Coating formation method and lamination body

Abstract

To provide a film formation method which coats a second coating material containing a specific polyol component (A) onto a first coating material containing a polyol component, a polyisocyanate component and a plasticizer, and forms a film.SOLUTION: A film formation method coats a first coating material and a second coating material, wherein the first coating material contains a plasticizer, the first coating material and the second coating material contain a polyol component (A) and a polyisocyanate component (B) as resin components, the second coating material contains a polyol component (A2) having a hydroxyl value larger than that of the polyol component (A1) of the first coating material, and the polyol component (A2) contains a polyol component having a hydroxyl value of 200 mgKOH / g or more.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a novel method for forming a coating. [Background technology]

[0002] Conventionally, surfaces of buildings, civil engineering structures, and the like have sometimes been coated with urethane resin coating materials containing plasticizers ("plasticizer-containing coating materials"). Such plasticizer-containing coating materials contain a polyol component, a polyisocyanate component, and a plasticizer. Furthermore, a coating material may be laminated onto the surface of the plasticizer-containing coating material for protection, design, or other purposes. However, the plasticizer may migrate into the coating material over time, and the adhesion of contaminants to the coating material surface may result in a decrease in aesthetics or adhesion.

[0003] In response to this, for example, Patent Document 1 proposes a non-migratory polymer plasticizer, which is described as not migrating to the surface due to its high molecular weight. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2001-226442 Summary of the Invention [Problem to be solved by the invention]

[0005] However, in general, low-molecular-weight plasticizers are widely used in plasticizer-containing coating materials, and there is a need to develop a coating formation method that can be applied to such plasticizer-containing coating materials. [Means for solving the problem]

[0006] In order to solve these problems, the present inventors discovered that by forming a coating by applying a second coating material containing a specific polyol component (A) to the surface of a first coating material containing a polyol component, a polyisocyanate component, and a plasticizer, it is possible to form a coating that is excellent in preventing plasticizer migration and has excellent adhesion, and this discovery led to the completion of the present invention.

[0007] That is, the present invention has the following features. 1. After the first coating material is applied and dried, the surface of the coating (first coating) A coating forming method for applying a second coating material, wherein the first coating material contains a plasticizer; The first and second coating materials each contain a polyol component (A) and a polyisocyanate component (B) as resin components, the second coating material contains a polyol component (A2) having a hydroxyl value greater than that of the polyol component (A1) of the first coating material, A method for forming a coating film, wherein the polyol component (A2) contains a polyol component having a hydroxyl value of 200 mgKOH / g or more. 2. The first coating material and the second coating material contain a polyether polyol (Ax) as the polyol component (A), 1. The method for forming a coating according to 1, wherein the second coating material contains a polyether polyol (Ax2) having a hydroxyl value greater than that of the polyether polyol (Ax1) of the first coating material. 3. The method for forming a coating according to 2., wherein the polyether polyol (Ax2) contains a polyether polyol having a hydroxyl value of 200 mgKOH / g or more. 4. First coating formed by the first coating material On the surface of A laminate having a second coating formed by a second coating material, the first coating material contains a plasticizer; The first and second coating materials each contain a polyol component (A) and a polyisocyanate component (B) as resin components, the second coating material contains a polyol component (A2) having a hydroxyl value greater than that of the polyol component (A1) of the first coating material, The laminate is characterized in that the polyol component (A2) contains a polyol component having a hydroxyl value of 200 mgKOH / g or more. [Effects of the Invention]

[0008] The present invention provides a coating formation method for applying a first coating material and a second coating material, wherein the first coating material contains a plasticizer, the first coating material and the second coating material contain a polyol component (A) and a polyisocyanate component (B) as resin components, and the second coating material contains a polyol component (A2) having a higher hydroxyl value than the polyol component (A1) of the first coating material, thereby enabling the formation of a coating that is excellent in preventing plasticizer migration and has excellent adhesion. DETAILED DESCRIPTION OF THE INVENTION

[0009] The present invention will be described in detail below based on embodiments thereof.

[0010] The present invention relates to a coating film formation method in which a first coating material and a second coating material are applied in that order. Both the first coating material and the second coating material in the present invention contain a polyol component (A) and a polyisocyanate component (B) as resin components. The second coating material contains a polyol component (A2) having a higher hydroxyl value than the polyol component (A1) of the first coating material. First, common features of the first coating material and the second coating material (hereinafter, both will be collectively referred to simply as "coating materials") will be described.

[0011] The coating material of the present invention contains a polyol component (A) and a polyisocyanate component (B), and forms a coating film by reaction between them.

[0012] Examples of the polyol component (A) (hereinafter also referred to as "component (A)") of the present invention include polyether polyols, polyester polyols, castor oil, castor oil-modified polyols, epoxy-modified polyols, silicone-modified polyols, fluorine-modified polyols, acrylic polyols, polycarbonate polyols, polylactone polyols, polybutadiene polyols, and polypentadiene polyols. The coating material of the present invention preferably contains one or more polyols selected from polyether polyols and acrylic polyols. These polyols are preferably liquid at 20°C and can be used in the form of solvent-soluble or nonaqueous dispersion (NAD) types.

[0013] The polyether polyol (Ax) (hereinafter also referred to as "component (Ax)") is obtained by addition polymerization of a polyhydric alcohol, such as trimethylolpropane, glycerin, hexanetriol, a pentaerythritol derivative, sorbitol, or neopentyl glycol, with an alkylene oxide, such as ethylene oxide or propylene oxide. In the present invention, polymers obtained by addition polymerization of the above-mentioned polyhydric alcohol with ethylene oxide and / or propylene oxide are preferred, and those with ethylene oxide and / or propylene oxide attached to the terminals can also be used. Furthermore, in the present invention, the component (Ax) preferably contains a polyether polyol having three or more functional groups (hydroxyl groups) having active hydrogen atoms (functional number of three or more). In this case, the crosslinking density of the formed coating can be increased, and the effects of the present invention can be fully exerted.

