JPS6315315B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a moisture-proofing agent for the soil under the floor of a house. More specifically, the present invention aims to improve the antiseptic properties of wooden houses and highly increase the durability of the houses.
When applying moisture-proofing treatment to the soil under the floor of a house, it does not require a large amount of raw materials, is economical, and does not require the labor of laying or connecting film coatings, and can be easily applied by simply distributing it. This invention relates to a soil moisture-proofing agent that dries to form a coating layer with excellent moisture-proofing properties. BACKGROUND ART In recent years, problems have arisen in the construction and maintenance of houses, such as important structural parts such as foundations and pillars of houses rotting in a short period of time or being eaten by termites. The main cause of this rot and ant damage is that changes in building materials and construction methods have made houses more airtight, making it easier for these structural materials to remain in high humidity conditions. Needless to say, the biggest source of humidity under the floor is the soil under the floor, and blocking moisture from the soil is important for house maintenance. Wood-decaying fungi and termites prefer to breed in wood with high moisture content, and the fungi, which has recently caused great damage in areas such as Hokkaido, extend bundles of root-like hyphae into the ground to replenish moisture from the soil. However, in both cases, wood rotting under the floors of houses obtains the moisture necessary for reproduction from the soil under the floors, and blocking this moisture is an extremely effective means of preventing damage. Therefore, in the industry, there is an increasing need to apply moisture-proofing treatment to the soil under the floors of houses. Conventionally, three methods have been proposed for moisture-proofing soil.The first method is to form a concrete layer of a desired thickness on the surface of the soil under the floor of a house, or to lay a polyethylene film. The second method is to cover the soil with a three-layer composite material, which is made by layering kraft paper impregnated with an insect repellent (chlordane) on top of a polyethylene film, and then layering a polyethylene film on top of that. 3 flaky asphalt on the ground
This method covers the soil by spreading it to a thickness of ~5 cm and tamping it down. Methods 1 and 3 above not only require the foundation soil to be sufficiently smoothed before covering, but also have the disadvantage that covering is laborious and costly. Furthermore, method 2 requires the use of rubber tape to join the films together, and this method also has the disadvantage of being quite time-consuming and costly. The present inventors have made intensive studies to improve the shortcomings of the various conventional soil treatment methods described above and to develop an inexpensive soil moisture-proofing agent that has excellent moisture-proofing properties and requires as little effort as possible. The present inventors have discovered a soil moisture-proofing agent that can be easily dried to form a coating layer with excellent moisture-proofing properties, and have completed the present invention. That is, the present invention provides styrene-(meth)acrylic acid in which the contents of the styrene component and the unsaturated carboxylic acid component are 20 to 70% by weight and 0.1 to 5% by weight, respectively, and the remainder is a (meth)acrylic acid ester component. It consists of an ester-unsaturated carboxylic acid (hereinafter referred to as styrene-(meth)acrylic acid ester) copolymer resin emulsion (A) and gypsum (B), and the mixing ratio of (A) to (B) is the solid content. Weight ratio: 2:98~40
The present invention relates to a soil moisture-proofing agent that is applied to the underfloor part of a house and is characterized by having a moisture resistance of 60%. Generally, styrene-(meth)acrylic acid ester copolymer resin emulsion alone not only cures slowly but also has poor adhesion to soil.
