-(vinylbenzyl)-2-aminoethyl-3-aminopropyl, tris-(trimethoxysilylpropyl)isocyanurate, 3-ureidopropyl, 3-mercaptopropyl, 3-mercaptopropylmethyl, bis(triethoxysilylpropyl)tetrasulfide, 3-isocyanatopropyl, 3-propylsuccinic anhydride, and the like.

[0043] R B-2 Specific examples of the lower alkyl group represented by include linear or branched alkyl groups having about 1 to 6 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, n-pentyl, 1-ethylpropyl, isopentyl, and neopentyl.

[0044] The alkoxysilylene group is not particularly limited as long as it is an alkoxysilylene group having at least one alkoxy group. Examples of the alkoxysilylene group include, for example, the group represented by the general formula: (R B-3 ) n (R B-4 O) 2-n Si= (wherein R B-3 is a functional group, R B-4 is a lower alkyl group. n is an integer from 0 to 1).

[0045] R B-3 Examples of the functional group represented by R B-1Examples thereof include those similar to the functional group represented by

[0046] R B-4 Examples of the lower alkyl group represented by B-2 include those similar to the lower alkyl group represented by

[0047] The silicon compound is not particularly limited as long as it has at least one selected from the group consisting of an alkoxysilyl group, an alkoxysilylene group, and a siloxane bond as a partial structure. Examples of the silicon compound include resins, alkoxysilane oligomers, alkoxysilanes, etc. Among these, alkoxysilanes are preferably mentioned.

[0048] Examples of the resin include not only silicone resins but also various resins into which an alkoxysilyl group has been introduced (for example, acrylic resins, urethane resins, epoxy resins, polyester resins, melamine resins, etc.). Among these, acrylic resins and silicone resins into which an alkoxysilyl group has been introduced are preferably mentioned, and more preferably, acrylic resins into which an alkoxysilyl group has been introduced are mentioned.

[0049] The weight average molecular weight of the resin is not particularly limited, but is, for example, 11,000 to 200,000, preferably 11,000 to 100,000, more preferably 11,000 to 70,000, and still more preferably 11,000 to 50,000.

[0050] When the resin is a resin into which an alkoxysilyl group has been introduced, the content of the alkoxysilyl group is, for example, 1 to 70% by mass, preferably 2 to 60% by mass, more preferably 3 to 50% by mass, still more preferably 4 to 45% by mass, and even more preferably 5 to 40% by mass.

[0051] Examples of the alkoxysilane include Si(OCH3)4, Si(OC2H5)4, CH3Si(OCH3)3, CH3Si(OC2H5)3, C2H5Si(OCH3)3, C2H5Si(OC2H5)4, CHCH2Si(OCH3)3, CH2CHOCH2O(CH2)3Si(OCH3)3, CH2C(CH3)COO(CH2)3Si(OCH3)3, CH2CHCOO(CH2)3Si(OCH3)3, NH2(CH2)3Si(OCH3)3, SH(CH2)3Si(OCH3)3, and NCO(CH2)3Si(OC2H5)3.

[0052] The alkoxysilane oligomer is obtained by hydrolyzing and polycondensing an alkoxysilane. As the alkoxysilane oligomer, for example, those having a weight average molecular weight of about 500 to 10,000 can be used. The silicon compound may be a single species or a combination of two or more species.

[0053] The content of the silicon compound is, for example, 3 to 40% by mass, preferably 5 to 30% by mass, more preferably 8 to 25% by mass, based on 100% by mass of the antibacterial film treatment liquid of the present invention.

[0054] The antibacterial film treatment liquid of the present invention may contain a resin having no alkoxysilyl group, alkoxysilylene group, and siloxane bond (non-silicon-based resin). Examples of the non-silicon-based resin include epoxy resin, acrylic resin, urethane resin, polyester resin, melamine resin, etc. Among these, epoxy resin is preferably mentioned, and bisphenol A type epoxy resin is more preferably mentioned.

[0055] In the treatment liquid of the present invention, as the film-forming component, it preferably contains a combination of a resin ((B) component) having at least one selected from the group consisting of an alkoxysilyl group, an alkoxysilylene group, and a siloxane bond, and at least one component ((B') component) selected from the group consisting of an alkoxysilane, an alkoxysilane oligomer, and a non-silicon-based resin.

