JP2021133614A - Bug-proof coated base material and method for producing the same, and external facing building material - Google Patents

Abstract

To provide a bug-proof coated base material having good bug-proof performance.SOLUTION: A bug-proof coated base material has a base material, and a coated film arranged thereon. The coated film includes resin, and particles, each of the particles having an average primary particle diameter of 1-700 nm, and surface roughness Ra of the coated film is 0.04-0.20 μm.SELECTED DRAWING: Figure 1

Description

The present invention relates to an insect repellent coating base material, a method for producing the same, and an exterior building material.

Conventionally, indoors, around kitchen equipment such as sinks and gas tables with a lot of food waste, and in or around the electric circuits of home appliances such as refrigerators, washing machines, and microwave ovens where warm air is generated during use, etc. Living pests like it and it is easy to nest. Further, even outdoors, for example, the exterior plate of a vending machine is easily invaded by insects triggered by a light or the like. Therefore, materials and building materials used indoors and outdoors are required to be able to suppress the invasion and adhesion of insects.

The coated metal plate having such an insect repellent effect includes a base steel plate and a colored coating film, and the colored coating film includes a resin, a coloring pigment, a dibasic acid saturated dialkyl ester compound and a synthetic as an insect repellent. Insect repellent coated steel sheets containing a pyrethroid compound and an ultraviolet absorber are known (for example, Patent Document 1). However, since insect repellents are usually volatile, there is a problem that the insect repellent effect cannot be maintained if all of them are volatile.

On the other hand, a method of making it easier for insects to slide off and obtaining an insect repellent effect by imparting irregularities to the surface of the coating film has been studied. For example, an insect-sliding film having a base film and a cured resin layer having a concavo-convex structure composed of a plurality of convex portions is known (for example, Patent Document 2). Further, there is known an insect-sliding laminated film having a base material and an insect-sliding layer containing bead particles having an average particle size of 15 μm as an unevenness-imparting agent arranged on one surface thereof (for example, Patent Document). 3). It is said that these films can be used by attaching a base film to an object with an adhesive or the like.

Japanese Unexamined Patent Publication No. 2004-209788 Japanese Unexamined Patent Publication No. 2013-99269 JP-A-2017-74003

However, even if these insect-sliding films were attached to the wall surface of the object, sufficient insect-sliding property, that is, a sufficient insect repellent effect could not be obtained.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide an insect repellent coating base material having a sufficient insect repellent effect and a sustainable effect thereof, a method for producing the same, and an exterior building material. ..

The present invention relates to the following insect repellent coating base material, a method for producing the same, and an exterior building material.

The insect repellent coating base material of the present invention is an insect repellent coating base material having a base material and an insect repellent coating film arranged on the base material, and the insect repellent coating film has a resin and an average primary particle size of 1 to 700 nm. The surface roughness Ra of the insect repellent coating film is 0.04 to 0.20 μm.

The exterior building material of the present invention includes the insect repellent coating base material of the present invention.

The method for producing an insect-proof coating base material of the present invention is a curable resin composition containing a curable resin, particles having an average primary particle diameter of 1 to 700 nm, and a curing agent, and having a non-volatile component content of 50% by mass or less. The present invention comprises a step of applying the curable resin composition to the surface of the base material and then curing it to form an insect-proof coating film.

According to the present invention, it is possible to provide an insect repellent coating base material having a good insect repellent effect, a method for producing the same, and an exterior building material.

1A and 1B are cross-sectional views of an insect repellent coating base material according to the present embodiment.

The present inventors have found that a good insect repellent effect can be obtained by appropriately reducing the unevenness while imparting unevenness to the surface of the coating film.

Although the mechanism of insect sliding is not clear, it is considered that insects slide when the contact area between the back of the insect's leg and the base material is small. That is, if the surface roughness Ra is too large, the back of the insect's leg comes into contact with the large unevenness, so that the contact area becomes large and the sliding property is unlikely to appear. Further, even if the surface roughness Ra is too small, the back of the insect leg comes into contact with the smooth surface, so that the contact area becomes large and the insect slipperiness is less likely to occur. On the other hand, when a coating film having an appropriately small surface roughness Ra is formed on a wall surface, for example, the contact area with the back of the insect's leg becomes small, so that the insect easily slides down (difficult to invade). By appropriately adjusting the unevenness of the coating film in this way, good insect repellent performance can be obtained. Since the Ra on the surface of the coating film of the example of Patent Document 3 is 0.5 μm or more, it is clear that it is larger than the unevenness of the present application. Hereinafter, the configuration of the insect repellent coating base material of the present invention will be specifically described.

1. 1. Insect repellent coating base material FIG. 1A is a cross-sectional view of the insect repellent coating base material according to the present embodiment, and FIG. 1B is a partially enlarged view of FIG. 1A.

As shown in FIG. 1A, the insect repellent coating base material 10 according to the present embodiment has a base material 20 and an insect repellent coating film 30 arranged on the base material 20. The insect repellent coating film 30 contains the resin 31 and the particles 32.

1-1. Base material The base material is not particularly limited, and may be any of a metal plate, a resin film, and a glass plate.

Examples of the resin film include resin films such as acrylic resin, polycarbonate resin, styrene resin, polyester resin, cellulose resin, polyolefin resin, vinyl chloride resin, and polyurethane resin.

The metal plate can be selected from known metal plates. Examples of metal plates include cold-rolled steel sheets, galvanized steel sheets, Zn-Al alloy-plated steel sheets, Zn-Al-Mg alloy-plated steel sheets, aluminum-plated steel sheets, and stainless steel sheets (austenite-based, martensite-based, ferrite-based, ferrite-based). Includes (including martensite two-phase systems), aluminum plates, aluminum alloy plates and copper plates.

The metal plate is preferably a plated steel sheet or a stainless steel sheet from the viewpoint of corrosion resistance and weight reduction, and is preferably a plated steel sheet from the viewpoint of cost effectiveness. Further, the metal plate is preferably a molten 55% Al—Zn alloy plated steel sheet, a Zn—Al—Mg alloy plated steel sheet or an aluminum plated steel sheet from the viewpoint of further enhancing corrosion resistance. Of these, a hot-dip 55% Al—Zn alloy plated steel sheet, a Zn—Al—Mg alloy plated steel sheet, or an aluminum plated steel sheet is preferable.