Cracks are likely to occur due to shrinkage, and the strength of the film is also insufficient. On the other hand, gypsum alone cures too quickly, has a short pot life, and is poor in workability.Furthermore, the cured film is hard but brittle, prone to cracking, lacks density, and has a high water absorption rate, making it difficult to provide moisture-proof and waterproof properties. Styrene-(meth)acrylic acid ester type, which is a copolymerization of styrene, (meth)acrylic acid ester, and unsaturated carboxylic acid in a specific composition range, although it has the disadvantage of poor adhesion to soil. By mixing copolymer resin emulsion and gypsum in a specific ratio, styrene
The above drawbacks when using (meth)acrylic acid ester copolymer resin emulsion alone or gypsum alone are compensated for, and it has a suitable pot life, good workability, and is dense and flexible. A soil moisture-proofing agent with excellent moisture-proofing and waterproofing properties that forms a film with good properties and dimensional stability can be obtained. When the soil moisture-proofing treatment agent of the present invention is used for moisture-proofing the soil under the floor of a house, (1) it does not require a large amount of raw materials and is economical; (2) it can be water-resistant and moisture-resistant just by spraying it; Because it forms a film with excellent properties, it has the advantage that it is simple and does not require the labor of laying and connecting the film, unlike the conventional method of coating the soil with a ready-made film. Its practicality is great. Styrene-(meth) used in the present invention
The acrylic ester copolymer resin emulsion is a styrene-(meth)acrylic ester copolymer resin emulsion in which the content of the styrene component is in the range of 20 to 70% by weight, preferably 30 to 50% by weight. The (meth)acrylic esters mentioned here include acrylic esters such as methyl acrylate, ethyl acrylate, butyl acrylate, octyl acrylate, and 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, and methacrylic acid. Examples include methacrylic acid esters such as butyl and octyl methacrylate. If the content of the styrene component in the styrene and (meth)acrylic acid ester copolymer resin is less than 20% by weight, the film formed from the soil moisture-proofing agent containing the styrene component will be too soft and lack strength. On the other hand, if the content of the styrene component is more than 70% by weight, the film formed from the soil moisture-proofing agent containing it will be hard and brittle, and will have poor elasticity and impact resistance, so the desired moisture-proofing effect will not be achieved. It has the disadvantage that it is difficult to obtain. The unsaturated carboxylic acid used in the present invention is acrylic acid, methacrylic acid, itaconic acid, maleic acid, etc., and the proportion thereof used is 0.1 to 5% by weight. Styrene-(meth)acrylic acid ester copolymer resin emulsion is produced by a conventionally known method, for example, by radical copolymerization of monomers in water in the presence of a surfactant, a protective colloid, and a polymerization initiator. . In the present invention, not only styrene-(meth)acrylic acid ester copolymer resin emulsion but also acrylamide, 2-hydroxyethyl acrylate, dibutyl maleate, divinylbenzene, N-methylol A copolymer of a fourth component such as acrylamide, glycidyl methacrylate, triallyl cyanurate, ethylene glycol dimethacrylate, etc. can also be used. Among the fourth components, divinylbenzene, triallyl cyanurate, ethylene glycol dimethacrylate, etc. can be used to obtain a crosslinked synthetic resin emulsion, and as the third component, N-methylol acrylamide, glycidyl methacrylate, etc. can be used. A self-crosslinking synthetic resin emulsion can be obtained. The proportion of these third components in the resin is preferably 0.1 to 5% by weight. The styrene-(meth)acrylic acid ester copolymer resin emulsion may contain film-forming agents and plasticizers normally used in emulsion paints, such as ethylene glycol monobutyl ether, diethylene glycol monobutyl ether,
Diethylene glycol monobutyl acetate, texanol, dibutyl phthalate, dioctyl phthalate, etc. may be blended, and a hardening accelerator such as calcium chloride may be blended to accelerate hardening. In addition, for the styrene-(meth)acrylic acid ester copolymer resin emulsion, glycols such as ethylene glycol and propylene glycol, various surfactants, hydroxyethyl cellulose, methyl cellulose, polyvinyl Natural or synthetic polymeric substances such as alcohols may also be included. Examples of the gypsum used in the present invention include dihydrate gypsum, α-hemihydrate gypsum, β-hemihydrate gypsum, and the like.
