JP2013112782A - One-part type normal temperature crosslinkable aqueous coating composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a one-part type normal temperature crosslinkable aqueous coating composition achieving performance equal to or higher that of a conventional two-part crosslinkable or solvent-based composition and satisfying requirements meeting respective applications when used as a coating composition for various applications such as urethane waterproof materials, metallic materials, wooden materials, ceramic building materials, and plastic materials.SOLUTION: The one-part type composition self-crosslinking at normal temperature includes: a one-part normal temperature crosslinkable polymer emulsion (A) which is prepared by incorporating a hydrazine structure-containing (hydrazine group-containing) polyurethane and a carbonyl group-containing acrylic polymer inside particles dispersed in an aqueous medium and is used as a base component; a polyurethane dispersion (B) wherein particles have both a high Tg ingredient region and a low Tg ingredient region; and an ultrafine particle nanoemulsion (C) having the average particle diameter within the range of 5-140 nm.

Description

  The present invention includes a top coat for a waterproof coating method (particularly urethane waterproof method), or wood (including building interior materials, building exterior materials, various flooring materials, ceramic building materials and other various building materials, woodworking furniture, etc.) The present invention relates to an aqueous coating composition used as a top coat or primer coat for coating metal (raw material and molded product), plastic (raw material and molded product), and more particularly to a one-pack room temperature crosslinking type aqueous coating composition. .

  Conventionally, an acrylic copolymer aqueous dispersion has been widely used as a one-component type aqueous coating for room temperature drying that can be used conveniently and is advantageous in terms of environment and safety. Water-based paints composed of this type of acrylic copolymer aqueous dispersion require fusion of emulsion particles in a film forming process at room temperature after coating. Therefore, it is difficult to increase the glass transition temperature (Tg) of the resin due to the film-forming property of the acrylic copolymer used in the one-component room temperature drying water-based paint, so that the stain resistance is low. Vulnerability is undeniable in terms of water resistance.

  On the other hand, the market is becoming more and more expensive year by year, and water-based paints are required to have durability, toughness, and contamination resistance comparable to organic solvent-type urethane paints. Recently, there has also been a demand for water-based treatment from the viewpoint of environmental sanitation, firefighting law, etc. Therefore, a one-component room-temperature drying-type water-based paint having a coating performance equivalent to that of an organic solvent-type urethane paint. Development is strongly desired.

As a conventional measure to meet the above-mentioned demand, a two-part water-based paint of a water-based acrylic polyol containing a hydroxyl group and a water-dispersed polyisocyanate has been developed. In this type of paint, in addition to fusion, urethane is used. By causing the reaction (crosslinking reaction), improvement of weather resistance, water resistance and the like is achieved (see Patent Document 1).
However, in such a two-component cross-linking type water-based paint, in addition to the trouble of mixing the two components, color change, gloss change, thickening, and finished appearance accompanying the pot life after mixing the two components There was a problem with this.

  In addition, there are two-component undercoat paints that harden water-dispersed epoxy resins with amines for repairing steel structures, but this has a slow reaction rate and takes enough time to apply the top coat. There is a need.

  On the other hand, as an aqueous one-component type paint, there has been an attempt to crosslink a urethane polymer aqueous dispersion having a hydrazide residue to a carbonyl group-containing copolymer aqueous dispersion for the purpose of imparting a urethane function to the emulsion. (See Patent Document 2). However, with this composition alone, urethane waterproofing materials, interior / exterior materials, metal materials / metal moldings, wood flooring / wood moldings, ceramics interior / exterior materials, and film formation for plastic materials In addition, it is inferior to water-based two-component paints in terms of brittleness during crosslinking, finished appearance, gloss, dryness, water resistance, further weather resistance, outdoor exposure contamination, etc. The reality is that quality was not obtained.

Japanese Patent Laid-Open No. 2-105879 Japanese Patent Laid-Open No. 1-301761

The application of the coating composition is diverse, and there are various objects to be coated, and at the same time, the purpose of coating and the environment of use are also varied. However, coating compositions for paints that have been developed in the past have been able to satisfy a specific object, a specific use environment, and a specific use purpose, but for each of a wide variety of applications, A coating composition that can exhibit sufficient performance is rare, and it is excellent in various applications as a water-based coating composition that is a simple one-pack type room temperature drying type that is advantageous to the environment and safety. The actual situation is that a coating composition capable of ensuring the coating film performance has not been developed.
Next, problems and problems to be solved for conventional coating compositions for paints will be described for each main application.

[For waterproofing purposes]
The waterproofing method for buildings (including inside and outside of buildings) has the effect of preventing aging of buildings and extending their life, and is important for effective use of resources and reduction of waste materials.
The methods of waterproofing are roughly classified into asphalt waterproofing, sheet waterproofing, and urethane waterproofing (hand-painted, ultra-fast curing spray). In each waterproofing method, it is usual to apply a top coat having a coating film property excellent in weather resistance for the purpose of preventing deterioration of the base and imparting aesthetics. Here, when applying the top coat to the urethane waterproof layer, it is common to apply a top coat made of a solvent-based two-component polyurethane resin in order to obtain sufficient adhesion. In addition to the troublesome mixing, problems occur in the color change, gloss change, thickening, and finished appearance associated with the pot life after mixing the two liquids.
Furthermore, when the solution is made into one solution in order to eliminate the troublesome mixing of the two components, it is difficult to obtain satisfactory coating film performance because the molecular weight is not sufficient. In addition, when the molecular weight is increased in order to obtain a good coating film performance, the viscosity becomes high and a problem occurs in coating workability.
In recent years, in order to improve environmental problems, movements to make solvent-based polyurethane paints into two-component aqueous solutions have been promoted, but even in this case, in addition to the trouble of two-component mixing, the possibility of mixing after two-component mixing is also possible. No improvement in defects has been achieved in color change, gloss change, thickening, and finished appearance with use time (pot life).
Therefore, as a coating composition for waterproof topcoat, the development of a coating composition having excellent coating workability and appearance characteristics, particularly a one-component aqueous type room temperature drying coating composition, as well as excellent weather resistance and other coating performances. It is strongly desired.

[For metal coating: primer coat / top coat]
The coating of metal materials also has the effect of preventing the deterioration of the building and building material parts, preventing the building from aging and extending its life.
For coating metal materials, chemical-treated coatings with excellent corrosion resistance and adhesion, solvent-based epoxy primers, and powder paints are used to prevent metal deterioration, but they are all durable due to their poor weather resistance. Therefore, a urethane-based topcoat having a coating film property excellent in weather resistance is desired. The weather resistance has been solved to some extent by using a thermosetting resin as a solvent system, or by using a two-component type, and has already been used for many years.
However, in recent years, from the viewpoint of environmental problems and from the viewpoint of energy saving, a shift to a low-temperature curing type and a water-based two-part liquefaction of a top coat paint for reducing organic solvents have been promoted.
When a metal material is used as an object to be coated, it is conventionally known that a water-based acrylic emulsion or a polyurethane dispersion is used as a water-based paint for drying at room temperature for both the primer and the top coat. In addition, coating compositions are known in which epoxy resins modified with fatty acids are dehydrated and condensed in the air due to the effect of a metal catalyst. However, all of them have a slow curing reaction and stable coating workability is obtained by environmental factors. There is a problem that can not be.
Therefore, as a primer coating for metal materials, it has excellent coating performance such as corrosion resistance, adhesion, and durability (weather resistance), and at the same time has excellent coating workability, especially a one-part aqueous type room temperature dry coating composition. Development of is strongly desired.

Conventionally, a water-soluble paint containing an organic solvent that is soluble in water has been used as a top coat for a metal material, but it is insufficient for environmental protection due to the influence of a large amount of the organic solvent. Further, physical properties such as weather resistance and corrosion resistance to metals are not sufficient.
As a metal primer coat application, a one-part type normally dry paint technique using a water-dispersible acrylic-modified epoxy resin with excellent metal adhesion is known. Water resistance and corrosion resistance cannot be obtained.
Also known is a two-component primer that cures water-dispersed epoxy resin with an amine, but this is not only complicated by mixing two components, but also has a slow curing reaction, so that a sufficient time is required to apply the top coat. Need to take.
Therefore, as a top coat for metal materials, it has excellent coating performance such as weather resistance, corrosion resistance, adhesion, and durability, and at the same time has excellent coating workability, especially a one-part aqueous type room temperature dry coating composition. Development of is strongly desired.

