JP2010247069A - Coating method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a coating method suitable for the surface of a material containing a plasticizer, e.g. a sealing material. <P>SOLUTION: In the method of coating a surface part of a plasticizer-containing material or its vicinity with an aqueous primer, the aqueous primer is a two-part composition consisting of a main agent (I) and a polyisocyanate hardening agent (II), and the main agent (I) contains an acrylic resin emulsion (A) and a pigment (B). The acrylic resin emulsion (A) is a hydroxy-containing acrylic resin emulsion of a solubility parameter of ≥9.30 obtained by emulsion polymerization of a monomer mixture containing 5-20 mass% of a hydroxy-containing polymerizable unsaturated monomer (a) and higher than 0 mass% and equal to or lower than 10 mass% of a multi-vinyl compound (b) having at least two polymerizable unsaturated groups in one molecule and 70-95 mass% of other polymerizable unsaturated monomers (c). The equivalent of isocyanate groups of the polyisocyanate hardening agent (II) to one equivalent of hydroxy groups of the acrylic resin emulsion (A) contained in the main agent (I) is 0.05-1.4. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a coating method suitable for the surface of a material containing a plasticizer such as a sealing material.

  Conventionally, the joint parts (joint parts) of building materials such as various PC boards, ceramic building materials, metal building materials, etc., which are often used as constituents of buildings, are mainly waterproofed from rain water and external stresses. Sealing materials are placed in most field constructions to absorb the expansion and contraction of movement / building materials. Usually, a decorative coating material is applied to the surface of the sealing material and building material from the viewpoint of aesthetics and durability, covering the joints where the sealing material is placed, and finishing like a large wall with a sense of unity It has been.

  However, such joints may not be able to follow the peeling due to poor adhesion between the decorative coating material and the sealing material due to the composition of the sealing material, dirt contamination due to bleeding of the plasticizing component, and the high elasticity of the sealing material. Problems such as coating cracks occurred.

  With regard to these problems, the present applicant has found in Patent Document 1 that a coating composition containing a specific modified epoxy resin can realize suitability as a sealant primer. When such a coating composition is applied to the surface of the sealing material, a coating film having excellent adhesion, corrosion resistance, impact resistance, and the like can be obtained. There is a growing demand to switch to other materials.

On the other hand, Patent Document 2 proposes an aqueous paint containing specific amounts of a specific aqueous resin, a specific organic powder, and a specific core-shell type organic powder.
According to such a water-based paint, it is possible to form a primer coating film that can follow the high elasticity of the sealing material by applying it to the surface of the sealing material or the like, and the primer coating film is included in the sealing material. It is possible to prevent the plasticizer from transferring to the coating film of the upper-layer cosmetic coating material, but due to long-term exposure, a difference occurs in the degree of contamination between the sealing part and other parts, and the appearance is impaired. May end up.

Japanese Patent Laid-Open No. 11-92711 JP-A-2005-324187

  An object of the present invention is to provide a coating method suitable for the surface of a material containing a plasticizer such as a sealing material.

The present invention
1. A coating method for coating an aqueous primer on and near the surface of a plasticizer-containing material, wherein the aqueous primer is a two-component composition comprising a main agent (I) and a polyisocyanate curing agent (II), The main agent (I) contains the acrylic resin emulsion (A) and the pigment (B) as part of its components, and the acrylic resin emulsion (A) is a hydroxyl group-containing polymerizable unsaturated monomer (a) 5-20. The poly vinyl compound (b) having at least two polymerizable unsaturated groups in one molecule is more than 10% by mass and other polymerizable unsaturated monomer (c) is contained in an amount of 70 to 95% by mass. A hydroxyl group-containing acrylic resin emulsion having a solubility parameter value of 9.30 or more obtained by emulsion polymerization of a monomer mixture, the acrylic resin emulsion contained in the main agent (I) ( Coating method 1 equivalent of hydroxyl group against polyisocyanate curing agent in) isocyanate groups (II), characterized in that are in the range of a 0.05 to 1.4 equivalents,
2. 2. The coating method according to 1, wherein the other polymerizable unsaturated monomer (c) includes at least one selected from methyl (meth) acrylate and methoxyethyl acrylate as at least a part of its components.
3. The entire surface of the building material including the primer coating film formed by coating the water-based primer according to item 1 or 2 on and near the plasticizer-containing material surface portion of the building material in which the plasticizer-containing material is placed on the joint portion. The coating method that is applied by overcoating
4). The present invention relates to a coating method in which a water-based primer according to item 1 or 2 is applied to the entire surface of a building material in which a plasticizer-containing material is placed on a joint part, and an overcoat is applied on the formed primer coating.

