JPH1190325A - Applycation of external coating material on building - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide such a coating material and an applying method that a coating material can be applied directly on a building material or directly on a coating film or an intermediate coating layer already formed on a building material. SOLUTION: This external coating material for a building contains a core- shell type emulsion compsn. as a binder. The shell part consists of a polymer produced by polymn. of its monomer component which is added in the last stage of the multistage emulsion polymn. reaction when the compsn. is polymerized, while the core part consists of a polymer produced by polymn. of its monomer component which is added in the prior stage to the last stage. The monomer component which constitutes the shell part contains carboxyl group- contg. monomers in a large amt. than the carboxyl group-contg. monomers of the monomer component which constitutes the core part. The monomer component which constitutes the shell part contains 3 to 20 wt.% carboxyl group-contg. monomers.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for applying a paint for exterior of a building, and more particularly, to a method for exhibiting good adhesion to various building materials, and further having a stain resistance and a permeability. It is excellent in properties such as moisture and water resistance, and a coating using an emulsion composition capable of forming a coating film having good elasticity as a binder, without applying an undercoat treatment such as a sealer, directly on the material, or already on the material. The present invention relates to a method for directly applying a coating film or an intermediate coating material layer formed thereon.

[0002]

2. Description of the Related Art Paint films used as paints for building exterior walls include:
For example, "elasticity" to suppress the occurrence of cracks due to temperature changes and drying shrinkage, and to be able to follow minute cracks that occur on the substrate, and to maintain waterproofness and aesthetics
In addition to releasing excess moisture inside the wall to the outside to prevent dew condensation, "moisture permeability" to prevent blistering of the coating, and "contamination resistance" to prevent contaminants from adhering and fixing to the coating Are required. Recently, in addition to these required characteristics,
For the purpose of simplification of the process, it is demanded to have “adhesiveness” that can be applied directly without performing an undercoating treatment such as a sealer and that can adhere to a base material well.

In order to cope with such various required characteristics, for example, a core portion (inner core) and a shell portion (outer shell) in emulsion polymer particles are formed by using an emulsion polymerization method such as a seed polymerization method or a multi-stage polymerization method. Investigations have been made to control the properties of the coating film obtained from this emulsion by changing the properties of the emulsion (for example, see JP-A-4-45169).
No.).

[0004] However, it is difficult to obtain an emulsion polymer which satisfies all of the above-mentioned adhesive properties, stain resistance, moisture permeability and elasticity, and it is difficult to obtain an emulsion polymer directly on a material or on a coating material already formed on the material. An architectural exterior paint that can be applied directly to a film (including an old paint film) or an intermediate coating material layer and that exhibits satisfactory properties has not been found.

[0005]

Therefore, in the present invention, in order to respond to the simplification of the process, by finding a paint which can be directly applied without performing an undercoating treatment such as a sealer and can exhibit good adhesion, Directly on building materials,
Another object of the present invention is to provide a construction method capable of directly applying a coating film or an intermediate coating material layer already formed on a material.

[0006]

SUMMARY OF THE INVENTION The present invention relates to a method for applying an exterior coating composition for a building containing a core-shell type emulsion composition obtained by multi-stage emulsion polymerization as a binder, wherein the core-shell type emulsion composition comprises The polymer portion formed by polymerization of the monomer component added to the final stage of the multi-stage emulsion polymerization reaction at the time of polymerization is used as a shell portion, and is formed by polymerization of the monomer component added before the final stage. When the polymer portion as the core portion, the amount of the carboxyl group-containing monomer in the monomer component constituting the shell portion is the same as the carboxyl group-containing monomer in the monomer component constituting the core portion. And the monomer component constituting the shell portion contains a carboxyl group-containing monomer in an amount of 3 to 20% by weight, and this composition is contained as a binder. Building exterior paint, with the gist without undercoating treatment of sealer, where the construction directly on the coating film formed directly, or on the material on the material.

[0007] Even when the coating film formed on the material is an old coating film (one that has already been exposed outdoors), by applying the method of the present invention, the coating film can be directly applied without performing a primer coating treatment such as a sealer. Coating is possible and helps to simplify the process. Also, the coating film is excellent in stain resistance and moisture permeability.

