JPH1150046A - Sealing material composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition excellent in elasticity, elongation and weather resistance and having sealing effect and vibration-reducing effect by including a polymer of polyvalent metal salt of (meth)acrylic acid, clay mineral, a tacky agent and water. SOLUTION: This sealing material composition comprises (A) a polymer of a polyhydric metal salt of (meth)acrylic acid, e.g. polymer of a divalent metal salt (e.g. magnesium salt) and/or trivalent metal salt (e.g. aluminum salt) in an amount of 3-45 wt.% based on total amount of the components A and D, (B) clay mineral (e.g. clay) in an amount of 20-60 wt.% based on the composition, (C) a tacky agent, which is preferably emulsion of acrylic acid ester, in an amount of 3-50 wt.% based on the composition, (D) water in an amount of 55-97 wt.% based on total amount of the components A and D and (E) as necessary, polyacrylamide, glycerol, propylene glycol, thickener, antioxidant, ultraviolet absorber, pigment, filler, sagging-preventing material, perfume, surfactant, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a sealing material composition useful for construction and civil engineering, and more particularly to a sealing material composition having a vibration reducing effect.

[0002]

2. Description of the Related Art In the field of construction, civil engineering, etc., a sealing material is used to fill or seal joints of walls and partition plates, joints such as branch pipes of manholes and cracks for the purpose of watertightness or airtightness. The composition has been used. Such a sealing material composition is required to have excellent properties such as elasticity, weather resistance, and winter curability, and a modified polysulfide polymer-based or modified silicone polymer-based sealing material composition is used.

[0003]

However, when joints and joints are sealed with the above-mentioned conventional sealing material composition, the sealing portion transmits vibrations, so there is no effect of reducing the vibrations. There has been a problem that when the construction is performed or when an earthquake occurs after the construction, breakage or breakage occurs at the sealed joints or joints.

[0004] The present inventors have found a sealing agent composition comprising an aqueous solution containing a polyvalent metal salt of (meth) acrylic acid and a polymerization catalyst as a composition for solving these problems (Japanese Patent Application No. Hei 10-26139). No. 8-257663).

[0005] However, the composition of the present invention is intended to polymerize a polyvalent metal (meth) acrylate at a site to be sealed, and when a clay mineral is blended in the composition, If the composition is left standing after production, the polyvalent metal salt of (meth) acrylic acid will polymerize and the clay mineral will be unevenly dispersed in the cured product. It had to be manufactured in. Further, when sealing plastic such as a PVC pipe, the plastic may be deformed due to polymerization heat generated when the composition is cured. Further, since the composition has a low viscosity, when the composition is applied to a joint seal, the composition may hang down and may not be applied well. In addition, some of the sealing material composition of the invention and the conventional sealing material composition have insufficient adhesion to the base, and in this case, a primer treatment is required on the base to improve the adhesion. And there was also a problem in workability.

[0006] The inventors of the present invention have excellent elasticity, elongation and weather resistance, exhibit a sealing effect, have a vibration reducing effect, do not need to be manufactured at a construction site, and when applied to a plastic, the plastic can be used. Without deformation
Further, the present inventors have conducted intensive studies in order to find a sealing material composition having excellent adhesion to a substrate.

[0007]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that a composition comprising a polymer of a polyvalent metal salt of (meth) acrylic acid is effective. Thus, the present invention has been completed. In this specification, methacrylic acid and / or acrylic acid is referred to as (meth) acrylic acid.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION

○ Polymer of polyvalent metal salt of (meth) acrylic acid In the composition of the present invention, a polymer of a polyvalent metal salt of (meth) acrylic acid, for example, a polymer of a divalent metal salt and / or a trivalent metal salt Use When only a polymer of a monovalent metal salt of (meth) acrylic acid is used, the polymer does not have a cross-linking point, is liquid and does not gel, and thus does not exhibit a vibration reducing effect. As the divalent metal salt of (meth) acrylic acid as a raw material, various ones can be used, but an alkaline earth metal salt is preferable, and a magnesium salt or a strontium salt is more preferable. Various trivalent metal salts of (meth) acrylic acid can be used, and an aluminum salt is preferable.

[0009] The content of the polymer of the polyvalent metal (meth) acrylate is preferably 3 to 45% by weight based on the total amount of the polymer of the polyvalent metal (meth) acrylate and water. Preferably, it is 8 to 40% by weight. When the proportion is less than 3% by weight, a sufficient vibration-reducing effect may not be obtained. On the other hand, when the proportion is more than 45% by weight, kneading becomes difficult during the production of the composition or the composition can be obtained. In some cases, the composition becomes powdery and has poor adhesion to the substrate.