[0056] As the (B) component, preferably, an acrylic resin, a silicone resin, etc. into which an alkoxysilyl group is introduced can be mentioned, and more preferably, an acrylic resin into which an alkoxysilyl group is introduced can be mentioned.

[0057] As the (B') component, preferably, a non-silicon-based resin can be mentioned, more preferably, an epoxy resin can be mentioned, and even more preferably, a bisphenol A type epoxy resin can be mentioned.

[0058] The content ratio of the (B) component and the (B') component is not particularly limited. For example, the (B') component is, for example, 30 to 200 parts by mass, preferably 60 to 150 parts by mass, more preferably 80 to 120 parts by mass, and even more preferably 90 to 110 parts by mass with respect to 100 parts by mass of the (B) component.

[0059] ((C) Organometallic compound) The antibacterial film treatment liquid of the present invention contains a (C) organometallic compound (hereinafter, also referred to as the "(C) component").

[0060] The organometallic compound is not particularly limited as long as it can function as a catalyst for the condensation reaction. As the organometallic compound, for example, as the metal component, a water-soluble organometallic chelate compound containing titanium, zirconium, aluminum, tin, etc., a metal alkoxide, etc. can be used. Among these, as the organic titanium compound, titanium alkoxide compounds such as tetraisopropyl titanate, tetra-n-butyl titanate, butyl titanate dimer, tetra-tert-butyl titanate, tetraoctyl titanate, etc.; titanium chelate compounds such as titanium diisopropoxybisacetylacetonate, titanium tetraacetylacetonate, titanium dioctyloxybisethylacetoacetonate, titanium octylene glycolate, titanium diisopropoxybisethylacetylacetonate, titanium lactate, ammonium titanium lactate salt, titanium diisopropoxybistriethanolamineate, etc. can be exemplified. As the organic zirconium compound, zirconium alkoxide compounds such as normal propyl zirconate, normal butyl zirconate, etc.; zirconium chelate compounds such as zirconium tetraacetylacetonate, zirconium tributoxymonoacetylacetonate, zirconium dibutoxybisethylacetoacetate, zirconium tributoxymonostearate, etc. can be exemplified. As the organic aluminum compound, aluminum alkoxide compounds such as aluminum isopropylate, monobutoxyaluminum diisopropylate, aluminum butyrate, etc.; aluminum chelate compounds such as ethylacetoacetate aluminum diisopropylate, aluminum trisethylacetate, alkylacetoacetate aluminum diisopropylate, aluminum monoacetylacetonate bisethylacetoacetate, etc. can be exemplified.

[0061] The organometallic compound may be a single species or a combination of two or more species.

[0062] The content of the organometallic compound is not particularly limited, but it is usually about 0.01 to 50 parts by mass, preferably about 0.1 to 30 parts by mass, more preferably 1 to 30 parts by mass, still more preferably 5 to 30 parts by mass, even more preferably 10 to 25 parts by mass, and even more preferably 15 to 25 parts by mass, based on 100 parts by mass of the (B) silicon compound.

[0063] In the antibacterial film treatment liquid of the present invention, it is also allowed to contain a catalyst other than the (C) organometallic compound. However, preferably, the antibacterial film treatment liquid of the present invention does not contain a catalyst other than the organometallic compound.

[0064] ((D) Water) The antibacterial film treatment liquid of the present invention contains (D) water.

[0065] The content of water is not particularly limited, but it is, for example, 1 to 100 parts by mass, preferably 10 to 100 parts by mass, more preferably 20 to 100 parts by mass, based on 100 parts by mass of the (B) silicon compound.

[0066] ((E) Organic solvent) The antibacterial film treatment liquid of the present invention contains (E) an organic solvent (hereinafter, also referred to as the "(E) component").

[0067] As the organic solvent, a hydrophilic organic solvent can be preferably used. For example, organic solvents such as alcohol-based, glycol-based, glycol ether-based, ether-based, ether alcohol-based, and ketone-based can be used alone or in appropriate combinations as needed. Among these, polar solvents are preferred, and glycol ether-based solvents are more preferred.

[0068] As the glycol ether-based solvent, for example, the general formula: HO-R E-1 -O-R E-2 (In the formula, R E-1 represents a lower alkylene group. R E-2 represents an alkyl group.) The solvent represented by this can be mentioned.