In the present invention, an architectural exterior paint containing the above-mentioned core-shell type emulsion composition as a binder is provided.
After forming a layer (including both a continuous layer and a partially formed layer) made of an intermediate coating material on a material, it is also possible to apply directly to the intermediate coating material layer. The paint used in the method of the present invention exhibits good adhesion to the intermediate coating material layer and forms a topcoat layer having good stain resistance and moisture permeability, so that it has high performance as a so-called topcoat or finish topcoat. It is.

It is also preferable that all the monomer components constituting the core-shell emulsion contain a cyano group-containing monomer in order to improve the adhesion. In particular, in the embodiment in which the cyano group-containing monomer is contained in the monomer component constituting the shell portion in an amount of 3 to 20% by weight, the adhesive force is further improved.

A structure in which an epoxy group-containing monomer is contained in all the monomer components constituting the core-shell emulsion is also preferable for improving the adhesion. Further, since the shell portion contains a large amount of carboxyl groups, it also has an effect of improving water resistance, which tends to decrease. Therefore, in the monomer component constituting the shell portion, the epoxy group-containing monomer is 0.1 to 0.1.
The configuration containing 5% by weight is most preferable.

Further, the Tg (glass transition temperature) of the shell portion of the core-shell type emulsion is 0 to 80 ° C., the Tg of the core portion is −40 to + 40 ° C., and the Tg of the shell portion is higher than the Tg of the core portion. As described above, when a monomer component constituting the core-shell emulsion composition is selected, it is possible to form a coating film capable of exhibiting good elasticity and stain resistance without deteriorating a film-forming property. The Tg (K) of the polymer is given by the following equation.

[0012]

(Equation 1)

The weight of the monomer component constituting the shell portion is as follows:
It is preferable that the content be 10 to 90% by weight in all the monomer components constituting the core-shell emulsion composition. The architectural exterior paint includes an emulsion composition for an architectural exterior paint whose Tg of the entire core-shell emulsion is −30 to + 30 ° C., and contains a pigment and a filler in a total of 40% by volume in the solid content of the paint. Those having a configuration that does not exceed the range are preferred.

[0014]

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to
When a core-shell emulsion is used, a specific amount of carboxyl groups is present in the shell portion, which is the surface layer of the emulsion particles, to improve adhesion, stain resistance, and moisture permeability, and to improve the material or the coating already formed on the material. It has the greatest points where it is possible to apply it directly to the membrane. In addition, it has been found that the combined use of a cyano group-containing monomer can increase the adhesive force, and the combined use of an epoxy group-containing monomer improves the adhesive force, and furthermore, reduces the water resistance caused by the carboxyl group in the shell portion. We succeeded in preventing it. Hereinafter, first, the core-shell emulsion composition will be described.

In the method of the present invention, a core-shell type emulsion composition obtained by a multi-stage emulsion polymerization is used as a binder for a paint. The polymer portion formed by polymerization of the monomer component added to the final stage of the multi-stage emulsion polymerization reaction is defined as a shell portion. The multistage emulsion polymerization may be divided into two stages, a former stage (for core) and a latter stage (for shell), or may be divided into two or more stages. When performing multi-stage emulsion polymerization of two or more stages, since the polymer portion formed by polymerization of the monomer component added to the polymerization system in the final stage is located on the surface layer of the emulsion particles,
In the present invention, this polymer part is called a shell part. In the case of multi-stage polymerization of three or more stages, it can be distinguished from the core portion, the intermediate layer portion (plural), and the shell portion, but in the present invention, the monomer component added to the polymerization system before the final stage is used. Are all referred to as a core monomer component for convenience, and the polymer portion constituted by this monomer component is referred to as a core portion for convenience.

In the present invention, the monomer component constituting the shell portion must contain a carboxyl group-containing monomer in an amount of 3 to 20% by weight. If the amount of the carboxyl group-containing monomer is less than 3% by weight, a sufficient adhesive force cannot be obtained unless an undercoating treatment is performed. In addition, the coating film is easily contaminated,
It also has poor moisture permeability. However, when the content exceeds 20% by weight, the water resistance of the coating film is reduced, and even if an epoxy group-containing monomer is used in combination, the improvement of the water resistance becomes insufficient, which is not preferable. Although the carboxyl group may be present in the core, the present invention is based on the technical idea that the carboxyl group is present in the shell portion. If the total amount of the carboxyl group is too large, the water resistance is reduced. Must be smaller than the shell part.