  According to the method of the present invention, by applying an aqueous primer composed of a specific hydroxyl group-containing acrylic resin emulsion / polyisocyanate-based two-component composition on the surface of the plasticizer-containing material, the bleeding of the plasticizer is prevented. A primer coating film suitable for the above can be formed.

  The plasticizer-containing material, which is a substrate to which the method of the present invention is applied, is a material containing a plasticizer without any particular limitation, and examples thereof include a sealing material. Specific examples of the sealing material include silicone-based sealing materials, modified silicone-based sealing materials, polysulfide-based sealing materials, modified polysulfide-based sealing materials, urethane-based sealing materials, SBR-based sealing materials, and butyl rubber-based sealing materials. .

  Examples of the plasticizer include phthalic acid esters such as dibutyl phthalate, diheptyl phthalate, di (2-ethylhexyl) phthalate, and butyl benzyl phthalate; non-aromatic such as dioctyl adipate, dioctyl sebacate, dibutyl sebacate, and isodecyl succinate. Dibasic acid esters; Aliphatic esters such as butyl oleate and methyl acetylricinolinate; Phosphate esters such as tricresyl phosphate and tributyl phosphate; Trimellitic acid esters; Chlorinated paraffins; Alkyldiphenyl And hydrocarbon oils such as partially hydrogenated terphenyl; process oils; epoxy plasticizers such as epoxidized soybean oil and epoxy benzyl stearate;

  The aqueous primer used in the method of the present invention is a two-component composition comprising a main agent (I) and a polyisocyanate curing agent (II). The main agent (I) is an acrylic resin emulsion (A) as a part of its components. And pigment (B).

As said acrylic resin emulsion (B), 3-20 mass% of hydroxyl-containing polymerizable unsaturated monomers (a), especially 5-18 mass%,
Polyvinyl compound (b) having at least two polymerizable unsaturated groups in one molecule exceeding 10% by mass, in particular 1 to 7% by mass, and other polymerizable unsaturated monomers (c) 70 to 97 It is a hydroxyl group-containing acrylic resin emulsion having a solubility parameter value of 9.3 or more obtained by emulsion polymerization of a monomer mixture containing mass%, particularly 75 to 94 mass%.

  If the copolymerization ratio of the hydroxyl group-containing polymerizable unsaturated monomer is less than 5% by mass, it is insufficient in terms of preventing plasticizer migration. On the other hand, if it exceeds 20% by mass, the water resistance of the primer coating film is deteriorated. Absent. Further, if the polyvinyl compound (b) having at least two polymerizable unsaturated groups in one molecule is not copolymerized, it is insufficient in terms of preventing plasticizer migration. This is not preferable because cracks are easily generated in the coating film.