The thickness of the metal plate can be appropriately set according to the use of the insect repellent coated metal plate. For example, when the insect-proof coated metal plate is used as an exterior building material, the thickness of the metal plate is preferably 0.2 to 3.0 mm, for example, and from the viewpoint of further improving workability, 0.25 to 2. It is preferably 0 mm.

1-2. Insect repellent coating The insect repellent coating is placed in contact with the surface of the substrate or via another coating. It is preferable that the insect repellent coating film is arranged on the outermost side of the insect repellent coating base material, that is, the outermost layer coating film.

As mentioned above, the insect repellent coating contains resin and particles (see FIGS. 1A and 1B).

Specifically, the insect-proof coating film may be composed of a resin composition containing a thermoplastic resin such as a fluororesin or an acrylic resin and particles, or may include a curable resin, a curing agent, and particles. It may be composed of a cured product of a curable resin composition. Above all, since the insect-proof coating film arranged on the outermost surface is desired to have sufficient hardness and weather resistance, it is a cured product of a curable resin composition containing a curable resin, a curing agent, and particles. It is preferably configured.

1-2-1. Curable resin The curable resin may be a resin having a functional group that reacts with the curing agent. Examples of the group that reacts with the curing agent include a hydroxyl group, an epoxy group, an amino group, and the like, and a hydroxyl group is preferable. Examples of such curable resins include curable polyester resins, curable acrylic resins, epoxy resins and modified epoxy resins.

(Curable polyester)
The curable polyester resin is preferably a hydroxyl group-containing polyester resin. The hydroxyl group-containing polyester resin can be a polycondensate of a polyvalent carboxylic acid component and a polyhydric alcohol component (oil-free polyester resin, oil-modified polyester resin) or a modified product thereof (urethane-modified product, epoxy-modified product). ..

The polyvalent carboxylic acid component constituting the polycondensate may be any of an aliphatic polyvalent carboxylic acid, an alicyclic polyvalent carboxylic acid, and an aromatic polyvalent carboxylic acid. Examples of polyvalent carboxylic acid components include divalent phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, succinic acid, fumaric acid, adipic acid, sebacic acid, maleic anhydride and the like. Carboxylic acids and esterified products thereof; trivalent or higher polyvalent carboxylic acids such as trimellitic anhydride, methylcyclohexcentricarboxylic acid, and pyromellitic anhydride are included. The polyvalent carboxylic acid may be used alone or in combination of two or more. Among them, the polyvalent carboxylic acid component preferably contains a divalent carboxylic acid (preferably an aromatic divalent carboxylic acid).

The polyhydric alcohol component constituting the polycondensate may be any of an aliphatic polyhydric alcohol, an alicyclic polyhydric alcohol, and an aromatic polyhydric alcohol. Examples of polyhydric alcohol components include ethylene glycol, diethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 3-methylpentanediol, 1,4-hexanediol, and 1,6-hexanediol. Alcohols of value; include trihydric or higher alcohols such as glycerin, trimethylolethane, trimethylolpropane, pentaerythritol. The polyhydric alcohol may be used alone or in combination of two or more. Among them, the polyhydric alcohol component preferably contains a trihydric or higher alcohol (preferably a trihydric or higher aliphatic alcohol).

The hydroxyl group-containing polyester resin may be one obtained by further reacting an oil fatty acid in addition to the reaction of the polyvalent carboxylic acid and the polyhydric alcohol (oil-modified polyester resin). Examples of oil fatty acids include coconut oil fatty acid, soybean oil fatty acid, flaxseed oil fatty acid, safflower oil fatty acid, tall oil fatty acid, dehydrated castor oil fatty acid, and millet oil fatty acid.

The urethane-modified polyester resin may be obtained by reacting a hydroxyl group of a low molecular weight polycondensate obtained by reacting a polyvalent carboxylic acid with a polyhydric alcohol with a polyisocyanate compound. Examples of the polyisocyanate compound used include hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and 4,4'-methylenebis (cyclohexyl isocyanate).

The epoxy-modified polyester resin is a reaction product obtained by reacting a carboxyl group of a polycondensate obtained by reacting a polyvalent carboxylic acid with a polyhydric alcohol with an epoxy group-containing compound; It contains a reaction product in which and a hydroxyl group of a modified epoxy resin are bonded via a polyisocyanate compound.

The hydroxyl value of the curable polyester resin is preferably 7 to 50 mgKOH / g, more preferably 10 to 40 mgKOH / g. The higher the hydroxyl value, the higher the crosslink density of the obtained cured product and the higher the elastic modulus. The hydroxyl value refers to the number of mg of potassium hydroxide required to neutralize acetic acid bonded to the hydroxyl group when the hydroxyl group contained in 1 g of the sample is acetylated. The hydroxyl value can be measured according to JIS K 0070.

(Curable acrylic resin)
The curable acrylic resin is not particularly limited, and may be, for example, an acrylic resin having a hydroxyl group in the molecule (also referred to as a hydroxyl group-containing acrylic resin or an acrylic polyol). The hydroxyl group-containing acrylic resin can be a (co) polymer of the hydroxyl group-containing acrylic monomer.

Examples of hydroxyl group-containing acrylic monomers include (meth) acrylate monomers having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate, and hydroxyl groups. Includes ring-opening additions of γ-butyrolactone to the (meth) acrylate monomers having. The hydroxyl group-containing acrylic monomer may be used alone or in combination of two or more.

Examples of other ethylenically unsaturated monomers that can be copolymerized with a hydroxyl group-containing acrylic monomer include (meth) acrylic acid esters, styrenes, vinyl esters, and (meth) acrylamides that do not have a hydroxyl group.

(Epoxy resin)
The epoxy resin is not particularly limited and may be a resin having two or more epoxy groups in the molecule (unmodified epoxy resin). Examples of epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, hydrogenated bisphenol A type epoxy resins, brominated bisphenol A type epoxy resins and other bisphenol type epoxy resins; polyglycidyl ethers of phenol or alkylphenol novolac resins. A novolak type epoxy resin is included.