[0014] The acrylic polyol (Ay) (hereinafter also referred to as "component (Ay)") contains, as constituent components, an alkyl (meth)acrylate ester, a hydroxyl group-containing monomer, and, if necessary, other monomers, and a polymer of these can be used. The alkyl (meth)acrylate ester is a compound having a (meth)acryloyl group and an alkyl group. In the present invention, the alkyl acrylate ester and the alkyl methacrylate ester are collectively referred to as alkyl (meth)acrylate ester. The monomer is a general term for a compound having a polymerizable unsaturated double bond.

[0015] Examples of such alkyl (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, n-pentyl (meth)acrylate, isopentyl (meth)acrylate, neopentyl (meth)acrylate, t-pentyl (meth)acrylate, 1-ethylpropyl (meth)acrylate, 2-methylbutyl (meth)acrylate, and 2-methylbutyl (meth)acrylate. Examples include 3-methylbutyl acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylbutyl (meth)acrylate, 2-methylpentyl (meth)acrylate, 4-methylpentyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-nonyl (meth)acrylate, n-decyl (meth)acrylate, n-undecyl (meth)acrylate, n-lauryl (meth)acrylate, etc. These can be used alone or in combination of two or more.

[0016] Examples of the hydroxyl group-containing monomer include (meth)acrylic acid hydroxyalkyl esters such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate, which can be used alone or in combination of two or more.

[0017] Examples of the other monomers include aromatic monomers, carboxyl group-containing monomers, amino group-containing monomers, pyridine-based monomers, nitrile group-containing monomers, amide group-containing monomers, epoxy group-containing monomers, carbonyl group-containing monomers, alkoxysilyl group-containing monomers, fluorine-containing monomers, ultraviolet absorbing group-containing monomers, photostable group-containing monomers, etc. These can be used alone or in combination of two or more.

[0018] Furthermore, in the present invention, a polyester-containing acrylic polyol containing an acrylic polyol and a polyester can also be used as component (Ay). The polyester-containing acrylic polyol can be obtained, for example, by reacting a polyester resin having a polymerizable unsaturated group with a (meth)acrylic acid alkyl ester, a hydroxyl group-containing monomer, and, if necessary, other polymerizable monomers.

[0019] A polyester resin having a polymerizable unsaturated group can be obtained by using a polybasic acid and / or a polyhydric alcohol having a polymerizable unsaturated group as part of the polybasic acid and / or polyhydric alcohol used to obtain a polyester resin through a condensation reaction of the polybasic acid and the polyhydric alcohol. Alternatively, a polyester resin having a polymerizable unsaturated group can be obtained by reacting a polyester resin with a monomer capable of reacting with a hydroxyl group or a carboxyl group in the polyester resin, specifically maleic acid, (meth)acrylic acid, glycidyl (meth)acrylate, or the like.

[0020] The hydroxyl value of the above component (A) is preferably 1 to 1000 mgKOH / g (more preferably 3 to 900 mgKOH / g). By including such a component (A), the effects of the present invention can be fully exerted. The hydroxyl value referred to here is a value expressed in mg of potassium hydroxide equivalent to the moles of hydroxyl groups contained in 1 g of solid content (KOH mg / g). In the present invention, "α to β" is synonymous with "α or more and β or less."

[0021] The polyisocyanate component (B) (hereinafter also referred to as "component (B)") in the coating material of the present invention is a component that undergoes a curing reaction with the component (A). In the present invention, this curing reaction exhibits sufficient effects in terms of adhesion, prevention of plasticizer migration, etc.

[0022] Examples of component (B) include toluene diisocyanate (TDI), 4,4-diphenylmethane diisocyanate (pure-MDI), polymeric MDI, xylylene diisocyanate (XDI), hexamethylene diisocyanate (HMDI), isophorone diisocyanate (IPDI), hydrogenated XDI, hydrogenated MDI, and the like, as well as derivatives thereof which have been allophanated, biurated, dimerized (uretidione), trimerized (isocyanurated), adducted, or carbodiimided; and blocked isocyanates obtained by blocking these with alcohols, phenols, ε-caprolactam, oximes, active methylene compounds, or the like, and one or more selected from these may be used.

[0023] In the present invention, the component (B) preferably contains hexamethylene diisocyanate (HMDI) and / or its derivatives (hereinafter also referred to as "HMDIs"). The content of the HMDIs is preferably 90% by weight or more (more preferably 95% by weight or more) of the total amount (solid content) of the component (B). An embodiment in which the component (B) consists solely of HMDIs is also suitable. Furthermore, a biuret derivative is suitable as the derivative. In this case, the formed coating has excellent curing properties and can have improved adhesion, plasticizer migration resistance, etc.

[0024] The NCO content of component (B) is preferably 10 to 35% by weight (more preferably 13 to 32% by weight, and even more preferably 15 to 30% by weight). In such a case, adhesion can be improved. The NCO content refers to the weight percentage of NCO contained in component (B).

[0025] The components (A) and (B) are mixed in such a ratio that the NCO / OH equivalent ratio of the components (A) and (B) is preferably 0.6 to 3.5 (more preferably 1 to 3.0, and even more preferably 1.1 to 2.5). In such a case, the curability is excellent and the effects of the present invention can be fully exhibited.

