JP6483595B2 - Coating composition and method for producing painted parts - Google Patents

Description

  The present invention relates to a coating composition, a painted part, a method for producing the painted part, and a washing machine.

Generally, organic substances such as human sebum and excess food that have been detached from the laundry are likely to adhere to the parts of the washing machine such as washing tubs and drain pipes that come into contact with the washing water. For this reason, bacteria and fungi are likely to propagate in the areas where the washing water comes into contact.
Conventionally, for the purpose of sterilization, a washing machine including a hypochlorous acid generator is known (for example, see Patent Document 1). However, the hypochlorous acid generator of this washing machine requires not only a salt water adjustment mechanism and a salt water electrolysis mechanism, but also a regular salt replenishment. Therefore, in this washing machine, not only the initial cost but also the running cost increases.
Therefore, it is conceivable to form a coating film of an antibacterial paint (for example, see Patent Document 2) on a part that is touched by washing water. According to such an antibacterial paint, antibacterial performance can be imparted to the washing machine without greatly changing the structure of the washing machine.

JP 2013-90813 A JP 2003-277686 A

  However, the antibacterial coating film of conventional antibacterial paint has a sufficient antibacterial effect even when used in parts such as washing machines where bacteria and fungi tend to propagate because the antibacterial component is dispersed in the base. There are no challenges.

An object of the present invention is to provide a manufacturing how the coating composition and a coated component which can form a coating film excellent in antibacterial effect than the prior art.

The coating composition of the present invention that has solved the above-mentioned problems includes a salt of an amino group-containing alkoxysilane and cyclohexanecarboxylic acid, and a silica sol in which the salt is dispersed.
Also, a method of manufacturing painted parts of the present invention which has solved the above problems includes forming a first coating film by applying the coating composition onto a substrate, a carbon number of 3 on the first coating A step of forming a second coating film by applying a coating containing an alkoxysilane having -18 fluorine-containing organic groups or a dialkoxysilane having an alkyl group having 1 to 5 carbon atoms, and the surface of the second coating film And a step of washing with a basic solution .

According to the present invention, it is possible to provide a conventionally coating composition to form a coating film excellent in the antibacterial effect paint composition and preparation how the paint components.

It is composition explanatory drawing of the washing machine which concerns on embodiment of this invention. It is sectional drawing of the coating component used for the washing machine of FIG. It is a manufacturing-process figure of the coating component of FIG. It is sectional drawing of the coating component which concerns on other embodiment of this invention.

Next, embodiments of the present invention will be described in detail with reference to the drawings as appropriate.
The main feature of the coated part of the present invention is that it has more amino groups on the surface of the coating film than the inside of the coating film (water repellent coating film described later) formed on the substrate. And In other words, the amino group is localized on the surface of the coating film on the substrate.
In the following, a coating member used in a washing machine will be described as an example, and then a coating composition used for the painted part and a method for manufacturing the painted part using the coating composition will be described.

<Washing machine>
FIG. 1 is a configuration explanatory diagram of a washing machine according to an embodiment of the present invention.

As shown in FIG. 1, the washing machine L according to the present embodiment includes an outer tub 2 and an inner tub 3 as washing tubs inside a housing 1, and an inner lid 4 is provided on the upper portion of the washing tub. ing. The housing 1 is provided with an outer lid 5 above the inner lid 4.

A stirring blade 6 is provided at the bottom of the inner tub 3 to stir clothing with washing water.
The stirring blade 6 is rotationally driven by a motor 7.
Water supply to the inner tank 3 is performed by a water supply mechanism 8. The drainage of the wash water after washing and the drainage at the time of dehydration are led from the outer tub 2 to the sewage port (not shown) through the drain pipe 9.

In such a washing machine L, washing water tends to remain inside the outer tub 2 and the outer side of the inner tub 3. Also, the washing water tends to remain on the inner surface of the drain pipe 9. The washing water contains organic substances such as human sebum and excess food that have been detached from the laundry as described above. Therefore, bacteria and fungi (fungi) generally tend to propagate on the surface of the member that is touched by the washing water.
In the washing machine L according to the present embodiment, the coating parts described below are arranged at a place where such bacteria and fungi (fungi) are likely to propagate.

<Coated parts>
FIG. 2 is a cross-sectional view schematically showing a painted component 20 used in the washing machine L of FIG.
As shown in FIG. 2, the painted component 20 according to the present embodiment includes a base material 10 and a water-repellent coating film 11 formed on the base material 10.

As the base material 10, a part in which bacteria and the like easily propagate in a conventional washing machine, for example, the outer tub, the inner tub, the drain pipe, and the like correspond to this. The painted component 20 according to the present embodiment is configured by forming the water-repellent coating film 11 on these components.
Therefore, the material and shape of the base material 10 in the present embodiment correspond to an outer tub, an inner tub, a drain pipe, and the like in a conventional washing machine.