  Examples of the hydroxyl group-containing polymerizable unsaturated monomer (a) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate. C2-C8 hydroxyalkyl ester of acrylic acid or methacrylic acid; Monoester of polyether polyol such as polyethylene glycol, polypropylene glycol, polybutylene glycol and unsaturated carboxylic acid such as (meth) acrylic acid; Vinyl ether, allyl alcohol, hydroxyalkyl ester of (meth) acrylic acid, (poly) alkylene glycol mono (meth) acrylate and the like and lactones (for example, ε-caprolactone, γ-valero) Lactones); monoethers of polyether polyols such as polyethylene glycol, polypropylene glycol and polybutylene glycol and hydroxyl group-containing unsaturated monomers such as 2-hydroxyethyl (meth) acrylate; α, β-unsaturated carboxylic acids And adducts of mono-epoxy compounds such as Cardura E10 (manufactured by Shell Chemical Co., Ltd.) and α-olefin epoxides; Adducts with monobasic acids; monoesters or diesters of acid anhydride group-containing unsaturated compounds such as maleic anhydride and itaconic anhydride and glycols such as ethylene glycol, 1,6-hexanediol and neopentyl glycol Hydroxyethyl vinyl ester Hydroxyalkyl vinyl ethers such as ether, 3-chloro-2-hydroxypropyl (meth) hydroxyl group-containing monomers containing chlorine such as acrylate, allyl alcohol and the like.

  Examples of the polyvinyl compound (b) having at least two polymerizable unsaturated groups in one molecule include diallyl phthalate, diallyl isophthalate, triallyl isocyanurate, diallyl tetrabromophthalate, pentaerythritol diallyl ether, allyl Allyl monomers such as glycidyl ether; perfluoroalkyl (meth) acrylates such as perfluorobutylethyl (meth) acrylate, perfluoroisononylethyl (meth) acrylate, perfluorooctylethyl (meth) acrylate; ethylene glycol di ( (Meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) Acrylate, 1,4-butanediol diacrylate, glycerin di (meth) acrylate, glycerin tri (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol di (meth) acrylate , Pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, hydroxyisocyanurate tri (meth) acrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, Glycerol allyloxydi (meth) acrylate, 1,1,1-tris (hydroxymethyl) ethanedi (meth) acrylate, 1,1,1-tri (Meth) of polyhydric alcohols such as (hydroxymethyl) ethane tri (meth) acrylate, triallyl isocyanurate, triallyl trimellitate, diallyl terephthalate, diallyl phthalate, diallyl isophthalate, pentaerythritol diallyl ether, divinylbenzene Acrylic esters and the like can be mentioned.

  Examples of other polymerizable unsaturated monomer (c) include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, 2-carboxyethyl (meth) acrylate, and 2-carboxypropyl (meth) acrylate. Carboxyl group-containing unsaturated monomers such as 5-carboxypentyl (meth) acrylate; methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, (meth ) Butyl acrylate (n-, i-, t-), hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, decyl (meth) acrylate, (meth) Lauryl acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate C1-C18 alkyl ester or cycloalkyl ester of acrylic acid or methacrylic acid; acrylic acid or methacrylic acid such as methoxybutyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxybutyl (meth) acrylate C2-C18 alkoxyalkyl esters of the above; chain alkyl vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, butyl vinyl ether, t-butyl vinyl ether, pentyl vinyl ether, hexyl vinyl ether, octyl vinyl ether; cyclopentyl vinyl ether, cyclohexyl Cycloalkyl vinyl ethers such as vinyl ether; Aryl vinyl ethers such as phenyl vinyl ether and trivinyl phenyl ether Aralkyl vinyl ethers such as benzyl vinyl ether and phenethyl vinyl ether; Allyl ethers such as allyl glycidyl ether and allyl ethyl ether; Vinyl acetate, vinyl propionate, vinyl lactate, vinyl butyrate, vinyl isobutyrate, vinyl caproate, vinyl isocaproate , Vinyl esters such as vinyl pivalate, vinyl caprate, and beova monomer (manufactured by Shell Chemical Co.); propenyl esters such as isopropenyl acetate and isopropenyl propionate; olefinic compounds such as ethylene, propylene, butylene, and vinyl chloride; styrene , Α-methylstyrene, vinyltoluene, α-chlorostyrene, and other vinyl aromatic compounds; N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate Rate, nitrogen-containing alkyl (meth) acrylates such as Nt-butylaminoethyl (meth) acrylate; acrylamide, methacrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-methylol (meth) Acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N, N-dimethylaminoethyl ( Polymerizable amides such as (meth) acrylamide; aromatic nitrogen-containing monomers such as 2-vinylpyridine, 1-vinyl-2-pyrrolidone and 4-vinylpyridine; polymerizable nitriles such as acrylonitrile and methacrylonitrile; vinyltrimethoxysilane ,vinyl Triethoxysilane, vinyltris (2-methoxyethoxy) silane, γ- (meth) acryloyloxypropyltrimethoxysilane, vinyltriacetoxysilane, β- (meth) acryloyloxyethyltrimethoxysilane, γ- (meth) acryloyloxy And propyltriethoxysilane.