As the polymer of the polyvalent metal salt of (meth) acrylic acid, those produced by various methods can be used. An aqueous solution of the polyvalent metal salt of (meth) acrylic acid is prepared by adding an aqueous solution of the polyvalent metal salt of (meth) acrylic acid in the presence of a polymerization catalyst. It is preferable that the polymer is produced by polymerizing the (meth) acrylic acid polyvalent metal salt by stirring at room temperature or under heating.
Examples of the polymerization catalyst include an azo compound having a hydrophilic group, a water-soluble organic peroxide, and a redox catalyst including an oxidizing agent and a reducing agent. As a polymer of a polyvalent metal salt of (meth) acrylic acid, a polymer produced using an azo compound having a hydrophilic group as a polymerization catalyst may be used when the part to be sealed has a metal part. This is preferable because parts are hardly corroded.

There are various azo compounds having a hydrophilic group, and examples of the hydrophilic group include an amino group, a hydroxyl group and a carboxyl group. Examples of those having an amino group include azoamidine and cyclic azoamidine, and examples thereof are 2,2′-azobis [2- (imidazolin-2-yl) propane] and 2,2′-azobis [2-
(Imidazolin-2-yl) propane] dihydrochloride, 2,2′-azobis (2-methylpropionamidine) dihydrochloride, 2,2′-azobis [2- (5
-Methyl-2-imidazolin-2-yl) propane] dihydrochloride. Examples of those having a hydroxyl group include 2,2'-azobis (2-methylpropionamide) dihydrate, and those having a carboxyl group include 4,4'-azobis (4-cyanovaleroic acid). There is. Among the azo compounds having a hydrophilic group, 2,2′-azobis [2- (imidazolin-2-yl) propane] and 2,2′-azobis [2- (imidazolin-2-yl) propane] dihydrochloride are represented by ( It is preferable in that the curability of the polyvalent metal salt of (meth) acrylic acid is excellent. The mixing ratio of the azo compound having a hydrophilic group to the polyvalent metal salt of (meth) acrylic acid is preferably 0.5 to 5% by weight in the aqueous solution of the polyvalent metal salt of (meth) acrylic acid. , More preferably 0.3 to 1% by weight
It is. If this ratio is less than 0.1% by weight,
In some cases, it may be difficult to cure the polyvalent metal salt of (meth) acrylic acid uniformly, and when it exceeds 5% by weight, the polymerization may proceed in a short time, and it may be difficult to remove the heat of polymerization. The azo compound having a hydrophilic group is added to the polymerization system as it is or as an aqueous solution.

Examples of the hydrophilic organic peroxide include those having a carboxyl group such as t-butyl hydroperoxide and cumene hydroperoxide. The mixing ratio of the hydrophilic organic peroxide to the polyvalent metal (meth) acrylate is preferably 0.5 to 5% by weight in the aqueous solution of the polyvalent metal (meth) acrylate, More preferably, it is 0.3 to 1% by weight.

When a redox catalyst is used, the oxidizing agent includes peroxides such as sodium peroxide, calcium peroxide, calcium peroxide and barium peroxide, sodium percarbonate, sodium perborate, ammonium persulfate, and persulfate. Examples thereof include persulfates such as sodium and potassium persulfate, and these may be used in combination of two or more.

Examples of the reducing agent include amines such as diethanolamine, triethanolamine, hydrazine, hydroxylamine, dimethylaminopropionitrile, dimethylaminoethanol, dimethylaminopropanol, piperazine and morpholine, ferrous salts, sodium sulfite and the like. There are sulfites, thiosulfates such as sodium thiosulfate, thiourea, sodium erythorbate, Rongalit and the like, and two or more of them can be used in combination.

The combination and amount of the oxidizing agent and the reducing agent are
The type and concentration of the polyvalent metal salt of (meth) acrylic acid to be used,
The pH, the curing time, the strength, and the like may be taken into consideration, and may be selected as appropriate. However, it is usually preferable to use each of them in an amount of 0.1 to 30% by weight based on the polyvalent metal (meth) acrylate.

The polymer of the polyvalent metal salt of (meth) acrylic acid is such that the polyvalent metal salt of (meth) acrylic acid itself functions as a crosslinking agent and exerts an excellent effect. In order to further improve stability and durability, even a monovalent acrylate such as sodium acrylate or a copolymer of a water-soluble divinyl monomer such as methylene bisacrylamide and hydroxyethylene bisacrylamide is used. good. In the case of sodium acrylate, if the copolymerization ratio is too large, there is a possibility that a crosslink density sufficient to exhibit the vibration reducing effect may not be obtained. And more preferably 1 to 50% by weight. In the case of the above-mentioned divinyl monomer, it is preferably 0.01 to 30% by weight, more preferably 0.1 to 10% by weight, based on the polyvalent metal (meth) acrylate.