The water-repellent coating film 11 includes a first coating film 11a formed on the substrate 10 and a second coating film 11b formed on the first coating film 11a.
As will be described in detail later, the first coating film 11a is formed by applying the first paint described later on the base material 10. The first paint corresponds to the paint composition of the present invention.
Moreover, the 2nd coating film 11b is formed by apply | coating a 2nd coating material on the 1st coating film 11a so that it may demonstrate in detail later.

The first coating film 11a in this embodiment includes an amino group-containing polysiloxane and a polymer compound in which the amino group-containing polysiloxane is dispersed in the first coating film 11a.
The polysiloxane structure of the amino group-containing polysiloxane is formed by polycondensation of an alkoxysilane that forms a salt contained in the first paint described later.
The amino group of the amino group-containing polysiloxane is generated by washing a salt contained in the first coating material forming the first coating film 11a with a basic solution, as will be described in detail later.

This amino group is a functional group exhibiting antibacterial properties, and is generated so as to be more unevenly distributed on the surface of the water-repellent coating 11 than on the inside of the water-repellent coating 11 as described above. That is, the amino group-containing polysiloxane is a constituent component of the first coating film 11a, but the amino group portion is localized on the surface of the second coating film 11b described later formed on the first coating film 11a. Formed.
The principle of the invention in which more amino groups are formed on the surface than the inside of the water-repellent coating film 11 will be described in detail later together with a method for manufacturing a coated part.
As for the thickness of such 1st coating film 11a, 10-100 nm is desirable.

The 2nd coating film 11b in this embodiment is comprised including the water repellent compound. This water repellent compound is formed by polycondensation of alkoxysilane contained in the second paint described later. Examples of the water repellent compound include, but are not limited to, a polysiloxane having a fluorine-containing organic group having 3 to 18 carbon atoms and a polydialkylsiloxane having an alkyl group having 1 to 5 carbon atoms.
Further, the second coating film 11b in the present embodiment is assumed to be a layer made of a water repellent compound such as polysiloxane (including polyorganosiloxane) obtained by condensation polymerization of the alkoxysilane. As the two coating film 11b, a siloxane monomolecular film formed by chemically bonding an alkoxysilane contained in the second paint to the polymer compound constituting the first coating film 11a is also allowed. That is, the second coating film 11b in the present invention is not particularly limited as long as it can chemically bond to the polymer compound of the first coating film 11a and introduce a water repellent functional group described later.
As for the thickness of the 2nd coating film 11b in this invention, 1-10 nm is desirable.

<Coating composition>
As described above, the first coating film 11a is formed by applying the following first coating material (the coating composition of the present invention) on the substrate 10, and the second coating film 11b is formed on the first coating film 11a. Next, the second coating material is applied and formed.

≪First paint≫
The first paint includes a salt of an amino group-containing alkoxysilane and a hydrocarbon group-containing monocarboxylic acid or a hydrocarbon group-containing sulfonic acid, and a polymer compound in which the salt is dispersed.

(salt)
As an amino group containing alkoxysilane which comprises the said salt, what is shown by following formula (1) and following formula (2) etc. are mentioned, for example.
(R ³ O) ₂ SiR ² —X—NHR ¹ Formula (1)
(In the formula (1), R ¹ is a hydrogen atom or a monovalent hydrocarbon group, R ² is an alkyl group, R ³ is an alkyl group which may be the same or different, and X is a divalent hydrocarbon.) Base)
(R ³ O) ₃ Si—X—NHR ¹ Formula (2)
(However, in the formula ^(2), R 1, ^{R 3} and X have the same meanings as ^R 1, ^{R 3} and X in the formula (1))

Examples of the monovalent hydrocarbon group represented by R ¹ in the formula (1) and the formula (2) include a linear, branched or cyclic alkyl group, an alkynyl group, an aryl group, an aralkyl group, and the like. Can be mentioned.

Examples of the alkyl group represented by R ¹ include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and decyl. Etc. Further, it may be a group having an oxygen atom between carbon-carbon, for example, methyloxymethyl, ethyloxymethyl, propyloxymethyl, butyloxymethyl, propyloxyethyl, propyloxypropyl and the like.

Examples of the alkynyl group represented by R ¹ include ethynyl, 2-propynyl, butynyl, hexynyl, heptynyl, octynyl, decynyl, undecynyl, dodecynyl, tridecynyl, tetradecynyl, pentadecynyl, hexadecynyl, heptadecynyl, octadecynyl and the like.

Examples of the aryl group represented by R ¹ include phenyl, tolyl, xylyl, naphthyl, azulenyl, biphenyl and the like.