[For wood: especially for wood floors]
For repairing wood floors (gymnasiums / halls / classrooms / studios / stores), the hardness of the paint film, abrasion resistance, gloss of lighting, and leveling are required.
Conventionally, one-component oil-based paint (solvent-based) is often used for repairing wood floors, but in recent years, the use of water-based paints is increasing from the viewpoint of improving environmental problems. There are many.
At present, oxidation polymerization type one-component aqueous solution is the mainstream, but this has a problem of poor dryability and fleshiness. . In addition, due to the two-component reaction of the hydroxyl-containing acrylic polyol and the water-dispersed isocyanate, the amount of the two-component aqueous urethane that has good physical properties and durability and quick drying has increased, but in this case, since an acrylic emulsion is used, It is difficult to obtain high glossiness and fleshiness like a one-component oil-based paint (solvent type).
Therefore, for wood, particularly wood floor, a coating composition having high hardness, wear resistance, leveling, drying, and durability, high gloss, and other excellent coating workability, especially 1 There is a strong demand for the development of a liquid aqueous type room temperature drying coating composition.

[For wood: especially for container wood floors]
For container wood floors (shipping container bottom floor), contamination resistance, oil bleed resistance, odor sealing effect (fish meal / bone meal / feed / alcohol / coconut), alkali cleaning resistance and painting workability are required.
Conventionally, a one-component oil-based paint (solvent type) has been used to repaint the container floor when the container ship has finished voyage. However, the functions required for the container floor (contamination resistance, oil bleed resistance, odor sealing effect, alkali cleaning resistance) have not been cleared. In addition, the problem of odor is great, and since it takes a long time to dry, there is a problem such as adhesion of dust.
On the other hand, in recent years, water-based paints have been used from the viewpoint of improving environmental problems, but the above required performance (contamination resistance, oil bleed resistance, odor sealing effect, alkali cleaning resistance) and painting workability have been improved. It is difficult to be satisfied.
Therefore, for wood, especially for container wood flooring, a coating composition excellent in contamination resistance, oil bleed resistance, odor sealing effect, alkali cleaning resistance, and painting workability, especially one-component aqueous type room temperature drying. Development of mold coating compositions is highly desired.

[For wood: Especially for finishing wood furniture]
The required properties of the coating film for finishing woodwork furniture include, for example, fleshiness, sealability, gloss, hardness, penetration into the conduit, whitening resistance (boiling water resistance), and the like.
Conventionally, solvent-based nitrified cotton lacquer, 2-component aminoalkyd, 2-component polyurethane, etc. have been widely used. In recent years, development of one-component and two-component water-based paints has been actively promoted from the viewpoint of improving environmental problems. Yes. However, performance such as fleshiness, sealability, gloss, hardness, penetration into the conduit, and whitening resistance (boiling water resistance) cannot be obtained sufficiently. Unevenness has not been improved.
Therefore, for finishing woodwork furniture, a coating composition that is excellent in performance such as stickiness, sealability, luster, hardness, penetration into a conduit, and resistance to whitening, and at the same time, is excellent in painting workability, especially a one-part aqueous solution. There is a strong desire to develop a type of room temperature dry coating composition.

[For ceramics building materials interior / exterior]
The performance and coating workability required for ceramic building materials such as calcium silicate boards and coating workability are stain resistance, chemical resistance, hardness, weather resistance, flow coater paintability, and non-adhesiveness ( Traces).
Conventionally, mass production is performed by flow coater coating based on solvent-based acrylic urethane, but in recent years, development of two-component water-based paints has been actively promoted from the viewpoint of improving environmental problems. However, the actual situation is that the problems of non-adhesion (remaining contact marks) and performance at the time of loading immediately after the flow coater coating have not been cleared. That is, simply by applying the conventional two-component water-based paint, the crosslinking reaction does not proceed at low temperature and forced drying for a short time, and it is impossible to clear the tack-free property.
Therefore, as a ceramic building material interior / exterior coating composition with excellent non-adhesiveness as well as stain resistance, chemical resistance, hardness, weather resistance, flow coater paintability, especially one-component water-based room temperature dry type Development of coating compositions is highly desired.

[For plastic]
In the case of painting on a plastic material, adhesion, water resistance, weather resistance, deterioration protection of the material, drying property, and painting workability are required. Conventionally, solvent-based two-component paint has been used as a top coat for plastic materials, but one-component and two-component water-based systems are being promoted from the viewpoint of eliminating the inconvenience of mixing two components and reducing organic solvents. . However, in the case of two aqueous liquids, the problem remains in the troublesome mixing of the two liquids as in the solvent system. In the case of a one-part aqueous solution, a water-soluble paint using an organic solvent that is soluble in water is used, but in this case, since it contains a large amount of an organic solvent, it is insufficient as an environmental measure. Problems remain in tack-free.
Therefore, for plastics, a coating composition with excellent adhesion, water resistance, weather resistance, material deterioration protection, drying and coating workability, as well as excellent non-adhesiveness, especially one-component water-based type room temperature drying. Development of mold coating compositions is highly desired.

  The present invention has been made against the background as described above. Basically, as a one-component room-temperature drying type, particularly as a one-component room-temperature crosslinking type aqueous coating composition, the conventional two-part type, Compared to two-component cross-linking type coating compositions and solvent-based coating compositions, it has performance comparable to that of various types of applications such as urethane waterproofing materials, interior / exterior materials, metals, etc. As a coating composition used for materials, metal moldings, wood flooring materials, wood moldings, ceramic building materials inside and exterior materials, plastic materials, etc., coating compositions that can satisfy the requirements according to each application The issue is to provide.

In order to solve the problems as described above, the present inventors have conducted intensive experiments and studies, and as a result, the composition contains the following three components (A), (B), and (C) at the same time. The inventors have found that the above problems can be solved, and have made the present invention.
That is,
(A) One-part room temperature cross-linked polymer emulsion in which polyurethane having a hydrazine structure (that is, having a hydrazine residue) and a carbonyl group-containing acrylic polymer are contained in particles dispersed in an aqueous medium, in other words, at room temperature. Based on a one-part cold crosslinking polymer emulsion that can be cross-linked by ketimine reaction,
(B) A polyurethane dispersion having both a portion composed of a component having a high glass transition temperature (Tg) (high Tg component) and a portion composed of a component having a low glass transition temperature (Tg) (low Tg component). When,
(C) By blending with ultrafine nano-emulsion with an average particle diameter in the range of 5 to 140 nm, it is self-cross-linked at room temperature as a one-liquid aqueous type, and various performances are conventional solvent-type and two-liquid mixed cross-linking. The present inventors have found that a coating composition can be obtained that is inferior to the type and can satisfy the performance required for each application.

  Therefore, the one-pack room-temperature-crosslinking aqueous coating composition according to the basic aspect (first aspect) of the present invention is a polyurethane having a hydrazine structure (that is, having a hydrazine residue) in particles dispersed in an aqueous medium. And a glass transition temperature (part of a component having a high glass transition temperature (Tg) (high Tg component)) and a glass transition temperature (A) A polyurethane dispersion (B) having both a component composed of a component having a low Tg) (low Tg component) and an ultrafine particle nanoemulsion (C) having an average particle size in the range of 5 to 140 nm. It is characterized by.

In the one-part cold crosslinking aqueous coating composition according to the basic aspect of the present invention, the one-pack cold crosslinking polymer emulsion component (A) has a carbonyl group and a hydrazine residue at the same time. A room temperature crosslinking reaction (ketimine reaction) can be obtained at the time of coating film formation.
This reaction is a dehydration condensation reaction between a carbonyl group and a hydrazine group, and the crosslinking reaction proceeds rapidly simultaneously with the evaporation of water. At this time, if the crosslinking reaction proceeds to some extent, it will not be redispersed in water, so that the coating properties such as water resistance can be improved from the beginning of drying. In addition, since this crosslinking reaction is interparticle crosslinking, the crosslinking reaction point is on the particle surface, and therefore the crosslinking density is higher than that of normal self-crosslinking type reactions (oxidative curing, hydrolysis condensation of alkoxysilane, etc.). A denser coating film can be formed. That is, since this reaction is an interparticle cross-linking reaction, the curing rate is high, and a coating film having a high cross-linking density can be obtained as compared with other one-component reactions (oxidative polymerization, silanol group reaction, etc.).

The polyurethane dispersion (B) has different Tg components of a high Tg component and a low Tg component in the same particle. The high Tg component is desirably Tg: 100 to 160 ° C., and such a high Tg component imparts coating film properties such as hardness (toughness) and stain resistance to the coating film. On the other hand, the low Tg component is desirably Tg: −50 to 0 ° C., and this low Tg component sufficiently imparts flexibility to the coating film and at the same time imparts coating film properties such as adhesion. It is.
Thus, by blending polyurethane dispersions having two different Tg characteristics, toughness, flexibility and adhesion can be simultaneously imparted to the coating film. Furthermore, it is possible to improve physical properties such as alkali resistance by appropriately selecting the polyurethane dispersion from ionicity, skeleton (polyester, polyether, polycarbonate) and the like.