[0026] In the present invention, a curing catalyst that promotes the reaction between component (A) and component (B) can be used in combination. A curing catalyst is a substance that promotes the reaction and curing of isocyanate groups. Examples of curing catalysts include amine catalysts, organometallic catalysts, and inorganic catalysts. Examples of amine catalysts include ethylenediamine, triethylenediamine, triethylamine, ethanolamine, diethanolamine, and hexamethylenediamine, or derivatives thereof, or mixtures thereof with solvents. Examples of organometallic catalysts include organometallic compounds such as dibutyltin dilaurate and dibutyltin diacetate; and organometallic salts such as potassium acetate, zinc stearate, calcium stearate, lead stearate, aluminum stearate, and tin octoate. Examples of inorganic catalysts include tin chloride. These catalysts can be used alone or in combination, or they can be mixed with a solvent. In the present invention, it is particularly preferable to include an organometallic catalyst. In this case, curing is accelerated and sufficient effects are exhibited from the initial stage of film formation in terms of adhesion, prevention of plasticizer migration, etc.

[0027] In addition to the components described above, the coating material of the present invention can also contain various other components within the range that does not significantly impair the effects of the present invention. Such components include, for example, color pigments, extender pigments, flame retardants, foaming agents, carbonizing agents, thickeners, plasticizers, preservatives, antifungal agents, anti-algae agents, defoaming agents, leveling agents, pigment dispersants, anti-skinning agents, driers, matting agents, UV absorbers, light stabilizers, antioxidants, stain-reducing agents, and catalysts.

[0028] In the present invention, a coating film is formed by applying (painting) such coating materials (first coating material and second coating material) to a substrate. In the present invention, it is desirable to apply the first coating material to the substrate, allow the coating (first coating) to dry, and then apply the second coating material. The substrate constitutes the surface of a building, civil engineering structure, etc. Specifically, the present invention can be applied to various substrates such as walls, pillars, floors, beams, roofs, stairs, ceilings, and doors. Examples of applicable substrates include concrete, mortar, siding board, extruded board, gypsum board, perlite board, brick, plastic, wood, metal, steel frame (steel), glass, and porcelain tile. These substrates may already have a coating formed on their surface, may have undergone some kind of surface treatment (rust prevention treatment, flame retardant treatment, etc.), or may have wallpaper attached.

[0029] The second coating material can be applied directly to the first coating film, or via some other layer (e.g., a primer layer, an intermediate coating layer, etc.). In the present invention, it is preferable to apply it directly to the first coating film. This allows for sufficient effects in terms of preventing plasticizer migration and adhesion. Such a second coating material is effective as a coating material for preventing plasticizer migration.

[0030] Next, the characteristics of the first and second coating materials will be explained. The first and second coating materials each contain the polyol component (A) as a resin component. Furthermore, the present invention is characterized in that the second coating material contains a polyol (A2) having a higher hydroxyl value than the polyol component (A1) of the first coating material. That is, the first coating material contains a polyol component (A1) with a relatively low hydroxyl value, and the second coating material contains a polyol component (A2) with a relatively high hydroxyl value. By using the first and second coating materials of this type in the present invention, excellent plasticizer migration prevention properties and sufficient adhesion can be achieved.

[0031] In the present invention, the difference in hydroxyl value between the polyol component (A1) and the polyol component (A2) is preferably 5 mgKOH / g or more (more preferably 10 mgKOH / g or more, even more preferably 50 mgKOH / g or more, particularly preferably 100 mgKOH / g or more, and most preferably 150 mgKOH / g or more). In such a case, excellent plasticizer migration prevention properties can be exhibited. Specifically, the hydroxyl value of the polyol component (A1) is preferably 1 to 200 mgKOH / g (more preferably 3 to 150 mgKOH / g). The hydroxyl value of the polyol component (A2) is preferably 30 to 1,000 mgKOH / g (more preferably 35 to 900 mgKOH / g). When either or both of the first coating material and the second coating material contain multiple polyol components, it is sufficient that at least one polyol component (A1) of the first coating material and at least one polyol component (A2) of the second coating material satisfy the above conditions.

[0032] The first and second coating materials preferably contain a polyether polyol (Ax) as the polyol component (A), and the second coating material preferably contains a polyether polyol (Ax2) having a hydroxyl value greater than that of the polyether polyol (Ax1) of the first coating material. Specifically, the hydroxyl value of the polyether polyol component (Ax1) contained in the first coating material is preferably 1 to 200 mgKOH / g (more preferably 3 to 180 mgKOH / g, even more preferably 5 to 150 mgKOH / g, particularly preferably 8 to 100 mgKOH / g, and most preferably 10 to 35 mgKOH / g). The hydroxyl value of the polyether polyol (Ax2) contained in the second coating material is preferably 50 mgKOH / g or greater (more preferably 100 mgKOH / g or greater, even more preferably 150 mgKOH / g or greater, particularly preferably 200 mgKOH / g or greater, and most preferably 250 mgKOH / g or greater). The upper limit is not particularly limited, but is preferably 1000 mg KOH / g or less (more preferably 800 mg KOH / g or less), in which case the effects of the present invention can be further enhanced.

[0033] Furthermore, it is preferable that the second coating material contains a polyether polyol (Ax2) having a lower molecular weight than the polyether polyol (Ax1) of the first coating material. That is, it is preferable that the first coating material contains a polyether polyol (Ax1) having a relatively high molecular weight, and the second coating material contains a polyether polyol (Ax2) having a relatively low molecular weight. This can further improve the resistance to plasticizer migration and adhesion.