(Modified epoxy resin)
The modified epoxy resin is a resin (modified epoxy resin having a functional group that reacts with a curing agent) obtained by reacting the epoxy resin with a compound having a functional group that reacts with a curing agent and a group that reacts with an epoxy group. be. The modified epoxy resin is, for example, a modified epoxy resin having a functional group that reacts with an isocyanate group such as an amino group or a hydroxy group in the molecule (for example, an amine-modified epoxy resin or an amino alcohol-modified epoxy resin such as an alkanolamine). ) Can be.

Among these, a curable polyester resin is preferable from the viewpoint of being used as an exterior building material, and an oil-free polyester resin is more preferable from the viewpoint of further enhancing the weather resistance.

The weight average molecular weight of the curable resin is preferably 2000 to 12000. When the weight average molecular weight of the curable resin is 12000 or less, it may be difficult to bleed out low molecular weight components such as pyrethroid compounds. On the other hand, when the weight average molecular weight of the curable resin is 2000 or more, the strength and weather resistance of the cured product can be easily increased. The weight average molecular weight of the curable resin is more preferably 3000 to 10000 from the above viewpoint.

The weight average molecular weight of the curable resin can be calculated based on the molecular weight of standard polystyrene from the chromatogram measured by the gel permeation chromatograph according to JIS K 0124-2011. The specific measurement conditions may be the same as the measurement conditions in the examples described later.

The content of the curable resin is preferably 10% by mass or more and 50% by mass or less with respect to the total non-volatile components of the curable resin composition. When the content of the curable resin is 10% by mass or more, not only the adhesion to the base material is easily obtained, but also the particles are easily held stably. When the content of the curable resin is 50% by mass or less, the obtained insect repellent coating film can not only have sufficient strength but also have good corrosion resistance and the like. From the same viewpoint, the content of the curable resin is more preferably 10 to 20% by mass with respect to the total non-volatile components of the curable resin composition.

1-2-2. Curing agent The curing agent may be any one that cures the curable resin, and can be appropriately selected depending on the curable resin. For example, examples of a curing agent for curing a curable resin having a hydroxyl group or an amino group such as a hydroxyl group-containing polyester resin, a hydroxyl group-containing acrylic resin, and an amine-modified epoxy resin include an isocyanate compound and a melamine compound. Examples of epoxy resin curing agents include amine compounds, acid anhydrides and imidazole compounds.

Among them, since the curable resin is preferably a hydroxyl group-containing polyester resin, the curing agent is preferably an isocyanate compound or a melamine compound.

Examples of isocyanate compounds include aliphatic isocyanate compounds such as hexamethylene diisocyanate (HDI), lysine diisocyanate and dimerate diisocyanate (DDI); norbornene diisocyanate (NBDI), isophorone diisocyanate (IPDI), cyclohexanediisocyanate, dicyclohexylmethane diisocyanate and the like. Alicyclic isocyanate compounds; methylenediphenyl diisocyanate (MDI), tolylene diisocyanate (TDI), xylylene diisocyanate (XDI), naphthylene 1,5-diisocyanate (NDI), tetramethylene xylylene diisocyanate (TMXDI), phenylenedi isocyanate, etc. Contains aromatic isocyanate compounds. Above all, an aliphatic isocyanate compound is preferable from the viewpoint of obtaining a primer layer having good adhesion.

Examples of melamine compounds include methylolated melamine compounds obtained by reacting melamine with aldehyde, and at least a part of the methylol groups thereof are alcohols (for example, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n- Examples thereof include those etherified with monohydric alcohols such as butyl alcohol, isobutyl alcohol, 2-ethylbutanol, and 2-ethylhexanol).

The content of the curing agent is preferably 10 to 35% by mass with respect to the curable resin. When the content of the curing agent is 10% by mass or more, the curable resin can be sufficiently cured, so that an insect repellent coating film having sufficient strength can be easily obtained. When the content of the curing agent is 35% by mass or less, the amount of the curing agent remaining unreacted can be reduced.

1-2-3. Particles Particles impart irregularities to the surface of the insect repellent coating film. That is, at least a part of the particles can be exposed from the surface of the insect repellent coating film to form a convex portion.

The average primary particle size of such particles is preferably 1 to 700 nm. That is, when the average particle size of the particles is within the above range, the area where the unevenness formed on the surface of the insect repellent coating film and the back of the insect's leg are in contact with each other becomes small, so that the insect can easily slide down. From the same viewpoint, the average primary particle size of the particles is more preferably 7 to 440 nm.

The average primary particle size of the particles contained in the insect repellent coating film can be measured by the following procedure.
First, the surface of the insect repellent coating film is observed with a scanning electron microscope (SEM). In the image of the obtained electron image, after measuring the primary particle size of any 50 particles, the average value thereof can be defined as the "average primary particle size".

The type of particles is not particularly limited, but may be inorganic particles or organic particles.

Examples of inorganic particles include silica, alumina, titanium oxide, iron oxide (bengala), zirconium oxide (zirconia), chromium oxide, metal oxides such as cobalt oxide, metal compounds such as calcium carbonate and barium sulfate, and Al powder. It contains particles such as metals such as Ni powder and Cu powder.

Examples of organic particles include resin particles such as acrylic resin, urethane resin, benzoquanamine resin, styrene resin, polyethylene resin, polypropylene resin, and fluororesin.

Among them, inorganic particles are preferable from the viewpoint of cost, metal oxide particles are more preferable, and silica particles are particularly preferable from the viewpoint of easy production.

The silica particles may be surface-treated with a hydrophobic agent from the viewpoint of increasing the dispersibility in the resin and making it difficult to aggregate. Surface treatment with a hydrophobizing agent means that the hydrogen atom of the hydroxy group on the surface of the silica particles is replaced with a silyl group such as a dimethylsilyl group, a trimethylsilyl group, an octylsilyl group, or a dimethylpolysiloxane group.