Examples of the aralkyl group represented by R ¹ include benzyl, 1-phenethyl, 2-phenethyl, 1-phenylpropyl, 2-phenylpropyl, 3-phenylpropyl, diphenylmethyl, o-methylbenzyl, m-methylbenzyl, p-methylbenzyl, o-ethylbenzyl, m-ethylbenzyl, p-ethylbenzyl, o-isopropylbenzyl, m-isopropylbenzyl, p-isopropylbenzyl, o- (tert-butyl) benzyl, m- (tert-butyl) ) Benzyl, p- (tert-butyl) benzyl, 2,3-dimethylbenzyl, 2,4-dimethylbenzyl, 2,5-dimethylbenzyl, 2,6-dimethylbenzyl, 3,4-dimethylbenzyl, 3,5 -Dimethylbenzyl, 2,3,4-trimethylbenzyl, 2,3,4-trimethylbenzene Benzyl, 3,4,5-trimethylbenzyl, 2,4,6-trimethylbenzyl, 5-isopropyl-2-methylbenzyl, 2-isopropyl-5-methylbenzyl, 2-methyl-5- (tert-butyl) benzyl 2,4-diisopropylbenzyl, 2,5-diisopropylbenzyl, 3,5-diisopropylbenzyl, 3,5-di (tert-butyl) benzyl, 1- (2-methylphenyl) ethyl, 1- (3-isopropyl Phenyl) ethyl, 1- (4-isopropylphenyl) ethyl, 1- (2- (t-butyl) benzylethyl, 1- (4- (tert-butyl) benzylethyl, 1- (2-isopropyl-4-methyl) Phenyl) ethyl, 1- (4-isopropyl-2-methylphenyl) ethyl, 1- (2,4-dimethylphenyl) ethyl, 1- (2 5- dimethylphenyl) ethyl, 3,5-dimethylphenyl) ethyl, 1- (3,5-di - (tert-butyl) phenyl) such as ethyl.

Examples of the alkyl group represented by R ^{2 in} the formula (1), R ³ in the formula (1), and R ³ in the formula (2) include methyl, ethyl, propyl, and the like.
Examples of the divalent hydrocarbon group represented by X in the formula (1) and the formula (2) include methylene, ethylene, trimethylene, isopropylidene, pentamethylene, hexamethylene, heptamethylene and the like. Further, a group having an oxygen atom between carbon and carbon, for example, methyleneoxymethylene, ethyleneoxymethylene, propyleneoxymethylene, butyleneoxymethylene, propyleneoxyethylene, propyleneoxypropylene and the like may be used.

  The hydrocarbon group in the hydrocarbon group-containing monocarboxylic acid or hydrocarbon group-containing sulfonic acid constituting the salt is preferably a monovalent hydrocarbon group having 1 to 12 carbon atoms, and is a linear, branched or cyclic alkyl group. The group is more desirable.

  Examples of such an alkyl group having 1 to 12 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, 2-pentyl, tert- Pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, 2-ethylhexyl, nonyl, decyl, isodecyl, undecyl, dodecyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cyclo Examples include undecyl and cyclododecyl.

  The salt in this embodiment can be obtained by adding 0.9 to 1.1 chemical equivalents of amino group-containing alkoxysilane per one chemical equivalent of hydrocarbon group-containing monocarboxylic acid or hydrocarbon group-containing sulfonic acid. it can.

And the salt of such an amino group-containing alkoxysilane and a hydrocarbon group-containing monocarboxylic acid or hydrocarbon group-containing sulfonic acid is a functional group containing an ionic bond represented by the following formula (3) or the following formula (4). It will have a group.
-R ^{< 1 >} NH ^{<+> -} COO ^- R ^{< 4 >} ... Formula (3)
(In the formula (3), R ¹ has the same meaning as in the formulas (1) and (2), and R ⁴ represents carbonization in the hydrocarbon group-containing monocarboxylic acid or the hydrocarbon group-containing sulfonic acid. Is a hydrogen group)
_{^{-R 1 NH + -SO 3 - R}} 4 ··· Equation (4)
(Wherein (4), ^{R 1} and ^{R 4} have the same meanings as ^{R 1} and ^{R 4} in the formula (3))

(Polymer compound)
The polymer compound contained in the first paint disperses the salt in the first paint and holds the amino group-containing alkoxysilane in the first coating film 11a on the substrate 10.
Examples of the polymer compound in the present embodiment include polyalkoxysilane, a hydrocarbon resin having an ester bond in the side chain, a resin having a urethane bond in the main chain, and a resin having an ether bond in the main chain. These polymer compounds can be used alone or in combination of two or more.

  Examples of the polyalkoxysilane include silica sol obtained by condensation polymerization of alkoxysilane such as tetraalkoxysilane, trialkoxysilane, dialkoxysilane and the like.

  Examples of the hydrocarbon resin having an ester bond in the side chain include acrylates or methacrylates containing an alkyl group, a hydroxy group, a glycidyl group, a carboxy group, an amide group, an oxazoline group, butadiene, vinyl acetate, vinyl chloride, propylene, It can be obtained by polymerizing or copolymerizing ethylene, vinylidene chloride, methacrylonitrile, acrylonitrile and the like.

  The resin having a urethane bond in the main chain can be obtained by polymerizing a polyol and a polyisocyanate.