[0034] The difference in molecular weight between the polyether polyol (Ax1) and the polyether polyol (Ax2) is preferably 2,000 or more (more preferably 3,000 or more, even more preferably 4,000 or more, particularly preferably 6,000 or more, and most preferably 6,500 or more). In such a case, excellent plasticizer migration prevention properties can be exhibited. Specifically, the molecular weight of the polyether polyol (Ax1) is preferably 1,000 or more (more preferably 3,000 or more, even more preferably 5,000 or more, particularly preferably 6,000 or more, and most preferably 6,500 or more), and the upper limit is preferably 18,000 or less (more preferably 15,000 or less, and even more preferably 12,000 or less). The molecular weight of the polyether polyol (Ax2) is preferably 4,000 or less (more preferably 2,000 or less, even more preferably 1,000 or less, particularly preferably 900 or less, and most preferably 600 or less), and the lower limit is preferably 50 or more (more preferably 100 or more, and even more preferably 150 or more). The use of such a component (Ax2) can enhance the plasticizer migration prevention property. Note that, in the present invention, the molecular weight of the polyol component is a number average molecular weight (Mn), which is a so-called polystyrene-equivalent molecular weight determined by gel permeation chromatography using a polystyrene polymer as a reference.

[0035] When either or both of the first coating material and the second coating material contain multiple polyether polyols (Ax), it is sufficient that at least one polyether polyol component (Ax1) of the first coating material and at least one polyether polyol component (Ax2) of the second coating material satisfy the above-mentioned conditions. It is more preferable that all polyether polyols (Ax2) of the second coating material satisfy the above-mentioned conditions for all polyether polyols (Ax1) of the first coating material.

[0036] In the first coating material, the solid content of the polyether polyol (Ax1) in the solid content of the component (A1) is preferably 50% by weight or more (more preferably 80% by weight or more, and even more preferably 90% by weight or more). There is no particular upper limit, and the component (A1) may consist solely of the polyether polyol (Ax1). In such a case, the effects of the present invention can be fully achieved.

[0037] On the other hand, the second coating material preferably further contains an acrylic polyol (Ay2) as the polyol component (A2). In this case, the hydroxyl value of the acrylic polyol (Ay2) is preferably 1 to 200 KOHmg / g (more preferably 3 to 100 KOHmg / g, and even more preferably 5 to 80 KOHmg / g). If the hydroxyl value of the acrylic polyol (Ay2) is within this range, it has excellent plasticizer migration prevention properties and is advantageous in terms of improving adhesion. Furthermore, the weight ratio (solid content) of the polyether polyol (Ax2) to the acrylic polyol (Ay2) is preferably 90:10 to 10:90 (more preferably 80:20 to 20:80, and even more preferably 70:30 to 50:50). In such a case, it has excellent plasticizer migration prevention properties and is advantageous in terms of improving adhesion.

[0038] In the present invention, the solid content (total) of the polyether polyol (Ax2) and the acrylic polyol (Ay2) in the solid content of the component (A2) is preferably 50% by weight or more (more preferably 80% by weight or more, and even more preferably 90% by weight or more). There is no particular upper limit, and the component (A2) may consist only of the polyether polyol (Ax2) and the acrylic polyol (Ay2). In such a case, the effects of the present invention can be fully exerted.

[0039] The first coating material of the present invention contains a plasticizer as an essential component in addition to the resin component. Such a first coating material is not particularly limited as long as it is a material containing a plasticizer in the resin component, but examples thereof include coating materials, sheets, sealants, plastisols, etc., which may have various functionalities (e.g., waterproofness, flame retardancy, heat resistance, etc.).

[0040] The plasticizer is not particularly limited, and examples thereof include phthalate ester compounds such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diheptyl phthalate, dihexyl phthalate, di-2-ethylhexyl phthalate, dioctyl phthalate, diisononyl phthalate, diisodecyl phthalate, diundecyl phthalate, and butyl benzyl phthalate; diethyl adipate, dibutyl adipate, diisobutyl adipate, dihexyl adipate, di-2-ethylhexyl adipate, dioctyl adipate, diisononyl adipate, and diisodecyl adipate; Aliphatic dibasic acid ester compounds such as bis(butyl diglycol adipate), diethyl sebacate, dibutyl sebacate, dihexyl sebacate, and di-2-ethylhexyl sebacate; adipic acid polyester compounds such as 1,3 butylene glycol adipate polyester and 1,2 propylene glycol adipate polyester; maleic acid ester compounds such as dimethyl maleate, diethyl maleate, dibutyl maleate, dihexyl maleate, di-2-ethylhexyl maleate, diisononyl maleate, and diisodecyl maleate;

[0041] Examples of suitable esters include phosphate compounds such as triethyl phosphate, tributyl phosphate, tri-2-ethylhexyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, and 2-ethylhexyl diphenyl phosphate; trimellitic acid ester compounds such as tris-2-ethylhexyl trimellitate; ricinoleic acid ester compounds such as methyl acetyl risinoleate; epoxy ester compounds such as di-2-ethylhexyl epoxyhexahydrophthalate, diepoxystearyl epoxyhexahydrophthalate, epoxidized fatty acid butyl, epoxidized fatty acid 2-ethylhexyl, epoxidized soybean oil, and epoxidized linseed oil; benzoic acid ester compounds such as benzoic acid glycol ester; chlorinated paraffins; aromatic hydrocarbon compounds such as 1-phenyl-1-xylylethane and 1-phenyl-1-ethylphenylethane; lactones such as γ-butyrolactone; and mixtures of petroleum resins (polymers of aromatic hydrocarbon fractions having 8 to 10 carbon atoms) and styrylxylene. These may be used alone or in combination.