  In the acrylic resin emulsion (A), the other polymerizable unsaturated monomer (c) contains at least one selected from methyl (meth) acrylate and methoxyethyl acrylate as at least a part of its components. It is preferable from the viewpoint of preventing plasticizer migration.

  The amount of the monomer used is suitably 80% by mass or less, particularly 5 to 60% by mass in the other polymerizable unsaturated monomer (c).

  In addition, the other polymerizable unsaturated monomer (c) preferably contains a carboxyl group-containing polymerizable unsaturated monomer as a part of its component from the viewpoint of preventing plasticizer migration.

  Examples of the carboxyl group-containing polymerizable unsaturated monomer include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, 2-carboxyethyl (meth) acrylate, 2-carboxypropyl (meth) acrylate, 5-carboxypentyl (meth) acrylate etc. are mentioned.

  The amount used is suitably in the range of 0.5 to 10% by mass, particularly 1 to 5% by mass in the other polymerizable unsaturated monomer (c).

  The acrylic resin emulsion (A) may be a so-called single layer type obtained by emulsion polymerization of the whole amount of the monomer components exemplified above, or a so-called multilayer type (2) obtained by emulsion polymerization of monomer components having different compositions in stages. In the case of step polymerization, it may be a core-shell type).

  In the present invention, the solubility parameter value of the acrylic resin emulsion (A) is in the range of 9.30 or more, and particularly preferably in the range of 9.30 to 10.50. When the solubility parameter value of the acrylic resin emulsion (A) is less than 9.30, the plasticizer migration preventing property of the coating film formed by the aqueous primer is lowered, which is not preferable.

  In the present specification, the solubility parameter (SP value) can be measured by cloud point titration, which is a simple measurement method. W. SUH, J. et al. M.M. This is a value calculated according to the CORBETT equation (see the description of Journal of Applied Polymer Science, 12, 2359, 1968).

Formula SP = (√Vml · δH + √Vmh · δD) / (√Vml + √Vmh)
In cloud point titration, when 0.5 g of sample was dissolved in 10 ml of acetone, n-hexane was added and the titration amount H (ml) at the cloud point was read, and similarly deionized water was added to the acetone solution. The titration amount D (ml) at the cloud point is read and applied to the following formula to calculate Vml, Vmh, δH, and δD. The molecular volume (mol / ml) of each solvent is acetone: 74.4, n-hexane: 130.3, deionized water: 18, and the SP of each solvent is acetone: 9.75, n- Hexane: 7.24, deionized water: 23.43.

Vml = 74.4 × 130.3 / ((1−VH) × 130.3 + VH × 74.4)
Vmh = 74.4 × 18 / ((1−VD) × 18 + VD × 74.4)
VH = H / (10 + H)
VD = D / (10 + D)
δH = 9.75 × 10 / (10 + H) + 7.24 × H / (10 + H)
δD = 9.75 × 10 / (10 + D) + 23.43 × D / (10 + D).