Examples of hydrophobic agents used for surface treatment include alkoxysilanes such as methyltrichlorosilane, dimethyldichlorosilane and trimethylchlorosilane; alkylsilanes such as triethylsilane and octylsilane; silazanes such as hexamethyldisilazane; dimethyl. Straight silicone oils such as silicone oils; modified silicone oils such as alkyl-modified silicone oils, chloroalkyl-modified silicone oils, polyether-modified silicone oils, and alkoxy-modified silicone oils; siloxanes such as hexamethylcyclotrisiloxane are included.

The content of the particles depends on the particle size and type of the particles, but is 10 to 400% by mass with respect to the resin (preferably a curable resin) from the viewpoint of forming appropriate irregularities on the surface of the insect repellent coating film. Is preferable. When the content of the particles is 10% by mass or more, an appropriate number of convex portions can be formed on the surface of the insect repellent coating film, so that it is easy to improve the sliding property of the insects. Since it is difficult to exceed the amount of oil absorbed by the paint, the handleability as a paint is not easily impaired. From the same viewpoint, the content of the particles is more preferably 20 to 300% by mass with respect to the resin (preferably a curable resin). Alternatively, the content of the particles may be 10 to 50% by volume with respect to the resin (preferably a curable resin).

1-2-4. Other components The curable resin composition constituting the insect repellent coating film arranged on the outermost surface may further contain other components other than the above, if necessary. Examples of other ingredients include insect repellents, UV absorbers and the like.

(Insect repellent)
The curable resin composition constituting the insect repellent coating film arranged on the outermost surface may further contain an insect repellent. Thereby, the insect repellent performance of the insect repellent coating base material can be further improved. The type of insect repellent is not particularly limited, and examples thereof include pyrethroid compounds.

The pyrethroid compound is not particularly limited, but a pyrethroid compound having a vapor pressure of 1 × 10 ^-5 Pa or less at 25 ° C. is preferable. Since such a pyrethroid compound does not easily volatilize from the insect repellent coating film, good insect repellent performance can be maintained even after the weather resistance test. From the above viewpoint, the vapor pressure of the pyrethroid compound at 25 ° C. ^{is preferably 1 × 10 -11} to 1 × 10 ^-5 Pa, and more preferably 1 × 10 ^-10 to 1 × 10 ^-6 Pa. preferable.

The vapor pressure of the pyrethroid compound at 25 ° C. can be measured by the gas saturation method described in 104 of the OECD test guideline.

Examples of pyrethroid compounds with a vapor pressure of 1 × ^10-5 Pa or less at 25 ° C. include cyphenothrin, phenothrin, cyphenothrin, permethrin, cypermethrin, tralomethrin, bifenthrin, resmethrin, phthalthrin, imiprothrin, monfluorothrin, and eth. Includes phenprox. Of these, permethrin and etofenprox are preferable from the viewpoint of maintaining good insect repellent performance not only in the initial stage but also after the weather resistance test.

The content of the pyrethroid compound is preferably 0.5 to 10% by mass with respect to the total non-volatile components of the curable resin composition. When the content of the pyrethroid compound is 0.5% by mass or more, the pyrethroid compound that is not decomposed by ultraviolet rays or the like remains appropriately even after the weather resistance test, so that good insect repellent performance is maintained even after the weather resistance test. Can be done. When the content of the pyrethroid compound is 10% by mass or less, high insect repellent performance can be obtained without increasing the cost. From the above viewpoint, the content of the pyrethroid compound is more preferably 1 to 10% by mass with respect to the total non-volatile components of the curable resin composition.

The content of the pyrethroid compound can be confirmed by gas chromatography, gas chromatography-mass spectrometry, or high performance liquid chromatography.

(UV absorber)
The ultraviolet absorber is not particularly limited, but is preferably a triazine-based ultraviolet absorber or a benzotriazole-based ultraviolet absorber from the viewpoint of having good heat resistance even at the baking temperature. Of these, a triazine-based ultraviolet absorber is preferable from the viewpoint of having good heat resistance. The ultraviolet absorber may be used alone or in combination of two or more.

Examples of such UV absorbers include TINUVIN 384, TINUVIN 400, TINUVIN 411L, TINUVIN 900, TINUVIN 928 (all manufactured by Ciba Specialty Chemicals).

The content of the UV absorber can be, for example, less than 10% by mass based on the total non-volatile components of the curable resin composition.

(About the surface shape of the insect repellent coating film)
A plurality of convex portions are formed on the surface of the insect repellent coating film by exposing some of the particles (see FIGS. 1A and 1B).

Specifically, the surface roughness Ra (arithmetic mean height of the roughness curve) of the insect-proof coating film is preferably 0.04 to 0.2 μm at a measurement length of 50 μm. When the surface roughness Ra of the insect repellent coating film is within the above range, the area where the insect repellent coating film and the back of the insect's leg are in contact with each other becomes small, so that the insect can easily slide down. From the same viewpoint, Ra is more preferably 0.08 to 0.17 μm.

The ten-point average height Rzjis (ten-point average height in the roughness curve) of the surface of the insect repellent coating film is not particularly limited, but is preferably 0.10 to 0.8 μm. When Rzjis is within the above range, the area where the insect repellent coating film and the back of the insect's leg are in contact with each other becomes small, so that the insect can easily slide down. From the same viewpoint, Rzjis is more preferably 0.2 to 0.6 μm.

The surface roughness Ra and the ten-point average height Rzjis of the insect repellent coating film can be measured according to JIS B 0601-2001 (ISO 4287-1997).

The average length Rsm (average length of the roughness curve element) of the surface element of the insect repellent coating film is not particularly limited, but is preferably 5.0 to 18.0 μm. When Rsm is within the above range, the convex portions are appropriately densely packed, so that insects easily slide down (difficult to invade). From the same viewpoint, the Rsm is preferably 7.0 to 15.0 μm.