[0042] In the present invention, it is preferable that the first coating material contains one or more compounds selected from the group consisting of phthalate ester compounds, aliphatic dibasic acid ester compounds, phosphate ester compounds, and chlorinated paraffins. In this case, the effects of the present invention can be fully achieved. Furthermore, in the present invention, even if the first coating material contains a relatively low-molecular-weight plasticizer with a molecular weight of 1,000 or less (preferably 100 to 800), the effects of the present invention can be fully achieved. Note that the molecular weight of the plasticizer is a value calculated from the molecular formula.

[0043] The content of the plasticizer in the first coating material is preferably 5 to 200 parts by weight (more preferably 10 to 150 parts by weight) relative to 100 parts by weight of the total solid content of the polyol component (A1) and the polyisocyanate component (B1) (hereinafter also referred to as "resin component (solid content)"). Thus, even when a relatively large amount of plasticizer is contained, sufficient effects can be obtained in terms of plasticizer migration prevention and adhesion in the coating formation method of the present invention.

[0044] Furthermore, the first coating material may contain functional powders for imparting various functions. Examples of functional powders that can be used include powders that exhibit desired functions, such as heat insulation powders, heat resistance powders, ultraviolet shielding powders, and infrared shielding powders. By including such functional powders, desired performance can be imparted to the coating. Examples of such functional powders include heat insulation powders, heat resistance powders, and ultraviolet shielding powders. These powders can be used alone or in combination of two or more.

[0045] The first coating material of the present invention preferably contains a heat-resistance imparting powder as the functionality imparting powder. Such a first coating material is suitable as an intumescent fire-resistant coating material applied to the surface coating of structures such as buildings and civil engineering structures. The heat-resistance imparting powder may be any powder that exhibits at least one of the following effects at high temperatures: dehydration and cooling effect, non-flammable gas generation effect, binder carbonization promotion effect, carbonized heat insulation layer formation effect, and the like, and has a combustion-suppressing effect. Examples of the heat-resistance imparting powder include a foaming agent, a carbonizing agent, and a flame retardant.

[0046] Specific examples of foaming agents include melamine and its derivatives, dicyandiamide and its derivatives, azobistetrazole and its derivatives, azodicarbonamide, urea, and thiourea. These can be used alone or in combination of two or more. The content of the foaming agent is preferably 10 to 200 parts by weight (more preferably 20 to 150 parts by weight) per 100 parts by weight of the resin component (solid content). The foaming agent of the present invention imparts a foaming action to the coating due to a temperature rise such as during a fire, and specifically, imparts a foaming action when the temperature of the coating surface preferably reaches 200°C or higher.

[0047] Examples of carbonizing agents include pentaerythritol, dipentaerythritol, trimethylolpropane, starch, and casein. These can be used alone or in combination of two or more. In the present invention, pentaerythritol and dipentaerythritol are particularly preferred because they have excellent dehydration and cooling effects and the ability to form a carbonized heat insulating layer. The content of the carbonizing agent is preferably 10 to 200 parts by weight (more preferably 20 to 120 parts by weight) per 100 parts by weight of the resin component (solid content). The carbonizing agent of the present invention imparts the ability to form a carbonized heat insulating layer by dehydrating and carbonizing the resin component when the temperature rises during a fire, etc.

[0048] Examples of flame retardants include organic phosphorus compounds such as tricresyl phosphate and diphenyl cresyl phosphate; chlorine compounds such as chlorinated polyphenyl ether, chlorinated polyethylene, diphenyl chloride, triphenyl chloride, chlorinated paraffin, pentachlorinated fatty acid esters, perchloropentacyclodecane, chlorinated naphthalene, and tetrachlorophthalic anhydride; antimony compounds such as antimony trioxide and antimony pentachloride; phosphorus compounds such as phosphorus trichloride, phosphorus pentachloride, ammonium phosphate, ammonium polyphosphate, melamine phosphate, melam polyphosphate, boron phosphate, boron polyphosphate, aluminum phosphate, and aluminum polyphosphate; and inorganic compounds such as zinc borate and sodium borate. These compounds can be used alone or in combination. The content of the flame retardant is preferably 100 to 1,000 parts by weight (more preferably 200 to 800 parts by weight) per 100 parts by weight of the resin component (solid content).

[0049] The first coating material may further contain fillers, fibers, etc. Examples of fillers include talc, calcium carbonate, sodium carbonate, aluminum oxide (alumina), titanium oxide, zinc oxide, silica, clay, shirasu, mica, silica sand, silica stone powder, quartz powder, barium sulfate, aluminum hydroxide, magnesium hydroxide, etc. These may be used alone or in combination of two or more. Examples of fibers include organic fibers such as acrylic fiber, acetate fiber, aramid fiber, cuprammonium fiber (cupra), nylon fiber, novoloid fiber, pulp fiber, viscose rayon, vinylidene fiber, polyester fiber, polyethylene fiber, polyvinyl chloride fiber, polychlor fiber, boronosic fiber, polypropylene fiber, and cellulose fiber; and inorganic fibers such as carbon fiber, rock wool fiber, glass fiber, silica fiber, alumina fiber, silica-alumina fiber, slag wool fiber, ceramic fiber, carbon fiber, and silicon carbide fiber. These may be used alone or in combination of two or more.