  As the pigment (B) in the present invention, known color pigments and extender pigments can be used without limitation, and among these, for example, white pigments such as titanium dioxide; carbon black, acetylene black Black pigments such as lamp black, bone black, graphite, iron black, aniline black; yellow iron oxide, titanium yellow, monoazo yellow, condensed azo yellow, azomethine yellow, bismuth vanadate, benzimidazolone, isoindolinone, isoindoline Yellow pigments such as quinophthalone, benzidine yellow and permanent yellow; orange pigments such as permanent orange; red iron oxide, naphthol AS azo red, ansanthrone, anthraquinonyl red, perylene maroon, quinacridone red pigment, diketopiro Red pigments such as pyrrole, watching red, and permanent red; purple pigments such as cobalt violet, quinacridone violet, and dioxazine violet; blue pigments such as cobalt blue, phthalocyanine blue, and selenium; and green pigments such as phthalocyanine green. These can be used alone or in combination of two or more.

  Examples of extender pigments include silica, barita powder, precipitated barium sulfate, barium carbonate, calcium carbonate, gypsum, clay, white carbon, diatomaceous earth, talc, magnesium carbonate, alumina white, gloss white, and tancal. Can be used alone or in combination of two or more.

  In the present invention, the pigment volume concentration of the pigment contained in the water-based primer coating is preferably 60% or less, particularly preferably in the range of 10 to 50%, from the viewpoint of the prevention of plasticizer migration and tackiness of the primer coating. is there.

  In the present specification, the “pigment volume concentration” is a volume ratio of the pigment in the total solid content of the total resin and the total pigment in the paint.

  In the present specification, the specific gravity of the pigment, which is the basis for calculating the pigment volume, is according to “Coating Material Handbook 6th Edition” (Japan Paint Manufacturers Association), and the specific gravity of the resin solid content. Is approximate to 1.

  The main agent (I) may contain a resin and paint additives other than the acrylic resin emulsion (A) as necessary. The paint additives include film-forming aids, neutralizing agents, thickeners, antistatic agents, softeners, antibacterial agents, fragrances, curing catalysts, pH adjusters, humidity control agents, powdery or fine particles. Activated carbon, photocatalytic titanium oxide, aqueous water repellent, dispersant, defoaming agent, antiseptic, antifungal agent, antifreezing agent, UV absorber, light stabilizer, zinc whisker, curing accelerator, aldehyde adsorbent, wax And flame retardants such as antimony trioxide, antimony pentoxide, and aluminum hydroxide.

  Among these, as the film forming aid, for example, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, 2,2,4-trimethyl-1,3-pentanediol diisobutyrate, 2, Ester compounds such as 2,4-trimethyl-1,3-pentanediol mono 2-ethylhexanoate, 2,2,4-trimethyl-1,3-pentanediol di-2-ethylhexanoate, propylene glycol mono Examples include polypropylene glycol monoalkyl ethers such as butyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monobutyl ether, and polyethylene glycol dialkyl ethers such as ethylene glycol dibutyl ether and diethylene glycol dibutyl ether. Or it may be used in combination of two or more in Germany.

  The amount used in the case of using the film-forming auxiliary is within the range of 10 to 50% by mass, particularly 15 to 45% by mass, based on the resin solid content contained in the aqueous primer, from the viewpoint of preventing plasticizer migration. It is suitable to be adjusted.

Polyisocyanate curing agent (II)
The polyisocyanate curing agent (II) used in the method of the present invention is a curing agent having two or more isocyanate groups in the molecule and capable of being dispersed or dissolved in water, for example, modified with a polyethylene oxide chain. Examples thereof include those obtained by dispersing polyisocyanate with an anionic or nonionic dispersant.

  More specifically, “Aquanate 100”, “Aquanate 110”, “Aquanate 200”, “Aquanate 210”, (trade name, manufactured by Nippon Polyurethane Industry Co., Ltd.), “Vivijour TPLS-2032” , “Baihijoule VPLS-2319”, “Baihijoule VPLS-2336”, “Baihijoule VPLS-2150 / 1”, “SUB-isocyanate-L801” (trade name, manufactured by Sumitomo Bayer Urethane Co., Ltd.), “Takenate WD-720”, “Takenate WD-725”, “Staffyroid WD-220” (trade name, manufactured by Takeda Pharmaceutical Co., Ltd.), “Rezamin D-56” (trade name, Dainichi Seika Kogyo ( Etc.)) etc. can be illustrated. These can be used alone or in combination.