These plasters may be used in combination of two or more. The mixing ratio of styrene-(meth)acrylic acid ester copolymer resin emulsion and gypsum is solid content weight ratio: copolymer resin emulsion to gypsum = 2:98
~40:60, preferably 5:95 to 30:70. If the mixing ratio of the copolymer resin emulsion is less than 2 in terms of solid content weight ratio, curing is quick, but the film is hard and brittle, has poor elasticity and impact resistance, and increases water absorption, resulting in a decrease in moisture-proofing and waterproofing functions. On the other hand, if the mixing ratio of the copolymer resin emulsion is more than 40 in terms of solid content weight ratio, curing is slow and the film loses its hardness, resulting in not only insufficient strength but also lack of dimensional stability. It has the following drawback. It is possible to mix and use various agents for controlling termites, such as chlordane and organic phosphorus agents, in the soil moisture-proofing treatment agent of the present invention, and various fungicides suitable for controlling rot caused by mushrooms, etc. may be added to the soil moisture-proofing agent, which is more effective because moisture-proofing, termite prevention, and antiseptic measures can be taken out at the same time. The soil moisture-proofing agent of the present invention may include, if necessary,
Sand, aggregates, pigments, cements, surfactants, thickeners, antifoaming agents, etc. may be added. Examples of sand and aggregates include quartz, perlite, vermiculite, shirasu balloons, silica powder, silica sand, river sand, etc.; examples of pigments include kaolin, talc, clay, various calcium carbonates, titanium oxide, mica,
Acid clay, diatomaceous earth, iron powder, ferrite, lithopone, baryta, zirconia, carbon black,
Examples include white carbon. Further, examples of cements include various types of Portland cement, blast furnace cement, and alumina cement. Sand, aggregates, pigments, and cements may be used alone or in combination of two or more. The amount added is preferably up to 300 parts by weight, more preferably 100 parts by weight, based on 100 parts by weight of the total amount of styrene-(meth)acrylate copolymer resin emulsion and gypsum in the soil moisture-proofing agent of the present invention. It is as follows. Thickeners are important to adjust the workability when spraying soil moisture-proofing agents, and the ones that can be used include natural polymer thickeners such as gelatin and casein, oxidized, methylated, Starch and cellulose treated with carboxymethylation, hydroxyethylation, hydroxypropylation, phosphorylation, cationization, etc., semi-synthetic polymeric thickeners such as sodium alginate, ammonium alginate, etc., polyvinyl alcohol, polyvinylpyrrolidone , synthetic polymer thickeners such as sodium polyacrylate and polyacrylamide, surfactant thickeners such as polyethylene oxide and its derivatives, colloidal silica, bentonite,
Examples include inorganic thickeners such as Attagel. Thickener: 0.01 to 3% by weight of soil moisture-proofing agent
It is preferable to mix them. If the amount is too small, the aggregates and pigments tend to settle in a short period of time, and if the amount is too large, the water resistance of the film may decrease. Examples of antifoaming agents include octyl alcohol, caprylic alcohol, lauryl alcohol, and cyclohexanol. It is preferable to add about 1 part. The amount of non-volatile content in the soil moisture proofing agent in the present invention may be arbitrary, but is usually preferably in the range of 30 to 80% by weight. If the amount of non-volatile content exceeds 80% by weight, the workability during spraying will be poor, and even if the amount of non-volatile content is lower than 30% by weight, the permeability of the soil moisture-proofing agent into the soil will be too high, making it difficult to prevent moisture. effectiveness decreases. The soil moisture-proofing agent of the present invention is applied or sprayed to the soil under the floor of a house to form a film.
The viscosity of the soil moisture-proofing agent is preferably 10 to 20,000 cps (B-type viscometer, 10 rpm, rotor No. 3, 30°C),
More preferably, it is about 100 to 10,000 cps. If the viscosity is too high, not only will the workability during spraying be poor, but also the leveling after spraying will be poor, making it difficult to uniformly cover the soil. On the other hand, if the viscosity of the soil moisture-proofing agent is too low, its permeability into the soil is too high and the coating film lacks tightness, making it difficult to obtain the expected moisture-proofing effect. The dry film thickness of the soil moisture-proofing agent of the present invention is 0.2
The thickness is preferably 0.4 to 2 mm, more preferably 0.4 to 2 mm. If the film thickness is too small, the moisture-proofing effect will be low and the intended purpose will not be achieved, and if the film thickness is too thick, a proportional moisture-proofing effect will not be obtained, which is uneconomical. When the soil moisture-proofing treatment agent of the present invention is applied to the subfloor of a house, it can be easily sprayed, does not pollute the environment, and the coating film after drying and curing has an extremely excellent moisture-proofing effect, and is effective in preventing corrosion of houses. It has the feature of having great effects. Next, the present invention will be explained in more detail with reference to Examples. In addition, the water absorption rates of Examples and Comparative Examples were measured according to the following method. Add 1 kg of dilution water to ² kg of soil moisture-proofing agent (2 kg of soil moisture-proofing agent and add 1 kg of dilution water, m ²
The amount of removal is 3 kg per person. ) and leave it at room temperature.