[0050] The second coating material of the present invention preferably contains, in addition to the resin component, a powder component such as a color pigment or an extender pigment. This increases the cohesive force during coating formation, and provides better effects in terms of adhesion, etc. To achieve such effects, a desirable embodiment contains 1 to 200 parts by weight (preferably 5 to 150 parts by weight) of the powder component per 100 parts by weight of the total solids content of the polyol component (A2) and the polyisocyanate component (B2). Examples of color pigments include titanium oxide, zinc oxide, carbon black, graphite, black iron oxide, iron-manganese composite oxide, iron-copper-manganese composite oxide, iron-chromium composite oxide, iron-chromium-cobalt composite oxide, copper-chromium composite oxide, copper-manganese-chromium composite oxide, copper-magnesium composite oxide, bismuth-manganese composite oxide, red iron oxide, molybdate orange, permanent red, permanent carmine, anthraquinone red, perylene red, quinacridone red, yellow iron oxide, titanium yellow, fast yellow, benzimidazolone yellow, chrome green, cobalt green, phthalocyanine green, ultramarine blue, Prussian blue, cobalt blue, phthalocyanine blue, quinacridone violet, dioxazine violet, aluminum pigments, and pearl pigments. These can be used alone or in combination. Examples of extender pigments include heavy calcium carbonate, clay, kaolin, talc, precipitated barium sulfate, barium carbonate, white carbon, and diatomaceous earth.

[0051] The coating material of the present invention can be applied by mixing a base agent containing a polyol component (A) and a curing agent containing a polyisocyanate component (B) immediately before application. The solvent can be contained in either the base agent or the curing agent, or both. Furthermore, in the present invention, a solvent can be mixed as a diluent during application, separate from the base agent and the curing agent. In particular, the solvent content of the second coating material is preferably 5 to 500 parts by weight (preferably 10 to 400 parts by weight, more preferably 20 to 300 parts by weight) per 100 parts by weight of the total solids content of components (A) and (B). A solvent content within this range is advantageous in terms of preventing plasticizer migration and the finish quality of the topcoat material. In particular, the solids content of the coating material of the present invention after dilution is preferably 25 to 90% by weight (more preferably 30 to 85% by weight). Within this range, the above-mentioned effects can be further enhanced.

[0052] The coating material of the present invention can be applied using various methods, such as brush coating, roller coating, and spray coating. The amount of coating and the number of coats of the first coating material when applied may be determined according to the functionality of the various coating materials. The amount of coating of the first coating material when applied is preferably 0.5 to 5.0 kg / m 2 (More preferably 0.8 to 3.0 kg / m 2 The first coating material is preferably applied once or twice. On the other hand, the amount of the second coating material applied is preferably 30 to 500 g / m 2 (More preferably 50 to 300 g / m 2 The number of coats of the second coating material may be determined appropriately depending on the surface condition of the coating film formed by the first coating material, but is preferably 1 to 2 coats. Note that the coating material of the present invention can sufficiently prevent plasticizer migration even when coated once.

[0053] In the present invention, in order to protect the coating film formed by the above-mentioned coating materials (first coating material and second coating material), a topcoat material can also be applied as necessary. Such topcoat materials can be formed by applying known topcoat materials. As topcoat materials, for example, any of clear type or colored type, glossy type or matte type, hard type or elastic type, thin film type or thick film type, etc. can be used. In addition, either water-based or solvent-based may be used, and can be appropriately selected according to the desired purpose.

[0054] The topcoat material of the present invention preferably contains a resin component. Examples of such resin forms include solvent-soluble resins, non-aqueous dispersion resins, solventless resins, water-dispersed resins, and water-soluble resins. Examples of resin types include acrylic resins, urethane resins, epoxy resins, vinyl chloride resins, vinyl acetate resins, acrylic silicone resins, fluororesins, silicon resins, polyvinyl alcohol, cellulose derivatives, and the like, as well as composites thereof. These can be used in one or more types. In the present invention, it is particularly preferable to include one or more types selected from urethane resins, epoxy resins, acrylic resins, acrylic silicone resins, and fluororesins.

[0055] Furthermore, the resin component may be crosslinkable. When the resin component is a crosslinkable resin, the water resistance, durability, and adhesion of the formed coating are enhanced, and swelling and peeling of the coating due to rainfall, condensation, etc. can be suppressed. Furthermore, when the first coating material contains a functional powder, various functionalities (e.g., heat resistance) can be stably maintained. Such a crosslinkable resin may either undergo a crosslinking reaction by itself or undergo a crosslinking reaction when a crosslinking agent is added separately. Such crosslinking reactivity can be imparted by combining reactive functional groups, such as a hydroxyl group and an isocyanate group, a carbonyl group and a hydrazide group, an epoxy group and an amino group, an aldo group and a semicarbazide group, a keto group and a semicarbazide group, two alkoxyl groups, a carboxyl group and a metal ion, a carboxyl group and a carbodiimide group, a carboxyl group and an epoxy group, a carboxyl group and an aziridine group, or a carboxyl group and an oxazoline group. Among these, it is preferable to contain a crosslinking reactive resin that causes a crosslinking reaction between one or more groups selected from the group consisting of a hydroxyl group and an isocyanate group, a carbonyl group and a hydrazide group, and an epoxy group and an amino group.

[0056] As components other than the resin component of the above-mentioned topcoat material, for example, color pigments, extender pigments, aggregates, etc. can be mixed. By appropriately blending such components, it is possible to express the desired color and texture. The amount of color pigments, extender pigments, aggregates, etc. mixed is not particularly limited as long as it does not hinder the effect of the above-mentioned coating material, but is preferably 1 to 2000 parts by weight (more preferably 5 to 1000 parts by weight) per 100 parts by weight of the solid content of the resin component.