  The blending ratio of the polyisocyanate curing agent (II) is generally such that the isocyanate group of the polyisocyanate curing agent (II) is 0.1% relative to 1 equivalent of the hydroxyl group in the acrylic resin emulsion (A) contained in the main agent (I). It is desirable to use it in such a ratio that it is within the range of 05 to 1.4 equivalents, particularly within the range of 0.1 to 1.0 equivalents, and more particularly within the range of 0.3 to 0.9 equivalents. .

  When the equivalent ratio of isocyanate groups is less than 0.05 equivalent, the plasticizer migration preventing property is insufficient, and when it exceeds 1.4 equivalents, cracking of the primer coating film is not preferable.

The aqueous primer coating used in the method of the present invention is a two-component composition comprising the above main agent (I) and polyisocyanate curing agent (II), and the main agent (I) and polyisocyanate curing agent (II) immediately before use. In the range of 10 to 200 g / m ² , preferably 20 to 150 g / m ² in terms of the two-component mixed dry mass of the main agent (I) and the polyisocyanate curing agent (II). It can be coated on the surface of the substrate so as to be inside. The coating can be performed by a coating means known per se, for example, air spray, airless spray, brush coating, roller coating and the like.

  In the case where the base material is a building material in which a plasticizer-containing material is placed on the joint portion, the water-based primer is disposed on the plasticizer-containing material surface and in the vicinity thereof (for example, 3 to 10 mm wider than the plasticizer-containing material surface width). The entire surface of the building material including the formed primer coating may be overcoated, or the above water-based primer may be applied over the entire surface of the building material, and the overcoated coating may be applied over the formed primer coating. Also good.

  As the top coating used for top coating, conventionally known acrylic resins, acrylic silicon resins, polyolefin resins, silicon resins, polyurethane resins, epoxy resins, phenol resins, polyester resins, alkyd resins, raw resins Examples of the coating material include a water-based or solvent-based resin composed of a resin type such as a degradable resin as a resin binder, and the coating can be performed by a coating means known per se.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated further more concretely, this invention is not limited only to these Examples. In the following examples, “parts” and “%” mean “parts by mass” and “% by mass”, respectively.

Production of acrylic emulsion In a 4-liter flask with a capacity of 2 liters, 300 parts of deionized water, “Newcol 707SF” (trade name, manufactured by Nippon Emulsifier Co., Ltd., an anionic surfactant having a polyoxyethylene chain, non-volatile content of 30%) 0 .1 part was added and kept at 85 ° C. after purging with nitrogen. In the pre-emulsion formed by emulsifying the following composition, 3% by mass and 30% by mass of the following catalyst aqueous solution were added and stirred. From 20 minutes after the addition, 97% by mass of the following pre-emulsion and 70% by mass of the following aqueous catalyst solution were added dropwise over 4 hours.
≪Pre-emulsion≫
287 parts of deionized water,
8 parts methacrylic acid,
496 parts of styrene,
120 parts of n-butyl acrylate,
16 parts acrylic acid,
120 parts of hydroxyethyl methacrylate,
40 parts of 1,6-hexanediol diacrylate,
"Newcol 707SF" 53 parts,
≪Catalyst aqueous solution≫
1.5 parts ammonium persulfate,
120 parts deionized water,
After completion of the dropwise addition, 56 parts of deionized water was added, and this was further maintained at 80 ° C. for 2 hours, and then the temperature was lowered to 40 ° C. or lower. Next, the pH was adjusted to 8 to 9 with aqueous ammonia to obtain an acrylic emulsion (A1) having a solid content of 50%.

