JPS6046226B2 - A laminate consisting of a waterproof layer and a finishing layer formed on the surface of a structure. - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a laminate comprising a waterproof layer and a finishing layer formed on the surface of a construction.

In particular, the present invention relates to a laminate consisting of a waterproof layer and a finishing layer that is free from surface tackiness and has excellent stain resistance and weather resistance when formed on the surface of a construction. In recent years, waterproof finishing construction materials for structures have been developed and are attracting attention, not only for the purpose of waterproofing structures, but also for the aesthetic function of having vivid colors. The performance required for a coating material used for this purpose is that it can form a thick coating film, especially a thick coating film of O, 3wTm or more, and that the coating formed on the structure should not cause structural cracks in the structure. In addition, it is required to not break easily and to have the ability to follow structural cracks, and coating materials mainly made of rubber latex that meet this purpose have been used. Furthermore, in order to use this coating as an aesthetic finishing coating for a structure, it is required that this coating has no surface tackiness and has excellent weather resistance and stain resistance. A method has been developed in which a large amount of inorganic filler is added to the coating material, but the waterproof coating formed by this coating material satisfies the purpose in cold climates such as winter, but does not work in high temperatures in summer. The problem was that the tackiness of the coating film increased, causing the coating film to peel off from the structure and causing accidents such as contamination of other objects that came into contact with the waterproof coating film. Waterproofing materials for structures to overcome these difficulties have been studied, and currently the most effective one is a laminate in which a cross-linked urethane finish film is formed on a waterproof film provided on the structure, but this urethane cross-linked coating has good adhesion with the underlying waterproof layer, but due to its high crosslinking density, it is difficult to follow the expansion and contraction behavior of the waterproof layer that occurs when the waterproof layer is subjected to temperature changes or when structural cracks occur in the structure itself. It has been pointed out that there are problems with this, such as the fact that it cracks relatively easily and its performance as a finishing film deteriorates rapidly, and there is a desire for a waterproofing material that does not have these drawbacks.

Therefore, the present inventors are currently considering finding a waterproofing material for structures that can achieve the above objectives.After applying an appropriate sealer treatment to the surface of the structure, the
A finishing agent that can be thickly coated is made of a heavy aqueous liquid having a specific Tg (abbreviated as "g") and a filler, and then a clear organic solvent solution of a vinyl copolymer having a specific Tg is applied and dried. The inventors have now found that the object can be achieved and have completed the present invention.

The gist of the present invention is that zero unsaturated carboxylic acid is present on the surface of the construct.

10 parts by volume of an aqueous solution of a vinyl polymer having a glass transition temperature of -25 to -70°C (50% in terms of polymer content) obtained by copolymerizing 1% to 1% by volume with other copolymerizable vinyl monomers A waterproof layer is formed by applying a waterproofing agent with a viscosity of 500 centiboad or more, which is made by adding 10 to 1 parts by weight of an inorganic filler and 1 to 5 parts by weight of short fibers, and an unsaturated carboxylic acid on this waterproof layer. Glass transition temperature 10-600 when copolymerized with 0.5-10% by weight and other copolymerizable vinyl monomers
The first invention is a laminate consisting of a finishing layer formed by applying a finishing resin solution made of an organic solvent solution of a vinyl polymer having a C1 average molecular weight of 50,000 to 300,000; Aqueous liquid of a vinyl polymer with a glass transition temperature of -25 to -70°C obtained by copolymerizing 0.1 to 10% by weight of a saturated carboxylic acid with other copolymerizable vinyl monomers (50% in terms of polymer content) A waterproof layer formed by applying a waterproofing agent with a viscosity of 500 centiboad or more, which is made by adding 10 to 15 parts by weight of an inorganic filler and 1 to 5 parts by weight of short fibers to 1 part by weight; An organic solvent solution of a vinyl polymer having a glass transition temperature of 10 to 60°C and an average molecular weight of 50,000 to 300,000, which is obtained by copolymerizing 0.5 to 10% by weight of an unsaturated carboxylic acid with another copolymerizable vinyl monomer. 80-99.0% by weight and extender pigment 10-0
.