Leave to dry for several days to create a cured film with a thickness of 1 to 2 mm. After measuring the weight of this cured film, 40 ml of water was poured onto the film in an amount sufficient to cover the film, and the film was left overnight to absorb sufficient water. Next, after removing the water in the shear dish, the water adhering to the film was immediately wiped off with paper. Immediately after water stopped adhering to the paper, the film was weighed to measure the amount of water absorbed by water injection, and the water absorption rate was determined using the following formula. Water absorption rate (%) = Water absorption film weight - Film weight before water absorption / Film weight before water absorption x 100 Examples 1 to 6 and Comparative Examples 1 to 2 (A) Production of styrene-2-ethylhexyl acrylate copolymer resin emulsion Anion interface Activity (1 part by weight used per 100 parts by weight of polyoxyethylene nonylphenol ether sulfate ammonium salt monomer)
and nonionic surfactant (polyoxyethylene nonyl phenyl ether, HLB=17, monomer
using 2 parts by weight for 100 parts by weight),
A styrene-2-ethylhexyl acrylate copolymer resin emulsion with the properties shown in Table 1 was prepared by a conventional method (monomer composition of the copolymer resin: 40% by weight of styrene, 59% by weight of 2-ethylhexyl acrylate, itaconic acid). 1% by weight).

[Table] (B) Preparation of moisture-proofing agent The styrene-2-ethylhexyl acrylate copolymer resin emulsion and calcined gypsum were mixed at a solid content weight ratio as shown in Table 2. 1 kg of water was added to 2 kg of the obtained moisture-proofing agent to prepare a soil moisture-proofing agent. The water absorption rate was measured using this soil moisture proofing agent. The results are shown in Table 2. As a reference example, a similar experiment was conducted using an ethylene-vinyl acetate copolymer resin emulsion (solid content: 45% by weight, ethylene component: 15% by weight).

[Table] Note) * The film obtained from the soil moisture-proofing agent of Comparative Example 1 lost its hardness and lacked strength.
Lacks dimensional stability.
For 2 kg of the moisture-proof treatment agent produced in Example 4, an emulsifier solution containing 50% chlordane as a termiticide (manufactured by Co., Ltd.) was added.
Manufactured by Koshii Preserving Co., Ltd., trade name: Koshiklor
A50) 0.12Kg and dilution water 0.88Kg were mixed, stirred and mixed well, and then the treatment agent was sprayed onto the soil surface at a rate of 3.0Kg/m ² . One day after application, the surface formed a uniform gray coating, and within three days it had become a durable, hard, dry surface. Place a glass cylinder (inner diameter 50 mm, thickness approx. 3 mm, height 30 mm) on top of this surface coating without leaving any gaps.
Twenty-seven domestic termite worker ants and three soldier ants were introduced into the system, and the behavior of the ants was observed. For comparison, a sample containing only the moisture-proofing agent without chlordane was tested in the same manner as above. The results are shown in the table below.