Specific examples of the carboxyl group-containing monomer include acrylic acid, methacrylic acid, itaconic acid, fumaric acid, maleic acid, crotonic acid, citraconic acid, maleic monoester, fumaric monoester, and itaconic monoester. And carboxylic acids containing a polymerizable unsaturated group such as citraconic acid monoester. These can be used alone or in combination of two or more.

In order to improve the adhesion, a constitution in which a cyano group-containing monomer is contained in all the monomer components constituting the core-shell type emulsion composition may be used in combination. Adhesion is improved by using a cyano group-containing monomer. Further, the elasticity, water resistance and stain resistance of the coating film are also improved. The cyano group-containing monomer may be present in any of the core and the shell, but by having a specific amount present in the shell portion, the above effects can be surely exerted without lowering the weather resistance. Therefore, in the monomer component constituting the shell portion, the cyano group-containing monomer contains 3 to 20
It is recommended that it be included by weight. 3% by weight
If the amount is smaller, the properties such as adhesion are inferior, and conversely,
If it exceeds, the weather resistance decreases. When a cyano group-containing monomer is used also in a portion other than the shell portion, the amount of the cyano group-containing monomer in all the monomer components may be set within the above range. As the cyano group-containing monomer, acrylonitrile,
Methacrylonitrile and the like can be used.

In the present invention, an epoxy group-containing monomer may be contained in all the monomer components constituting the core-shell type emulsion composition. Since the epoxy group-containing monomer reacts with the carboxyl group, poor water resistance due to the carboxyl group can be prevented. further,
It is also effective in improving the adhesion. Since the carboxyl group may be present in the core, the epoxy group-containing monomer may be present in either the core or the shell.

However, in order to improve water resistance, which tends to decrease due to the presence of a large amount of carboxyl groups in the shell, it is more effective to include an epoxy group in the shell. The most preferred configuration is that the epoxy group-containing monomer is contained in the monomer component constituting 0.1 to 5% by weight. When an epoxy group-containing monomer is used also in a portion other than the shell portion, the amount of the epoxy group-containing monomer in all the monomer components may be set within the above range. Specific examples of the epoxy group-containing monomer include glycidyl (meth) acrylate, allyl glycidyl ether and the like.

The core-shell type emulsion composition used in the present invention comprises a carboxyl group-containing monomer which is an essential component, a cyano group-containing monomer and an epoxy group-containing monomer which are preferably used, and other than these monomers. Can be used for the core part or the shell part.

Specific examples of "other monomers" include:
Methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, (meth) acrylic acid
(Meth) acrylic acid such as 2-ethylhexyl and C ₁ -C
(Meth) acrylic acid esters which are esters of ₁₈ (including aliphatic, alicyclic and aromatic) alcohols;
Hydroxyl group-containing (meth) acrylates such as 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth) acrylate, monoester of (meth) acrylic acid and polypropylene glycol; (meth) acrylamide, N-monomethyl (Meth) acrylamide, N
-(Meth) acrylamide derivatives such as monoethyl (meth) acrylamide and N, N-dimethyl (meth) acrylamide; dimethylaminoethyl (meth) acrylate;
Basic polymerizable monomers such as dimethylaminoethyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, vinylpyridine, vinylimidazole, vinylpyrrolidone; N-methylol (meth) acrylamide, N-butoxymethyl (meth) Crosslinkable (meth) acrylamides such as acrylamide; styrene derivatives such as styrene, vinyltoluene, α-methylstyrene, and chloromethylstyrene; vinyl esters such as vinyl acetate and vinyl propionate; vinyl fluoride, vinylidene fluoride; Halogenated monomers such as vinyl chloride and vinylidene chloride; conjugated dienes such as butadiene and isoprene; olefins such as ethylene, propylene and butene; and the like. Can be used

When the above “other monomer” is selected to polymerize the core-shell type emulsion, the Tg (glass transition temperature) of the shell portion of the core-shell type emulsion is set to 0 to 0.
At 80 ° C., the Tg of the portion other than the shell portion (core portion) is −40 to + 40 ° C., and the Tg of the shell portion is the Tg of the core portion.
g. It is possible to form a coating film that can exhibit both good elasticity and stain resistance without deteriorating the film forming property. Tg of the whole emulsion
Is too high, the minimum film-forming temperature becomes high and the film-forming property is reduced. Therefore, in order to secure the film-forming property, it is preferable that the Tg of the core is lower than the Tg of the shell. However, when the Tg of the core or shell deviates from the above range, it becomes difficult to improve various coating properties in a well-balanced manner.