[0057] In the present invention, it is particularly preferable to use pigments that are infrared reflective and / or infrared transparent as the color pigments and extender pigments, as this can further enhance the durability of the formed coating.

[0058] Examples of pigments having infrared reflectivity include aluminum flakes, titanium oxide, barium sulfate, zinc oxide, iron oxide, calcium carbonate, silicon oxide, magnesium oxide, zirconium oxide, yttrium oxide, indium oxide, alumina, iron-chromium composite oxide, manganese-bismuth composite oxide, manganese-yttrium composite oxide, black iron oxide, iron-manganese composite oxide, iron-copper-manganese composite oxide, iron-chromium-cobalt composite oxide, copper-chromium composite oxide, and copper-manganese-chromium composite oxide, and one or more of these can be used.

[0059] Examples of pigments having infrared transparency include perylene pigments, azo pigments, yellow lead, titanium red, cadmium red, quinacridone red, isoindolinone, benzimidazolone, phthalocyanine green, phthalocyanine blue, cobalt blue, indanthrene blue, ultramarine, and iron blue, and one or more of these can be used.

[0060] Furthermore, the topcoat material can also be blended with various additives that can be used in regular paints. Such additives include, for example, thickeners, film-forming aids, leveling agents, wetting agents, plasticizers, antifreeze agents, pH adjusters, preservatives, antifungal agents, anti-algae agents, antibacterial agents, dispersants, antifoaming agents, adsorbents, UV absorbers, light stabilizers, antioxidants, fibers, anti-fouling agents, hydrophilizing agents, water repellents, coupling agents, catalysts, etc.

[0061] The topcoat material can be applied by any known application method, for example, by brush coating, roller coating, spray coating, etc. The amount of coating is preferably 30 to 5000 g / m 2 (More preferably 50 to 3000 g / m 2 The number of times the topcoat material is applied can be set appropriately, but is preferably 1 to 2 times. In addition, drying can be preferably performed at room temperature.

[0062] According to the present invention, a laminate having a first coating formed from the first coating material and a second coating formed from the second coating material can be obtained. The laminate of the present invention has excellent plasticizer migration prevention properties and can exhibit excellent adhesion. Furthermore, by having a top coat layer formed from a top coat material on the second coating, the laminate of the present invention has excellent plasticizer migration prevention properties, excellent adhesion, and improved aesthetics and weather resistance. [Example]

[0063] The following examples will clarify the features of the present invention, but the present invention is not limited to these examples.

[0064] <Coating material> (Main ingredient 1-15) According to the formulation shown in Table 1, component (A), color pigment, curing catalyst, and additives were mixed in a conventional manner to prepare a base resin. The following raw materials were used:

[0065] Polyol (A) Polyether polyol (Ax) (Ax-1) Polyether polyol (hydroxyl value 17 mg KOH / g, functionality 3, number average molecular weight 10,000, solid content 100% by weight) (Ax-2) Polyether polyol (hydroxyl value 24 mg KOH / g, functionality 3, number average molecular weight 7000, solid content 100% by weight) (Ax-3) Polyether polyol (hydroxyl value 55 mg KOH / g, functionality 3, number average molecular weight 3000, solid content 100% by weight) (Ax-4) Polyether polyol (hydroxyl value 160 mg KOH / g, functionality 3, number average molecular weight 1000, solid content 100% by weight) (Ax-5) Polyether polyol (hydroxyl value 230 mg KOH / g, functionality 3, number average molecular weight 700, solid content 100% by weight) (Ax-6) Polyether polyol (hydroxyl value 400 mg KOH / g, functionality 3, number average molecular weight 400, solid content 100% by weight) Acrylic polyol (Ay) (Ay-1) Acrylic polyol (hydroxyl value 40 KOH mg / g, solid content 50 wt%, medium: aromatic hydrocarbon compound, ester compound) (Ay-2) Polyester-containing acrylic polyol (hydroxyl value 40 KOH mg / g, polyester ratio 10 wt%, solid content 50 wt%, medium: aromatic hydrocarbon compound, ester compound) The component (A) is a liquid at 20°C.

[0066] Plasticizer 1: Diisononyl phthalate (molecular weight 419) Plasticizer 2: Diisononyl adipate (molecular weight 399) Functional powders: flame retardants, foaming agents, carbonizing agents, etc. Color pigment: titanium dioxide, average particle size 0.3 μm ·Curing catalyst: Organometallic catalyst Additives 1: Dispersants, antifoaming agents, etc. Additive 2: Dilution solvent (aromatic hydrocarbon)

[0067] (Hardening agent 1) A curing agent was prepared by mixing 80 parts by weight of polyisocyanate (B) (biuret type hexamethylene diisocyanate, NCO content 23.5%) and 20 parts by weight of a dilution solvent (aromatic hydrocarbon).

[0068] (Preparation of coating material) The base materials 1 to 15 shown in Table 1 and the curing agent were mixed so that the NCO / OH equivalent ratio of the polyol component and the polyisocyanate component was 1.2, to obtain coating materials 1 to 15.

[0069] [Table 1]

[0070] <Top coat material> The base material was prepared by uniformly mixing and stirring 100 parts by weight of acrylic polyol (hydroxyl value 20 KOH mg / g, solids content 50 wt%, medium: aliphatic hydrocarbon compound), 40 parts by weight of titanium dioxide, and 10 parts by weight of additives (thickener, defoamer) in the usual manner. Next, 50 parts by weight of polyisocyanate (adduct-type hexamethylene diisocyanate, NCO content 12%) and 50 parts by weight of dilution solvent (aliphatic hydrocarbon) were mixed to prepare the curing agent. The base material and curing agent were mixed so that the NCO / OH equivalent ratio of the polyol component and polyisocyanate component was 1.0, respectively, to prepare the topcoat material.