The second invention is a laminate comprising a finishing layer formed by applying a finishing agent of 1%.

The vinyl polymer constituting the waterproof finishing agent used in the present invention must be water-soluble or water-dispersible, and in order to impart this property to the vinyl polymer, unsaturated carboxylic acid must be It is necessary to copolymerize at a ratio of .1 to 1% by weight.

If the copolymerization amount of this acid is less than 0.1% by weight, the dissolution or dispersion stability of the vinyl polymer in an aqueous medium will be insufficient, making it difficult to produce an aqueous composition with good waterproof finishing properties. A coating film formed from an aqueous solution of a copolymer in which the amount of copolymerized acid exceeds 10% by weight has poor water resistance and is difficult to be used as a composition for carrying out the present invention. Specific examples of unsaturated carboxylic acids include acrylic acid, crotonic acid, methacrylic acid, itaconic acid, maleic acid, monosuccinate of hydroxyethyl acrylate or methacrylate, monophthalate, monomaleate, monofumarates, monosuccinate of hydroxypropyl acrylate or methacrylate. Aqueous dispersions of vinyl polymers copolymerized with these unsaturated carboxylic acids in the above range have good mechanical stability and are highly effective against short fibers and bone. It has excellent compatibility with additives such as wood, and has good adhesion to the concrete base, making it possible to form a finish coating with excellent waterproof properties.The Tg of the above vinyl polymer is - 2
5 is required to be C or less, and vinyl polymers with Tg higher than -25°C lack flexibility and adhesiveness, so waterproofing made from such polymers The coating can be used in the event of structural cracks in the structure.
This is not preferable because it has a strong tendency to break without being able to follow the cracks and lose its waterproof properties. In order to make a vinyl polymer having such characteristics, a vinyl monomer having a homopolymer Tg of -200C or less, such as an arylekyl group having 2 to 2 carbon atoms, is used.
The main starting materials are vinyl monomers such as 18 alkyl acrylates, octadecyl methacrylate, dodecyl methacrylate, octyl methacrylate, lauryl methacrylate, and stearyl methacrylate, and further copolymerizable vinyl monomers such as methyl acrylate, methyl methacrylate, and ethyl methacrylate. , butyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, vinyl acetate, vinyl propionate, styrene, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, hydroxyethyl acrylate or methacrylate, hydroxypropyl acrylate or methacrylate, N-alkoxyalkyl acrylamide Alternatively, methacrylamide, diethylene glycol di(meth)acrylate, butanediol di(meth)acrylate, dialkylaminoalkyl acrylate, dialkylaminoethyl acrylamide, diacetone acrylamide, and the like can be mentioned. A coating film formed from a vinyl polymer copolymerized with a large amount of these vinyl monomers having a functional group is undesirable because its water resistance tends to decrease, and the total amount should be 50% by weight or less. is necessary. In addition, since coating films formed from this vinyl polymer are often used outdoors and are required to have good weather resistance, the total amount of acrylate and methacrylate is copolymerized at a ratio of 20% by weight or more. Preferably. In addition, if the Tg of the vinyl polymer is too low, the paint film will sag when it is formed, and the formed paint film will remain sticky, allowing dirt to adhere to it and causing the paint film to deteriorate significantly. Since it is undesirable because it becomes dark and dirty, it is usually preferable that the Tg is -70'C or more.