From the above viewpoint, it is preferable that the weight of the monomer component constituting the shell part is 10 to 90% by weight based on all the monomer components constituting the core-shell type emulsion composition. Particularly preferably, it is 20 to 70% by weight. The weight of the monomer component constituting the shell part is 90% of the whole.
If the content is more than 10% by weight, the film-forming property is inferior even if the above-mentioned Tg range is set, and there arises a disadvantage that a large amount of a film-forming auxiliary must be used. Conversely, if the content is less than 10% by weight, the shell portion is too small, and the effect of improving the properties such as stain resistance, moisture permeability, elasticity, water resistance, film forming property, and adhesion may not be sufficiently exhibited.

The core-shell emulsion composition can be produced by performing two or more stages of multi-stage emulsion polymerization. In the final stage, the monomer component for the shell portion is polymerized, but before that, the monomer component for the core portion may be polymerized in any number of stages.

The method for adding the monomer components for the core and shell to the polymerization reaction system is not particularly limited.
For the subsequent polymerization, a method such as batch addition, monomer dropping, and pre-emulsion dropping can be used.

In the multistage emulsion polymerization, any known radical polymerization initiator can be used without any particular limitation. Specifically, persulfates and peroxides such as ammonium persulfate, sodium persulfate, hydrogen peroxide, t-butyl hydroperoxide, t-butyl peroxybenzoate;
2′-azobisisobutyronitrile, 2,2′-azobis (2-amidinopropane) hydrochloride,
2′-azobis (2,4-dimethylvaleronitrile),
Water-soluble azo compounds such as 4,4'-azobis (4-cyanopentanoic acid) can be mentioned. The amount used is preferably about 0.1 to 1% by weight of the monomer component. In addition, a reducing agent such as sodium bisulfite, ferrous chloride, ascorbate, or Rongalite may be combined in order to accelerate the polymerization rate or when polymerizing at a low temperature.

The emulsifier is not particularly limited either, and fatty acid salts such as sodium lauryl sulfate, higher alcohol sulfates, alkylbenzene sulfonates such as sodium dodecylbenzenesulfonate, polyoxyethylene alkyl ether sulfate, polyoxynonylphenyl Anionic surfactants such as alkyl allyl polyether sulfates such as ammonium ether sulfonate, reactive emulsifiers such as polyoxyethylene polyoxypropylene glycol ether sulfate, and monomers having a sulfonic acid group or a sulfate ester group; Polyoxyethylene alkylphenyl such as ethylene alkyl ether and polyoxynonylphenyl ether, sorbitan fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene-polyoxy Nonionic surfactants such as propylene block copolymers and reactive nonionic surfactants; cationic surfactants such as alkylamine salts and quaternary ammonium salts; and a known emulsifier such as (modified) polyvinyl alcohol are added. Just do it.

The above-mentioned emulsifiers can be used alone or in combination of two or more.
It is preferable to use about 01 to 10% by weight. Further, if necessary, t-dodecyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, mercaptoacetic acid,
A chain transfer agent such as mercaptopropionic acid and 2-mercaptoethanol can be used. The polymerization temperature is 0 to 100 ° C, preferably 50 to 80 ° C, and the polymerization time is 1 to 15 hours. At the time of emulsion polymerization, a hydrophilic solvent or an additive may be added.

In the building exterior paint, together with the core-shell type emulsion composition described above, raw materials and various additives used for the paint formulation can be used as needed. For example, pigments, inorganic or organic fillers, thickeners, lubricants, hydrophilizing agents, water-soluble or aqueous resins,
Dispersants, surfactants, water-proofing agents, crosslinking agents, film-forming auxiliaries, heat-fusible substances, pH adjusters, viscosity adjusters and the like can be added. As the pigment, rutile-type or anatase-type titanium dioxide, lithopone, inorganic pigments such as iron oxide, chromium oxide, and paint pigments such as known organic pigments are used.
Fillers include calcium carbonate, barite, mica,
Silica sand or the like is used. As the thickener, a known compound having a thixotropic effect such as a polyethylene oxide type, an amide type, a crosslinked polyacryl type, or a silica type may be used.