Ra, Rzjis, and Rsm on the surface of the insect-proof coating film can be obtained by any method, for example, the size (average primary particle diameter) and content of particles contained in the insect-proof coating film, the dispersed state, the thickness (T) of the coating film, and the particles. It can be adjusted by the ratio with the average primary particle size (R) of.
For example, when Ra is reduced, it is preferable to reduce the amount of particles having a small average primary particle size (for example, 100 nm or less) and increase the amount of particles having a large average primary particle size (for example, more than 100 nm). When Rzjis is reduced, for example, the average primary particle size (R) and R / T of the particles are preferably reduced, and the dispersed state is preferably increased (difficult to agglutinate). When the Rsm is reduced, it is preferable to reduce the size (average primary particle size) of the particles contained in the coating film or increase the content.

(Thickness)
The thickness (T) of the insect repellent coating film is not particularly limited as long as the above surface shape (Ra, Rzjis, Rsm) can be obtained, but is preferably 0.1 to 5 μm, for example. When the thickness of the insect repellent coating film is 5 μm or less, the particles are likely to be exposed or protrude from the surface of the coating film, and appropriate irregularities are likely to be formed on the surface. When the thickness of the insect repellent coating film is 0.1 μm or more, the surface of the base material can be sufficiently covered, so that sufficient corrosion resistance can be easily obtained. From the same viewpoint, the thickness (T) of the insect repellent coating film is more preferably 1 to 3 μm.

The thickness (T) of the insect repellent coating film refers to the thickness of the coating film that does not include exposed or protruding portions of particles (which become convex portions) (see FIG. 1B). Specifically, in the cross section along the thickness direction of the coating film, the distance between the line connecting the bottom portions (the lowest height portion) between the convex portions and the bottom surface (the surface on the base material 30 side) of the coating film. Can be calculated as the average value of.

The ratio (R / T) of the thickness (T) of the insect-proof coating film to the average primary particle diameter (R) of the particles varies depending on the average primary particle diameter (R), but is, for example, 0.0002 to 7. sell. Specifically, when the average primary particle size (R) of the particles is 200 nm or less, the R / T is preferably 0.0002 to 0.01, preferably 0.001 to 0.01. More preferred. When the average primary particle size (R) of the particles is more than 200 nm, the R / T is preferably 0.13 to 7, more preferably 0.13 to 5. When the R / T is a certain value or more, the size of the particles is relatively large, so that the particles are easily exposed from the surface of the coating film, and the above-mentioned surface shape is easily formed.

1-3. Other coating film The insect-proof coating base material may further have a coating film other than the above-mentioned insect-proof coating film, if necessary (not shown). When the base material is a metal plate, examples of other coating films include a chemical conversion coating film, an undercoat coating film, and a topcoat coating film. When the base material is a resin film, examples of other coating films include an adhesive layer arranged on the back surface of the base material (the surface opposite to the insect repellent coating film) and an undercoat coating film arranged on the front surface. Etc. are included. Hereinafter, an example will be described in which the base material of the insect repellent coating base material is a metal plate.

1-3-1. Chemical conversion coating The chemical conversion coating can be placed directly on the metal plate, that is, between the metal plate and the topcoat coating, for the purpose of improving the adhesion and corrosion resistance of the insect-proof coated metal plate. The chemical conversion treatment film is a layer formed in contact with the surface of the metal plate, and is composed of a composition adhered to the surface of the metal plate by pre-coating treatment. Examples of chemical conversion-treated layers include non-chromate-based coatings and chromate-based coatings. All of these are rust-preventive films.

The non-chromate film is preferable from the viewpoint of enhancing the corrosion resistance and from the viewpoint of reducing the burden on the environment in the manufacture and use of the insect-proof coated metal plate, and the chromate film is preferable from the viewpoint of enhancing the corrosion resistance.

Examples of non-chromate coatings include Ti-Mo composite coatings, fluoroacid coatings, phosphate coatings, resin coatings, resin and silane coupling agent coatings, silica coatings, silica and silane coupling agent coatings. , Zirconium-based coatings, as well as zirconium and silane coupling agent-based coatings.

The amount of non-chromate film adhered can be appropriately determined according to the type. For example, the adhesion amount of the Ti-Mo composite film ^{is preferably 10 to 500 mg / m 2} in terms of total Ti and Mo, and the adhesion amount of the fluoroacid-based film is 3 to 100 mg in terms of fluorine or total metal elements. preferably / is ^{m 2,} and the adhesion amount of the phosphate coating is preferably 0.1-5 g / ^{m 2} in terms of phosphorus, deposition of resin coating is 1-500 mg of resin terms is preferably / ^{m 2,} the adhesion amount of the resin and the silane coupling agent-based coating is preferably 0.1 to 50 mg / ^{m 2} in terms of Si, the adhesion amount of the silica-based coating, in terms of Si is preferably 0.1 to 200 mg / ^{m 2,} the adhesion amount of silica and silane coupling agent-based coating is preferably 0.1 to 200 mg / ^{m 2} in terms of Si, adhesion quantity of the zirconium-based coating is preferably 0.1-100 mg / ^{m 2} in terms of Zr coating weight of zirconium and a silane coupling agent-based coating is preferably 0.1-100 mg / ^{m 2} in terms of Zr.

Examples of chromate-based coatings include coating-type chromate-treated coatings and phosphoric acid-chromic acid-based treated chromate rust-preventive coatings. The amount of adhesion of these chromate-based coatings is preferably ^{20 to 80 mg / m 2 in terms of chromium element.}

1-3-2. Undercoat coating The undercoat coating is arranged between the metal plate and the topcoat, or between the chemical conversion coating and the topcoat, from the viewpoint of improving the adhesion and corrosion resistance of the coating on the insect-proof coated metal plate. sell.

The undercoat coating may be composed of a resin composition containing a thermoplastic resin. Examples of thermoplastic resins include polyester resins, modified silicone resins, acrylic resins, phenoxy resins, urethane resins, vinyl chloride resins and the like.

Further, the undercoat coating film may be composed of a cured product of a resin composition containing a curable resin and a curing agent. As the curable resin and the curing agent, the same curable resin and the same as those mentioned as the curing agent constituting the coating film can be used.