  Examples of the polyol include polyester polyol, polyether polyol, acrylic polyol, and low molecular weight polyol.

  Examples of the polyester polyol include polyethylene adipate diol, polybutylene adipate diol, polyethylene butylene adipate diol, polyhexamethylene isophthalate adipate diol, polyethylene succinate diol, polybutylene succinate diol, polyethylene sebacate diol, polybutylene sebacate Examples thereof include diol, poly-ε-caprolactone diol, poly (3-methyl-1,5-pentylene adipate) diol, and polycondensate of 1,6-hexanediol and dimer acid.

  Examples of the polyether polyol include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, ethylene oxide and propylene oxide, random copolymers and block copolymers of ethylene oxide and butylene oxide, and the like. Furthermore, a polyether polyester polyol having an ether bond and an ester bond can also be used.

  Examples of the low molecular weight polyol include ethylene glycol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, Examples include 2-methyl-1,8-octanediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanediol, and the like. Furthermore, low molecular weight polyhydric alcohols such as trimethylolpropane, pentaerythritol, sorbitol and the like may be used.

  Examples of the polyisocyanate include 2,4-tolylene diisocyanate, 2,6 tolylene diisocyanate, xylene-1,4-diisocyanate, xylene-1,3-diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4 ′. -Diphenylmethane diisocyanate, 4,4'-phenyl ether diisocyanate, 2-trodiphenyl-4,4'-diisocyanate, 2,2'-diphenylpropane-4,4'-diisocyanate, 3,3'-methyldiphenylmethane-4, 4'-diisocyanate, 4,4'-diphenylpropane diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, naphthylene-1,4-diisocyanate, naphthylene-1,5-diisocyanate, 3,3'-diisocyanate Aromatic diisocyanates such as toxidiphenyl-4,4'-diisocyanate, aromatic polyisocyanates such as polyphenylene polymethylene polyisocyanate, crude tolylene diisocyanate, aliphatics such as tetramethylene diisocyanate, hexamethylene diisocyanate, decamethylene diisocyanate, lysine diisocyanate Diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylene diisocyanate, hydrogenated diphenylmethane diisocyanate, tetramethylxylene diisocyanate and other alicyclic diisocyanates, organic polyisocyanate modified biuret, uretdione modified, carbodiimide modified, isocyanurate Denatured body, uretonimine modified body, this A mixed modification of al and the like.

  Examples of the resin having an ether bond in the main chain include those obtained by polymerizing an epoxy resin containing an alkyl group, a hydroxy group, a carboxy group, an amide group, an oxazoline group, and the like with a curing agent.

  The first paint can include a solvent. The solvent can be selected in consideration of the drying temperature, the drying time, the chemical influence on the substrate 10 and the like when the first paint is applied onto the substrate 10 and dried as will be described later.

As a solvent, an organic solvent can be used individually by 1 type or in mixture of 2 or more types. Of these, alcohol is desirable.
Examples of the alcohol include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 1-pentanol, 3-methyl-1-butanol, and 2-methyl. -2-butanol and the like.
Further, when the substrate 10 is formed of a resin, a slight amount of a material that dissolves the resin can be added to the solvent. By using such a solvent, the surface of the base material 10 can be roughened to improve the adhesion of the first coating film to the base material 10.
Moreover, the condensation catalyst of the said alkoxysilane can also be added to a 1st coating material as needed.

The blending ratio of the salt and the polymer compound in the first paint as described above is desirably set so that the blending amount of the polymer compound is larger than the salt by mass ratio. Specifically, it is desirable to set the ratio of salt / (salt + polymer compound) in the range of 0.1 to 0.3 by mass ratio.
Moreover, although the mixture ratio of a solvent can be suitably set according to the coating method of the 1st coating material with respect to the base material 10, 90 mass% or more is desirable for the solvent in a 1st coating material.

≪Second paint≫
The second coating material in the present embodiment includes an alkoxysilane that forms polysiloxane that is a water repellent compound in the second coating film 11b, that is, an alkoxysilane having the water repellent functional group.
Examples of the alkoxysilane include, but are not limited to, an alkoxysilane having a fluorine-containing organic group having 3 to 18 carbon atoms and a dialkoxysilane having an alkyl group having 1 to 5 carbon atoms.

Examples of the fluorine-containing organic group having 3 to 18 carbon atoms include, but are not limited to, a perfluoroalkyl group and a perfluoropolyether group.
The second coating material of the present invention includes a reactive functional group that chemically bonds to the polymer compound that constitutes the first coating film 11a, and a water-repellent functional group that imparts water repellency to the second coating film 11b. If it has, it is not limited to the said alkoxysilane, dialkoxysilane, etc., The thing containing another silane compound is also accept | permitted.

  In addition, the second paint can contain a solvent. The solvent can be selected in consideration of the drying temperature, the drying time, the chemical influence on the substrate 10 and the like when the first paint is applied onto the substrate 10 and dried as will be described later.