On the other hand, coatings made from vinyl polymers with a Tg higher than -25°C not only have the above-mentioned disadvantageous properties, but also lack coating resistance, adhesion to substrates, elongation, etc. It is disadvantageous when used as a waterproof finish coating for structures. To prepare an aqueous solution of the vinyl polymer, a predetermined amount of the vinyl monomers mentioned above is combined and polymerized by a conventional emulsion polymerization method, followed by stabilization by adding an appropriate neutralizing agent, or alcohol, ethylene glycol, It can be prepared by solution polymerizing the vinyl monomer using a water-soluble organic solvent such as cellosolve, adding a neutralizing agent, and then diluting with water. May be used in

10 parts of aqueous solution of the above vinyl polymer (5 parts in terms of polymer)
Specific examples of fillers added at a ratio of 10 to 15 parts by weight per weight%) include talc, mica, diatomaceous earth, acid clay, carrion, quartz, iron powder, fly ash, ultra white, white carbon, and ferrite. , lithopone, titanium oxide, pearlite, barite, sulfite, zirconia, carbon black, calcium oxide, magnesium oxide, zinc oxide, barium oxide, lead oxide, aluminum oxide, calcium carbonate, magnesium carbonate, barium carbonate, strontium carbonate, sulfuric acid Barium, magnesium hydroxide, calcium hydroxide, etc. can be mentioned.

The coating formed from vinyl copolymer containing these fillers is strong, has high cracking resistance, and is aesthetically pleasing, and its properties are best demonstrated when used as a finishing waterproof membrane for structures. However, coatings formed from vinyl polymers containing 15 parts or more of these fillers have reduced adhesion to the surface of the structure, and their elongation and elasticity have decreased, causing structural cracks and other unexpected problems in the structure. When stress is applied, this coating film may partially peel off from the surface of the structure or break, which is not preferable. Further, specific examples of short fibers added in a ratio of 1 to (4) parts by weight to 100 parts by weight of the aqueous solution of the vinyl polymer include rock wool, bulb powder, glass wool powder, slag wool, asbestos powder, polyvinyl chloride short fibers, etc. Mention may be made of short fibers such as fibres, polypropylene or polyethylene staple fibers, nylon or polyester staple fibers, vinylon staple fibers, cotton flooring and the like.

The coating film formed from the waterproof finishing agent containing these short fibers in the above ratio has high strength and beautiful patterns, and exhibits excellent waterproof properties, so it is used as a waterproof finishing coating for structures. is extremely useful. Waterproof finishing agents containing the short fibers above the specified amount have a lower coating workability, a lower ability to form beautiful patterns, and a lower adhesion of the formed coating film to the surface of the structure and flexibility of the coating film. This is not desirable as it will cause damage to the In addition, antifoaming agents, viscosity stabilizers,
white cement, blast furnace cement, holtland cement,
Alumina cement, other coloring agents, ionic crosslinking agents, etc. can be added as appropriate, but at 25°C, the B type viscometer rotor No. l~NO. The viscosity measured under the condition of 42 rotations and 12 rotations is 500 CPS or more, preferably 1000~
It needs to be 100,000 CpS.

If the viscosity is too low, the paint film will sag, making it difficult to form a beautiful paint film in one spraying operation, and the thickness of the paint film tends to be uneven, so it is difficult to form a paint film with uniform properties. cannot form a membrane. On the other hand, if the viscosity is too high, the coating workability will drop rapidly, which is not preferable. The unsaturated carboxylic acid, which is the starting material for the copolymer constituting the transparent finishing resin solution used in carrying out the present invention, was used as the starting material for producing the vinyl polymer constituting the waterproof finishing agent. Exactly the same unsaturated carboxylic acid can be used.