[0069] RE-1 The lower alkylene group represented by E-1 is not particularly limited and includes both linear and branched (preferably branched) ones. The number of carbon atoms of the alkylene group is, for example, 1 to 6, preferably 1 to 5, more preferably 2 to 4, and even more preferably 3. Specific examples of the alkylene group include a methylene group, an ethylene group, an n-propylene group, an isopropylene group, an n-butylene group, an isobutylene group, etc.

[0070] R E-2 The alkyl group represented by E-2 is not particularly limited and includes both linear and branched (preferably linear) ones. The number of carbon atoms of the alkyl group is, for example, 1 to 6, preferably 1 to 4, more preferably 1 to 2, and even more preferably 1. Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a sec-butyl group, etc.

[0071] The content of the organic solvent is not particularly limited and may be the balance after adding the above components (A) to (D).

[0072] (Other components) The treatment liquid of the present invention may contain other components in addition to the above components. Examples of the above other components include a surface conditioner, a filler component, a colorant, a coating film curing accelerator, etc.

[0073] The total content of the above other components is, for example, 0 to 20% by mass, preferably 0 to 10% by mass, more preferably 0 to 5% by mass, even more preferably 0 to 1% by mass, and still more preferably 0% by mass, based on 100% by mass of the antibacterial film treatment liquid of the present invention.

[0074] (Method for producing an antibacterial film treatment liquid) The method for producing the antibacterial film treatment liquid of the present invention is not particularly limited, and it can be produced by appropriately mixing each component. The method for producing the antibacterial film treatment liquid of the present invention is preferably a method in which component (A), component (B), and, if necessary, other components are added to component (E), and then component (C) and component (D) are mixed.

[0075] In the antibacterial film treatment liquid of the present invention, the intermolecular and / or intramolecular of the film-forming component may be in a partially crosslinked state.

[0076] 2. Antibacterial film treatment method The antibacterial film treatment method of the present invention is an antibacterial film treatment method having a step 1 of attaching an antibacterial film treatment liquid to a surface to be treated and a step 2 of performing a heat treatment. The antibacterial film treatment liquid is an antibacterial film treatment liquid containing (A) an antibacterial polymer having a unit (a) having an alkoxysilane in the side chain, a unit (b) having an ammonium salt in the side chain, and a unit (c) having a hydrophobic group in the side chain, (B) a silicon compound having at least one selected from the group consisting of an alkoxysilyl group, an alkoxysilylene group, and a siloxane bond, (C) an organometallic compound, (D) water, and (E) an organic solvent. Hereinafter, each step will be described in detail.

[0077] (Step 1) Step 1 is a step of attaching an antibacterial film treatment liquid to a surface to be treated. As the antibacterial film treatment liquid, the antibacterial film treatment liquid of the present invention described above can be used.

[0078] The surface to be treated is the surface of the object to be treated to which the antibacterial film treatment liquid adheres. The object to be treated is not particularly limited, and examples include glass, metal materials, resins, ceramics, plated products, and the like.

[0079] The glass is not particularly limited, and known glass can be used. Examples of such glass include soda-lime glass, lead glass, borosilicate glass, crystallized glass, quartz glass, and the like.

[0080] When using glass as the object to be treated, before applying the antibacterial film treatment liquid to the surface to be treated, it is preferable to immerse the surface to be treated in an alkaline solution for degreasing to clean the surface and make it hydrophilic, and then attach the antibacterial film treatment liquid.

[0081] The metal material is not particularly limited as long as at least a part of its surface is composed of metal. Examples of the metal include various metals such as zinc, aluminum, magnesium, cobalt, nickel, iron, copper, tin, gold, and their alloys, and preferably aluminum. More specifically, examples of the metal material include articles made of only metal, composite articles in which other articles (such as ceramic materials, plastic materials, etc.) other than metal are combined with metal, and plated articles having a metal plating film on the surface (for example, plated steel articles having a zinc plating film or a zinc alloy plating film on the surface). Also, the metal constituting the surface of the metal material may be untreated metal or metal subjected to pretreatment such as degreasing treatment or acid activation treatment.

[0082] The method for attaching the antibacterial film treatment liquid to the surface to be treated is not particularly limited, and the antibacterial film treatment liquid may be applied to the surface to be treated by a known method.

[0083] As the coating method, for example, known methods such as dip coating, spray coating, roll coating, spin coating, and bar coating can be adopted.