As a solvent, an organic solvent can be used individually by 1 type or in mixture of 2 or more types. Of these, alcohol is desirable.
Examples of the alcohol include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 1-pentanol, 3-methyl-1-butanol, and 2-methyl. -2-butanol and the like.

Moreover, the condensation catalyst of the said alkoxysilane can also be added to a 2nd coating material as needed.
As for the alkoxysilane in a 2nd coating material, 0.01-1.0 mass% is desirable.
Further, the solvent in the second paint is desirably 99% by mass or more.

<Manufacturing method of painted parts>
The manufacturing method of the coating component 20 (refer FIG. 2) which concerns on this embodiment apply | coats a 1st coating material (coating composition) on the base material 10 (refer FIG. 2), and the 1st coating film 11a (refer FIG. 2). Forming a second coating film 11b (see FIG. 2) by applying a second paint on the first coating film 11a, and washing the surface of the second coating film 11b with a basic solution And a process.

  Examples of the method of applying the first paint on the base material 10 include a method of applying wet coating in the atmosphere. Specifically, the first paint is applied onto the substrate 10 by, for example, dip coating, spray coating, spin coating, or the like, but the application method is not limited to these. The application method can be appropriately selected depending on the shape and material of the substrate 10.

  In addition, when the first paint is applied to the base material 10, a surface treatment can be applied to the base material 10. Examples of the surface treatment include oxygen plasma irradiation, blast treatment, and primer treatment. By appropriately selecting such a surface treatment and applying it to the base material 10, the adhesion of the first coating film 11a to the base material 10, the flatness of the first coating film 11a on the base material 10, and the like are improved.

  Next, the first coating film is formed on the base material 10 by polycondensation of alkoxysilane constituting the salt contained in the first paint applied to the base material 10 to generate polysiloxane and evaporating the solvent. 11a is formed.

  When the first coating film 11a is formed on the substrate 10, the condensation polymerization of the alkoxysilane proceeds even at room temperature, but considering the evaporation time of the solvent, the first coating film 11a is heated on the substrate 10. Is desirable. The heating temperature can be appropriately set according to the solvent used. For example, when the solvent is ethanol, the heating temperature can be set to about 60 to 80 ° C.

In the first coating film 11a, the carboxylate or sulfonate of the amino group-containing polysiloxane is retained in the polymer compound that is a constituent component of the first paint.
And the functional group containing the ionic bond shown by the said Formula (3) or the said Formula (4) localizes on the surface of the 1st coating film 11a. This localization principle will be described in detail later.

As a method of applying the second paint on the first coating film 11a, the same application method as the method of applying the first paint on the substrate 10 can be used.
Then, the alkoxysilane contained in the second paint applied on the first coating film 11a is polycondensed to form polysiloxane and the solvent is evaporated, whereby the second coating is applied on the first coating film 11a. A film 11b is formed.

  Further, when the second coating film 11b is formed on the first coating film 11a, the condensation polymerization of the alkoxysilane proceeds even at room temperature, but considering the evaporation time of the solvent, the second coating material is formed on the first coating film 11a. It is desirable to heat. The heating temperature can be appropriately set according to the solvent used. For example, when the solvent is ethanol, the heating temperature can be set to about 60 to 80 ° C.

  In addition, the functional group of the 1st coating film 11a containing the ionic bond shown by the said Formula (3) or the said Formula (4) localizes on the surface of such a 2nd coating film 11b. This localization principle will be described in detail later.

Next, the surface of the second coating film 11b is washed with a basic solution.
Examples of the basic solution include an aqueous sodium hydroxide solution and an aqueous potassium hydroxide solution. The pH of the basic solution is preferably 9-12.

FIG. 3 is a cleaning process diagram of the second coating film 11b with a basic solution in the manufacturing process diagram of the painted component 20 of FIG.
Here, the cleaning process of the second coating film 11b will be described by taking an example in which the first coating film 11a contains polysiloxane having a functional group represented by the formula (3).

The surface of the water-repellent coating film 11 (second coating film 11b) before cleaning shown on the left side of FIG. 3 has a functional group (—R ¹ NH ⁺ —COO) of polysiloxane contained in the first coating film 11a. ^- R ⁴⁾ is localized. However, R ¹ is hydrogen atom or a monovalent hydrocarbon group, R ⁴ is a monovalent hydrocarbon group.

When the surface of the second coating film 11b is washed with a basic solution, an amino group in which the functional group (—R ¹ NH ⁺ —COO ^— R ⁴ ) exhibits antibacterial properties as shown on the right side of FIG. Chemical change to (—NHR ¹ ). Thereafter, the surface of the second coating film 11b is washed with pure water and dried to complete the painted component according to the present embodiment.