[0071] (Examples 1 to 12, Comparative Examples 1 to 3) The following evaluations were carried out for each coating material, and the results are shown in Table 2.

[0072] Preparation of test specimen [I] The first coating material was applied to a 150mm x 70mm steel plate at 1.5kg / m 2 The coating was then sprayed onto the surface at a rate of 100 g / m² and left to cure for 7 days. 2 The specimens were then brushed with 100% acrylic acid and left to cure for 24 hours to prepare specimen [I]. The combinations of the first and second coating materials are shown in Table 2. All painting and curing were carried out under standard conditions (temperature 23°C, relative humidity 50%). <Evaluation of plasticizer migration prevention> The prepared specimen [I] was left in an incubator at 50°C or 80°C for one week. The specimen was removed from the incubator, placed horizontally, and black silica sand was sprinkled on it. The specimen was then immediately stood upright and the black silica sand was allowed to fall naturally. The extent of the adhered black silica sand was visually confirmed to evaluate the plasticizer migration prevention properties. The evaluation was done on a four-point scale (A>B>C>D), with "A" being a rating for items with almost no black silica sand adhering and "D" being a rating for items with significant black silica sand adhering.

[0073] <Adhesion evaluation 1> The prepared specimen [I] was evaluated for adhesion to the surface of the plasticizer-containing material using the cross-cut tape method in accordance with JIS K 5600-5-6. The evaluation criteria were as follows: A: Defect area is less than 10% B: Defect area is 10% or more but less than 25% C: Defect area is 25% or more but less than 50% D: Defective area is 50% or more

[0074] [Table 2]

[0075] In Examples 1 to 12, good plasticizer migration prevention properties were obtained and coatings with good adhesion were formed. In particular, in Examples 6 to 11, excellent plasticizer migration prevention properties were exhibited, and furthermore, in Examples 5 to 11, coatings with excellent adhesion were formed.

[0076] Next, the following evaluations were carried out for Examples 6 to 11. The results are shown in Table 2. Preparation of test specimen [II] The first coating material was applied to a 150mm x 70mm steel plate at 1.5kg / m 2 The coating was then sprayed onto the surface at a rate of 100 g / m² and left to cure for 7 days. 2 The coating was then brushed on and left to cure for 24 hours. The combinations of the first and second coating materials are shown in Table 2. Next, apply the top coat at a rate of 0.3 kg / m 2 The test specimens were spray-painted with 100% fluorine and cured for 72 hours. All painting and curing were carried out under standard conditions (temperature 23°C, relative humidity 50%).

[0077] <Adhesion evaluation 2> The prepared specimen [II] was evaluated for adhesion to the coating material and topcoat material using the cross-cut tape method in accordance with JIS K 5600-5-6. The evaluation criteria were the same as those in Adhesion Evaluation 1 above.

[0078] <Heat resistance protection evaluation> The prepared specimen [II] was left in an incubator at 80°C for one week, and then the resulting specimen was subjected to radiant heat of 50 kW / m² on the surface of the specimen for 15 minutes using an electric heater (CONE III, manufactured by Toyo Seiki Co., Ltd.) according to ISO 5660-1 cone calorimeter method. The expansion ratio and the backside temperature of the steel plate were measured. The evaluation criteria were as follows. The results are shown in Table 2. (Expansion ratio) AA: Expansion ratio over 35 times A: Expansion ratio: over 25 times and up to 35 times B: Expansion ratio: 20 times or more and 25 times or less C: Foaming ratio more than 15 times and less than 20 times D: Foaming ratio 15 times or less (backside temperature) AA: below 430℃ A: 430℃ or higher and lower than 470℃ B: 470℃ or higher and less than 500℃ C: 500℃ or higher but lower than 550℃ D: 550℃ or more

[0079] In Examples 6 to 11, a carbonized heat insulating layer was formed with excellent foaming properties, and heat-resistant protection of the substrate was achieved.

Claims

1. A coating formation method comprising applying a first coating material and drying it, and then applying a second coating material to the surface of the coating (first coating), wherein the first coating material contains a plasticizer, The first coating material and the second coating material each contain a polyol component (A) and a polyisocyanate component (B) as resin components, the second coating material contains a polyol component (A2) having a hydroxyl value greater than that of the polyol component (A1) of the first coating material, The method for forming a coating film, wherein the polyol component (A2) contains a polyol component having a hydroxyl value of 200 mgKOH / g or more.

2. the first coating material and the second coating material each contain a polyether polyol (Ax) as the polyol component (A), 2. The coating method according to claim 1, wherein the second coating material contains a polyether polyol (Ax2) having a hydroxyl value greater than that of the polyether polyol (Ax1) of the first coating material.

3. 3. The method for forming a coating film according to claim 2, wherein the polyether polyol (Ax2) contains a polyether polyol having a hydroxyl value of 200 mg KOH / g or more.

4. A laminate having a second coating formed from a second coating material on a surface of a first coating formed from a first coating material, the first coating material contains a plasticizer, The first coating material and the second coating material each contain a polyol component (A) and a polyisocyanate component (B) as resin components, the second coating material contains a polyol component (A2) having a hydroxyl value greater than that of the polyol component (A1) of the first coating material, The laminate is characterized in that the polyol component (A2) contains a polyol component having a hydroxyl value of 200 mgKOH / g or more.

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