When the above core-shell type emulsion composition is used for the above-mentioned architectural exterior paint, if the Tg of the whole core-shell type emulsion is set to -30 to + 30 ° C., cracks due to temperature change and drying shrinkage are suppressed, and a crack is generated on the substrate. This is preferable because an architectural exterior paint capable of exhibiting elasticity capable of following a minute crack can be provided. When a pigment and a filler are added, it is preferable that the volume concentration (PVC) of the pigment and the filler in the solid content of the paint does not exceed 40% by volume to obtain good coating performance. Is preferred.

The material (substrate) to which the method of the present invention can be applied is preferably an outer wall constituting material, specifically, mortar, concrete, ALC (lightweight cellular concrete),
PC (prestressed concrete) board, slate board,
Examples thereof include inorganic materials such as various (metal-based and gypsum-based) siding boards, and organic materials such as wood and various plastics (including FRP).

The method of the present invention relates to a method of directly applying an architectural exterior paint on these materials without an undercoat, and a method of applying an architectural exterior paint directly on an already formed coating film without an undercoat. The `` already formed coating '' is an old coating that has been exposed to the outdoors, and a method of directly applying an architectural exterior coating without an undercoat on this old coating, applying a basecoat treatment such as a sealer, or It can be divided into a method of providing an intermediate coating material layer without applying it, and directly applying an architectural exterior paint thereon.

Existing finish coating materials constituting "already formed coating films" on the material include single-layer elastic coating materials, synthetic resin emulsion paints, urethane resin paints, acrylic resin enamel paints, and vinyl chloride resin paints. , Spraying tiles,
There are resin-based lysine-based paints and other known various organic-based paints, cement lysine-based, cement stucco-based, and siliceous-based inorganic paints. The intermediate coating material is mainly applied for the purpose of enhancing the design of the architectural exterior, and is particularly limited as long as it can form a ball-blowing pattern, unevenness, a wavy pattern, or the like continuously or partially. In addition, paints such as cement-based, polymer-cement-based, siliceous-based paints, and emulsion-type or solution-type resin-based paints can be used. If necessary, a sealer, a primer treatment, or another base adjustment material may be used on the material before providing the intermediate coating material layer.

As a coating method, a known method such as a roller method, an air spray method, or an airless spray method can be adopted.
In the method of the present invention, since a paint having excellent adhesion is used, when applying the raw material or an old coating film, it is not necessary to perform a sealer or a primer treatment, and the coating can be performed directly. In the case where simplification of the process is not particularly regarded as important, a sealer or a primer treatment may be performed.

The amount of application may be appropriately changed according to the solid content concentration and specific gravity of the coating material, the type and use of the material, the old coating film or the intermediate coating material layer, the presence or absence of a pattern, and the like. Usually, in order to form a coating film having a uniform thickness, the viscosity of the coating material should be 5 to 25 Pa ·
It is preferable that the coating amount is 0.1 to 1.5 kg / m ² . When a wavy pattern is imparted using the paint of the present invention, use of a porous roller, a wool roller, or the like is recommended. The paint viscosity is set to 10 to 25 Pa · s, and the coating amount is set to 0.4 to 1. 5 kg / m ² should be used.
It is preferable that the application amount is 0.4 to 1.5 kg / m ² in terms of a · s, and it is preferable that the coating be performed using a spray gun such as a tile gun or a ricin gun. When an intermediate coating material layer is provided to impart a pattern, the coating of the present invention can be directly applied as a top coating.

[0037]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which do not limit the present invention.
Modifications and alterations that do not depart from the spirit described below are all included in the technical scope of the present invention. In addition, "part", "%"
Represents "parts by weight" and "% by weight", respectively, unless otherwise noted.

Production Example 1 651 parts of ion-exchanged water was charged into a 2 L separable flask equipped with a stirrer, a reflux condenser, a dropping funnel, a nitrogen inlet tube, and a temperature sensor.
Under stirring, the temperature was raised to 70 ° C. Next, 2-ethylhexyl acrylate 21 previously prepared was added from the dropping funnel.
9 parts, methyl methacrylate 125 parts, styrene 150
Parts, acrylic acid 6 parts (calculated Tg of polymer obtained from the above monomers: 0 ° C.), ammonium polyoxyethylene nonyl phenyl ether sulfate (trade name “HYTENOL N-08”, a 15% aqueous solution; Daiichi Kogyo Co., Ltd.) Pharmaceutical company) 33
The first-stage monomer component was prepared by mixing a pre-emulsion (A) consisting of 40 parts of a 25% aqueous solution of polyoxyethylene nonylphenyl ether (trade name “Nonipol 200”; manufactured by Sanyo Chemical Co., Ltd.) and 102 parts of deionized water. Over 1 hour and 30 minutes. At this time, 30 parts of a 5% aqueous solution of ammonium persulfate was simultaneously added dropwise over 1 hour and 30 minutes.