Above all, the undercoat coating is preferably composed of a cured product of a resin composition containing a curable resin and a curing agent, and from the viewpoint that adhesion to the chemical conversion coating and adhesion to the topcoat coating can be easily obtained. Therefore, it is more preferable to consist of a cured product of a resin composition containing an epoxy resin and a curing agent.

The resin composition or the curable resin composition constituting the undercoat coating film may further contain additives such as rust preventive pigment particles. Examples of rust preventive pigment particles include non-chromium rust preventive pigment particles including modified silica, vanazine salt, magnesium hydrogen phosphate, magnesium phosphate, zinc phosphate, and aluminum polyphosphate, and chromic acid. It contains particles of a chromium-based rust preventive pigment containing strontium, zinc chromate, barium chromate, calcium chromate and the like.

The amount of the rust-preventive pigment contained in the undercoat coating film may be such that the desired rust-preventive performance can be obtained, and can be, for example, 10 to 70% by mass.

The thickness of the undercoat coating film is not particularly limited, but is preferably 1 to 10 μm, more preferably 3 to 7 μm, for example.

1-3-3. Topcoat The topcoat may be placed between the undercoat and the insect repellent. The topcoat coating film can improve the design property and corrosion resistance of the insect repellent coating base material.

The type of resin (base resin) constituting the topcoat coating film is not particularly limited. Examples of the resin constituting the topcoat coating film include polyester, epoxy resin, acrylic resin and the like. These resins may be crosslinked with a curing agent. The type of curing agent may be appropriately selected according to the type of resin used, baking conditions, and the like. Examples of curing agents include melamine compounds, isocyanate compounds and the like. Examples of melamine compounds include imino-based, methylol imino-based, methylol-based or fully alkyl-based melamine compounds.

The topcoat coating film may or may not be transparent, but when the insect repellent coating film is transparent, the topcoat coating film is not transparent (that is, colored) from the viewpoint of enhancing the design. That) is preferable. That is, the topcoat coating film preferably contains an arbitrary coloring pigment. Examples of coloring pigments are inorganic pigments such as titanium oxide, calcium carbonate, carbon black, iron black, titanium yellow, red iron oxide, dark blue, cobalt blue, cerulean blue, ultramarine, cobalt green, molybdenum red; Composite oxide fired pigments containing metal components such as CoNiZnTi, CoCrZnTi, NiSbTi, CrSbTi, FeCrZnNi, MnSbTi, FeCr, FeCrNi, FeNi, FeCrNiMn, CoCr, Mn, Co, SnZnTi; metallic pigments such as Al, resin coating Al, Ni ; And Resole Red B, Brilliant Scarlet G, Pigment Scarlet 3B, Brilliant Carmine 6B, Lake Red C, Lake Red D, Permanent Red 4R, Bordeaux 10B, Fast Yellow G, Fast Yellow 10G, Para Red, Watching Red, Benzgin Yellow, Includes organic pigments such as Benzidine Orange, Bonmaroon L, Bonmaroon M, Brilliant Fast Scarlet, Vermilion Red, Phthalocyanine Blow, Phthalocyanine Green, Fast Sky Blue, and Aniline Black. In addition, other pigments such as extender pigments may be blended in the topcoat coating film. Examples of extender pigments include barium sulfate, titanium oxide, silica, calcium carbonate and the like. The content of the coloring pigment in the topcoat coating film is not particularly limited, but may be, for example, 0 to 70% by mass.

The film thickness of the topcoat coating film is not particularly limited, but is preferably 5 to 30 μm. When the film thickness is 5 μm or more, it is easy to give a desired appearance, and when it is 30 μm or less, it is unlikely that the appearance is poor or the workability is deteriorated due to the generation of armpits when the paint is dried.

1-4. Applications Since the insect repellent coating base material according to the present embodiment has excellent insect repellent performance as described above, it can be preferably used as various materials and building materials (interior building materials and exterior building materials).

2. Method for Producing Insect Repellent Coating Base Material The insect repellent coating base material can be produced by any method. For example, the insect-proof coating base material forms an insect-proof coating film by 1) preparing a curable resin composition and 2) applying the obtained curable resin composition to the surface of the base material and then curing the coating material. Has a process of

Regarding the step 1) (step of preparing the curable resin composition), the curable resin composition containing the above-mentioned curable resin, curing agent and particles is prepared.

The curable resin composition may further contain water or a solvent in addition to the above components. Examples of solvents include hydrocarbons such as toluene and xylene, esters such as ethyl acetate and butyl acetate, ethers such as cellosolve, and ketones such as methyl isobutyl ketone, methyl ethyl ketone, isophorone and cyclohexanone.

From the viewpoint of obtaining a coating film having the above-mentioned surface shape, the viscosity of the curable resin composition is preferably low. By lowering the viscosity of the curable resin composition, the thickness (T) of the insect repellent coating film becomes relatively thin with respect to the average primary particle diameter (R) of the particles, so that the particles are exposed from the surface of the insect repellent coating film. It is easy to make it, and it is easy to form irregularities on the surface of the insect repellent coating film.

Specifically, the amount of the non-volatile component of the curable resin composition is preferably 50% by mass or less, more preferably 10 to 50% by mass, and further preferably 10 to 20% by mass. .. The amount of the non-volatile component refers to the amount of the non-volatile component (solid content) other than the volatile component such as water and solvent with respect to the total amount of the curable resin composition. When the amount of the non-volatile component is small, the viscosity of the curable resin composition tends to be low.

Regarding the step 2) (step of forming an insect repellent coating film), the obtained curable resin composition is then applied to the surface of the base material.

The curable resin composition can be applied by a known method such as roll coating, curtain flow coating, spray coating, or immersion coating.

Then, the insect repellent coating film applied to the surface of the base material is cured (baked). Specifically, the solvent is volatilized from the curable resin composition, and the curable resin composition is cured. As a result, an insect repellent coating film made of a cured product of the curable resin composition is obtained.

The curable resin composition can be baked by heating. The baking is preferably carried out, for example, at a reaching plate temperature of 200 to 280 ° C. for 20 to 80 seconds.