In order to further improve the water stoppage and water retention, polyethylene glycol di (meth) acrylate having a polyoxyethylene unit of an arbitrary length may be copolymerized. In this case, the addition amount is preferably 1 to 30% by weight based on the polyvalent metal salt of (meth) acrylic acid.
20% by weight is more preferred.

Clay Mineral In the composition of the present invention, the clay mineral has a function of a filler, and is superior in dispersibility in the composition as compared with other fillers. Examples of the clay mineral include clay, talc, bentonite and the like. As clay minerals,
Clay or talc is preferred because the physical properties of the composition do not change over time as compared with the case where bentonite is used, and clay is more preferred because it is cheaper and easier to handle. Clay minerals are present in the composition in an amount of from 20 to 60.
% By weight, more preferably from 30 to 30% by weight.
50% by weight. If this proportion is less than 20% by weight, the composition may not be putty-like and may be difficult to perform, while if it exceeds 60% by weight, it may be difficult to knead the composition during production. In some cases, the resulting composition becomes powdery and has poor adhesion to a substrate.

O pressure-sensitive adhesive The composition of the present invention contains
Adhesive is compounded. As the pressure-sensitive adhesive, it is preferable to use a polymer emulsion because the composition of the present invention is an aqueous composition. Specifically, an acrylic ester polymer, natural rubber, SBR and ethylene-acetic acid are used. Emulsions such as vinyl copolymers may be mentioned, and acrylate polymer emulsions are preferred because they are excellent in water resistance and weather resistance. As a more preferred example of the emulsion of the acrylate polymer, butyl acrylate and 2-ethylhexyl acrylate may be
% Or more, and 1 to 20% by weight of methyl methacrylate and ethyl acrylate, etc., to obtain a more stable emulsion, and these are further copolymerized with (meth) acrylic acid. Is more preferred. The content of the adhesive is 3 to 50 in the composition.
% By weight, more preferably 5 to 20% by weight. If the amount is less than 3% by weight, the effect of improving the adhesiveness to the base material may not be exhibited. On the other hand, if the amount exceeds 50% by weight, tack may be exhibited during construction, making it difficult to use,
In some cases, the cured product of the composition becomes too hard after the film formation, so that the effect of reducing vibration cannot be obtained.

Water In the composition of the present invention, water is used in the production of the composition.
It is preferable to mix it as an aqueous solution of a (meth) acrylic acid polyvalent metal salt. The content of water in the composition is preferably from 55 to 97% by weight, more preferably from 60 to 92% by weight, based on the total amount of the polymer of the polyvalent metal (meth) acrylate and water. It is.

Other components The composition of the present invention contains, in order to ease drying of the cured product,
Polyacrylamide, glycerin, propylene glycol and those obtained by cross-linking these, and the like, and methylcellulose and its derivatives, polyethylene oxide and the like as a thickener can also be contained. In addition, in addition to these, antioxidants, ultraviolet absorbers, glass balloons, pigments such as titanium oxide, fillers such as calcium carbonate,
An anti-sagging agent such as inorganic fibers such as sepiolite or organic polymer fibers such as polypropylene, a fragrance, a surface treatment agent, and the like can be blended.

Production Method The sealing material composition of the present invention can be obtained by mixing a polymer of a polyvalent metal salt of (meth) acrylic acid, a clay mineral, an adhesive, water and, if necessary, other components. Although a more preferable production method is, a polyvalent metal salt of (meth) acrylic acid, a polymerization catalyst, a clay mineral, a pressure-sensitive adhesive, water and other components as necessary are mixed at room temperature or under heating with a mixer or the like. The method of polymerizing the polyvalent metal salt of (meth) acrylic acid by mixing by means such as agitation by means of the above is preferable because the polymer and the clay mineral can be uniformly dispersed in the composition. The sealing material composition of the present invention is generally a putty-like or viscoelastic material, and stirring becomes difficult with the progress of the polymerization reaction of the polyvalent metal salt of (meth) acrylic acid. In the case of performing, if the composition has a certain degree of viscosity and the stirring is stopped at the time when the composition becomes a gel, then the polymerization of the polyvalent metal salt of (meth) acrylic acid proceeds without the need for stirring, Complete. Also, in this case, the clay mineral does not disperse unevenly in the composition. The polymerization temperature may be appropriately selected depending on the catalyst used.