[0084] The coating thickness of the antibacterial film treatment liquid in Step 1 is preferably 0.5 to 500 μm, and more preferably 5 to 150 μm.

[0085] The temperature of the antibacterial film treatment liquid in Step 1 may be a temperature at which the antibacterial film treatment liquid is easily applied and does not harden, and is preferably 10 to 40°C, and more preferably 20 to 30°C.

[0086] Through Step 1 described above, the antibacterial film treatment liquid can be attached to the surface to be treated.

[0087] (Step 2) Step 2 is a heat treatment step.

[0088] The heating temperature is not particularly limited, for example, it is 20°C or higher, preferably 50 - 300°C, more preferably 70 - 250°C.

[0089] The heating time is not particularly limited, for example, it is 5 minutes to 2 hours, preferably 10 minutes to 1 hour, more preferably 20 minutes to 40 minutes.

[0090] The heating method is not particularly limited, and heating can be performed by a conventionally known heating method. Examples of such heating methods include a heating method using a panel heater, a heating method using hot air, and a heating method using a forced-air constant-temperature thermostat. Among these, the heating method using a forced-air constant-temperature thermostat is preferred.

[0091] The thickness of the film is not particularly limited, preferably 0.1 - 100 μm, more preferably 0.5 - 50 μm, and even more preferably 1 - 30 μm. If the film thickness is too thin, the coating water resistance may decrease. Also, if the film thickness is too thick, there is a risk of film peeling, and since the antibacterial property is expressed on the film surface, the coating amount used may be large with respect to the antibacterial expression area, resulting in uneconomicalness.

[0092] By the above-described Step 2, an antibacterial film is formed on the surface to be treated, and an antibacterial film treatment is performed.

[0093] 3. Article The article of the present invention is an article formed with a film using the above antibacterial film treatment liquid. As the antibacterial film treatment liquid, the antibacterial film treatment liquid of the present invention described above can be used, and as a method for forming the film, a method of forming by the above antibacterial film treatment method of the present invention can be mentioned. Such an article of the present invention has the above-described film of the present invention, is excellent in antibacterial property and curability, and is excellent in antibacterial persistence and water resistance.

Examples

[0094] The present invention will be described in detail below based on examples, but the present invention is not limited to these examples.

[0095] The (A) antibacterial polymers used in the examples and comparative examples are shown in Table 1 below.

[0096] Example 1 (Preparation of Antibacterial Film Treatment Liquid) A 30.8 mass% antibacterial polymer solution was mixed with 79.6 mass% (24.50 mass% of the antibacterial polymer shown in Table 1 and 55.10 mass% of ethanol which is a solvent for the antibacterial polymer), 10.50 mass% of a silicon compound (5.25 mass% of methyltrimethoxysilane oligomer and 5.25 mass% of 3-glycidoxypropyltrimethoxysilane), and 2.60 mass% of aluminum bis(ethylacetoacetate) monoacetylacetonate. Then, 7.30 mass% of water was added and stirred for 1 hour to prepare an antibacterial film treatment liquid. The antibacterial polymer used was the one shown in Table 1.

[0097] (Preparation of Test Specimens) Soda-lime glass was alkali-dipped and degreased at 60°C for 10 minutes to make the surface clean and hydrophilic. In order to improve the spray coating property, 30 mass% of propylene glycol monomethyl ether was added to 100 mass% of the antibacterial film treatment liquid and mixed. The prepared antibacterial film treatment liquid was spray-coated so that the film thickness was about 5 μm, and heat treatment was performed at 100°C for 30 minutes using a dryer to form an antibacterial film.

[0098] Example 2 The antibacterial polymer solution was treated with an evaporator to remove ethanol as the solvent and concentrated to 100.0% by mass from 30.8% by mass. 60.00% by mass of the concentrated antibacterial polymer solution, 6.67% by mass of a silicon compound (3.33% by mass of methyltrimethoxysilane oligomer and 3.34% by mass of 3-glycidoxypropyltrimethoxysilane), 1.65% by mass of aluminum bis(ethylacetoacetate) monoacetylacetonate, 27.03% by mass of propylene glycol monomethyl ether were mixed, and 4.65% by mass of water was added and stirred for 1 hour to prepare an antibacterial film treatment liquid. Otherwise, in the same manner as in Example 1, an antibacterial film treatment liquid was prepared and test pieces were produced.