Other Steps The method for producing the insect repellent coating base material may further include other steps other than the above, if necessary. For example, when the base material is a metal plate, examples of other steps include 3) a step of forming a chemical conversion treatment film (chemical conversion treatment step) and 4) a step of forming an undercoat coating film.

About the step 3) (step of forming a chemical conversion treatment film) The step of forming a chemical conversion treatment film can be performed before the step 2) (step of forming a coating film). Specifically, the chemical conversion treatment film can be dried after applying the chemical conversion treatment liquid to the surface of the metal plate by a known method such as a roll coating method, a spin coating method, or a spray method. Can be done.

From the viewpoint of productivity, the drying temperature and the drying time may be, for example, 60 to 150 ° C. for 2 to 10 seconds at the ultimate temperature of the metal plate.

About step 4) (step of forming undercoat coating film) The step of forming an undercoat coating film is before the step of 2) (step of forming a coating film) or the step of 3) (forming a chemical conversion treatment film). It can be performed between the step (step) and the step 2) (step of forming a coating film). Specifically, the undercoat coating film is obtained by applying an undercoat coating material (resin composition for undercoat coating film or curable resin composition) to the surface of a base material or a chemical conversion treatment film, and then drying and curing the undercoat coating film. Can be done. The undercoat paint may contain a solvent or an additive, if necessary.

The curing temperature (baking temperature) can be, for example, 180 to 260 ° C., which is the ultimate temperature of the base material.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to these Examples.

1. 1. Preparation of painted original plate (manufacturing of painted original plate 1)
1-1. Preparation of metal plate As a base material, a molten 55% Al—Zn alloy plated steel sheet (plate thickness 0.35 mm, double-sided adhesion amount 150 g / m ² ) was prepared by alkali degreasing.

1-2. Chemical conversion treatment Next, apply a chromate treatment solution of "Surfcoat NRC300NS"("Surfcoat" is a registered trademark of Nippon Paint Co., Ltd.) manufactured by Nippon Paint Co., Ltd. to the surface of the plated steel sheet, and wash the coated steel sheet with water. It was dried at 100 ° C. As a result, chromate treatment (formation of a chemical conversion treatment film) was performed with an adhesion amount of 30 mg / m ^{2 in terms of total chromium.}

1-3. Formation of Undercoat Coating Next, an epoxy resin-based undercoat coating having the following composition is applied to the chromate-treated surface of the plated steel sheet, and then heated so that the ultimate temperature of the plated steel sheet reaches 200 ° C., and the dry film thickness is 5 μm. A coating original plate 1 having an undercoat coating film was obtained.
Phosphate mixture (rust preventive pigment): average primary particle size 10 μm, 23% by mass (solid content)
Barium sulfate (constituent pigment): average primary particle size 1 μm, 15% by mass (solid content)
Silica (constituent pigment): Average primary particle size 4 μm, 1% by mass (solid content)
Epoxy resin base paint: 60% by mass (solid content)

(Preparation of painted original plate 2)
On the surface of the undercoat coating of the original coating plate 1, a commercially available polyester-based clear paint, "CA clear" (a paint containing a curable polyester resin and a curing agent) manufactured by Nippon Fine Coatings Co., Ltd., and carbon black as a coloring pigment After applying a coating material containing 10% by mass (7% by volume) of the above, the plated steel sheet was heated so as to reach 220 ° C. to form a topcoat coating film having a dry film thickness of 15 μm. As a result, a coating original plate 2 having a metal plate, an undercoat coating film, and a topcoat coating film was obtained.

(Preparation of painted original plate 3)
A welded 55% Al—Zn alloy plated steel sheet (plate thickness 0.35 mm, double-sided adhesion amount 150 g / m ² ) was alkaline degreased and used as a coating original plate 3.

(Preparation of painted original plate 4)
Simulating Example 1 of Patent Document 3, an ink raw material (manufactured by Tokyo Ink Co., Ltd., trade name: LG-HT liquor) containing 10 parts by mass of an unevenness-imparting agent having an average particle diameter of 15 μm with respect to 100 parts by mass of the resin composition. B) 10 parts by mass and 40 parts by mass of ethyl acetate were mixed to obtain an undercoat coating material.
This is applied to the chromate-treated surface of the plated steel sheet so that the film density in a dry state is 0.5 g / m ^2, and then heated so that the ultimate temperature of the plated steel sheet is 200 ° C., and the undercoat is applied. A coated original plate 4 having a film was obtained.

2. Fabrication and evaluation of painted metal plates 2-1. Insect repellent paint material (curable polyester)
Curable polyester: Hydroxyl-containing polyester (weight average molecular weight 3000, hydroxyl value 37 mgKOH / g)

The weight average molecular weight and hydroxyl value of the curable polyester were measured by the following methods.

[Weight average molecular weight]
It was calculated based on the molecular weight of standard polystyrene from the chromatogram measured by the gel permeation chromatograph according to JIS K 0124-2011. The measurement conditions were as follows.
(Measurement condition)
Column type: TSKgel SuperHM-H (6.0 mm ID x 15 cm x 2)
Eluent: THF
Column temperature: 40 ° C
Detector: RI

[Hydroxy group value]
The hydroxyl value was measured according to JIS K 0070.

(Hardener)
Melamine compound (Simel 303 manufactured by Mitsui Cytec)

(Pigment particles)
Silica particles 1: Average primary particle diameter 1 nm, hydrophobic treatment: none Silica particles 2: average primary particle diameter 170 nm, hydrophobic treatment: yes Silica particles 3: average primary particle diameter 700 nm, hydrophobic treatment: none Silica particles 4: average Primary particle size 5000 nm, hydrophobic treatment: None Acrylic particles: Nippon Catalyst Co., Ltd. MX020W, average primary particle size 20 nm
Bengara (iron oxide particles): Ozeki BAYFERROX140M, average primary particle size 300 nm
Particles (matte): X-52-1621 (silicone resin powder) manufactured by Shin-Etsu Chemical Co., Ltd., average primary particle size 5 μm

(others)
Insect repellent: Permethrin (manufactured by Daiwa Chemical Industry Co., Ltd., vapor pressure at 25 ° C. 6.82 × ^10-7 kPa)

2-2. Preparation of insect repellent paint (curable resin composition) (preparation of insect repellent paints 1 to 24 and 26 to 45)
Insect repellent paints 1 to 24 and 26 to 45 are mixed with curable polyester resin, hardener, particles, and benzene, toluene, and xylene as solvents so that the composition in the paint is the composition shown in Table 1 or 2. Got

(Preparation of insect repellent paint 25)
An insect repellent paint 25 was obtained in the same manner as the insect repellent paint 1 except that the above insect repellent (permethrin) was further added so that the composition in the paint had the composition shown in Table 1.