<Localization principle>
Next, the principle that amino groups (—NHR ¹ ) are localized on the surface of the water-repellent coating film 11 (second coating film 11b) will be described.
As described above, in the manufacturing process of the painted component 20, the first paint is applied on the base material 10. At this time, the salt of the amino group-containing alkoxysilane and the hydrocarbon group-containing monocarboxylic acid or hydrocarbon group-containing sulfonic acid contained in the first paint is dispersed in the first paint together with the polymer compound. When the polysiloxane obtained by condensation polymerization of alkoxysilane is held by the polymer compound, the hydrocarbon group of the hydrocarbon group-containing monocarboxylic acid or hydrocarbon group-containing sulfonic acid exhibits water repellency. ) Or a functional group containing an ionic bond represented by the formula (4) is localized on the surface of the first coating film 11a.

  Next, when the second coating material is applied onto the first coating film 11a, the surface of the first coating film 11a includes a second coating film containing polysiloxane obtained by condensation polymerization of alkoxysilane contained in the second coating material. 11b is formed.

In addition, when the second paint is applied on the first coating film 11a, between the functional groups containing the ionic bond, the polymer compound that is a component of the first coating film 11a, The alkoxysilane contained in the second paint reacts. Specifically, when the polymer compound is polyalkoxysilane (silica sol), the alkoxy groups and silanol groups remaining in the polyalkoxysilane and the alkoxy groups of the alkoxysilane contained in the second paint are subjected to polycondensation. . For example, when the polymer compound is a hydrocarbon resin having an ester bond in the side chain, a resin having a urethane bond in the main chain, or a resin having an ether bond (such as an epoxy group) in the main chain, it remains in these. The hydroxy group and the alkoxy group of the alkoxysilane contained in the second paint undergo condensation polymerization.
Thereby, on the surface of the second coating film 11b formed on the first coating film 11a, the second coating film 11b leaves the functional group containing the ionic bond of the first coating film 11a almost as it is. Water repellency is imparted to the surface of the water repellent coating film 11.

Then, as described above, the surface of the water-repellent coating film 11 (second coating film 11b) is washed with a basic solution, so that the surface of the water-repellent coating film 11 (second coating film 11b) has amino The group (—NHR ¹ ) is localized. Such a water-repellent coating film 11 includes a first coating film 11a and a functional group —X—NHR ¹ (where X and R ¹ are defined by the formula (1)) formed on the surface of the first coating film 11a. And the same as X and R ^{1 in the} formula (2)), the first coating film 11 a is formed on the first coating film 11 a so that at least the —NHR ¹ portion is exposed on the surface of the water-repellent coating film 11. 2 coating films 11b.

According to the coating component 20 as described above, since the amino group (—NHR ¹ ) that exhibits antibacterial properties is localized on the surface of the water-repellent coating film 11 (second coating film 11b), antibacterial properties are present in the coating film. Unlike painted parts in which components are dispersed, it can exhibit excellent antibacterial and antifungal effects.
Moreover, since the 2nd coating film 11b contains the water repellent compound, the coating component 20 is hard to adhere | attach moisture and the organic substance contained in this moisture. This suppresses the growth of bacteria and fungi. That is, according to the painted component 20 according to the present embodiment, the amino group (—NHR ¹ ) localized on the surface of the water-repellent coating film 11 and the water-repellent compound contained in the second coating film 11 b cooperate. By this, the propagation of bacteria and fungi is suppressed synergistically and more reliably.

As mentioned above, although embodiment of this invention was described, this invention is not limited to the said embodiment, It can implement with a various form.
In the embodiment, as shown in FIG. 2, the first coating film 11 a and the second coating film 11 b are provided on the base material 10, but another layer is provided on the base material 10. You can also.
FIG. 4 is a cross-sectional view of a painted component 20a according to another embodiment of the present invention.
As shown in FIG. 4, the painted component 20 a has a third layer between the base material 10 and the first coating film 11 a constituting the water repellent coating film 11. Examples of the third layer include an adhesive layer such as a primer, and an antibacterial agent-containing layer that supplies other antibacterial components to the water-repellent coating film 11.

Further, ^{R 1} of the amino group (-NHR ¹⁾ is in the case of a hydrocarbon group having water repellency, it is also possible to omit the second coating 11b.

  The amino group contained in the water-repellent coating film 11 is preferably localized on the surface of the water-repellent coating film 11. Good. Accordingly, the coating parts 20 and 20a in which amino groups are distributed in the water-repellent coating film 11 may be used so that the proportion of the amino group gradually decreases inward from the surface of the water-repellent coating film 11. it can.

  Moreover, the coating components 20 and 20a are not limited to the components of the washing machine L, and can be applied to all other devices and apparatuses that involve moisture, such as an air conditioner, a humidifier, and a refrigerator. Moreover, the coating components 20 and 20a can be used independently for piping etc. instead of one component of an apparatus and an apparatus.