[0099] Example 3 62.6% by mass of an antibacterial polymer solution (19.32% by mass of the antibacterial polymer in Table 1 and 43.28% by mass of ethanol), 19.20% by mass of a silicon compound (9.60% by mass of methyltrimethoxysilane oligomer and 9.60% by mass of 3-glycidoxypropyltrimethoxysilane), 4.80% by mass of aluminum bis(ethylacetoacetate) monoacetylacetonate were mixed, and 13.40% by mass of water was added and stirred for 1 hour to prepare a treatment liquid for film formation. Otherwise, in the same manner as in Example 1, an antibacterial film treatment liquid was prepared and test pieces were produced.

[0100] Example 4 As the antibacterial polymer, the antibacterial polymer in Table 1 was used. Otherwise, in the same manner as in Example 1, an antibacterial film treatment liquid was prepared and test pieces were produced.

[0101] Example 5 As the antibacterial polymer, the antibacterial polymer in Table 1 was used. Otherwise, in the same manner as in Example 1, an antibacterial film treatment liquid was prepared and test pieces were produced.

[0102] Example 6 As the antibacterial polymer, the antibacterial polymer in Table 1 was used. Otherwise, in the same manner as in Example 1, an antibacterial film treatment liquid was prepared and test pieces were produced.

[0103] Example 7 As the antibacterial polymer, the antibacterial polymer shown in Table 1 was used. Otherwise, in the same manner as in Example 1, an antibacterial film treatment liquid was prepared and test pieces were produced.

[0104] Example 8 As the antibacterial polymer, the antibacterial polymer shown in Table 1 was used. Otherwise, in the same manner as in Example 1, an antibacterial film treatment liquid was prepared and test pieces were produced.

[0105] Comparative Example 1 Instead of the antibacterial polymer solution, 79.60% by mass of propylene glycol monomethyl ether was added. Otherwise, in the same manner as in Example 1, an antibacterial film treatment liquid was prepared and test pieces were produced.

[0106] Comparative Example 2 Instead of the silicon compound, 10.50% by mass of propylene glycol monomethyl ether was added. Otherwise, in the same manner as in Example 1, an antibacterial film treatment liquid was prepared and test pieces were produced.

[0107] Comparative Example 3 As the antibacterial polymer, the antibacterial polymer shown in Table 1 was used. Otherwise, in the same manner as in Example 1, an antibacterial film treatment liquid was prepared and test pieces were produced.

[0108] Comparative Example 4 As the antibacterial polymer, the antibacterial polymer shown in Table 1 was used. Otherwise, in the same manner as in Example 1, an antibacterial film treatment liquid was prepared and test pieces were produced.

[0109] Comparative Example 5 Instead of aluminum bis(ethylacetoacetate) monoacetylacetonate, 2.60% by mass of propylene glycol monomethyl ether was added. Otherwise, in the same manner as in Example 1, an antibacterial film treatment liquid was prepared and test pieces were produced.

[0110] Comparative Example 6 Instead of water, 7.30% by mass of propylene glycol monomethyl ether was added. Otherwise, in the same manner as in Example 1, an antibacterial film treatment liquid was prepared and test pieces were produced.

[0111] Comparative Example 7 As the antibacterial polymer, the antibacterial polymer shown in Table 1 was used. Otherwise, in the same manner as in Example 1, an antibacterial film treatment liquid was prepared and test pieces were produced.

[0112] (Evaluation method) The following evaluations were conducted for the examples and comparative examples.

[0113] (Antibacterial property (initial)) In accordance with the measurement method based on JIS Z2801, the initial antibacterial property of the antibacterial film was evaluated. Specifically, the antibacterial activity values of Escherichia coli and Staphylococcus aureus were measured using the antibacterial film, and evaluated according to the following evaluation criteria. Note that if the evaluation is Δ or higher, it is evaluated that there is no problem in actual use. ○: The antibacterial activity values of both Escherichia coli and Staphylococcus aureus are 2.0 or higher, and at least one of them is 4.0 or higher Δ: The antibacterial activity values of both Escherichia coli and Staphylococcus aureus are 2.0 or higher and less than 4.0. ×: At least one of the antibacterial activity values of Escherichia coli and Staphylococcus aureus is less than 2.0.