2-3. Fabrication and evaluation of painted metal plates (fabrication of painted metal plates 1 to 24, 29 and 32 to 55)
The insect repellent paint shown in Table 1 or 2 was applied to the surface of the prepared coating original plate 1 and baked (cured) at an ultimate temperature of 230 ° C. for 50 seconds. As a result, the coated metal plates 1 to 24, 29 and 32 to 55 having the insect-proof coating film (coating film made of a cured product of the curable resin composition) having the thickness shown in Table 1 or 2 are formed on the surface of the coated original plate. Made.

(Manufacturing of painted metal plates 25 to 28)
Painted metal plates 25 to 28 were obtained in the same manner as the painted metal plates 1 or 7 except that the thickness of the insect repellent coating film was changed as shown in Table 1.

(Manufacturing of painted metal plates 30 and 31)
Painted metal plates 30 and 31 were obtained in the same manner as in the painted metal plate 1 except that the types of the painted original plates were changed as shown in Table 1.

(Manufacturing of painted metal plate 56)
The same as in Example 4 except that the insect repellent coating material 4 was applied onto the coating original plate 4 and the obtained undercoat coating film so that the amount of fine particles adhered in a dry state was 0.2 g / m ^2. , A painted metal plate 56 was obtained.

(evaluation)
The surface roughness Ra of the insect-proof coating film of the obtained coated metal plates 1 to 56, the average height Rzjis at ten points, the average length Rsm of the elements, and the sliding property of insects (sliding property of Formica japonica and jumping spider) are as follows. Evaluated by method.

(Surface roughness Ra, 10-point average height Rzjis, average element length Rsm)
The surface roughness Ra, the ten-point average height Rzjis, and the average length Rsm of the elements were measured as values at a measurement length of 50 μm in accordance with JIS B 0601-2001 (ISO 4287-1997).

(Sliding insects)
The obtained painted metal plate was cut into 100 mm squares and four sheets were laminated to prepare a square pillar. Ten insects were put in it, and they climbed up the inner wall surface of the square pillar and visually observed whether or not the insects could come out. Evaluation was performed on Formica japonica and jumping spider, respectively.

Then, it was evaluated according to the following criteria.
◎: No 10 animals can climb at all ○: 3-9 animals cannot climb at all △: 1 or 2 animals cannot be climbed, but others can be climbed ×: All 10 animals can be climbed without slipping ○ It was judged to be good.

The evaluation results of the coated metal plates 1 to 31 are shown in Table 1, and the evaluation results of the coated metal plates 32 to 56 are shown in Table 2.

As shown in Table 1, the coated metal plates 1-31 having Ra on the surface of the insect repellent coating film in the range of 0.04 to 0.20 μm are excellent in insect sliding property and sufficient insect repellent performance can be obtained. You can see that.

In particular, it can be seen that Ra and Rzjis can be appropriately increased by reducing the amount of the non-volatile component in the insect repellent paint (comparison between the coated metal plates 1 to 9 and 10 to 18).

On the other hand, as shown in Table 2, the coated metal plates 32 to 56 (comparative example) in which Ra on the surface of the insect repellent coating film is less than 0.04 μm or more than 0.20 μm have low insect sliding property. , It turns out that sufficient insect repellent performance cannot be obtained.

Since the insect repellent coating base material of the present invention has good insect repellent performance, it is suitable as, for example, various materials and building materials.

10 Insect repellent coating base material 20 base material 30 coating film (top coating coating film)
31 resin 32 particles

Claims (14)

An insect repellent coating base material having a base material and an insect repellent coating film arranged on the base material.
The insect repellent coating film contains a resin and particles having an average primary particle diameter of 1 to 700 nm, and the surface roughness Ra of the insect repellent coating film is 0.04 to 0.20 μm.
Insect repellent coating base material. The ten-point average height Rzjis of the surface of the insect repellent coating film is 0.10 to 0.80 μm.
The insect repellent coating base material according to claim 1. The average length Rsm of the surface elements of the insect repellent coating film is 5 to 18 μm.
The insect repellent coating base material according to claim 1 or 2. The particles are inorganic particles,
The insect repellent coating base material according to any one of claims 1 to 3. The inorganic particles are metal oxide particles.
The insect repellent coating base material according to claim 4. The content of the particles is 10 to 400% by mass with respect to the resin.
The insect repellent coating base material according to any one of claims 1 to 5. The insect repellent coating film is a cured product of a curable resin composition containing a curable resin, the particles, and a curing agent.
The insect repellent coating base material according to any one of claims 1 to 6. The curable resin is a curable polyester resin.
The insect repellent coating base material according to claim 7. The insect repellent coating further contains a pyrethroid compound.
The insect repellent coating base material according to any one of claims 1 to 8. The base material is a metal plate.
The insect repellent coating base material according to any one of claims 1 to 9. The insect repellent coating film is arranged on the outermost side of the insect repellent coating base material.
The insect repellent coating base material according to any one of claims 1 to 10. The insect repellent coating substrate according to any one of claims 1 to 11 is included.
Exterior building materials. A step of preparing a curable resin composition containing a curable resin, particles having an average primary particle diameter of 1 to 700 nm, and a curing agent, and having a non-volatile component content of 50% by mass or less.
It has a step of applying the curable resin composition to the surface of a base material and then curing it to form an insect repellent coating film.
A method for manufacturing an insect repellent coating base material. The content of the particles is 10 to 400% by mass with respect to the curable resin.
The method for producing an insect repellent coating base material according to claim 13.

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