JP5090703B2 - Water-based coating material - Google Patents

Description

  The present invention relates to a decorative water-based coating material applicable to inner and outer wall surfaces of buildings.

  Conventionally, as a material for decorating the inner and outer wall surfaces of a building, a coating material in which natural aggregate or artificial aggregate is blended with a binder such as a synthetic resin emulsion is often used. For example, in Japanese Patent Publication No. 2-40702 (Patent Document 1), as a coating material capable of forming a natural stone pattern such as granite, a binder, a colored aggregate, and a transparent aggregate that form a colorless and transparent film are disclosed. The coating material which combined with is described. JP-A-11-130980 (Patent Document 2) discloses an aggregate coloring coating composition containing an aggregate having a particle size of 0.05 to 5 mm and an acrylic resin emulsion containing silicon atoms in the resin skeleton. Have been described. Japanese Patent Application Laid-Open No. 2000-15999 (Patent Document 3) is formed by mixing and dispersing colored particles of two or more colors having a uniform particle diameter within a range of 10 to 1000 μm in a colorless and transparent binder. The coating material is described. JP-A-2001-240807 (Patent Document 4) describes a colored particle having a small particle size (0.5 to 10 μm) and a colored particle having a large particle size (10 to 150 μm) that are different in color in the vehicle. A coating material in which is dispersed is described.

Japanese Patent Publication No. 2-40702 JP-A-11-130980 JP 2000-15999 A JP 2001-240807 A

  The above-mentioned patent documents all aim at imparting a sense of depth in the formed coating film, and a coating film is formed in which the aggregate is covered with resin, that is, the aggregate is visible behind the resin layer. For this reason, in any of the patent documents, the aggregate appears to be slightly blackened by the resin, has a different finish from the texture of the aggregate itself, and may have an artificial appearance.

  The present invention has been made in view of these points, and an object thereof is to provide a novel decorative coating material that can take advantage of the original texture of the aggregate and express a natural texture. It is.

In order to solve these problems, the present inventor has intensively studied and conceived of adopting an acrylic silicone emulsion having a specific composition as a binder, thereby completing the present invention.
That is, the present invention has the following characteristics.

1. A synthetic resin emulsion (A) in which an acrylic resin derived from (meth) acrylic acid alkyl ester and a silicone resin derived from a cyclic siloxane compound are mixed in the emulsion particles at a weight ratio of 99: 1 to 30:70,
As an essential component, at least one kind of aggregate (B) selected from pulverized natural stone, pulverized ceramic, and colored aggregate,
The synthetic resin emulsion (A) is a multilayer structure type synthetic resin emulsion (A-1) having an outer layer in which the acrylic resin and the silicone resin are mixed, and an inner layer containing the acrylic resin.
Wherein the solid content 100 parts by weight of synthetic resin emulsion (A), the aggregate (B) a 100-2000 parts by weight seen including, forming a coating film coated with the amount 0.8~10kg / ^{m 2} A characteristic water-based coating material.
2. On the inside and outside walls of the building,
A synthetic resin emulsion (A) in which an acrylic resin derived from (meth) acrylic acid alkyl ester and a silicone resin derived from a cyclic siloxane compound are mixed in the emulsion particles at a weight ratio of 99: 1 to 30:70,
As an essential component, at least one kind of aggregate (B) selected from pulverized natural stone, pulverized ceramic, and colored aggregate,
The synthetic resin emulsion (A) is a multilayer structure type synthetic resin emulsion (A-1) having an outer layer in which the acrylic resin and the silicone resin are mixed, and an inner layer containing the acrylic resin.
Wherein the solid content 100 parts by weight of synthetic resin emulsion (A), the aggregate (B) an aqueous coating material comprising 100 to 2000 parts by weight of, to painted coat-weight 0.8~10kg / ^{m 2} Characteristic painting method.

  With the aqueous coating material of the present invention, a coating film having a natural texture utilizing the original texture of the aggregate can be formed.

  Hereinafter, the best mode for carrying out the present invention will be described.