After completion of the dropping, the mixture was aged for 40 minutes, and subsequently, 2-ethylhexyl acrylate 11 prepared in advance was prepared.
6 parts, methyl methacrylate 206 parts, styrene 150
Parts, acrylic acid 28 parts (calculated Tg of polymer obtained from the above monomers: 40 ° C.), 33 parts of 15% aqueous solution of Hytenol N-08, 25% aqueous solution of Nonipol 200
Was added dropwise over 1 hour and 30 minutes as a pre-emulsion (B) consisting of 40 parts and 102 parts of deionized water as a final stage monomer component. At this time, 30 parts of a 5% aqueous solution of ammonium persulfate was simultaneously added dropwise over 1 hour and 30 minutes. After completion of dropping, aging was performed for 1 hour. Cool, 25
The mixture was neutralized by adding 4.6 parts of aqueous ammonia to obtain a core-shell emulsion composition. This core-shell emulsion composition had a nonvolatile content of 49.2% and a pH of 6.
0, viscosity 550 mPa · s (B-type viscometer, rotor N
o. 2, 30 times / min, measured at 25 ° C .; the same applies hereinafter), minimum film forming temperature (MFT; measured with a minimum film forming temperature measuring instrument; the same applies hereinafter) 28 ° C., average particle diameter 140 nm (light scattering particle diameter measuring apparatus) And the same hereafter).

Production Examples 2 to 17 and Comparative Production Examples 1 to 11 Emulsion compositions were synthesized in the same manner as in Production Example 1 except that the monomers used and the polymerization conditions were changed as shown in Tables 1 to 5. The characteristics and characteristic values of each example are also shown in Tables 1 to 5.

The abbreviations used in the following tables have the following meanings. The values in parentheses indicate the Tg of the homopolymer of each monomer. 2EHA: 2-ethylhexyl acrylate (-70
C) MMA: Methyl methacrylate (105C) St: Styrene (100C) AA: Acrylic acid (95C) MAA: Methacrylic acid (130C) AN: Acrylonitrile (96C) GMA: Glycidyl methacrylate (40C) aq. : Aqueous solution APS: Ammonium persulfate PVC: Volume% of pigment and inorganic filler in paint solids

[0042]

[Table 1]

[0043]

[Table 2]

[0044]

[Table 3]

[0045]

[Table 4]

[0046]

[Table 5]

EXAMPLES, COMPARATIVE EXAMPLES AND REFERENCE EXAMPLES Using the emulsion compositions synthesized in the above Production Examples and Comparative Production Examples, paints were prepared in the following formulations, and the coating film properties were evaluated. The results are shown in Tables 6 and 7.

[Preparation of paint] First, a styrene maleate dispersant (manufactured by Alcochemical Co .; SMA144)
0) 15 parts, titanium dioxide 100 parts, calcium carbonate 1
00 parts and 70 parts of water were mixed and dispersed to prepare a dispersion paste. 50 parts of the emulsion composition, 1 part of an antifoaming agent, 2 parts of a thickener and a dispersion paste were mixed and stirred to obtain a paint.
The mixing amount of the dispersion paste is 15 parts when PVC is 10% by volume, 30 parts when PVC is 20% by volume, P
80 parts when VC is 40% by volume, 50% by volume PVC
Is 115 parts. In Examples 8a to 8c, the same emulsion composition synthesized in Production Example 8 was used.
C was changed as shown in Table 6, and in the reference example, PVC was adjusted to 50% by volume outside the preferred range by using the emulsion of Production Example 8 in the same manner.