Method of Use The sealing material composition of the present invention is generally putty-like or viscoelastic, and is used for sealing in places where vibration is severe or where propagation of vibration during an earthquake must be suppressed. It can be used effectively for sealing in.
Specific examples include joints such as walls and partition plates. As a method of using the sealing material composition of the present invention, the sealing material may be cut into an appropriate size and pressed against a target portion. In addition, when working in a narrow gap, it can be injected.

[0024]

The present invention will now be described more specifically with reference to examples and comparative examples. In the following, “%” means “% by weight”. Example 1 4,500 g of a 5% aqueous solution of magnesium acrylate, 24 g of 2,2'-azobis [2- (imidazolin-2-yl) propane] dihydrochloride as a polymerization catalyst, 5,800 g of clay as a clay mineral, and HV of an adhesive -C-6280
[Emulsion of acrylic acid ester polymer, manufactured by Toagosei Co., Ltd.] 3,000 g was mixed to form a suspension, which was stirred at room temperature for 30 minutes, and then allowed to stand to obtain a sealing agent composition. .

The obtained composition is 15 cm long × 15 c wide.
The shape was mx 30 cm in height, and this was used as a test body. Exciter [MS-406 manufactured by San-S Co., Ltd.] and vibration analyzer [FFT analyzer AD-3 manufactured by Toa Denpa Kogyo Co., Ltd.]
525] was used to measure the vibration damping constant of the test specimen. The vibrations applied to the specimen were 8 Hz and 10 H, respectively.
z, 13Hz, 20Hz, 36Hz, 50Hz and 70
The maximum amplitude in Hz was measured, and the maximum peak attenuated before and after the use of the composition of the present invention was evaluated. Table 1 shows the results.
As a result of the experiment, the composition of the present invention showed that
The vibration peak was able to be reduced. In addition, using the obtained composition, the Japan Geotechnical Society standard (T311-199) was used.
When the hydraulic conductivity was measured according to 0), it was 10 ⁻⁸ cm / s.
The order of ec was excellent in water stoppage.

Examples 2 and 3 A sealing material was prepared in the same manner as in Example 1 except that the concentration of the aqueous solution of magnesium acrylate was changed to that shown in Table 1. A composition was prepared. Evaluation was performed in the same manner as in Example 1 using the obtained composition. Table 1 shows the results. As a result of the experiment, the composition of the present invention was able to reduce the vibration peak at 8 Hz to 70 Hz. The water permeability of the obtained composition was measured in the same manner as in Example 1. As a result, the water permeability was excellent in the order of 10 ⁻⁸ cm / sec. The composition of Example 3 was sandwiched between mortar plates of 4 × 4 cm, and after curing for one day, the mortar plates were cut into a size that could be measured by an adhesion tester. When this was subjected to an adhesion test using a Kenken-type adhesion tester, the adhesion was 18.
The weight was ² kgf / cm ² and the adhesiveness was excellent.

[0027]

[Table 1]

Comparative Example 1 The same procedure as in Example 1 was carried out except that 4,500 g of a 30% aqueous solution of sodium acrylate, which is a monovalent metal acrylate shown in Table 2, was used instead of magnesium acrylate. Using the raw materials, a sealing material composition was produced by the same production method. Using the resulting composition,
Table 2 shows the results of the evaluation performed in the same manner as in Example 1. In this case, no vibration reducing effect was observed even when the acrylate was at a high concentration. The water permeability of the obtained composition was measured in the same manner as in Example 1, and it was found that the composition had almost no water stoppage.

[0029]

[Table 2]

Comparative Example 2 A composition was obtained in the same manner as in Example 3 except that the pressure-sensitive adhesive was not used. When the adhesion test was performed on the obtained composition in the same manner as in Example 3, the adhesion was only 1.2 kgf / cm ² .

[0031]

The sealing material composition of the present invention does not need to be produced locally, does not deform the plastic when sealing the plastic, and can be used even when the joint is sealed. It does not hang down. In addition, the composition of the present invention has excellent adhesiveness to a substrate, and can be used to inject or fill joints such as branch pipes of manholes, joints of concrete structures, etc. Since vibration can be reduced in the range of up to 70 Hz, it can be effectively used for sealing where vibration reduction and soundproofing are required.

Claims (2)

[Claims] 1. A sealing material composition comprising a polymer of one or more polyvalent metal salts of (meth) acrylic acid, a clay mineral, an adhesive and water. 2. A polyvalent metal salt of (meth) acrylic acid, a polymerization catalyst, a clay mineral, an adhesive and water are mixed to polymerize the polyvalent metal salt of (meth) acrylic acid. 2. A method for producing the sealing material composition according to item 1.