The amount of copolymerization is preferably in the range of 0.5 to 1% by weight, and the amount of copolymerization exceeds 1% by weight than the transparent finishing resin containing a large copolymer. The transparent film formed on the film has poor water resistance, alkali resistance, stain resistance, weather resistance, etc., and cracks may occur in the film due to slight expansion and contraction of the waterproof finish film layer, resulting in poor appearance and poor weather resistance. This is not preferable because it significantly impairs waterproofness. On the other hand, a transparent coating formed on the waterproof finishing coating described above using a transparent finishing resin solution containing a copolymer with an acid copolymerization amount of less than 0.5% by weight has poor interlayer adhesion and is slightly Even if it is applied, it is not preferable because it may cause peeling or cracking. As other vinyl monomers copolymerizable with the unsaturated carboxylic acid used in producing the above copolymer, all the copolymerizable vinyl monomers used in obtaining the aqueous vinyl copolymer liquid can be used. The monomers are combined so that the resulting copolymer has a Tg of 10 to 60°C;
And among these monomers, vinyl monomers containing polar functional groups other than carboxyl groups, such as amide groups, alkylamido groups, alkylaminoalkyl groups, hydroxyalkyl groups, glycidyl groups, silanol groups, diacetontoacrylamide, or those of the formula ( In the formula, R1 is a C3-21 hydrocarbon group, R2 is H, a Cl-4 alkyl group, or -
CH2-0-C-R group, R3 is
11. The functional group-containing vinyl monomer represented by 4H or C1-4 alkyl group, R4 represents a C2-20 hydrocarbon group) has a content of 3% in other copolymerizable vinyl monomers. % or less.

A coating formed from a transparent finishing resin composition obtained by using these functional group-containing vinyl monomers as a starting material for a vinyl polymer improves interlayer adhesion with the underlying thick waterproof finishing coating. However, coatings formed by copolymerizing large amounts of these functional group-containing vinyl monomers have good weather resistance,
This is not preferable because the water resistance becomes poor and the interlayer adhesion with the thick waterproof finish film also deteriorates. Furthermore, the Tg of this copolymer must be in the range of 10 to 60°C, and a film formed from a copolymer with a Tg lower than 10°C will lack weather resistance and stain resistance. A coating formed from a copolymer with a carbon content higher than 60'C has a structure that is too rigid, resulting in insufficient adhesion with the thick waterproof finishing layer, and is prone to cracking if structural cracks occur in the structure. Therefore, it is not preferable, and usually 20 to 5
A range of 0°C is preferred.

The molecular weight of the copolymer is 50,000 to 300,000.
The molecular weight must be within the range of 50,00
A clear finish film with excellent weather resistance, stain resistance, and crack resistance cannot be formed from a copolymer with a molecular weight of less than 300,000; on the other hand, a transparent resin solution containing a copolymer with a molecular weight of 300,000 This is not preferable because the coating workability is significantly reduced. The copolymer contained in the transparent finishing resin solution can be made by a commonly used solution polymerization method, and organic solvents that can be used to dissolve this copolymer include aromatic solvents such as toluene and xylene. group hydrocarbons, isopropanol, n-butano 1-
Organic solvents such as alcohols such as alcohol, isobutanol, ketones such as methyl ethyl ketone and methyl isobutyl ketone, esters such as ethyl acetate and butyl acetate, and ethers such as ethyl cellosolve and butyl cellosolve may be used alone or in combination. The resin solution used to form the clear finishing film must be organic solvent-based, and it has better water resistance and weather resistance than the clear film formed with a water-based creamer resin solution. It is possible to improve the adhesiveness and adhesion to the lower waterproof layer.

When painting the above-mentioned transparent resin solution on a thick waterproof finish film with a pattern formed on it, there may be a large difference in the thickness of the dried film between the protrusions of the pattern and other parts. The finished coating is not preferable because it is significantly lacking in crack resistance and damage resistance.

In order to prevent such non-uniformity in the thickness of the rear finishing film, an extender pigment can be added to the transparent resin solution within a range that does not impair the transparency of the film formed. Extender pigments to be used include various known extender pigments, such as finely powdered silica, aluminum hydroxide, etc., and have a particle size of 2μ or less, such as Aerosil 200 (manufactured by Nippon Aerosil), Thyroid 266, etc. (manufactured by Fuji Davison), APS-200 (manufactured by Hayashi Kagaku), CABO SEAL (manufactured by Gabottsu), and KC-SS (manufactured by Kawabe Clay). The amount of these extender pigments added to the transparent resin solution is 1% by weight or less, preferably 0.0% by weight.
It is in the range of 1 to 5% by weight. If the amount of the extender pigment added is too large, the film formed from the resin solution will become matte, and the finished coating layer of the structure will become more porous than necessary, which is not preferable. In addition, a dye may be added to this transparent resin solution if necessary, and 1 weight% of a polyepoxy compound having an epoxy equivalent of 100 to 4000 is added.
It can also be added in the following proportions. To carry out the present invention, first, if necessary, a thermoplastic polymer having a temperature below TgO°C is applied to the surface of the structure at a rate of 10 to 500 y per block by brush coating, roller coating, spray coating, etc. After applying and drying properly, T? Ku-2
Apply a waterproof finishing composition with a viscosity of 500 centiboad or more, which is prepared by adding a specified amount of inorganic filler, short fibers, and other additives as necessary to 100 parts by weight of an aqueous vinyl polymer liquid at 5°C or lower, by brushing, rolling, spraying, etc. The thickness of the film is 0.
1 to 10m: Apply approximately In.