Production Examples 2-6 and 8-11
In Production Example 1, acrylic emulsions (A2) to (A6) and (A8) to (A11) were obtained in the same manner as Production Example 1 except that the pre-emulsion composition to be dropped was changed to Table 1 below.

Production Example 7
257 parts by mass of deionized water and “Newcol 707SF” (trade name, manufactured by Nippon Emulsifier Co., Ltd., an anionic surfactant having a polyoxyethylene chain, non-volatile content of 30%) in a 4-liter flask having a volume of 2 liters And maintained at 85 ° C. after nitrogen substitution. 25 parts of 10.5 parts by weight of a solution prepared by dissolving 3 parts by weight of a pre-emulsion (for core) obtained by emulsifying the following composition and 0.5 parts by weight of ammonium persulfate in 10 parts by weight of deionized water. The mass% was added, and after 20 minutes of addition, 70 mass% of the pre-emulsion and 50 mass% of the ammonium persulfate aqueous solution were added dropwise over 2 hours.
≪Pre-emulsion (core) composition≫
73.6 parts deionized water,
288 parts of styrene,
56 parts of n-butyl acrylate,
24 parts of hydroxyethyl acrylate,
8 parts methacrylic acid,
24 parts of 1,6-hexanediol diacrylate,
6.6 parts Newcol 707SF,
After completion of the dropwise addition, this was further maintained at 85 ° C. for 2 hours, and then 30% by mass of a pre-emulsion (for shell) formed by emulsifying the following composition therein and 25% by mass of the aqueous ammonium persulfate solution for 2 hours. It was dripped over.
≪Pre-emulsion (for shell) ≫
73.6 parts deionized water,
208 parts of styrene,
80 parts of n-butyl acrylate,
96 parts of hydroxyethyl acrylate,
16 parts acrylic acid,
6.6 parts Newcol 707SF,
After completion of the dropwise addition, this was further maintained at 85 ° C. for 2 hours, and then cooled to 40-60 ° C. Next, the pH was adjusted to 8 to 9 with aqueous ammonia to obtain an acrylic emulsion (A7) having a solid content of 50%.

Production of primer paint Production Examples 12 to 29
Each base paint was obtained by stirring and mixing the components shown in Table 2. Next, the primer shown in Table 2 was blended and stirred immediately before use to obtain each primer paint (B1) to (B18).

(Note 1) Film-forming auxiliary: “TEXNOL” (trade name, manufactured by Eastman Chemical Co.), 2,2,4-trimethylpentanediol monoisobutyrate,
(Note 2) extender pigment: calcium carbonate having a specific gravity of 2.7,
(Note 3) Titanium white; “JR605” trade name, manufactured by Teica, titanium white, specific gravity 4.1,
(Note 4) Antifoaming agent: “SN deformer A63”, trade name, manufactured by San Nopco,
(* 5) Dispersant: “DISPER BYK-190”, trade name, manufactured by BYK,
(Note 6) Thickener: “Adecanol UH-420”, trade name, manufactured by Asahi Denka Co., Ltd.
(Note 7) “Takenate WD-220”: trade name, manufactured by Takeda Pharmaceutical Company Limited, water-dispersible polyisocyanate, isocyanate content 17 wt%,
(Note 8) “Baihijoule VPLS-2336”: trade name, manufactured by Sumitomo Bayer Urethane Co., Ltd., isocyanate content 17.5%,
(Note 9) “Baihijoule 3100”: trade name, manufactured by Sumitomo Bayer Urethane Co., Ltd., isocyanate content 17%.

≪Sealing material≫
A: “Hamatite Super II” (trade name, manufactured by Yokohama Rubber Co., Ltd., two-component modified silicone sealing material),
B: “Penguin seal 2500” (trade name, manufactured by Sunstar Giken Co., Ltd., two-component modified silicone sealing material),
C: “PS seal” (trade name, manufactured by Konishi, two-component polysulfide type).