The synthetic resin emulsion (A) in the aqueous coating material of the present invention (hereinafter referred to as “component (A)”) is an emulsion particle comprising an acrylic resin derived from an alkyl (meth) acrylate and a silicone resin derived from a cyclic siloxane compound. Are mixed together. The form of the acrylic resin and the silicone resin in the component (A) is not particularly limited, and may be a uniformly mixed form, but a form separated from each other by a sea-island structure or the like is preferable.
The weight ratio of the acrylic resin and the silicone resin in the component (A) is usually 99: 1 to 30:70, preferably 97: 3 to 40:60. By mixing both components at such a ratio, it is possible to express the original texture of the aggregate. In addition, advantageous effects can be obtained also in physical properties such as water resistance, weather resistance, and fire resistance.

  In the present invention, by mixing the acrylic resin and the silicone resin in the component particle (A) as described above, the natural texture can be expressed by utilizing the original texture of the aggregate. The reason for this is not clear, but it is presumed that the acrylic resin and the silicone resin are incompatible with each other and that the refractive index of the acrylic resin and the silicone resin are appropriately different.

  (A) The acrylic resin which comprises a component is a polymer which has (meth) acrylic-acid alkylester as a main component, and copolymerizes another monomer as needed. Examples of (meth) acrylic acid alkyl esters include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and t-butyl (meth) acrylate. , N-amyl (meth) acrylate, isoamyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (Meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate and the like. The amount of such (meth) acrylic acid alkyl ester is usually 30% by weight or more, preferably 40-99.9% by weight, more preferably 50-99. 5% by weight.

  Examples of other monomers include carboxyl group-containing monomers, amino group-containing monomers, pyridine monomers, hydroxyl group-containing monomers, nitrile group-containing monomers, amide group-containing monomers, epoxy group-containing monomers, carbonyl group-containing monomers, and alkoxysilyl group-containing monomers. And aromatic monomers. The usage-amount of these monomers is 0.1 to 60 weight% normally with respect to all the monomers which comprise (A) component, Preferably it is 0.5 to 50 weight%.

  Among these, when a carboxyl group-containing monomer is copolymerized to obtain a carboxyl group-containing acrylic resin, the stability of the component (A) can be increased, and a compound capable of reacting with a carboxyl group is added separately. Therefore, various physical properties of the coating film can be improved. Examples of the carboxyl group-containing monomer include acrylic acid, methacrylic acid, crotonic acid, maleic acid or a monoalkyl ester thereof, itaconic acid or a monoalkyl ester thereof, fumaric acid or a monoalkyl ester thereof. Among these, at least one selected from acrylic acid and methacrylic acid is particularly preferable. The usage-amount of a carboxyl group-containing monomer is 0.1 to 40 weight% normally with respect to all the monomers which comprise (A) component, Preferably it is 0.5 to 20 weight%.

  The silicone resin in component (A) is obtained by polymerizing a cyclic siloxane compound. Examples of the cyclic siloxane compound include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and the like. When polymerizing such a cyclic siloxane compound, a linear siloxane compound, a branched siloxane compound, an alkoxysilane compound, or the like can also be used. Of these, as the alkoxysilane compound, a silane compound having one or more alkoxyl groups in the molecule can be used. For example, tetramethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, vinylmethyldimethoxysilane, γ- Silane coupling agents such as (meth) acryloyloxytrimethoxysilane and 3-mercaptopropyltrimethoxysilane can be used. The average molecular weight of the silicone resin is usually 10,000 or more, preferably 50,000 or more.

  As the component (A) in the present invention, in particular, a synthetic resin emulsion in which an acrylic resin and a silicone resin are mixed as described above, and a multilayer structure having an outer layer in which an acrylic resin and a silicone resin are mixed, and an inner layer containing the acrylic resin A type synthetic resin emulsion (A-1) (hereinafter referred to as “component (A-1)”) is preferred. If such a component (A-1) is used, the effect of the present invention can be obtained more reliably. The weight ratio of the outer layer to the inner layer in the component (A-1) is usually 80:20 to 20:80, preferably 70:30 to 30:70.