Next, the present invention will be described more specifically with reference to Examples and Comparative Examples in which the operational effects of the present invention are verified.
Example 1
In this example, a test piece assuming a painted part used for a washing machine was produced. The test piece was formed by applying the following first paint on the surface of a quartz glass plate (40 mm × 40 mm × 1 mm) as a substrate to form a first coating film, and then forming the following on the surface of the first coating film. A second paint is applied to form a second coating film.

<Preparation of the first paint>
First, a small amount of nitric acid as an acid catalyst was added to a solution in which 70 parts by mass of tetraethoxysilane was dissolved in 980 parts by mass of ethanol, and the mixture was heated at 50 ° C. for 1 hour. As a result, 1000 parts by mass of a silica sol solution having a silicon concentration of 1% by mass and a silicon dioxide concentration of 2% by mass was obtained.

  Next, 2 parts by mass of cyclohexanecarboxylic acid as a monocarboxylic acid and 2 parts by mass of 3-aminopropyltrimethoxysilane as an amino group-containing alkoxysilane are dissolved in 196 parts by mass of ethanol. 200 parts by mass of a carboxylate ethanol solution was obtained.

  And the 1st coating material was obtained by mixing 5 mass parts of obtained silica sol liquids, and 1 mass part of carboxylate ethanol solution.

<Preparation of second paint>
A second coating material was obtained by dissolving 1 part by mass of alkoxysilane (Optool [registered trademark] DSX, manufactured by Daikin Industries, Ltd.) having a modified perfluoropolyether group in 1000 parts by mass of ethanol.

<Preparation of test piece>
The 1st coating material was apply | coated on the base material by the dip-coating method (pulling speed 1.3mm / s). The base material coated with the first paint was heated at 60 ° C. for 30 minutes in a heating furnace to form a first coating film on the base material. After this substrate was cooled to room temperature, the contact angle with water on the surface of the first coating film was measured. The contact angle was 19 degrees.

  Next, the 2nd coating material was apply | coated on the 1st coating film of the base material by the dip coating method (pickup speed 1.3mm / s). The base material coated with the second paint on the first paint film was heated in a heating furnace at 60 ° C. for 30 minutes to form a second paint film on the first paint film of the base material.

After cooling the base material on which the second coating film was formed to room temperature, the surface of the second coating film was washed with an aqueous sodium hydroxide solution (0.001 mol / L) as a basic solution. Next, the surface of the second coating film was washed with pure water and then dried to prepare a test piece in this example.
The contact angle with water on the surface of the test piece was measured. The contact angle was 115 degrees. The surface of the test piece had water repellency.

<Verification of amine localization on specimen surface>
The ratio of nitrogen atoms, which are constituent elements of amine, on the coating film surface of the test piece was determined by XPS analysis. The ratio of nitrogen atoms was 2.4%. The ratio of nitrogen atoms at a depth of 10 nm from the surface of the coating film having a thickness of 50 nm was 0.8%. That is, the ratio of nitrogen atoms on the surface of the test piece in this example was three times the ratio of nitrogen atoms in the coating film. From this, it was verified that the amine was localized on the surface of the test piece in this example.

(Example 2)
A test piece was prepared in the same manner as in Example 1 except that an aluminum plate (20 mm × 30 mm × 0.2 mm) was used as the substrate. Further, in this example, a control test piece was prepared in which only the second coating film was formed without forming the first coating film on the surface of the aluminum plate.

  In this example, the test piece and the control test piece were screwed to the inner surface of the outer tub of the washing machine (see reference numeral 2 in FIG. 1), and the washing machine was used with the maximum amount of water stored in the washing tub. A washing operation was performed. After the end of this washing operation, the washing machine was kept at 30 ° C. and 90% RH in a constant humidity and constant temperature bath and left for 1 week.

  When the inner surface of the outer tank was visually observed, the occurrence of black mold was confirmed on the inner surface of the outer tank over substantially one surface (including the control test piece portion) except for the attached test piece portion. Thereby, the antifungal effect of the test piece in the present Example was confirmed.

(Example 3)
In the present embodiment, the first paint is applied to a part of the drain pipe of the washing machine (see reference numeral 9 in FIG. 1) to form the first paint film. Two paints were applied to form a second coating film.
A part of the drain pipe on which the first coating film and the second coating film are formed is a cylindrical member made of resin (polypropylene) separately prepared so as to correspond to the drain pipe part in the vicinity of the outer tub (see reference numeral 2 in FIG. 1). (Inner diameter 45 mm, length 100 mm).

Moreover, the 1st coating material and the 2nd coating material used the same thing as Example 1. FIG. The formation of the first coating film and the second coating film uses a dip coating method (pickup speed 1.3 mm / s), heating and cooling in a heating furnace, washing of the second coating film with a basic solution, and washing with water. Each was performed under the same conditions as in Example 1. Hereinafter, a part of the drainage officer is referred to as a test drain pipe.
Moreover, in this example, a part of the drain pipe in which only the second coating film was formed was prepared separately without forming the first coating film as the control drain pipe.