After drying this thick waterproof layer to an appropriate state, a transparent resin solution adjusted to an appropriate viscosity may be applied thereon by brushing, roller coating, spray coating, or the like. The thickness of this clear coating is usually 1 to 1
00μ, preferably in the range of 5 to 50μ.
The waterproof finish film formed by the method of the present invention exhibits excellent adhesion to the surface of a structure formed from a waterproofing material mainly consisting of a polymer lux with a low glass transition temperature and an inorganic filler, and exhibits excellent adhesion to the structure of the structure. Forms a waterproof layer that shows good followability even when cracks occur, and has a clear finish on the top surface that has good adhesion, water resistance, stain resistance, and moderate hardness to this waterproof layer. This is the first success in forming a waterproof coating on a construction surface that does not cause cracks in the clear coating even when used for a long period of time.

The waterproof coating thus obtained has no surface tackiness and is weather resistant.
It has extremely good stain resistance, excellent waterproof properties, and can be used as an aesthetic finishing coating for structures. By forming the clear layer of the waterproof finish film into a laminate using a one-component finishing agent, the workability of the work is improved, and the occurrence of uneven coating of the clear finish film is prevented.
The laminate of the present invention is much superior to conventional waterproof materials, such as improved weather resistance of the clear finish film, and will greatly contribute to the future development of this industry. The present invention will be explained in more detail with reference to Examples below.

Example 1 10 parts by weight of the monomer composition shown in Table 1 were mixed with 1.25 parts by weight of sodium dodecylbenzenesulfonate, 3.75 parts by weight of polyoxyethylene nonylphenyl ether, 0.54 parts by weight of ammonium persulfate, and hydrogen sulfite. Add to a mixture of 0.3 parts of sodium and 10 parts of deionized water, polymerize at 70'C for 6 hours, and then add P with aqueous ammonia.
Neutralize so that the H value is in the range of 8.0 to 8.5.
An emulsion containing a polymer having Tg shown in 1 was obtained. Titanium oxide 6. Weight: 75 parts by weight of calcium carbonate, 1.5 parts by weight of asbestos, 1 part by weight of bulb powder, 1 part by weight of polyoxyethylene noniphenyl ether, 1 part by weight of antifoaming agent, 1 part by weight of thickener, 14 parts by weight of water. Add parts by weight, solid content concentration 65-70% by weight, viscosity 30,000-48,000Cp
We created five types of waterproof finishing agents for S.

Production of clear finishing agent Monomer mixture 1 of methyl methacrylate/ethyl acrylate/methacrylic acid (64/35/1: weight ratio)
(4) 185 parts by weight of toluene, 0.0 parts by weight of benzoyl peroxide. Polymerization was carried out at 1000C for 11 hours using a weighing section, solid content concentration 35.1% by weight, average molecular weight 250.0
Prepare a toluene solution of a copolymer with a zero road price of 2.6 Tg at 46°C, and add acetone/toluene/xylene/to this resin solution.
A diluting solvent of Cellosolve Acetate 28/42/12/18 (volume ratio) was added to dilute to a solid content concentration of 15% by weight to prepare a transparent finishing resin solution.