  Such component (A-1) can be obtained, for example, by a method of synthesizing an acrylic resin constituting the inner layer by emulsion polymerization and then synthesizing an acrylic resin and a silicone resin constituting the outer layer by emulsion polymerization. In the component (A-1), the silicone resin as described above may be contained as a resin constituting the inner layer. By including a silicone resin in the inner layer, it is possible to enhance crack prevention properties and the like.

As the component (A-1), those in which the glass transition temperature of the acrylic resin in the inner layer is set lower than the glass transition temperature of the acrylic resin in the outer layer are preferable. By using a multilayer structure type synthetic resin emulsion set to such a glass transition temperature (hereinafter referred to as “Tg”), it is possible to improve the crack prevention property of the coating film. In addition, compared to the case of using a normal synthetic resin emulsion, it is possible to design a coating material having various physical properties such as flexibility and adhesion with a smaller amount of resin, in terms of improving the texture of the aggregate. Is also advantageous.
Here, the Tg of the acrylic resin constituting the inner layer may be usually set to −60 to 20 ° C. (preferably −50 to 10 ° C.). Tg of an outer layer is 20-100 degreeC normally (preferably 30-90 degreeC). When the Tg of the acrylic resin in each layer is within such a range, the above-described effects can be stably obtained. Note that Tg in the present invention is a value obtained by the Fox calculation formula.

  In the present invention, when the carboxyl group-containing acrylic resin is contained in the component (A), effects such as swelling prevention and peeling prevention can be enhanced by separately adding a compound capable of reacting with the carboxyl group. Furthermore, the tackiness of the coating film surface is reduced and the stain resistance is increased. Examples of such a compound include compounds having one or more functional groups selected from a carbodiimide group, an epoxy group, an aziridine group, an oxazoline group, and the like. Among these, in the present invention, a reactive compound having an epoxy group is particularly suitable.

  Examples of the reactive compound having an epoxy group include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, glycerol polyglycidyl ether, diglycerol polyglycidyl ether, polyglycerol poly Examples thereof include glycidyl ether, dihydroxyalkane polyglycidyl ether, polyhydroxyalkane polyglycidyl ether, and sorbitol polyglycidyl ether. In addition, a water-soluble resin or emulsion made of a polymer (homopolymer or copolymer) of an epoxy group-containing monomer can also be used. The mixing amount of such a compound is usually 0.1 to 50 parts by weight, preferably 0.3 to 20 parts by weight with respect to 100 parts by weight of the resin solid content of the component (A).

  In this invention, although the said (A) component is used as a binder, binders other than (A) component can also be used together with (A) component as needed.

In the present invention, in addition to the component (A) described above, at least one aggregate (B) (hereinafter referred to as “component (B)”) selected from natural stone pulverized products, ceramic pulverized products, and colored aggregates is essential Ingredients. This component (B) is a component that imparts decorativeness. Specifically, for example, marble, granite, serpentinite, granite, fluorite, cryolite, feldspar, quartzite, quartz sand, etc., ceramic pulverized material, ceramic pulverized material, glass pulverized material, glass beads, resin pulverized material , Resin beads, metal particles, etc., and those whose surfaces are colored and coated.
The particle size of the component (B) is desirably 0.01 mm to 5.0 mm. If the particle size is less than 0.01 mm, the natural stone-like variety due to the aggregate decreases, and if it exceeds 5.0 mm, the workability during painting tends to decrease.

  (B) The compounding quantity of a component is 100-2000 weight part normally with respect to 100 weight part of solid content of (A) component, Preferably it is 300-1500 weight part. When the component (B) is less than 100 parts by weight, the texture due to the aggregate cannot be obtained, and the concealability of the formed coating film cannot be ensured. When the amount is more than 2000 parts by weight, the stain resistance, water resistance, crack resistance and the like are lowered, which is not practical.