[Adhesiveness] The above-mentioned paint was applied to a substrate to be described later with a doctor blade (or a wool roller) to a thickness of 1 mm and dried at room temperature for 2 weeks.
m, cut into 10cm length with a cutter knife,
The degree of peeling was visually evaluated according to the following criteria. ：: Peeled off on the undercoat side without peeling at the interface between the undercoat and the coating film △: Peeled off at the interface between the undercoat and the coating film but with strong adhesion (practical acceptable level) ×: Undercoat and the coating film That peel off without resistance at the interface of

[Stain Resistance] The above paint was applied to a thickness of 1 mm on a slate plate with a doctor blade and dried at room temperature for 3 days to prepare a test piece. The test piece was set on an exposure rack provided with a roof so that the rain flowed down the surface of the coating film of the test piece during rainfall, and the degree of contamination of the coating film surface after 6 months was visually evaluated according to the following criteria. . ○: Dirt and rain streaks are not noticeable ×: Dirt and rain streaks are noticeable

[Moisture permeability] The moisture permeability was evaluated according to ASTM-E96-99. ：: 100 g / m ² or more in 24 hours ×: Less than 100 g / m ^{2 in} 24 hours

[Elasticity] In accordance with the elongation test of JIS-A-6909, the paint was applied on release paper, dried for 14 days, and punched out into a 1 mm thick dumbbell-shaped No. 2 mold to obtain a test piece. ◎: The elongation exceeds 300% ：: The elongation exceeds 120 to 300% ×: The elongation is 120% or less

[Water resistance] On a slate plate, the above coating material was applied to a thickness of 1 mm with a doctor blade, dried at room temperature for 2 weeks, immersed in water at 20 ° C. for 7 days, and taken out. It was visually evaluated according to the following criteria. ：: No blisters are generated. Δ: A degree of small blisters is generated (a practical pass level). ×: Large blisters are generated. The types and treatment methods of various coated articles used for evaluation of adhesion are as follows. It is.

[Substrate A-1 (Multilayer Coating Material E Type)] A chlorinated rubber sealer is applied to a slate plate substrate (undercoating treatment). Next, an acrylic intermediate coating material (“Tile Rack EMA-S 100K” manufactured by Nippon Paint Co., Ltd.) is applied to a thickness of 2 mm with a doctor blade and dried for one day. afterwards,
Various paints for the test were applied with a wool roller, dried for 2 weeks, and evaluated for adhesion.

[Substrate A-2] Like the substrate A-1,
After the undercoating treatment and the coating and drying of the intermediate coating material, the acrylic overcoating material (“Tile Rack EM” manufactured by Nippon Paint Co., Ltd.)
"A topcoat" was applied with a wool roller and held in a sunshine weatherometer for 2000 hours. Thereafter, various coating compositions for testing were applied to a thickness of 1 mm with a doctor blade, dried for 2 weeks, and evaluated for adhesion.

[Coating A-3] Coating A-2 except that a polyurethane topcoat ("Tilerack U Topcoat" manufactured by Nippon Paint Co., Ltd.) was used instead of the acrylic topcoat.
Same as.

[Coating object B-1 (waterproof type multilayer coating material E type)] The same as the coating object A-1 except that "DAN tile coating" manufactured by Nippon Paint Co., Ltd. was used as the intermediate coating material.

[Coating object B-2] Coating material was used except that "DAN tile middle coating" manufactured by Nippon Paint Co., Ltd. was used as the intermediate coating material, and "DAN tile SN top coating" manufactured by Nippon Paint Co., Ltd. was used as the top coating material. Same as A-2.

[Coating object B-3] "DAN tile U top coating super" manufactured by Nippon Paint Co., Ltd. was used as the top coating material, using "NAN tile middle coating" manufactured by Nippon Paint Co., Ltd.
Except for using, the same as Coating A-3.

[Substrate C (Waterproof exterior thin coating material type)]
A chlorinated rubber sealer is applied to the base material of the slate plate (undercoating treatment). Next, Nippon Paint Co., Ltd. “DAN Uni” was applied as a resilient coating material to a thickness of 1 mm with a doctor blade, and was applied in a sunshine weatherometer for 2,000 hours.
Held. Thereafter, various paints for testing were applied to a thickness of 1 mm with a doctor blade, dried for 2 weeks, and evaluated for adhesion.

[Coating object D (multilayer coating material CE type)] A cement-based spray tile ("Filler 200" manufactured by Nippon Paint Co., Ltd.) is directly applied to a slate plate with a doctor blade to a thickness of 1 mm and dried for 2 days. . After that, various paints for the test were applied to a thickness of 1 mm with a doctor blade and dried for 2 weeks.
The adhesion was evaluated.