  Furthermore, the ultrafine particle nanoemulsion (C) has an average particle diameter of 5 to 140 nm. By blending such ultrafine particles, a large cohesive force acts between the particles, and the coating film Since it has a dense structure, it is possible to enhance the expression of various physical properties, to impart toughness to the coating film, and because the permeability to the base material is good due to the ultrafine particles, Contributes to improving the adhesion of the coating film.

  Further, the one-component room temperature cross-linking aqueous coating composition according to the second aspect of the present invention is the one-component room temperature cross-linking aqueous coating composition according to the first aspect, wherein the 1 The solid content of the liquid crosslinked emulsion (A) is 5 to 50% by weight, the solid content of the polyurethane dispersion (B) is 5 to 50% by weight, and the solid content of the ultrafine nanoemulsion (C) is 5 to 50% by weight. It is characterized by being blended so as to be in the range of.

Here, if the solid content of the one-component crosslinked emulsion (A) is less than 5% by weight, the reactivity of the (A) one-component crosslinked emulsion (A) becomes insufficient.
If the solid content of the one-component crosslinked emulsion (A) exceeds 50% by weight, the flexibility and toughness exhibited by (B) polyurethane dispersion (B) become insufficient, and the cohesive strength of the ultrafine nanoemulsion , The substrate permeability is insufficient.
On the other hand, when the solid content of the polyurethane dispersion (B) is less than 5% by weight, flexibility and toughness become insufficient.
If the solid content of the polyurethane dispersion (B) exceeds 50% by weight, (A) the reactivity of the one-part crosslinked emulsion (A), (C) the ultrafine particle nanoemulsion (C), cohesive strength, and substrate permeability However, it becomes insufficient.
Furthermore, when the solid content of the ultrafine nanoemulsion (C) is less than 5% by weight, the cohesive force and substrate permeability of the ultrafine nanoemulsion (C) are insufficient.
Further, if the solid content of the ultrafine particle nanoemulsion (C) exceeds 50% by weight, the reactivity of the one-component crosslinked emulsion (A) and the flexibility and toughness of the polyurethane dispersion (B) become insufficient.
Therefore, in the coating composition of the present invention, it is desirable that the blending ratio of (A), (B), (C) is within the above range.

  Furthermore, the one-component room temperature cross-linking aqueous coating composition according to the third aspect of the present invention is the one-component room temperature cross-linking aqueous coating composition according to the first aspect, wherein the glass transition temperature of the polyurethane dispersion (B) particles is low. Tg of a high component (high Tg component) is in the range of 100 ° C. to 160 ° C., and Tg of a component having a low glass transition temperature (low Tg component) is in the range of −50 ° C. to 0 ° C. To do.

Thus, by setting the Tg of the high Tg component in the polyurethane dispersion (B) particles to 100 ° C. to 160 ° C. and setting the Tg of the low Tg component to −50 ° C. to 0 ° C., the coating film has toughness and flexibility. And adhesion can be simultaneously imparted.
When the Tg of the high Tg component is less than 100 ° C., it becomes difficult to impart sufficient toughness.
On the other hand, if the Tg of the high Tg component exceeds 160 ° C., the flexibility is lost and it becomes difficult to follow the object to be coated, and it becomes difficult to provide adhesion.
On the other hand, if the Tg of the low Tg component is lower than −50 ° C., the surface of the coating film is softened and causes dirt.
If the Tg of the low Tg component exceeds 0 ° C., it becomes difficult to impart sufficient flexibility and adhesion to the coating film.
The Tg of the low Tg component is more preferably −20 ° C. or higher.

  Further, the one-part cold crosslinking aqueous coating composition of the fourth aspect of the present invention is an ultrafine particle constituting the ultrafine particle nanoemulsion (C) in the one-part cold crosslinking aqueous coating composition of the first aspect. Is composed of one or more selected from acrylic resins, epoxy resins, and alkyd resins.

  Here, the particle material of the ultrafine particle nanoemulsion (C) is basically not particularly limited, but if ultrafine particles composed of one or more selected from acrylic resin, epoxy resin, and alkyd resin are used. It is advantageous in terms of cohesive force during film formation and permeability to the substrate.

  Further, the one-component room temperature cross-linking aqueous coating composition of the fifth aspect of the present invention is the one-component room temperature cross-linking aqueous coating composition of the first aspect, wherein the polyurethane dispersion (B) has a glass transition temperature of 0. It is -50 degreeC, It is characterized by the above-mentioned.

  The glass transition temperature (Tg) of the one-component room temperature cross-linked polymer emulsion (A) is basically not limited, but is usually preferably in the range of 0 ° C to 50 ° C as described above. That is, if the Tg of the one-component room temperature cross-linked polymer emulsion (A) is less than 0 ° C., there is a fear that sufficient coating film hardness may not be obtained, while if it exceeds 50 ° C., the cross-linking reaction is sufficiently performed during drying at room temperature. There is a possibility that the film does not progress, the film forming property is inferior, and sufficient coating film performance cannot be obtained.

  In addition, the one-part cold crosslinking aqueous coating composition of the sixth aspect of the present invention is the one-part cold crosslinking aqueous coating composition of the first aspect, wherein the ultrafine particle nanoemulsion (C) has a glass transition temperature. It is characterized by being 30 ° C to 50 ° C.

  The glass transition temperature (Tg) of the ultrafine particle nanoemulsion (C) is basically not limited, but is preferably in the range of 30 ° C. to 50 ° C. as described above. That is, when the Tg of the ultrafine particle nanoemulsion (C) is less than 30 ° C., there is a possibility that sufficient coating film hardness and drying property may not be obtained. On the other hand, when it exceeds 50 ° C., the film forming property is inferior when drying at room temperature. There is a risk that sufficient coating performance cannot be obtained.

  Furthermore, typical applications of the one-component room temperature cross-linking aqueous coating composition of the present invention are for waterproof top coats, wood top coats (building interior materials / exterior materials, building floor materials, container floor materials, woodworking) Furniture), ceramic building materials, metal top coats, metal primer coats, and plastic top coats. In these applications, the required characteristics may differ depending on the difference in the material to be coated and the usage environment, and therefore, the one-component crosslinked emulsion (A), the polyurethane dispersion (B), which constitutes the coating composition of the present invention, More desirable ranges are slightly different for the blending ratio of the ultrafine particle nanoemulsion (C) and the Tg of the high Tg component and the low Tg component of the polyurethane dispersion (B). Each preferable range in each application is as in the following seventh to twelfth aspects.

Seventh aspect: For waterproof top coat As the one-component room temperature cross-linking aqueous coating composition for waterproof top coat, the solid content of the one-component cross-linked emulsion (A) is 5 to 5 with respect to the solid content of the entire coating composition. 40 wt%, the polyurethane dispersion (B) has a solid content of 5 to 50 wt%, and the ultrafine particle nanoemulsion (C) has a solid content of 5 to 50 wt%, and The glass transition temperature of the portion having a high glass transition temperature in the polyurethane dispersion (B) is in the range of 100 ° C. to 160 ° C., and the glass transition temperature of the portion having a low glass transition temperature is in the range of −50 ° C. to 0 ° C. It is desirable to be within.

Here, the coating composition for waterproof top coat is mainly applied with urethane waterproof material on the target material by hand coating or spraying to form a waterproof layer and then improve the weather resistance on the surface of the waterproof layer And a coating composition for a coating film applied as a top coat in order to improve the appearance characteristics.
As a coating composition for waterproof top coat, the above composition and composition, high / low Tg characteristics of polyurethane dispersion are required. Adhesion, water resistance, weather resistance, chemical resistance, drying property, coating film appearance requirements In particular, due to the reactivity of one-component crosslinking reaction, the flexibility / toughness of polyurethane dispersion with high / low Tg characteristics and high / low Tg characteristics, and the permeability / cohesiveness of ultrafine nanoemulsions Thus, good performance can be obtained with respect to contamination, weather resistance, and color change with pot life.
In addition, the conventional highly reflective paint has high reflectivity by using glass beads or the like in order to impart a highly reflective pigment and high reflectivity. However, in the coating film using the conventional coating composition, It was difficult to maintain high reflectivity due to the resulting dirt. However, the coating composition for a waterproof top coat of the present invention has excellent stain resistance, so that it is easy to maintain high reflectivity.
The Tg of the one-component room temperature cross-linked polymer emulsion (A) in the coating composition for the waterproof top coat is preferably in the range of 0 ° C. to 50 ° C. as described above, and the Tg of the ultrafine nanoemulsion (C) is also In the same manner as described above, the range of 30 ° C. to 50 ° C. is preferable.

Eighth aspect: For wood top coat As a one-component room-temperature cross-linking aqueous coating composition for wood top coat, the solid content of the one-component cross-linked emulsion (A) is 5 to 5 with respect to the solid content of the entire coating composition. 50 wt%, the solid content of the polyurethane dispersion (B) is 5 to 50 wt%, and the solid content of the ultrafine particle nanoemulsion (C) is in the range of 5 to 50 wt%, and The glass transition temperature of the portion having a high glass transition temperature in the polyurethane dispersion (B) is in the range of 100 ° C. to 160 ° C., and the glass transition temperature of the portion having a low glass transition temperature is in the range of −50 ° C. to 0 ° C. It is desirable to be within.

  As a coating composition for wood topcoats, the above composition, high dispersion / low Tg characteristics of polyurethane dispersions, demands for adhesion, water resistance, weather resistance, chemical resistance, drying, and coating appearance It becomes possible to satisfy. In particular, the hardness, gloss, durability and dryness of polyurethane dispersion with high reactivity and low Tg characteristics, glossiness, flexibility and toughness of ultra-fine nanoemulsion and cohesion Good performance can be obtained with respect to properties and appearance.

  In addition to interior and exterior materials for general buildings, wood top coats are used for repairing timber floors in gymnasiums, halls, classrooms, studios, stores, etc., and timber floors for shipping container bottom floors (container timber floors) The above-mentioned coating composition for wood top coat can be applied to any of these, and the top coat for repairing wood floors. The application requires hardness, abrasion resistance, gloss, smoothness, dryness, and durability of the coating film, but the coating composition for the wood top coat has specific requirements for these wood floors. The performance can also be satisfied. However, in the use of wood floor repair, it is more preferable that the solid content of the one-component cross-linked emulsion (A) is in the range of 5 to 40% by weight in the above-described blending. This is because wear resistance and heel mark resistance are particularly required for repairing wood floors.

  Among the above-mentioned wood top coat applications, in particular, the use of container wood floors is stain resistance, chemical resistance (including alkali cleaning resistance), oil resistance (oil bleed resistance), non-adhesiveness, and odor sealing. Although it is required that the stopping effect is excellent, the coating composition for the wood top coat can also satisfy the required performance specific to these container wood floors.

  In addition, among the above wood top coat applications, in woodwork furniture applications, especially finishing applications, fleshiness (holding property), sealability, gloss, hardness, penetration into the ground, and whitening resistance. However, the coating composition for the wood top coat can satisfy the required performance specific to the wood furniture finish.

  The Tg of the one-component room temperature cross-linked polymer emulsion (A) in the coating composition for the wood top coat is preferably in the range of 0 ° C. to 50 ° C. as described above, and the Tg of the ultrafine nanoemulsion (C) is also In the same manner as described above, the range of 30 ° C. to 50 ° C. is preferable.

Ninth aspect: For ceramic building materials As a one-component room-temperature-crosslinking aqueous coating composition for ceramic building materials, the solid content of the one-component cross-linked emulsion (A) is 5 to 50 weights based on the solid content of the entire coating composition. %, The polyurethane dispersion (B) has a solid content of 5 to 50% by weight, and the ultrafine particle nanoemulsion (C) has a solid content of 5 to 50% by weight, and the polyurethane dispersion In the particles of John (B), the glass transition temperature of the high glass transition temperature is in the range of 100 ° C. to 160 ° C., and the glass transition temperature of the low glass transition temperature is in the range of −50 ° C. to 0 ° C. It is desirable to be.

As a coating composition for ceramic industry building material topcoats, by adopting the above composition, high / low Tg characteristics of polyurethane dispersion, adhesion, water resistance, weather resistance, chemical resistance, drying, coating appearance, etc. Can be satisfied. Especially for ceramic building material top coat applications, it is required to have excellent contamination resistance, chemical resistance, hardness, weather resistance, flow coater paintability, and non-adhesiveness (remaining contact marks) when loaded immediately after painting. In the ceramic composition building material topcoat coating composition, the required performance specific to these ceramic industry building material topcoats can be sufficiently satisfied.
Here, as a ceramic building material, a calcium silicate board is representative, but a fiber-reinforced cement board sizing material is also included.
The Tg of the one-component room temperature cross-linked polymer emulsion (A) in the coating composition for ceramic building material top coat is preferably in the range of 0 ° C. to 50 ° C., as already described, and the Tg of the ultrafine nanoemulsion (C). In the same manner as described above, the range of 30 ° C. to 50 ° C. is preferable.

Tenth aspect: For metal top coat As a one-part cold crosslinking aqueous coating composition for a metal top coat, the solid content of the one-part crosslinked emulsion (A) is 5 to 5 with respect to the solid content of the entire coating composition. 40 wt%, the polyurethane dispersion (B) has a solid content of 10 to 50 wt%, and the ultrafine particle nanoemulsion (C) has a solid content of 10 to 50 wt%, and It is desirable that the Tg of the high Tg component in the polyurethane dispersion (B) particles is in the range of 100 ° C to 150 ° C, and the Tg of the low Tg component is in the range of -50 ° C to -10 ° C.

If the solid content of the one-component cross-linked emulsion (A) exceeds 40% by weight as the coating composition for the metal top coat, the toughness and the adhesiveness to the base are lowered. The solid content of the liquid crosslinked emulsion (A) was in the range of 5 to 40% by weight. Further, since the coating film hardness cannot be obtained when the solid content of the polyurethane dispersion (B) is less than 10% by weight, the solid content of the urethane dispersion (B) in the coating composition for metal top coat is 10 to 50% by weight. It was. Further, when the Tg of the high Tg component in the particles of the polyurethane dispersion (B) is less than 100 ° C. and the Tg of the low Tg component is less than −50 ° C., sufficient film performance cannot be obtained, and the Tg of the high Tg component is 150 ° C. If the Tg of the low Tg component exceeds −10 ° C., sufficient flexibility cannot be obtained. Therefore, the Tg of the high Tg component was 100 ° C. to 150 ° C., and the Tg of the low Tg component was −50 ° C. to −10 ° C.
As a coating composition for a metal top coat, the adhesive composition, water resistance, weather resistance, corrosion resistance, chemical resistance, drying property, and coating film appearance can be achieved by using the above-described composition and high / low Tg characteristics of polyurethane dispersion. It becomes possible to satisfy such requests.
Here, as the material metal to which the metal top coat is applied, aluminum and steel are typical.
In addition, the Tg of the one-component room temperature cross-linked polymer emulsion (A) in the coating composition for the metal top coat is preferably in the range of 0 ° C. to 50 ° C. as already described, and the ultrafine particle nanoemulsion (C) Tg is also preferably in the range of 30 ° C to 50 ° C, as already described.

Eleventh aspect: For metal primer coating As the one-component room temperature cross-linking aqueous coating composition for metal primer coating, the solid content of the one-component cross-linking emulsion (A) is 5 to 5 with respect to the solid content of the entire coating composition. 40 wt%, the polyurethane dispersion (B) has a solid content of 5 to 50 wt%, and the ultrafine particle nanoemulsion (C) has a solid content of 5 to 50 wt%, and The glass transition temperature of the portion having a high glass transition temperature in the polyurethane dispersion (B) is in the range of 100 ° C. to 160 ° C., and the glass transition temperature of the portion having a low glass transition temperature is in the range of −50 ° C. to 0 ° C. It is desirable to be within.

If the solid content of the one-component cross-linked emulsion (A) in the coating composition for the metal primer coat exceeds 40% by weight, the toughness and the adhesion to the material are lowered, so that the solid of the one-component cross-linked emulsion (A) is solid. The content was 5 to 40% by weight.
As a coating composition for metal primer coating, it is possible to satisfy the requirements of adhesion, water resistance, corrosion resistance, workability, and drying properties by adopting the above-mentioned blending composition and high / low Tg characteristics of polyurethane dispersion. Become. In particular, in the use of a metal top coat, it is desired that the corrosion resistance and the adhesion to the metal base are excellent. However, in the above configuration, the average particle size of the ultrafine particle nanoemulsion (C) is extremely fine as 5 to 140 nm. Therefore, the fine particles of the nanoemulsion (C) can fill the gaps between the particles of the one-liquid cross-linked emulsion (A) and the polyurethane dispersion (B), thereby fusing the particles. The penetration can be prevented, high corrosion resistance can be imparted, and adhesion to the ground can be improved.
Here, examples of the metal material on which the coating film (undercoating film) of the one-part cold crosslinking aqueous coating composition for metal primer coating is formed include steel and aluminum.
In addition, the Tg of the one-part cold crosslinking polymer emulsion (A) in the coating composition for metal primer coating is preferably in the range of 0 ° C. to 50 ° C. as described above, and the Tg of the ultrafine nanoemulsion (C) Tg is also preferably in the range of 30 ° C to 50 ° C, as already described.

Twelfth aspect: For plastic top coat As a one-component room temperature cross-linking aqueous coating composition for plastic top coat, the solid content of the one-component cross-linked emulsion (A) is 5 to 5 with respect to the solid content of the entire coating composition. 40 wt%, blended so that the solid content of the polyurethane dispersion (B) is in the range of 5 to 40 wt%, and the solid content of the ultrafine particle nanoemulsion (C) is in the range of 5 to 30 wt%, and In the particles of the polyurethane dispersion (B), the glass transition temperature of the portion having a high glass transition temperature is in the range of 100 ° C. to 150 ° C., and the glass transition temperature of the portion having a low glass transition temperature is −50 ° C. to −10 ° C. It is desirable to be within the range.

If the solid content of the one-component cross-linked emulsion (A) exceeds 40% by weight as the plastic top coat coating composition, the toughness and workability will be poor. The solid content of the emulsion (A) was in the range of 5 to 40% by weight. If the solid content of the polyurethane dispersion (B) is less than 5% by weight, the coating film hardness and toughness will be inferior. If it exceeds 40% by weight, the physical properties of the film such as water resistance will be inferior. The solid content of the urethane dispersion (B) in the topcoat coating composition was 5 to 40% by weight. Furthermore, if the solid content of the ultrafine particle nanoemulsion (C) in the coating composition for a plastic top coat is less than 5% by weight, the expression of physical properties is inferior, and if it exceeds 30% by weight, (A) and (B) In order to reduce the characteristics, the ultrafine particle nanoemulsion (C) was made 5 to 30% by weight.
As a coating composition for a plastic top coat, the above composition, composition and high / low Tg characteristics of polyurethane dispersion satisfy the requirements of adhesion, water resistance, stain resistance, drying property, coating workability, etc. It becomes possible. In particular, in the use of a plastic top coat, adhesion, water resistance, weather resistance, material deterioration protection, drying property, and painting workability are required, but these required properties can be sufficiently satisfied.
In addition, the above-mentioned one-pack room temperature cross-linking aqueous coating composition for plastic top coat is most suitable for the top coat of HIPS (high impact styrene resin) and ABS resin (acrylonitrile-butadiene-styrene copolymer resin). It is also possible to apply to polycarbonate resin or the like.
The Tg of the one-part cold crosslinking polymer emulsion (A) in the coating composition for the plastic top coat is preferably in the range of 0 ° C. to 50 ° C. as described above, and the Tg of the ultrafine nanoemulsion (C) is also In the same manner as described above, the range of 30 ° C. to 50 ° C. is preferable.

  According to the one-component room temperature cross-linking aqueous coating composition of the present invention, the coating film has excellent coating properties such as corrosion resistance, weather resistance, adhesion, coating strength, durability, and stain resistance, and has good appearance quality. In addition, it is excellent in terms of coating workability such as drying properties, and is particularly inferior to conventional solvent-type coating compositions and two-pack type coating compositions as a simple one-liquid aqueous type. The coating film performance can be exhibited. In addition, the one-component room temperature cross-linking aqueous coating composition of the present invention is a waterproof top coat, or various kinds of wood (building interior / exterior, wood floor repair, container wood floor, woodwork furniture, etc.), ceramic building materials, and metal Each required characteristic can be satisfactorily satisfied in a wide range of applications such as top coat, primer coat, and plastic top coat.

Hereinafter, the one-part cold crosslinking aqueous coating composition of the present invention will be described in more detail.
The one-component room temperature cross-linking aqueous coating composition of the present invention has the following basic components:
(A) One-part room temperature cross-linked polymer emulsion containing polyurethane having a hydrazine structure and a carbonyl group-containing acrylic polymer in particles dispersed in an aqueous medium;
(B) a polyurethane dispersion having both a part composed of a component having a high glass transition temperature (high Tg component) and a part composed of a component having a low glass transition temperature (low Tg component) in the particles;
(C) an ultrafine particle nanoemulsion having an average particle diameter in the range of 5 to 140 nm,
And three components.

As described above, the one-component room temperature cross-linked polymer emulsion (A) is based on a polyurethane-acrylic copolymer as emulsion particles, and has a hydrazine structure in the molecular structure of the polyurethane (that is, one or more hydrazine residues). And a carbonyl group in the acrylic molecule.
Such an emulsion undergoes a room-temperature crosslinking reaction (ketimine reaction) due to a dehydration condensation reaction between a carbonyl group and a hydrazine group during film formation at room temperature. And since this reaction is an interparticle cross-linking reaction, the reactivity is high, the curing speed is high, and a coating film having a high cross-linking density is obtained compared to other one-component reactions (oxidative polymerization and silanol group reaction). Can do.

  An example of the structure and crosslinking reaction of such a one-part cold crosslinking polymer emulsion is shown by the following chemical formula. The emulsion before cross-linking has a structure as shown on the left side of the following chemical formula, and water starts to evaporate during film formation to cause a cross-linking reaction (right side).

Here, R ₁ and R ₂ acrylic monomers in the acrylic molecule containing a carbonyl group include methacrylate esters such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, hexyl methacrylate, acrylic acid, and the like. Examples include esters. Furthermore, not only those described above, but also other polymerizable unsaturated monomers may be used in combination as needed, as long as the effects of the present invention are not impaired.
Further, the polyurethane portion having a hydrazine structure (NH 2 _{NHR 3)} is obtained by chain extension of isocyanate and carboxyl key containing glycol as essential components a hydrazine derivative.

  The polyurethane dispersion (B) is composed of polyurethane particles having a different phase structure having a high Tg component and a low Tg component in the same particle. As the particles having such a different phase structure, those using different Tg components in the core (center) and the shell (surface layer), for example, the core (center) of the same particle is formed with a high Tg component. A dispersion made of composite type polyurethane particles in which the shell portion (surface layer portion) is formed with a low Tg component, or conversely, the core portion (center portion) is formed with a low Tg component, and the shell portion (surface layer portion) is A composite type polyurethane particle formed with a high Tg component is typical. Such high / low Tg composite type polyurethane particles are obtained by, for example, multi-stage emulsion polymerization using a plurality of polymerizable monomer components having different Tg at each stage, thereby providing a high Tg portion (hard segment) and low Tg. Part (soft segment). Then, a high Tg component Tg and a low Tg component Tg may be selected and used depending on the application.

  The ultrafine particle nanoemulsion (C) has an average particle diameter in the range of 5 to 140 nm. Here, the particle material of the ultrafine particle nanoemulsion (C) is basically not particularly limited, but is usually an ultrafine particle composed of one or more selected from acrylic resin, epoxy resin, and alkyd resin. May be used.

Further, in producing a paint using the coating composition of the present invention, as appropriate, pigment, filler, aggregate, pigment dispersant, wetting agent, thickener, antifoaming agent, plasticizer, film-forming aid, Organic solvents, antiseptics, mildewproofing agents, pH adjusting agents, rustproofing agents, and the like can be selected and combined according to their respective purposes. Furthermore, by using an ultrafine pigment as the pigment, it is possible to impart structural viscosity, permeability to the substrate, and color stability. Moreover, it becomes possible to provide high reflectivity by selecting a highly reflective pigment. The coating composition of the present invention is excellent in weather resistance, water resistance, elasticity, toughness and stain resistance, and acid rain resistance, and is therefore suitable for coating exteriors of buildings, bridges, vehicles, etc. As compared with general solvent-based paints, there are many advantages in terms of safety and odor, so that it is suitable for indoor use.

  In addition, when the coating composition of the present invention is painted at a construction site or the like, it can be applied regardless of whether it is newly constructed or refurbished. It can also be applied to partial repairs. In addition, when coating this invention coating composition, various coating instruments, such as a spray, a roller, and a brush, can be used. In the case of painting, it is also possible to dilute with water.

Although the application amount of the composition of the present invention is not particularly limited, it is usually about 50 g to 300 g / m ² .
In addition, drying after coating the composition of the present invention may be usually performed at room temperature, but may be performed. The drying time is usually about 15 minutes to 2 hours at room temperature.

  Examples of the present invention will be described below together with comparative examples. The following examples are for explaining the effects of the present invention, and it goes without saying that the configurations, processes, and conditions described in the examples do not limit the technical scope of the present invention.

Example 1: Waterproof material top coat 1
A urethane waterproof layer is formed by hand coating on the surface of the concrete material. As shown in Table 1, a one-component room temperature cross-linked polymer emulsion (A), polyurethane dispersion (B), ultrafine nanoemulsion is formed on the surface of the urethane waterproof layer. (C) In addition, water was added to titanium white or the like as a coloring pigment, and an aqueous paint having a composition as shown in Table 1 was applied at a coating amount of 200 g / m ² with a paint roller. In addition, all the compounding ratios of Table 1 are shown in weight ratios. Of the tables shown in Table 2 and subsequent tables, all of the tables concerning the blending ratios are shown by weight.
Here, as the one-component room temperature cross-linked polymer emulsion (A), an emulsion having a polyurethane having a hydrazine structure in a particle and a carbonyl group-containing acrylic polymer having a Tg of 30 ° C. was used.
Further, as the polyurethane dispersion (B), one having a high / low Tg characteristic in which the core portion of the particle was formed with a high Tg component and the shell portion was formed with a low Tg component was used. The polyurethane dispersion (B) has a high Tg component having a Tg of 125 ° C. and a low Tg component having a Tg of −25 ° C.
Further, as the ultrafine particle nanoemulsion (C), one made of an acrylic resin having an average particle diameter of 90 nm was used. The Tg of this ultrafine particle nanoemulsion (C) is 35 ° C.
In addition, calcium carbonate having an average particle diameter of 30 nm is used as the ultrafine inorganic material (structural viscosity agent) shown in Table 1, texanol is used as the film forming aid, and polymer is used as the dispersant for improving pigment wetting. A block copolymer type was used, and a silicon-based antifoaming agent was used.

For comparison, an aqueous two-component cross-linking type conventional paint (Comparative Example 1) having a composition as shown in Table 2 was applied on the urethane waterproof layer in the same manner as described above.
About these coating films, the test and evaluation items as shown in Table 3 were tested and evaluated by the method as shown in Table 3. The results are shown in Table 4.

As shown in Table 4, the conventional aqueous two-component cross-linking type paint (Comparative Example 1) caused a significant color change in the pot life test. Contamination, weather resistance, dryness, and tackiness were also inferior to those of the product of the first embodiment.
On the other hand, the product of the present invention of Example 1 has a contamination property / weather resistance (SWOM, outdoor exposure), pot life (color change), compared with the conventional aqueous two-component cross-linking type (Comparative Example 1) paint. Good results were obtained with dryness and tackiness.
From these results, in the case of the product of the present invention, high reactivity due to the use of a one-component cross-linked emulsion, flexibility and toughness of polyurethane dispersion having high / low Tg characteristics, and permeability of ultrafine nanoemulsion. -It was confirmed that the cohesive strength can provide good results for stain resistance, weather resistance, and color change in pot life.

Example 2: Waterproof material top coat 2 (high reflection type)
Based on the composition of the waterproof top coat 1 shown in Example 1, a highly reflective pigment (azomethiazo black pigment: trade name Chromofine Black A-1103 (manufactured by Dainichi Seika Kogyo Co., Ltd .: Tokuhei 4) -26348) was blended as shown in Table 5 to form a highly reflective paint and applied onto the urethane waterproof layer at a coating amount of 200 g / m ² with a paint roller. As (A), polyurethane dispersion (B), and ultrafine particle nanoemulsion (C), the same ones as in Example 1 were used.
In Table 5, A-1103 (high reflection black), iron oxide ocher, and iron oxide red rust are all pigments for color tone adjustment. Other film-forming aids, dispersants and antifoaming agents are the same as in Example 1.
For comparison, a water-based acrylic (uncrosslinked) conventional paint (Comparative Example 2) containing glass beads having an average particle diameter of 60 μm as a reflector as shown in Table 6 was applied on the urethane waterproof layer in the same manner as described above. It was applied to.
About these coating films, the test and evaluation items as shown in Table 7 were tested and evaluated by the method as shown in Table 7. The results are shown in Table 8.

As shown in Table 8, the highly reflective paint of Comparative Example 2 based on water-based non-crosslinked soil is stained on the surface of the test specimen as the outdoor exposure progresses, resulting in a decrease in reflectivity and an increase in the coating surface temperature. As a result. That is, the use of glass beads results in high reflectivity in the initial stage, but is easily contaminated by exposure.
On the other hand, since the product of the present invention of Example 2 has good contamination, it has been confirmed that even if outdoor exposure is continued for a long period of time, high reflectivity is maintained and the rise in surface temperature is small. It was.

Example 3: Top coat for wood floor An undercoat layer is formed on the surface of the wood for floor, and one-part cold crosslinking polymer emulsion (A), polyurethane dispersion (B), ultrafine nano particles are formed on the surface of the undercoat layer. Emulsion (C) and other water-based paints having the composition shown in Table 9 were applied by brush coating at a coating amount of 100 g / m ² .
Here, the same one-component room temperature cross-linked polymer emulsion (A), polyurethane dispersion (B), and ultrafine particle nanoemulsion (C) as those in Example 1 were used.
In Table 9, a silicon leveling agent was used as the leveling agent, and a polyurethane resin thickener was used as the thickening agent. In addition, the film-forming aid and the antifoaming agent are the same as in Example 1.
For comparison, as shown in Table 10, a conventional aqueous one-liquid (Comparative Example 3), aqueous two-liquid (Comparative Example 4), and solvent-based one liquid (Comparative Example 5) paint is used as a wood floor topcoat. Applied.
For the undercoat, the same paint as the top coat was used. In addition, the product of the present invention (Example 3), aqueous 1 liquid (Comparative Example 3), aqueous 2 liquid (Comparative Example 4) was applied over 4 hours, and the solvent 1 liquid (Comparative Example 5) was the interval. The coating was repeated for 12 hours.
About these coating films, the test and evaluation items as shown in Table 11 were tested and evaluated by the method shown in Table 11 on the seventh day after the top coat was applied. The results are shown in Table 12.

As shown in Table 12, the aqueous 1 liquid of Comparative Example 3 has hardness and fleshiness, and the solvent 1 liquid of Comparative Example 5 produces poor results in hardness and dryness, and the aqueous 2 liquid of Comparative Example 4 Resulted in slightly inferior appearance and leveling.
On the other hand, the product of the present invention of Example 3 is more glossy and meaty than each comparative example (Comparative Example 3 of aqueous 1 liquid, Comparative Example 4 of aqueous 2 liquid, and Comparative Example 5 of solvent 1 liquid). Good results were obtained in terms of durability, appearance, dryness and hardness.
From these results, in the case of the product of the present invention, high reactivity due to the use of a one-component cross-linked emulsion, flexibility and toughness of polyurethane dispersion having high / low Tg characteristics, and permeability of ultrafine nanoemulsion. -It was confirmed that good results can be obtained in the evaluation of hardness, gloss, shelf life, dryness, and appearance by the cohesive force.

Example 4: Top coat for wood container floor An undercoat layer is formed on the surface of the wood for container floor, and the surface of the undercoat layer is a one-component room temperature cross-linked polymer emulsion (A), polyurethane dispersion (B), ultra A water-based paint in which the fine particle nanoemulsion (C) and others were blended as shown in Table 13 was applied at a coating amount of 100 g / m ² with a paint roller.
Here, the same one-component room temperature cross-linked polymer emulsion (A), polyurethane dispersion (B), and ultrafine particle nanoemulsion (C) as those in Example 1 were used.
In Table 13, talc was used as the particulate extender, and the same film forming assistant, antifoaming agent, and thickener as those in Example 3 were used.
For comparison, a conventional aqueous 1 liquid (Comparative Example 6), aqueous 2 liquid (Comparative Example 7), and solvent 1 liquid (Comparative Example 8) as shown in Table 14 were applied as a top coat for a wood container floor. did.
For the undercoat, the same paint as the top coat was used. In addition, the product of the present invention (Example 4), the aqueous 1 liquid (Comparative Example 6), and the aqueous 2 liquid (Comparative Example 7) are overlaid for 4 hours, and the solvent 1 liquid (Comparative Example 8) is the interval. The coating was repeated for 12 hours.
For these coating films, tests and evaluation items as shown in Table 15 were tested and evaluated by the method shown in Table 15 on the seventh day after the top coat was applied. The results are shown in Table 16.

As shown in Table 16, the aqueous one liquid of Comparative Example 6 was particularly poor in sealing effect and alkali resistance, and the solvent one liquid of Comparative Example 8 resulted in inferior oil resistance and alkali resistance, The aqueous two liquids of Comparative Example 7 were slightly inferior in terms of sealing effect.
On the other hand, the product of the present invention of Example 4 has a sealing effect, compared with the comparative aqueous solution 1 (Comparative Example 6), aqueous solution 2 (Comparative Example 7), and solvent solution 1 (Comparative Example 8). Good results were obtained with contamination, oil resistance, alkali resistance and non-sticking.
From these results, in the case of the product of the present invention, high reactivity due to the use of a one-component cross-linked emulsion, flexibility and toughness of polyurethane dispersion having high / low Tg characteristics, and permeability of ultrafine nanoemulsion. -It was confirmed that the cohesive strength can provide good performance in evaluation with sealing effect, contamination, oil resistance, alkali resistance, and non-adhesion.

Example 5: Topcoat for woodwork furniture An undercoat layer is formed on the surface of wood for woodwork furniture, and one-part room temperature cross-linked polymer emulsion (A), polyurethane dispersion (B), ultrafine particles are formed on the surface of the undercoat layer. The water-based paint which mix | blended nanoemulsion (C) and others as shown in Table 17 was apply | coated with the application amount of 60-80 g / m < ² > by air spray.
Here, the same one-component room temperature cross-linked polymer emulsion (A), polyurethane dispersion (B), and ultrafine particle nanoemulsion (C) as those in Example 1 were used.
In Table 17, silica and polyethylene wax were used as the matting agent, and the same ones as described above were used as the film-forming aid and antifoaming agent.
For comparison, conventional aqueous 1 liquid (Comparative Example 9), aqueous 2 liquid (Comparative Example 10), and solvent 2 liquid (Comparative Example 11) as shown in Table 18 were applied as a top coat for wood furniture. .
For the undercoat, the same paint as the top coat was used. In addition, recoating was performed at intervals of 3 hours.
About these coating films, the test and evaluation items as shown in Table 19 were tested and evaluated by the method shown in Table 19 on the seventh day after the top coat was applied. The results are shown in Table 20.

As shown in Table 20, the aqueous 1 liquid of Comparative Example 9 is particularly hard, firm, and sealable, and the aqueous 2 liquid of Comparative Example 10 is inferior particularly in terms of firmness and permeability. It was.
On the other hand, the product of the present invention of Example 5 has better results in hardness, stickiness, sealing, penetration, and whitening resistance than the aqueous 1 liquid of Comparative Example 9 and the aqueous 2 liquid of Comparative Example 10. was gotten.
From these results, in the case of the product of the present invention, high reactivity due to the use of a one-component cross-linked emulsion, flexibility and toughness of polyurethane dispersion having high / low Tg characteristics, and permeability of ultrafine nanoemulsion. -It was confirmed that the cohesive force can provide good performance in evaluation of hardness, firmness, sealing, penetration and whitening resistance.
In addition, although the solvent type | system | group 2 liquid of the comparative example 11 is not inferior in particular compared with this invention product in performance, it is inferior in workability | operativity.

Example 6: Top coat for ceramic building materials A primer layer is formed on the surface of a calcium silicate plate as a ceramic building material, and a one-component room temperature cross-linked polymer emulsion (A) and polyurethane dispersion (B) are formed on the surface of the primer layer. Then, an ultra-fine particle nanoemulsion (C) and the other water-based paint having the formulation shown in Table 21 were applied at a coating amount of 100 g / m ² by a curtain flow coater.
Here, the same one-component room temperature cross-linked polymer emulsion (A), polyurethane dispersion (B), and ultrafine particle nanoemulsion (C) as those in Example 1 were used.
In Table 21, titanium oxide was used for coloring the material, designability and concealment, and having an average particle size of 0.24 μm. Similarly, in Table 21, HEC and CMC were used as the fiber-based viscosity agent, and talc, charcoal, quartz, and alumina were used as the extender pigments. In addition, the film-forming aid, dispersant, and antifoaming agent are the same as described above.
For comparison, conventional aqueous two liquids (Comparative Example 12) and solvent two liquids (Comparative Example 13) as shown in Table 22 were applied as top coats for ceramic building materials.
For the undercoat, the same paint as the top coat was used. In addition, recoating was performed at intervals of 24 hours.
About these coating films, about the test and evaluation items as shown in Table 23, after top coat painting and after drying for 7 days at 20 ° C., the test and evaluation were performed by the method shown in Table 23. The results are shown in Table 24.

As shown in Table 24, the aqueous two liquids of Comparative Example 12 are particularly at the baking temperature (PMT) limit, non-adhesiveness, and stain resistance, and the solvent-based two liquids of Comparative Example 13 are particularly non-adhesive and antifouling. Resulted in inferior results.
On the other hand, the product of the present invention of Example 6 obtained better results in non-adhesiveness, chemical resistance, and contamination resistance compared to the two aqueous solutions of Comparative Example 12 and the two solvent solutions of Comparative Example 13. It was.
From these results, in the case of the product of the present invention, high reactivity due to the use of a one-component cross-linked emulsion, flexibility and toughness of polyurethane dispersion having high / low Tg characteristics, and permeability of ultrafine nanoemulsion. -It was confirmed that good performance can be obtained in the evaluation of non-adhesion, hardness, chemical resistance, and contamination resistance by the cohesive force.

Example 7: For metal top coat An undercoat layer is formed on the surface of an aluminum alloy material for building materials having a chromium oxide film formed on the surface of the material, and a one-component room temperature cross-linked polymer emulsion (A ), Polyurethane dispersion (B), ultrafine nanoemulsion (C), and other water-based paints formulated as shown in Table 25 were applied by air spray coating to a coating thickness of 25 to 35 μm. did.
Here, the same one-component room temperature cross-linked polymer emulsion (A), polyurethane dispersion (B), and ultrafine particle nanoemulsion (C) as those in Example 1 were used.
In Table 25, titanium white, film-forming aid, dispersant, antifoaming agent, and leveling agent are the same as described above.
For comparison, conventional aqueous two liquids (Comparative Example 14), aqueous one liquid (Comparative Example 15), and water solubility (Comparative Example 16) as shown in Table 26 were applied up to the subbing layer as described above. It was applied as a top coat of aluminum alloy material for building materials.
With respect to these coating films, tests and evaluation items as shown in Table 27 were tested and evaluated according to the methods and judgment criteria as shown in Tables 27 and 28. The results are shown in Table 29.
In addition, as a primer, the primer for metal which is the product of the present invention was used as the primer, and each test coating amount was applied on the primer layer, and after curing for 7 days, each test item was carried out.

As shown in Table 29, the aqueous two liquids of Comparative Example 14 were particularly poor in coating film appearance, and the aqueous one liquid of Comparative Example 15 was particularly inferior in weather resistance, drying properties, and coating film appearance. Further, the water solubility of Comparative Example 16 was inferior in all aspects except adhesion and coating film appearance.
In contrast, the product of the present invention has adhesion, water resistance, weather resistance, corrosion resistance, chemical resistance, compared to the aqueous two liquids of Comparative Example 14, the aqueous 21 liquid of Comparative Example 15, and the water solubility of Comparative Example 16. Good results were obtained in terms of drying and coating film appearance.
From these results, in the case of the product of the present invention, high reactivity due to the use of a one-component cross-linked emulsion, flexibility and toughness of polyurethane dispersion having high / low Tg characteristics, and permeability of ultrafine nanoemulsion. -It was confirmed that good performance can be obtained in the evaluation of weather resistance / chemical resistance, drying property, and coating film appearance by cohesive force.

Example 8: For primer coating for metal The surface of a rolled structural steel plate was degreased with toluene, and then a one-part cold crosslinking polymer emulsion (A), polyurethane dispersion (B), ultrafine nanoemulsion (C Other than that, an aqueous paint having a composition as shown in Table 30 was applied by air spray so that the film thickness became 35 ± 5 μm and dried at an air temperature of 23 ° C. for 7 days.
Here, the same one-component room temperature cross-linked polymer emulsion (A), polyurethane dispersion (B), and ultrafine particle nanoemulsion (C) as those in Example 1 were used.
In Table 30, scale-like zinc phosphate is used for enhancing rust prevention as a substitute for talc. Similarly, in Table 30, titanium white, a dispersant, an antifoaming agent, a thickening agent, and a film-forming aid were the same as those described above, and a urea-based viscosity controlling agent was used as the viscosity controlling agent.
For comparison, conventional aqueous one-liquid non-crosslinked (Comparative Example 17), aqueous two-liquid (Comparative Example 18), and solvent-based one liquid (Comparative Example 19) as shown in Table 31 were degreased with toluene as described above. The structural rolled steel sheet was coated with air spray to a film thickness of 35 ± 5 μm and dried at an air temperature of 23 ° C. for 7 days.
Furthermore, a top coat (top coat) was applied to the surface of these primer coating films (undercoat) under various conditions as described in (i) to (d) below.
B: Room temperature drying: The present invention 1 liquid room temperature drying type top coat was applied.
B: Baking type: Aqueous one-component acrylic melamine baking type paint was applied.
C: Solvent type: Room temperature dry 1-component oxidation polymerization type modified acrylic resin paint was applied.
D: Baking type: A one-component acrylic melamine baking type coating was applied.
Tests / evaluation items as shown in Table 32 were tested and evaluated according to the criteria shown in Table 33 in the state of only the undercoat and in the state where the top coats (i) to (d) were applied. The results are shown in Table 34 for the undercoat and in Table 35 for the topcoat.