  The coating material of the present invention can also contain components that can be used in ordinary paints as long as the effects of the present invention are not significantly impaired. Such components include, for example, thickeners, film-forming aids, leveling agents, wetting agents, plasticizers, antifreeze agents, pH adjusters, antiseptics, antifungal agents, antialgae agents, antibacterial agents, dispersions Agents, antifoaming agents, adsorbents, colored pigments, extender pigments, fibers, water repellents, crosslinking agents, ultraviolet absorbers, antioxidants, catalysts and the like. This invention coating material can be manufactured by mixing the above components uniformly by a conventional method.

  The coating material of the present invention can be used mainly for painting buildings and civil engineering structures. Applicable base materials include, for example, gypsum board, plywood, concrete, mortar, porcelain tile, fiber mixed cement board, cement calcium silicate board, slag cement perlite board, ALC board, siding board, extrusion board, steel sheet, plastic A board etc. are mentioned. The surface of these base materials may have been subjected to some surface treatment (for example, a sealer, a surfacer, a filler, a putty, etc.), or may have already been formed with a coating film.

  As a coating method of the coating material of the present invention, a known method can be adopted. For example, spray coating, roller coating, iron coating, brush coating, and the like are possible. When painting dry building materials in a factory, it is also possible to paint with a roll coater, a flow coater or the like.

The coating amount when applying the coating material of the present invention may be appropriately selected depending on the type and application of the coating material, but is usually about 0.5 to 10 kg / m ² , preferably about 0.8 to 8 kg / m ^2. It is. With the coating material of the present invention, a relatively thick film can be formed with such a coating amount. At the time of application, the viscosity of the paint can be appropriately adjusted by diluting with water or the like. The dilution ratio is usually about 0 to 20% by weight. The drying after applying the coating material of the present invention is usually carried out at room temperature, but it can also be heated.

  Examples are given below to clarify the features of the present invention.

(Manufacture of water-based coating materials)
In accordance with the formulation shown in Table 1, each raw material was mixed and stirred by a conventional method to produce an aqueous coating material. The following were used as raw materials.

Resin 1: multilayer structure type synthetic resin emulsion outer layer; acrylic resin (Tg 45 ° C., component: t-butyl methacrylate, n-butyl methacrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methacrylic acid; carboxyl group-containing monomer 5 weight %), Silicone resin (component: hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane), weight ratio of outer layer acrylic resin to silicone resin 80:20,
Inner layer: acrylic resin (Tg-50 ° C., component: n-butyl methacrylate, n-butyl acrylate, 2-ethylhexyl acrylate), outer layer / inner layer weight ratio 45:55, solid content 50% by weight

Resin 2: Multi-layer structure type synthetic resin emulsion outer layer; acrylic resin (Tg 45 ° C., component: t-butyl methacrylate, n-butyl methacrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methacrylic acid; carboxyl group-containing monomer 5 weight %), Silicone resin (component: hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane), weight ratio of outer layer acrylic resin to outer layer silicone resin 80:20,
Inner layer: acrylic resin (Tg-50 ° C., component: n-butyl methacrylate, n-butyl acrylate, 2-ethylhexyl acrylate), silicone resin (component: hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclo) Pentasiloxane), weight ratio of inner layer acrylic resin to inner layer silicone resin 80:20,
Weight ratio of outer layer to inner layer 45:55, solid content 50% by weight

Resin 3: multilayer structure type synthetic resin emulsion outer layer; acrylic resin (Tg 45 ° C., component: t-butyl methacrylate, n-butyl methacrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methacrylic acid; carboxyl group-containing monomer 5 weight %),
Inner layer: silicone resin (component: hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane),
Weight ratio of outer layer to inner layer 70:30, solid content 50% by weight