[0114] (Antibacterial property (after water resistance test: antibacterial persistence)) A water resistance test was conducted using the test pieces. Specifically, the test pieces were immersed in warm water at 50 °C for 16 hours. Using the test pieces after the water resistance test, the same test as the above initial antibacterial property was conducted to evaluate the antibacterial property (antibacterial persistence) after the water resistance test. Note that if the evaluation is Δ or higher, it is evaluated that there is no problem in actual use.

[0115] (Sclerosing property) After sufficiently slowly cooling the antibacterial film on the test piece, it was rubbed 10 times back and forth with a cloth impregnated with acetone, the state of the film was observed, and the curability was evaluated according to the following evaluation criteria. If the evaluation is △ or higher, it is evaluated that there is no problem in actual use. 〇: No change △: Damaged ×: The substrate is exposed due to film dissolution

[0116] (Water resistance) A water resistance test was performed using the test piece. Specifically, the test piece was immersed in warm water at 50 °C for 16 hours. It was taken out of the warm water, wiped thoroughly to remove moisture, the state of the film was observed, and the water resistance was evaluated according to the following evaluation criteria. If the evaluation is △ or higher, it is evaluated that there is no problem in actual use. 〇: No change △: There is cloudiness, cracks, or floating of the film, but the antibacterial test can be performed ×: The film peels off and the antibacterial test cannot be performed

[0117] The results are shown in Table 1 below.

[0118]

Table 1

Claims

1. An antibacterial film treatment liquid containing: (A) an antibacterial polymer containing a unit (a) having an alkoxysilane in the side chain, a unit (b) having an ammonium salt in the side chain, and a unit (c) having a hydrophobic group in the side chain; (B) a silicon compound having at least one selected from the group consisting of an alkoxysilyl group, an alkoxysilylene group, and a siloxane bond; (C) an organometallic compound; (D) water; and (E) an organic solvent. The antibacterial film treatment liquid.

2. The antibacterial polymer (A) is an antibacterial polymer represented by the following general formula (A-1). 【Chemical 1】 (In general formula (A-1), n represents a natural number of 1 or more. R Ａ－１ and R Ａ－２ are the same or different and represent H, a functional group derived from a radical initiator, or a functional group derived from a chain transfer agent. R Ａ－３ to R Ａ－５ are the same or different and represent an alkyl group having 1 to 6 carbon atoms. A ＋ represents an ammonium ion, and X － represents a halogen ion. R Ａ－６ represents a linear or branched alkyl group having 1 to 20 carbon atoms, a cyclohexyl group, or a phenyl group. f and g represent decimals. Unit (a), unit (b), and unit (c) may be randomly polymerized.) The antibacterial film treatment liquid according to Claim 1.

3. The ratio of each unit number to the total unit number in the antibacterial polymer (A) is such that, taking the total unit number as 100%, the unit (a) is 10 to 30%, the unit (b) is 20 to 40%, and the unit (c) is 40 to 60%. The antibacterial film treatment liquid according to Claim 1.

4. The weight average molecular weight of the antibacterial polymer (A) is 20,000 to 40,000. The side chain of the unit (a) is an alkoxysilane, and the hydrophobic group in the side chain of the unit (c) is a linear or branched alkyl group having 1 to 20 carbon atoms, a cyclohexyl group, or a phenyl group. The antibacterial film treatment liquid according to Claim 1.

5. The content of the antibacterial polymer (A) is 30 to 90% by mass or more, taking the antibacterial film treatment liquid as 100% by mass. The antibacterial film treatment liquid according to Claim 1.

6. The organometallic compound (C) is an aluminum chelate compound. The antibacterial film treatment liquid according to Claim 1.

7. The organic solvent (E) is a polar solvent. The antibacterial film treatment liquid according to Claim 1.

8. An antibacterial film treatment method having a step 1 of attaching the antibacterial film treatment liquid to the surface to be treated and a step 2 of heat treatment, wherein the antibacterial film treatment liquid is (A) an antibacterial polymer containing a unit (a) having an alkoxysilane in the side chain, a unit (b) having an ammonium salt in the side chain, and a unit (c) having a hydrophobic group in the side chain; (B) a silicon compound having at least one selected from the group consisting of an alkoxysilyl group, an alkoxysilylene group, and a siloxane bond; (C) an organometallic compound; (D) water; and (E) an organic solvent. The antibacterial film treatment method.

9. An article formed by forming a film with the antibacterial film treatment liquid according to any one of Claims 1 to 7.

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