[Coating Material E (Exterior Thin Coating Material C Type)] A cement lysine material was directly sprayed on a slate plate and held in a sunshine weatherometer for 2000 hours. Thereafter, various paints for testing were applied to a thickness of 1 mm with a doctor blade, dried for 2 weeks, and evaluated for adhesion.

[Substrate F (Exterior Thin Coating Material E Type)] A chlorinated rubber-based sealer is applied to a slate plate substrate (undercoating treatment). Next, acrylic lysine ("Nippe Acrylic Lysine" manufactured by Nippon Paint Co., Ltd.) was sprayed as a resin lysine-based paint, and was 2,000 hours in a sunshine weatherometer.
Held. Thereafter, various paints for testing were applied to a thickness of 1 mm with a doctor blade, dried for 2 weeks, and evaluated for adhesion.

[Coating object G] Mortar board (manufactured by Nippon Test Panel; prepared according to 10.4 of JIS R5201)
1 meter directly with a doctor blade for various paints for testing
After coating for a thickness of 2 m and drying for 2 weeks, the adhesion was evaluated.

[0065]

[Table 6]

[0066]

[Table 7]

[0067]

According to the method for applying an architectural exterior paint of the present invention, a core-shell type emulsion composition containing a specific amount of a carboxyl group in a shell portion more than a core portion is used as a paint binder. A coating film having excellent properties such as water resistance, stain resistance, moisture permeability, elasticity, and water resistance can be formed. In addition, because the adhesion of the paint is particularly good, it can be applied directly to the material or directly to the already formed coating film without applying the undercoat treatment, such as when renovating the exterior, Significant process simplification and cost reduction can be achieved. In addition, by using the method of the present invention, a high-performance top coat can be formed by directly applying a coating material on the intermediate coating material layer.

Continuation of the front page (51) Int.Cl. ⁶ Identification code FI C09D 133/20 C09D 133/20 151/00 151/00 (72) Inventor Shigeyasu Morihiro 5-8 Nishiminaburicho, Suita-shi, Osaka Co., Ltd. Within Nippon Shokubai (72) Inventor Satoshi Shiraishi 5-8 Nishiburi-cho, Suita-shi, Osaka Nippon Shokubai Co., Ltd.

Claims (7)

[Claims] 1. A method for applying a building exterior paint containing a core-shell type emulsion composition obtained by multi-stage emulsion polymerization as a binder, wherein the core-shell type emulsion composition undergoes a multi-stage emulsion polymerization reaction when polymerizing the composition. The polymer portion formed by polymerization of the monomer component added to the final stage is a shell portion, and the polymer portion formed by polymerization of the monomer component added before the final stage is the core portion. Sometimes, the amount of the carboxyl group-containing monomer in the monomer component constituting the shell portion is larger than the amount of the carboxyl group-containing monomer in the monomer component constituting the core portion, and the shell The monomer component constituting the part contains a carboxyl group-containing monomer in an amount of 3 to 20% by weight, and the building exterior paint is formed directly on the material or on the material. Directly on the coating film are, the construction method of building exterior coatings, characterized by construction. 2. The method according to claim 1, wherein the coating film formed on the material is an old coating film. 3. The method according to claim 1, wherein the coating film formed on the material is an intermediate coating material, and the coating film made of the intermediate coating material is formed continuously or partially on the material. The construction method of the building exterior paint described. 4. The architectural exterior paint according to claim 1, wherein all of the monomer components constituting the core-shell emulsion composition contain a cyano group-containing monomer. Construction method. 5. The architectural exterior paint according to claim 1, wherein the epoxy group-containing monomer is contained in all the monomer components constituting the core-shell emulsion composition. Construction method. 6. The Tg (glass transition temperature) of the shell portion of the core-shell type emulsion composition is from 0 to 80 ° C., the Tg of the core portion is from −40 to + 40 ° C., and the Tg of the shell portion is
The method for applying an architectural exterior paint according to any one of claims 1 to 5, wherein a monomer component constituting the core-shell type emulsion composition is selected such that is higher than Tg of the core portion. 7. A range containing a core-shell type emulsion composition having a Tg of -30 to + 30 ° C. in the whole core-shell type emulsion, and a pigment and a filler in a total amount of not more than 40% by volume in the solid content of the paint. The method for applying an architectural exterior paint according to any one of claims 1 to 6, wherein the method comprises: