JPH1046052A - Aqueous undercoating agent for inorganic porous substrate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an aqueous undercoating agent for an inorganic porous substrate, excellent in adhesivity and permeability to a substrate and efflorescence resistance. SOLUTION: In an aqueous dispersion of resins having 20-80 deg.C glass transition temperatures, respectively in which at least one of the resins is a crosslinking type resin and resin particles (A) and (B) different in average resin particle diameter are mixed, the average particle diameter of the resin particles (A) is 0.06-0.09μm, that of the resin particles (B) is 0.10-0.30μm and the solid content (Wa) of the resin particles (A) and the solid content (Wb) of the resin particles (B) are mixed in the weight ratio of Wa/(Wa+Wb)=0.1-0.6 to give the objective aqueous undercoating agent for an inorganic porous substrate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a primer for inorganic porous substrates such as tiles and exterior materials, and more particularly to an inorganic porous substrate excellent in substrate adhesion and efflorescence resistance. It relates to an aqueous primer.

[0002]

2. Description of the Related Art An aqueous resin dispersion having a large particle size is used as an aqueous resin dispersion to provide a tough adhesive film,
Suitable coating compositions for forming adhesive coatings and impregnated films comprising mixtures of aqueous dispersions of adhesive resins (2) having a smaller particle size and polar groups are known (Japanese Patent Publication No. 44-44). No. 21554). In this composition, the adhesive resin particles having a polar group (2) migrate to the surface of an adherend such as paper or wood, and the concentration of the polar group on this surface increases, and as a result, the adhesive effect increases. It gives a tough adhesive film.

On the other hand, the resin particle diameter is about 0.02 to 0.08
Aqueous dispersion of micron fine resin particles is used for paper, concrete,
It is also known that it is excellent as a primer coating material for porous adherends such as wood and an impregnating agent (Japanese Patent Publication No. Sho 62-28187).
issue). Further, an aqueous undercoat in which a specific copolymer resin is partly or wholly solubilized by adding an alkali and / or an organic solvent in an aqueous medium to be present is an undercoat for an inorganic porous substrate. (Japanese Patent Application No. 4-51088).

[0004]

However, these existing technologies do not consider the efflorescence resistance even if they aim at improving the adhesive effect of a primer coating material, an impregnating agent and the like. In recent years, autocure has been used as a method for producing an inorganic base material.
With the advent of the curing method, an aqueous primer having excellent adhesion to a substrate and excellent efflorescence resistance has been desired as a seal before curing. An object of the present invention is to provide an aqueous primer for an inorganic porous substrate, which is excellent in adhesion to a substrate and has excellent permeability, at the same time, has excellent efflorescence resistance and can provide a film capable of curing autoclave. Is what you do.

[0005]

Means for Solving the Problems The present inventors have conducted various studies in order to solve the above-mentioned problems, and as a result, have found that a resin aqueous dispersion in which resin particles having different average particle sizes are mixed at a specific ratio. In the liquid, the resin particles having a small average particle diameter penetrate into the inorganic porous base material to improve the adhesion to the base material, and at the same time, the resin particles having a large average particle size are formed on the surface of the base material. It has been found that the efflorescence resistance can be improved.

That is, according to the present invention, there are provided resin particles (A) having a glass transition temperature of 20 to 80 ° C. and at least one of which is a crosslinked resin, having different average resin particle diameters,
In the aqueous resin dispersion in which (B) is mixed, the average particle diameter of the resin particles (A) is 0.06 to 0.09 μm, and the average particle diameter of the resin particles (B) is 0.10 to 0.30 μm. Yes, solid content (Wa) of resin particles (A) and resin particles (B)
Wherein the solid content (Wb) of the above is mixed at a weight ratio of Wa / (Wa + Wb) = 0.1 to 0.6.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, resin particles (A)
Penetrates into the inside of the inorganic porous base material, thereby contributing to the improvement of the adhesion to the base material. The average resin particles (based on the light scattering method) of the resin particles (A) are 0.06 to 0.09 μm.
m. If the average resin particle diameter is less than 0.06 μm, the resin particles (A) may permeate and diffuse deeply into the inorganic porous substrate, and may not contribute to the improvement of the adhesion to the substrate. On the other hand, when the thickness exceeds 0.09 μm, the ratio of the resin particles permeating into the base material decreases, and there is a tendency that sufficient adhesion to the base material cannot be obtained. It is necessary that the resin particles have a glass transition temperature of 20 to 80 ° C., preferably 40 to 70 ° C. from the viewpoint of the blocking resistance of the film.

On the other hand, the resin particles (B) can coat the surface of the inorganic porous substrate and form a dense film, and remove bleed-out components such as alkali ions from the inside of the substrate to the surface of the substrate. Shielding contributes to improving the efflorescence resistance of the substrate. Resin particles (B)
Average resin particle diameter (by light scattering method) is 0.10 to
The range is 0.30 μm. The average resin particle diameter is 0.
If it is less than 10 μm, the proportion of the resin particles that penetrates the base material increases, and a film required for preventing efflorescence tends not to be formed on the surface of the inorganic porous base material. On the other hand, if the average resin particle diameter exceeds 0.30 μm, it is difficult to form a dense film on the surface of the substrate, so that the efflorescence resistance tends to decrease. Further, in this case, the resin is excessively loaded on the surface of the base material, so that the blocking resistance at the time of loading the base material tends to decrease. The glass transition temperature of the resin particles is 20 to 80 ° C., preferably 40 to 80 ° C.
The temperature is required to be 70 to 70 ° C. in view of the blocking resistance of the film. It is also necessary that a cross-linking group is introduced into at least one of the resin particles (A) and (B) from the viewpoint of the blocking resistance of the film.

Further, the resin solid content (W) of the resin particles (A)
The weight ratio of a) to the resin solid content (Wb) of the resin particles (B) is in the range of Wa / (Wa + Wb) = 0.1 to 0.6. When the weight ratio of the resin solid content (Wa) of the resin particles (A) is less than 0.1, the amount of the resin particles (A) penetrating into the inside of the inorganic porous base material is too small, and the sufficient amount of the resin particles (A) to the base material cannot Adhesion tends not to be obtained. When the ratio is more than 0.6, the amount of the resin particles (B) capable of densely covering and forming a film on the surface of the inorganic porous base material is reduced.
The effect of preventing efflorescence tends to decrease.

The mixture can be obtained by separately emulsifying the resin particles (A) and (B), respectively, or by two-step distribution of particle diameter at once by a seed polymerization method. It is also obtained by doing. In the emulsion polymerization, as is generally known, an emulsifier, a reactive emulsifier or a protective colloid is used as a dispersant, and a water-soluble initiator is used to (co) polymerize an unsaturated monomer in water. Is obtained by As the emulsifier, various anionic,
Cationic and nonionic emulsifiers, and furthermore, polymer emulsifiers are exemplified. Particularly preferred emulsifiers are carbonyl group-containing polymer emulsifiers described in JP-A-64-48801 according to the present invention (partly).

The polymerization initiator used in the emulsion polymerization is preferably an inorganic peroxide such as potassium persulfate, ammonium persulfate or hydrogen peroxide. One type of these initiators may be used alone, or two or more types may be appropriately used in combination. In addition, a redox initiator may be used by using a reducing agent such as Rongalit, L-ascorbic acid, or an organic amine together with these initiators.

The unsaturated monomers used in the emulsion polymerization include (a) alkyl esters of acrylic acid or methacrylic acid having 1 to 18 carbon atoms, vinyl aromatic compounds, vinyl halides, saturated vinyl carboxylate, acrylonitrile , Methacrylonitrile, ethylene, butadiene and a mixture of (b) other monomers.

Among the unsaturated monomers, (a) includes:
C1-C18 alkyl esters of acrylic acid or methacrylic acid (for example, esters of acrylic acid or methacrylic acid such as methyl, ethyl, n-propyl, n-butyl, isobutyl, t-butyl), vinyl aromatic compounds (for example, Styrene), vinyl halides (eg, vinyl chloride, vinyl bromide, vinylidene chloride), saturated vinyl carboxylate (eg, vinyl acetate, vinyl propionate), acrylonitrile, methacrylonitrile, ethylene, butadiene, and the like. Particularly preferred monomers (a) are alkyl esters of acrylic acid or methacrylic acid having 1 to 8 carbon atoms and styrene. Two or more of these monomers (a) may be contained in the copolymer.

Further, the monomer (b) is other than the above-mentioned monomer (a), and has at least one ald group or keto group and one polymerizable unsaturated doublet in the molecule. A carbonyl group-containing unsaturated monomer having a bond, for example, acrolein, diacetone acrylamide, formylstyro-
Vinyl alkyl ketones having 4 to 7 carbon atoms (eg, vinyl methyl ketone, vinyl ethyl ketone, vinyl butyl ketone, etc.), monoolefinically unsaturated carboxylic acids (eg, acrylic acid, methacrylic acid, itaconic acid, etc.), Monoolefinically unsaturated carboxylic acid amides (eg, acrylamide, methacrylic acid amide, etc.), N-alkyl and / or N-alkylol derivatives of monoolefinically unsaturated carboxylic acid amides (eg, N-methylacrylic acid amide, -Methylolacrylamide, N-
Methylol methacrylamide, etc.), monoolefinically unsaturated sulfonic acid (eg, vinyl sulfonic acid), butanediol diacrylate, butanediol dimethacrylate, propanetriol triacrylate, propanetriol trimethacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate, glycidyl Examples include acrylate, glycidyl methacrylate, and acryl (or methacryl) oxyalkyl propenal represented by the following general formula (1). Two or more of these monomers (b) may be contained in the copolymer.

[0015]

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In the above formula (1), R1 is H or CH3, R
2 is H or an alkyl group having 1 to 3 carbon atoms, and R3 is 1 carbon atom.
R3 represents an alkyl group having 1 to 3 carbon atoms, and R4 represents an alkyl group having 1 to 3 carbon atoms.

At least one of the resin particles (A) and (B) of the aqueous resin dispersion thus obtained is a copolymer containing at least one of the crosslinkable monomers listed in (b) above as a copolymerization component. It is necessary that the resin be a crosslinked resin that is a polymer in order to maintain the water resistance of the film. Particularly preferably, both of the resin particles (A) and (B) are cross-linked resins. In this case, since a complicated cross-linking can be formed between both the resins (A) and (B), Properties are further improved.

As a particularly preferred cross-linking form, at least one ald group or keto group and one aldehyde group in the molecule, which are exemplified as the other monomers of the above (b) as the constituent monomers of the copolymer resin, It is effective to carry out copolymerization using a carbonyl group-containing unsaturated monomer having a polymerizable unsaturated double bond, and then to further add a hydrazine derivative having at least two hydrazino groups in the molecule. .
The carbonyl group-containing unsaturated monomer is preferably used in a proportion of 0.5 to 30% by weight, more preferably 1 to 20% by weight in the total monomer mixture. If the amount of the monomer is too small, the content of the ald group or keto group of the copolymer resin is too small, and even if a hydrazine monomer is added, sufficient water resistance, improvement in solvent resistance, etc. I can't hope. On the other hand, if the amount of the monomer is too large, the alkali resistance and the weather resistance of the coating tend to decrease.

Examples of the hydrazine having at least two hydrazino groups in the molecule include carboxylic dihydrazides having 2 to 10, especially 4 to 6 carbon atoms (for example, oxalic dihydrazide, malonic dihydrazide, succinic dihydrazide). , Glutaric acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, maleic acid dihydrazide, fumaric acid dihydrazide, itaconic acid dihydrazide), aliphatic water-soluble dihydrazine having 2 to 4 carbon atoms (eg, ethylene-1,2-di) Hydrazine, propylene-1,3-dihydrazine, butylene-
1,4-dihydrazine and the like).

Further, as the hydrazine derivative, a polymer having a hydrazino group represented by the following general formula (2) can also be used. Such a polymer having a hydrazino group is described in detail, for example, in JP-A-55-6535.

[0021]

Embedded image

In the above formula (2), X is a hydrogen atom or a carboxyl group, Y is a hydrogen atom or a methyl group,
A is each unit of acrylamide, methacrylamide, acrylate, methacrylate or maleic anhydride, and B is a monomer copolymerizable with acrylamide, methacrylamide, acrylate, methacrylate or maleic anhydride. Is a unit of or,
k, m and n are numbers satisfying the following equations.

[0023]

1 mol% ≦ k ≦ 100 mol% 0 mol% ≦ (m + n) ≦ 98 mol% (k + m + n) = 100 mol%

The mixing ratio of the hydrazine derivative is such that the ratio of the carbonyl group to the hydrazino group contained in the copolymer resin and other additives (specifically, the aqueous resin dispersion described below) is
The molar ratio of (> C = O) / (-NHNH2) is preferably 0.2 to 5.0, more preferably 0.3 to 2.0. If the proportion of the hydrazine derivative is too small,
Improvement of water resistance cannot be expected because the cross-linking between the resins is not sufficiently performed, and even if the ratio is too large, not only the water resistance improvement effect corresponding to it is not obtained, but also the film It becomes opaque and brittle.

Various methods can be used for supplying the monomer in the emulsion polymerization. For example, various methods such as a batch charging method, a monomer addition method, and an emulsion addition method can be used. Further, a seed polymerization method in which the composition of the monomer to be added is sequentially changed, a power feed polymerization method, or the like can also be used. In addition to the resin particle components (A) and (B), defoaming agents, wetting agents, antifreezing agents, preservatives, viscosity modifiers, reaction accelerators, reaction retarders, dispersants, film-forming auxiliaries, Plasticizers, colorants, gypsum, cement, pigments, fillers and the like can be optionally added. In addition, some solvents and the like can be used for the purpose of improving the drying property and the coating property.

Further, in the present invention, in a system using a hydrazine derivative and a copolymer resin obtained by polymerizing using a carbonyl group-containing unsaturated monomer, the reaction between the carbonyl group and the hydrazino group is dried. Although it progresses with the formation of a film, it is slightly carried out even in an aqueous phase, so that it tends to gel. In order to prevent this, it is preferable to add a low molecular compound (aldehydes or ketones) containing a carbonyl group based on an aldo group or a keto group and having a boiling point of 200 ° C. or lower.
Its boiling point is preferably 120 ° C. or lower, more preferably 10 ° C.
The temperature is more preferably 0 ° C or lower.

This is because under the condition where a large amount of water is present, such as a film during storage of the aqueous primer of the present invention or before drying.
The blended low molecular weight aldehydes and ketones react with the hydrazino group of the hydrazine derivative to block the hydrazino group, thereby effectively preventing the crosslinking reaction between the polymers and stopping the gelation of the resin. It is considered that the gelation time can be extended.

Specific examples of the aldehydes or ketones include, for example, formaldehyde (boiling point −21 ° C.), β
-Hydroxyethyl methyl ketone (182 ° C), acetaldehyde (21 ° C), glyoxal (51 ° C)
° C), acetone (56 ° C) and ethyl methyl ketone (80 ° C). One type of these aldehydes or ketones may be used, or two or more types may be used in combination.

[0029]

[Examples] The following are examples of preparing aqueous resin dispersions.
An example and a comparative example will be described in detail. "Parts" and "%" described in these examples indicate parts by weight and% by weight, respectively. Preparation Example 1 of Resin Aqueous Dispersion After the inside of a reaction vessel equipped with a temperature controller, an anchor type stirrer, a reflux condenser, a thermometer and a nitrogen inlet tube was replaced with nitrogen, the following components were charged.

[0030]

Table 1 Water 50 parts 35% aqueous solution of sulfuric acid half ester sodium salt of ethylene oxide 20 mol added p-nonylphenol (referred to as “anionic emulsifier A”) 2 parts ethylene oxide 25 mol added p-nonylphenol (“nonionic emulsifier B”) ), The following mixture was prepared as Feed I: Feed I Water 50 parts 35% aqueous solution of anionic emulsifier A above 3 parts 20% aqueous solution of above nonionic emulsifier B 2 parts Styrene 65 parts Butyl acrylate 30 parts Acrylic acid 2 parts Acrylic amide 1 part N- Methylolacrylamide 2 parts

Separately, an aqueous solution prepared by dissolving 0.7 part of potassium persulfate in 20 parts of water was prepared as Feed II. After replacing the inside of the reaction vessel with nitrogen gas, 10% of the feed I was added to the charge, and the mixture was heated to 90 ° C. Then, 10% of Feed II was injected into the reaction vessel, and then the remaining Feeds I and II were fed in small portions in parallel over 3.5 hours. After the end of the supply, 1.
The emulsion polymerization was completed by maintaining the temperature at 90 ° C. for 5 hours. A 25% aqueous ammonia solution was added to the aqueous resin dispersion obtained as described above so that the pH became 9.

Resin aqueous dispersion Preparation Examples 2 and 3 The same procedure as in Preparation Example 1 was carried out except that the monomer composition of the feed was changed as shown in Table 7.

Preparation Example 4 of Resin Aqueous Dispersion After the inside of a reaction vessel equipped with a temperature controller, an anchor type stirrer, a reflux condenser, a thermometer and a nitrogen inlet tube was purged with nitrogen, the following components were charged.

[0034]

Table 2 Water 50 parts 35% aqueous solution of sulfuric acid half ester sodium salt of ethylene oxide 20 mol added p-nonylphenol (referred to as “anionic emulsifier A”) 3 parts ethylene oxide 25 mol added p-nonylphenol (“nonionic The following mixture was prepared as Feed I separately. Feed I Water 50 parts 35% aqueous solution of anionic emulsifier A above 4 parts 20% aqueous solution of above nonionic emulsifier B 2 parts Styrene 65 parts Butyl acrylate 30 parts Acrylic acid 2 parts Acrylic amide 1 part N- Methylolacrylamide 2 parts

Separately, as a feed II, an aqueous solution in which 0.7 part of potassium persulfate was dissolved in 20 parts of water was prepared. After replacing the inside of the reaction vessel with nitrogen gas, 10% of the feed I was added to the charge, and the mixture was heated to 90 ° C. Then, 10% of Feed II was injected into the reaction vessel, and then the remaining Feeds I and II were fed in small portions in parallel over 3.5 hours. After the end of the supply, 1.
The emulsion polymerization was completed by maintaining the temperature at 90 ° C. for 5 hours. A 25% aqueous ammonia solution was added to the aqueous resin dispersion obtained as described above so that the pH became 9.

Resin Aqueous Dispersion Preparation Examples 5, 6 and 7 The same procedure was carried out as in Preparation Example 4, except that the monomer composition of the feed was changed as shown in Table 8.

Preparation Example 8 of Resin Aqueous Dispersion After the inside of a reaction vessel equipped with a temperature controller, an anchor type stirrer, a reflux condenser, a thermometer and a nitrogen inlet tube was purged with nitrogen, the following components were charged.

[0038]

Table 3 Water 50 parts Sodium lauryl sulfonate 2 parts Feed I Water 50 parts Sodium lauryl sulfonate 3 parts Methyl methacrylate 65 parts Butyl acrylate 30 parts Methacrylic acid 2 parts Acrylic amide 1 part Diacetone acrylamide 2 parts

Separately, as a feed II, an aqueous solution in which 0.5 part of potassium persulfate was dissolved in 20 parts of water was prepared. After replacing the inside of the reaction vessel with nitrogen gas, 10% of the feed I was added to the charge, and the mixture was heated to 90 ° C. Then, 10% of Feed II was injected into the reaction vessel, and then the remaining Feeds I and II were fed in small portions in parallel over 3.5 hours. After the end of the supply, 1.
The emulsion polymerization was completed by maintaining the temperature at 90 ° C. for 5 hours. The aqueous resin dispersion having a fine particle diameter of 25%
An aqueous ammonia solution was added so that the pH became 9.

Example 1 70 parts of the aqueous copolymer resin dispersion obtained in Preparation Example 1 of an aqueous resin dispersion, 30 parts of the aqueous dispersion of copolymer resin obtained in Preparation Example 4 of an aqueous resin dispersion, and butyl cellosolve 5 Parts and 5 parts of Texanol. An undried cement mortar made of Portland cement and silica sand was used as a test piece.
Curing was performed at 0 ° C./5 hours to prepare an inorganic porous substrate having a substrate density of 0.9 g / cm ³ . The resulting dried film of the aqueous undercoat was tested for adhesion, non-uniform top coat, water resistance, hot water resistance, and frost resistance by the following test methods. The results of the evaluation are as shown in Table 9.

Efflorescence resistance: The presence or absence of efflorescence on the substrate surface after autoclaving is checked.

Topcoat unevenness: This test piece was used as a topcoat paint.
The film pressure after drying the paint obtained by mixing as follows is 50 μm
And dried at 100 ° C. for 10 minutes to form a film, and the appearance was visually evaluated.

[0043]

Table 4 Top coating composition water 64.6 parts Demol EP (manufactured by Kao Corporation) 20.0 parts Nopco 8034 (manufactured by San Nopco) 0.3 part Titanium oxide (rutile type) 54.0 parts kaolin 6. 0 part Acronal YJ2770D (Mitsubishi Chemical BASF) 146.7 parts Texanol (Eastman Kodak) 9.5 parts 5% ADEKANOL UH420 (Asahi Denka) 1.0 part

[0044]

[Table 5] ◎: No unevenness ○: Some unevenness △: Unevenness ×: Lifting

[0045]

[Table 6] Adhesion: After coating the top coat, the test piece was cut into 5 x 5 grids at 3 mm intervals with a cutter knife, and a polyester adhesive tape was pressed, then peeled off and the coating remained. I checked the condition. ◎: The coating film was not peeled at all. ○: The coating film was slightly peeled. Δ: The coating film was partially peeled. ×: The coating film was completely peeled.

Warm water resistance: After applying the top coat, 4
After being immersed in water at 0 ° C. for 5 days, it was dried at room temperature for 2 hours, and the adhesion was examined in the same manner as described above.

Freezing damage resistance: After applying the top coat, the test piece was
After immersion in water at 0 ° C. for 2 hours and freezing in air at −20 ° C. for 2 hours as one cycle, 200 cycles were performed.
After drying at room temperature for a day, the adhesion was examined in the same manner as described above.

Examples 2 to 5 and Comparative Examples 1 to 4 The types and amounts of the copolymer resin and the hydrazine derivative were changed as shown in Tables 9 and 10, and the other conditions were the same as in Example 1 except that the aqueous primer was used. It was prepared and similarly tested for its film properties. Tables 9 and 10 show the composition ratios (parts) of the aqueous primers obtained in each of the examples and comparative examples and the test results of the film properties.

[0049]

[Table 7]

[0050]

[Table 8]

[0051]

[Table 9]

[0052]

[Table 10]

[0053]

Effect of the Invention The aqueous primer of the present invention has an adhesive property to a substrate, an efflorescence resistance, a blocking resistance,
It is excellent in frost damage resistance and can give a film capable of autoclaving.

Claims (1)

[Claims] 1. A glass transition temperature of 20 to 80 ° C.
In an aqueous resin dispersion in which resin particles (A) and (B) having different average resin particle diameters are mixed, at least one of which is a crosslinked resin, the average particle diameter of the resin particles (A) is 0. 0.06 to 0.09 μm, the average particle size of the resin particles (B) is 0.10 to 0.30 μm, and the resin particles (A)
A solid content (Wa) of the resin particles (B) and a solid content (Wb) of the resin particles (B) are mixed at a weight ratio of Wa / (Wa + Wb) = 0.1 to 0.6. Water-based primer.