[Table] H: Healthy K: Surprised M: Dead From the above results and Table 2, it can be seen that the moisture-proof treatment agent of the present invention containing a termiticide has not only a moisture-proofing effect, but also a moisture-proofing effect without reducing the effectiveness of the termiticide. It is clear that it can be effective. Example 7 In Examples 1 to 6, styrene-ethyl acrylate copolymer resin emulsion (co) was prepared in the same manner as in Examples 1 to 6, except that ethyl acrylate was used instead of 2-ethylhexyl acrylate. Monomer composition of polymer resin: 40% by weight of styrene,
59% by weight of ethyl acrylate and 1% by weight of itaconic acid). The obtained copolymer resin emulsion had a solid content of 49% by weight and an average particle size of 0.5 μm or less. Example 8 A styrene-butyl acrylate copolymer resin emulsion (copolymer) was prepared in the same manner as in Examples 1 to 6, except that butyl acrylate was used instead of 2-ethylhexyl acrylate. Monomer composition of polymer resin: 40% by weight of styrene,
59% by weight of butyl acrylate and 1% by weight of itaconic acid). The obtained copolymer resin emulsion had a solid content of 49% by weight and an average particle size of 0.5 μm or less. Comparative Example 3 Examples 1 to 6 except that the monomer composition was changed so that the styrene content of the copolymer resin in the styrene-2-ethylhexyl acrylate copolymer resin emulsion was 80% by weight. A styrene-2-ethylhexyl acrylate copolymer resin emulsion (monomer composition of copolymer resin: 80% by weight of styrene, 19% by weight of 2-ethylhexyl acrylate, 1% by weight of itaconic acid) was obtained in the same manner as above. The obtained copolymer resin emulsion had a solid content of 49% by weight and an average particle size of 0.1 to 0.5 μm or less. The copolymer resin emulsions obtained in Examples 7 to 8 and Comparative Example 3 and calcined gypsum were mixed at a solid content weight ratio as shown in Table 3. 1 kg of water was added to 2 kg of the obtained moisture-proofing agent to prepare a soil moisture-proofing agent. The water absorption rate was measured using this soil moisture proofing agent. The results are shown in Table 3.

[Table] Note) * The film obtained from the soil moisture-proofing agent of Comparative Example 3 was hard and brittle, and cracked under the slightest impact, making it unsuitable as a soil moisture-proofing agent.
Example 9 In Examples 1 to 6, the composition of the copolymer resin was 40% by weight of styrene and 59% by weight of 2-ethylhexyl acrylate.
A styrene-2-ethylhexyl acrylate copolymer resin emulsion was obtained in the same manner as in Examples 1 to 6 except that the monomer composition was changed so that the amount of methacrylic acid was 1% by weight. The obtained copolymer resin emulsion had a solid content of 49% by weight and an average particle size of 0.1 to 0.5μ. Example 10 In Examples 1 to 6, the composition of the copolymer resin was 40% by weight of styrene and 2-ethylhexyl acrylate.
A styrene-2-ethylhexyl acrylate copolymer resin emulsion was obtained in the same manner as in Examples 1 to 6, except that the monomer composition was changed to 59% by weight and 1% by weight of acrylic acid. The obtained copolymer resin emulsion had a solid content of 49% by weight and an average particle size of 0.1 to 0.5μ. Example 11 A styrene-2-ethylhexyl acrylate system was prepared in the same manner as in Examples 1 to 6 except that the monomer composition was changed so that the styrene content of the copolymer resin was 60% by weight. A copolymer resin emulsion (monomer composition of copolymer resin: 60% by weight of styrene, 39% by weight of 2-ethylhexyl acrylate, 1% by weight of itaconic acid) was obtained. The obtained copolymer resin emulsion had a solid content of 49% by weight and an average particle size of 0.1 to 0.5μ. Example 12 A styrene-2-ethylhexyl acrylate system was prepared in the same manner as in Examples 1 to 6 except that the monomer composition was changed so that the styrene content of the copolymer resin was 30% by weight. A copolymer resin emulsion (monomer composition of copolymer resin: 30% by weight of styrene, 69% by weight of 2-ethylhexyl acrylate, 1% by weight of itaconic acid) was obtained. The obtained copolymer resin emulsion had a solid content of 49% by weight and an average particle size of 0.1 to 0.5μ. The copolymer resin emulsions obtained in Examples 9 to 12 and calcined gypsum were mixed to have a solid content weight ratio as shown in Table 4. 2 kg of the obtained moisture-proofing agent
1 kg of water was added to the mixture to prepare a soil moisture-proofing agent. The water absorption rate was measured using this soil moisture-proofing agent. The results are shown in Table 4.

【table】

Claims (1)

[Claims] 1 Styrene-(meth)acrylic acid ester-unsaturated carboxyl having a content of styrene component and unsaturated carboxylic acid component of 20 to 70% by weight and 0.1 to 5% by weight, respectively, and the remainder being a (meth)acrylic ester component Acid copolymer resin emulsion (A) and plaster
(B), and the mixing ratio of (A) to (B) is from 2:98 to 40:60 in terms of solid content weight ratio; .