Resin 4: Multilayer structure type synthetic resin emulsion Outer layer: Acrylic resin (Tg 45 ° C., component: t-butyl methacrylate, n-butyl methacrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methacrylic acid; carboxyl group-containing monomer 5 weight %),
Inner layer: acrylic resin (Tg-50 ° C., constituent components: n-butyl methacrylate, n-butyl acrylate, 2-ethylhexyl acrylate),
Weight ratio of outer layer to inner layer 50:50, solid content 50% by weight

Resin 5: acrylic resin emulsion (Tg 12 ° C., component: t-butyl methacrylate, n-butyl methacrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methacrylic acid; solid content 50% by weight)

-Film-forming aid: 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate-Thickener: Hydroxyethyl cellulose powder-Antifoaming agent: Silicone defoaming agent (solid content 50% by weight)
Aggregate: colored aggregate mixture having a particle size of 0.1 to 2 mm (white: pale yellow = 1: 2)

(Test method)
(1) Finished appearance Spray coating of epoxy resin primer at a coating amount of 0.1 kg / m ² on a 900 × 900 × 3 mm slate plate, drying in standard condition for 8 hours, and then applying each aqueous coating material The surface condition when spray-coating at an amount of 2 kg / m ² was confirmed. The evaluation criteria are four stages (◎>○>△> ×) where “◎” indicates that the texture of the colored aggregate is utilized, and “×” indicates that the colored aggregate is in a state of blackish discoloration. did.

(2) Wet and cold-heat repeatability A 150 × 70 × 3 mm slate plate was spray-coated with an epoxy resin primer at a coating amount of 0.1 kg / m ² , dried in standard conditions for 8 hours, and then each aqueous coating material. Was spray-coated at a coating amount of 2 kg / m ² and cured for 14 days to obtain a test specimen. The specimen was immersed in water at 23 ° C. for 18 hours, immediately cooled in a thermostat kept at −20 ° C. for 3 hours, and then heated in another thermostat kept at 50 ° C. for 3 hours. After this operation was repeated 10 times, it was placed in a standard state for about 1 hour, and the state of the coating film surface was visually observed. Evaluation criteria are based on checking the degree of occurrence of abnormalities (cracking, swelling, and peeling). “◎” indicates that no abnormality occurred, “○” indicates that no abnormality occurred, “△” indicates that a part of the mark was generated, and “X” indicates a case where the abnormality was significantly generated.

(Test results)
The test results are shown in Table 2. In Test Examples 1 to 3, good results could be obtained in any test.

Claims (2)

A synthetic resin emulsion (A) in which an acrylic resin derived from (meth) acrylic acid alkyl ester and a silicone resin derived from a cyclic siloxane compound are mixed in the emulsion particles at a weight ratio of 99: 1 to 30:70,
As an essential component, at least one kind of aggregate (B) selected from pulverized natural stone, pulverized ceramic, and colored aggregate,
The synthetic resin emulsion (A) is a multilayer structure type synthetic resin emulsion (A-1) having an outer layer in which the acrylic resin and the silicone resin are mixed, and an inner layer containing the acrylic resin.
Wherein the solid content 100 parts by weight of synthetic resin emulsion (A), the aggregate (B) a 100-2000 parts by weight seen including, forming a coating film coated with the amount 0.8~10kg / ^{m 2} A characteristic water-based coating material.
On the inside and outside walls of the building,
A synthetic resin emulsion (A) in which an acrylic resin derived from (meth) acrylic acid alkyl ester and a silicone resin derived from a cyclic siloxane compound are mixed in the emulsion particles at a weight ratio of 99: 1 to 30:70,
  As an essential component, at least one kind of aggregate (B) selected from pulverized natural stone, pulverized ceramic, and colored aggregate,
  The synthetic resin emulsion (A) is a multilayer structure type synthetic resin emulsion (A-1) having an outer layer in which the acrylic resin and the silicone resin are mixed, and an inner layer containing the acrylic resin.
  An aqueous coating material containing 100 to 2000 parts by weight of the aggregate (B) with respect to 100 parts by weight of the solid content of the synthetic resin emulsion (A) is applied in an amount of 0.8 to 10 kg / m. ² A painting method characterized by painting with.