Spray the above five types of waterproof finishing agents separately on the concrete exterior wall of the structure at a rate of 2.0 kg/Rfl, and after drying for 1 hour, apply the above transparent finishing resin solution at a rate of 0.2 k9/d. I spray painted it to look like this.

In addition, some unpainted parts were provided. The finished waterproof coating, which did not have a clear coating, did not have any problems with its waterproof properties, but three months after installation, it had become dark and discolored due to dust floating in the air adhering to it. Also, there was heavy dust adhesion in areas close to the ground. On the other hand, the finished waterproof membrane with a clear coating retains its waterproof properties well even after two and a half years have passed since installation, and there is almost no staining on the coating surface or loss of gloss, and there is no cracking of the clear coating layer. There were no inconvenient phenomena such as lifting or peeling, and the membrane maintained its clear, beautiful appearance. Example 2 Production of clear resin liquid 10 parts of the monomer mixture shown in Table 2 was polymerized by the same polymerization method as in Example 1, and then the diluent used in Example 1 was added to reduce the solid content to 1. Five types of clear resin solutions were prepared based on the weight percentage.

Finishing agent using emulsion A prepared in Example 1 was sprayed on five concrete outer walls at a rate of 2.0 kg/d, dried for 15 A, and then the above five types of clear resin solutions were sprayed at a rate of 0.2 kg/d. I sprayed it on and let it dry.

The results of evaluating the performance of this coating film are shown in Table 2. In addition, 3% by weight (resin solid content) of finely powdered silica sand (manufactured by Aerosil Nippon Aerosil) was added to 1 part of the clear resin solution, and emulsion A was used as a waterproof finishing agent on the concrete exterior wall of the structure by spraying. When it was sprayed onto a waterproof membrane having an uneven pattern and dried, it was confirmed that a clear film having a uniform thickness was formed even on the protrusions on the waterproof membrane surface.

Further, even after this waterproof coating was left for one year, no problems such as discoloration, cracking, or lifting occurred.

In addition, when a waterproof finish coating film was formed in exactly the same manner as above using a toluene solution of acrylic polyurethane resin (solid content concentration 2%) in place of the above clear resin solution, 6 months after application. Afterwards, cracks appeared on the clear film layer.

Claims (1)

[Claims] 1. A vinyl polymer having a glass transition temperature of -25 to -70°C obtained by copolymerizing 0.1 to 10% by weight of an unsaturated carboxylic acid and other copolymerizable vinyl monomers on the surface of the structure. It was formed by applying a waterproofing agent with a viscosity of 500 centipoise or more, which is made by adding 10 to 150 parts by weight of an inorganic filler and 1 to 50 parts by weight of short fibers to 100 parts by weight of the aqueous liquid of the coalescence (50% in terms of polymer content). a waterproof layer, on which 0.5 to 10% by weight of an unsaturated carboxylic acid and other copolymerizable vinyl monomers are copolymerized, with a glass transition temperature of 10 to 60°C and an average molecular weight of 50,000 to 300; A laminate comprising a finishing layer formed by applying a finishing resin solution made of an organic solvent solution of a vinyl polymer named 000. 2. An aqueous solution (polymer) of a vinyl polymer with a glass transition temperature of -25 to -70°C obtained by copolymerizing 0.1 to 10% by weight of an unsaturated carboxylic acid and other copolymerizable vinyl monomers is applied to the surface of the structure. A waterproofing layer formed by applying a waterproofing agent with a viscosity of 500 centipoise or more, which is made by adding 10 to 150 parts by weight of an inorganic filler and 1 to 50 parts by weight of short fibers to 100 parts by weight (based on combined content of 50%); A vinyl polymer having a glass transition temperature of 10 to 60°C and an average molecular weight of 50,000 to 300,000, which is copolymerized with 0.5 to 10% by weight of an unsaturated carboxylic acid and other copolymerizable vinyl monomers on the layer. Organic solvent solution 80~99.0% by weight and extender pigment 10~
A laminate consisting of a finishing layer formed by applying a finishing agent of 0.1%.