  In this example, a series of washing operations until the drainage of the washing water was performed by attaching the test drainer to the washing machine. In parallel with the washing operation of the washing machine equipped with the test drainer, the washing machine equipped with the control drain pipe was washed. And after completion | finish of washing operation, each washing machine was maintained at 30 degreeC and 90% RH in a thermo-hygrostat, and was left for one week.

  When the inside of the test drain pipe and the control drain pipe removed from each washing machine was observed with an endoscope, the occurrence of mold was observed on the inside of the control drain pipe, but the black inside the test drain pipe. Mold did not occur. Thereby, the fungicidal effect of the test drain pipe in the present Example was confirmed.

(Comparative example)
In Example 1, when the first coating material was prepared, 5 parts by mass of the silica sol solution and 1 part by mass of the carboxylate ethanol solution were mixed. In this comparative example, instead of 1 part by mass of the carboxylate ethanol solution. Then, an ethanol solution of the following amino group-containing alkoxysilane was used.
An ethanol solution of an amino group-containing alkoxysilane was obtained by dissolving 2 parts of 3-aminopropyltrimethoxysilane in 98 parts by weight of ethanol. Hereinafter, the ethanol solution of the amino group-containing alkoxysilane is referred to as a third paint.

  In the comparative example, after the third paint was applied to the surface of a quartz glass plate (40 mm × 40 mm × 1 mm) as a base material to form a third paint film, the second paint (implemented on the surface of the third paint film) A comparative test piece was prepared by applying the coating of Example 1) to form a second coating film (see Example 1).

<Production of comparative specimen>
The third paint was applied on the substrate by the dip coating method (pickup speed 1.3 mm / s). The base material coated with the third paint was heated at 60 ° C. for 30 minutes in a heating furnace to form a third coating film on the base material. After this substrate was cooled to room temperature, the contact angle with water on the surface of the third coating film was measured. The contact angle was 17 degrees.

  Next, the 2nd coating material (refer Example 1) was apply | coated on the 3rd coating film of the base material by the dip coating method (pull-up speed 1.3mm / s). A substrate coated with the second coating material on the third coating film is heated in a heating furnace at 60 ° C. for 30 minutes to form a second coating film similar to that of Example 1 on the third coating film of the substrate. did.

After cooling the base material on which the second coating film was formed to room temperature, the surface of the second coating film was washed with an aqueous sodium hydroxide solution (0.001 mol / L) as a basic solution. Next, the surface of the second coating film was washed with pure water and then dried to prepare a comparative test piece.
The contact angle with water on the surface of the comparative test piece was measured. The contact angle was 115 degrees. The surface of the test piece had water repellency.

  Moreover, the ratio of the nitrogen atom which is a structural element of the amine in the coating-film surface of a comparative test piece was calculated | required by XPS analysis. The ratio of nitrogen atoms was 2.4%. Further, the ratio of nitrogen atoms at a depth of 10 nm from the surface of the coating film having a thickness of 50 nm was 2.1%. That is, the ratio of nitrogen atoms on the surface of the comparative test piece was 1.1 times the ratio of nitrogen atoms inside the coating film. From this, it was confirmed that the amine was not localized on the surface of the comparative test piece and was distributed substantially evenly in the coating film.

DESCRIPTION OF SYMBOLS 1 Housing | casing 2 Outer tank 3 Inner tank 4 Inner lid 5 Outer lid 6 Stirring blade 7 Motor 8 Water supply mechanism 9 Drain pipe 10 Base material 11 Water-repellent coating film 11a First coating film 11b Second coating film 20 Painted part 20a Painted part L Washing machine

Claims (4)

A salt of an amino group-containing alkoxysilane and cyclohexanecarboxylic acid ;
A silica sol in which the salt is dispersed;
A coating composition comprising: The coating composition according to claim 1,
The said amino group containing alkoxysilane is shown by following formula (1), The coating composition characterized by the above-mentioned.
(R ³ O) ₂ SiR ² —X—NHR ¹ Formula (1)
(In the formula (1), R ¹ is a hydrogen atom or a monovalent hydrocarbon group, R ² is an alkyl group, R ³ is an alkyl group which may be the same or different, and X is a divalent hydrocarbon.) Base) The coating composition according to claim 1,
The said amino group containing alkoxysilane is shown by following formula (2), The coating composition characterized by the above-mentioned.
(R ³ O) ₃ Si—X—NHR ¹ Formula (2)
(In the formula (2), R ¹ is a hydrogen atom or a monovalent hydrocarbon group, R ³ is an alkyl group which may be the same or different from each other, and X is a divalent hydrocarbon group.) Applying the coating composition according to claim 1 on a substrate to form a first coating film;
A paint containing an alkoxysilane having a fluorine-containing organic group having 3 to 18 carbon atoms or a dialkoxysilane having an alkyl group having 1 to 5 carbon atoms is applied on the first paint film to form a second paint film. Process,
Washing the surface of the second coating film with a basic solution;
A method for producing a painted part, comprising:

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