Preparation of test plates Examples 1-12 and Comparative Examples 1-6
A flexible plate having a joint groove of 10 mm × 5 mm square is prepared as a base plate, and sealing materials having various compositions are placed on the joint groove, and then dried at room temperature for 3 days, and then 5 mm wider than the surface of the sealing material and its surface width. Primers (B1) to (B18) obtained in the above production examples were applied with a brush at a coating amount of 100 g / m ² over the part. After drying this for 1 day, "Aqua gloss white" (trade name, acrylic water-based paint, manufactured by Kansai Paint Co., Ltd.) was applied to the entire surface of the test plate with a roller (application amount: 150 g / m ² × 1 time). A test plate for a crack resistance test and a tack test was used.
(*) Crack resistance test After performing a total of 10 cycles of hot / cold cycle tests in which each of the test plates was immersed in water (23 ° C.) 18 hr → −20 ° C. × 3 hr → 50 ° C. × 3 hr. The appearance of the coating film was confirmed.
(Double-circle): There is no cracking in the coating film (microscope: no cracking even when magnified 100 times),
◯: No cracking occurred in the coating film (microscope: slight cracking is seen at 100 times magnification),
Δ: A crack that can be visually confirmed occurs in the coating film provided on the joint,
X: Cracking has occurred on the entire surface of the coating film.
(*) Tack test test The coating film provided on the joint part of the test plate was touched with a finger at room temperature of 50 ° C and evaluated according to the following criteria.
A: Tack feeling is not recognized at all.
○: Slight tackiness is recognized,
Δ: There is a tactile sensation that leaves fingerprint marks.
X: The tackiness is remarkable and the coating film adheres to the hand.

(*) Absorption DOP measurement The free film (30 mm x 30 mm) of each primer paint obtained in the above production example was immersed in a solution of dioctyl phthalate (DOP) for 24 hours, and the DOP absorption rate was determined from the change in mass before and after immersion. Was calculated. The lower the value, the better.
(*) Contamination resistance due to outdoor exposure: The test specimen was exposed for 6 months at an inclination of 30 degrees south,
The degree of soiling after exposure was visually evaluated according to the following criteria.
○: There is no difference in contamination between the application part of the sealing part and the application part other than the sealing part,
Δ: Slightly inferior in contamination between the application part of the sealing part and the application part other than the sealing part,
X: Significant contamination is observed in the application part of the sealing part as compared with the application part other than the sealing part.

Claims (4)

A coating method for coating an aqueous primer on and near the surface of a plasticizer-containing material, wherein the aqueous primer is a two-component composition comprising a main agent (I) and a polyisocyanate curing agent (II), The main agent (I) contains the acrylic resin emulsion (A) and the pigment (B) as part of its components, and the acrylic resin emulsion (A) is a hydroxyl group-containing polymerizable unsaturated monomer (a) 5-20. The poly vinyl compound (b) having at least two polymerizable unsaturated groups in one molecule is more than 10% by mass and other polymerizable unsaturated monomer (c) is contained in an amount of 70 to 95% by mass. A hydroxyl group-containing acrylic resin emulsion having a solubility parameter value of 9.30 or more obtained by emulsion polymerization of a monomer mixture, the acrylic resin emulsion contained in the main agent (I) ( Coating method 1 equivalent of hydroxyl group against polyisocyanate curing agent in) isocyanate groups (II), characterized in that in the range to be from 0.05 to 1.4 equivalents. The coating method according to claim 1, wherein the other polymerizable unsaturated monomer (c) contains at least one selected from methyl (meth) acrylate and methoxyethyl acrylate as at least a part of its components. The entire surface of the building material including the primer coating film formed by coating the water-based primer according to claim 1 on the plasticizer-containing material surface portion of the building material in which the plasticizer-containing material is placed on the joint portion and in the vicinity thereof. This is a coating method that consists of top coating. A coating method comprising applying the water-based primer according to claim 1 or 2 to the entire surface of a building material in which a plasticizer-containing material is cast on a joint portion, and overcoating the formed primer coating.