As shown in Tables 34 and 35, the aqueous one liquid of Comparative Example 17 was particularly dry, and the aqueous two liquid of Comparative Example 18 resulted in inferior adhesion, workability, and drying properties.
On the other hand, the product of the present invention of Example 8 is more adhesive, dry, and workable than the aqueous one-component uncrosslinked of Comparative Example 17, the aqueous two-component of Comparative Example 18, and the solvent-based one of Comparative Example 19. Good results in corrosion resistance.
From these results, in the case of the product of the present invention, high reactivity due to the use of a one-component cross-linked emulsion, flexibility and toughness of polyurethane dispersion having high / low Tg characteristics, and permeability of ultrafine nanoemulsion. -It was confirmed that good performance can be obtained in the evaluation of adhesion, water resistance, corrosion resistance, workability, and drying property by the cohesive force.

Example 9: Top coat for plastics (HIPS, ABS) Using HIPS resin as a plastic material, on its surface, one-part cold crosslinking polymer emulsion (A), polyurethane dispersion (B), ultrafine nanoemulsion (C), Other than this, a water-based paint having a formulation as shown in Table 36 was applied to a bar coater No. 43, with a coating thickness of 15 μm.
Here, the same one-component room temperature cross-linked polymer emulsion (A), polyurethane dispersion (B), and ultrafine particle nanoemulsion (C) as those in Example 1 were used.
In Table 36, the same film forming aid, titanium oxide, dispersant, antifoaming agent, and viscosity agent as those described above were used.
For comparison, the conventional aqueous 1 liquid (Comparative Example 20) and aqueous 1 liquid (Comparative Example 21) as shown in Table 37 were applied as a plastic topcoat to the surface of the material made of HIPS resin in the same manner as described above. .
About these coating films, about the test and evaluation items as shown in Table 38, after top coat painting, it was dried at 50 ° C. for 20 minutes, and the next day, the test and evaluation were performed by the methods shown in Table 38 and Table 39. I did it. The results are shown in Table 40.

As shown in Table 40, the aqueous one liquid of Comparative Example 20 contains a large amount of solvent and has good drying properties and adhesion, but is uncrosslinked, so that the durability is inferior, and the aqueous one liquid of Comparative Example 21 is also Further, since it is uncrosslinked, the drying property and durability are inferior, and the adhesion is also inferior due to the influence of the components of the acrylic emulsion.
On the other hand, the product of the present invention of Example 9 gave better results in dryness, gloss, adhesion, water resistance, and ethanol resistance than the aqueous one-part solutions of Comparative Examples 20 and 21.
From these results, in the case of the product of the present invention, high reactivity due to the use of a one-component cross-linked emulsion, flexibility and toughness of polyurethane dispersion having high / low Tg characteristics, and permeability of ultrafine nanoemulsion. -It was confirmed that the cohesive strength provides good performance in drying, gloss, adhesion, water resistance, and ethanol resistance.

Claims (12)

  One-part cold crosslinking polymer emulsion (A) containing polyurethane having a hydrazine structure and a carbonyl group-containing acrylic polymer in particles dispersed in an aqueous medium, and a glass transition temperature (Tg) in the particles. Blended with polyurethane dispersion (B) having both a high component portion and a low glass transition temperature (Tg) component, and ultrafine nanoemulsion (C) having an average particle size in the range of 5 to 140 nm. A one-component room temperature cross-linking aqueous coating composition, In the one-component room-temperature-crosslinking aqueous coating composition according to claim 1,
The solid content of the one-component crosslinked emulsion (A) is 5 to 50% by weight, the solid content of the polyurethane dispersion (B) is 5 to 50% by weight, and the ultrafine nanoparticle is based on the solid content of the entire coating composition. A one-pack room temperature cross-linking aqueous coating composition, wherein the solid content of the emulsion (C) is in the range of 5 to 50% by weight. In the one-component room-temperature-crosslinking aqueous coating composition according to claim 1,
In the particles of the polyurethane dispersion (B), the glass transition temperature of the component having a high glass transition temperature is in the range of 100 ° C. to 160 ° C., and the glass transition temperature of the component having a low glass transition temperature is −50 ° C. to 0 ° C. A one-component room-temperature crosslinking aqueous coating composition characterized by being in the range. In the one-component room-temperature-crosslinking aqueous coating composition according to claim 1,
One-part cold crosslinking aqueous coating composition characterized in that the ultrafine particles constituting the ultrafine particle nanoemulsion (C) comprise at least one selected from an acrylic resin, an epoxy resin, and an alkyd resin. object. In the one-component room-temperature-crosslinking aqueous coating composition according to claim 1,
The one-part cold crosslinking aqueous coating composition, wherein the one-part cold crosslinking polymer emulsion (A) has a glass transition temperature of 0 to 50 ° C. In the one-component room-temperature-crosslinking aqueous coating composition according to claim 1,
The one-part cold crosslinking aqueous coating composition characterized in that the ultrafine particle nanoemulsion (C) has a glass transition temperature of 30 ° C to 50 ° C. In the one-component room-temperature-crosslinking aqueous coating composition according to claim 1,
The solid content of the one-component crosslinked emulsion (A) is 5 to 40% by weight, the solid content of the polyurethane dispersion (B) is 5 to 50% by weight, and the ultrafine nanoparticle Blended so that the solid content of the emulsion (C) is in the range of 5 to 50% by weight, and the glass transition temperature of the portion having a high glass transition temperature in the polyurethane dispersion (B) particles is 100 ° C to 160 ° C. The one-component room temperature cross-linking aqueous coating composition for waterproof top coat, wherein the glass transition temperature of the portion having a low glass transition temperature is in the range of -50 ° C to 0 ° C. In the one-component room-temperature-crosslinking aqueous coating composition according to claim 1,
The solid content of the one-component crosslinked emulsion (A) is 5 to 50% by weight, the solid content of the polyurethane dispersion (B) is 5 to 50% by weight, and the ultrafine nanoparticle is based on the solid content of the entire coating composition. Blended so that the solid content of the emulsion (C) is in the range of 5 to 50% by weight, and the glass transition temperature of the portion having a high glass transition temperature in the polyurethane dispersion (B) particles is 100 ° C to 160 ° C. The one-part room temperature cross-linking aqueous coating composition for wood top coats, wherein the glass transition temperature of the portion having a low glass transition temperature is in the range of -50 ° C to 0 ° C. In the one-component room-temperature-crosslinking aqueous coating composition according to claim 1,
The solid content of the one-component crosslinked emulsion (A) is 5 to 50% by weight, the solid content of the polyurethane dispersion (B) is 5 to 50% by weight, and the ultrafine nanoparticle is based on the solid content of the entire coating composition. Blended so that the solid content of the emulsion (C) is in the range of 5 to 50% by weight, and the glass transition temperature of the portion having a high glass transition temperature in the polyurethane dispersion (B) particles is 100 ° C to 160 ° C. A one-component room-temperature cross-linking aqueous coating composition for ceramic building materials, wherein the glass transition temperature of the portion having a low glass transition temperature is in the range of −50 ° C. to 0 ° C. In the one-component room-temperature-crosslinking aqueous coating composition according to claim 1,
The solid content of the one-component crosslinked emulsion (A) is 5 to 40% by weight, the solid content of the polyurethane dispersion (B) is 10 to 50% by weight, and the ultrafine nanoparticle is based on the solid content of the entire coating composition. Blended so that the solid content of the emulsion (C) is in the range of 10 to 50% by weight, and the glass transition temperature of the high glass transition temperature in the polyurethane dispersion (B) particles is 100 ° C to 150 ° C. The one-part room temperature cross-linking aqueous coating composition for metal topcoats, wherein the glass transition temperature of the portion having a low glass transition temperature is in the range of −50 ° C. to −10 ° C. In the one-component room-temperature-crosslinking aqueous coating composition according to claim 1,
The solid content of the one-component crosslinked emulsion (A) is 5 to 40% by weight, the solid content of the polyurethane dispersion (B) is 5 to 50% by weight, and the ultrafine nanoparticle Blended so that the solid content of the emulsion (C) is in the range of 5 to 50% by weight, and the glass transition temperature of the portion having a high glass transition temperature in the polyurethane dispersion (B) particles is 100 ° C to 160 ° C. The one-part cold crosslinking aqueous coating composition for metal primer coating, wherein the glass transition temperature of the portion having a low glass transition temperature is in the range of −50 ° C. to 0 ° C. In the one-component room-temperature-crosslinking aqueous coating composition according to claim 1,
The solid content of the one-component crosslinked emulsion (A) is 5 to 40% by weight, the solid content of the polyurethane dispersion (B) is 5 to 40% by weight, and the ultrafine nanoparticle is based on the solid content of the entire coating composition. Blended so that the solid content of the emulsion (C) is in the range of 5 to 30% by weight, and the glass transition temperature of the portion having a high glass transition temperature in the polyurethane dispersion (B) particles is 100 ° C to 150 ° C. The one-component room-temperature-crosslinking aqueous coating composition for plastic primer coating, wherein the glass transition temperature of the portion having a low glass transition temperature is in the range of −50 ° C. to −10 ° C.