JP3844471B2 - Fast curing composition - Google Patents

Description

  The present invention relates to an acrylic high-speed curable composition, and relates to a civil engineering and architectural repair material that is easily cured even at a low temperature.

Acrylic resins are widely used in fields such as molding materials, paints, and adhesives because of their good durability and environmental friendliness. Usually, an acrylic curable composition is prepared by mixing an acrylic monomer or oligomer with an organic peroxide as a polymerization initiator and a curing initiator that decomposes the organic peroxide to generate radicals, and polymerizes the mixture. Curing is performed. Further, the two-part acrylic curing composition is a composition in which components are separated into a composition comprising the organic peroxide and a composition containing a curing initiator or a curing initiator. The two materials are mixed immediately before use and applied or coated on the adherend to be cured.
The acrylic monomer composition contains a monomer having tertiary hydrogen in the molecule, cumene hydroperoxide is used as the organic peroxide, and cobalt of fatty acid such as octylic acid or naphthenic acid is used as the curing initiator. Salt, so-called metal soap is used. In the curable composition described above, air curability due to fatty acid cobalt appears, and anaerobicity, which is a drawback of radical polymerization of acrylic monomers, is offset. As a result, even on a porous surface such as concrete having a large specific surface area. It has the property of being polymerized and hardened and has a strong adhesive property, and is widely used in the civil engineering and construction fields (Hardlock 2 series, manufactured by Electrochemical Industry Co., Ltd.). In addition, these compositions were prepared by dividing an acrylic liquid composition into two parts and blending an organic peroxide on one side and a liquid two-part type blending a metal soap on the other and an organic peroxide. There is a liquid two-material type consisting of an acrylic liquid composition and a metal soap.

  In addition, the two-component acrylic curable composition in liquid and powder form is one in which one material on the curing initiator side is a curing initiator-containing aggregate powder, and the two materials have good mixability and can be mixed in a short time. Although there is a feature that can be completed, the curability of these two-part acrylic curable compositions is 20 ° C., and a curing time of about 10 minutes is required even at the shortest, and high-speed curing such as emergency repair, , There is a disadvantage that it cannot be cured within a few minutes. In particular, an exponential cure time delay occurs with decreasing temperature. Therefore, for example, repair in a freezer reaching -30 ° C. is not limited to the conventional two-part composition, but there is a range from a non-curing to a curing required for many weeks. In addition, shortening of the curing time at low temperatures has been strongly desired.

  The present invention has a specific problem to be solved that the conventional curing composition cannot be cured in a few minutes at room temperature, or has a long curing time at a low temperature reaching -30 ° C. To provide a composition having high-speed curability such as short-time curability and low-temperature curability that cannot be achieved, that is, a composition having high-speed curability that can be applied to civil engineering and construction repair materials that could not be applied conventionally. The purpose is to provide goods.

  The present invention comprises (A) a polymerizable acrylic liquid composition, (B) cumene hydroperoxide, (C) fatty acid cobalt, and (D) a basic compound. Preferably, (D) the basic compound is composed of calcium hydroxide, calcium oxide and water, or 1,8-diazabicyclo [5,4,0] undecene-7. The fast-curing composition described above.

The present invention has contains (A) a polymerizable acrylic liquid composition, and (B) cumene hydroperoxide, and (C) a fatty acid cobalt, and (D) a basic compound, (D) a base sex compound calcium hydroxide, consists of calcium oxide and water, or 1,8-diazabicyclo [5,4,0] Ri undecene der, moreover, (B) and (C) but, (B) A high-speed curable composition characterized in that it is a two-material composition composed of two materials consisting of one material blended with one material and one material blended with (C).

The (A) acrylic liquid composition in the present invention contains an acrylic monomer. The acrylic monomer has at least a (meth) acrylic group in the molecule (general description of methacrylic acid ester and acrylic acid ester, hereinafter referred to as (meth) acrylate), for example, methyl (meth) acrylate, ethyl (Meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, isooctyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (Meth) acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, methoxylated cyclotriene (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl Pill (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol (meth) acrylate, alkyloxypolypropylene glycol (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2- Hydroxy-3-phenoxypropyl (meth) acrylate, glycidyl (meth) acrylate, caprolactone modified tetrafurfuryl (meth) acrylate, ethoxycarbonylmethyl (meth) acrylate, phenol ethylene oxide modified acrylate, paracumylphenol ethyleneoxy modified acrylate, nonylphenol ethylene oxide Modified acrylate, nonylphenol propylene oxide modified acrylate, 2-ethylhex Silcarbitol acrylate, polyglycerol di (meth) acrylate, polybutylene glycol di (meth) acrylate, 1,4 butanediol (meth) acrylate, 1,6 hexanediol di (meth) acrylate, neopentyl glycol di (meth) Acrylate, trimethylolpropane tri (meth) acrylate, dicyclopentenyloxyethyl methacrylate (QM-657 manufactured by Rohm and Haas), epoxy (meth) acrylate (Biscoat # 540 manufactured by Osaka Organic Chemical Co., Ltd.), 1.2 polybutadiene modified dimethacrylate -To (TE2000 manufactured by Nippon Soda Co., Ltd.), polyester (meth) acrylate (Aronix M-6100 manufactured by Toa Gosei Co., Ltd., epoxy ester 3000M manufactured by Kyoeisha Chemical Co., Ltd.), urethane acrylate Toagosei Co., Ltd. Aronix M-1100), acrylonitrile butadiene methacrylate (Hycar VTBN manufactured by Ube Industries), and the like. A plurality of these may be mixed and used for the purpose of improving the characteristics.

  The (B) cumene hydroperoxide used in the present invention functions as a polymerization initiator for the (A) acrylic liquid composition, but its thermal decomposability at room temperature is so small that it can be ignored. The addition amount is preferably 1 to 5 parts by mass with respect to parts.

  In the present invention, a phenol-based polymerization inhibitor such as hydroquinone or hydroquinone monomethyl ether may be added for the purpose of controlling the pot life, and a curing accelerator such as a tertiary amine or a short-term surface. Paraffin wax may be added as a desiccant, and ultrafine silica may be added for the purpose of viscosity adjustment and property improvement. Moreover, a silane coupling agent may be added for the purpose of improving adhesive properties, and for example, silica powder, calcium carbonate powder, ceramic powder, or the like may be blended as a filler.

  (C) Fatty acid cobalt used in the present invention is (B) a curing initiator that decomposes cumene hydroperoxide to generate radicals. For example, strong surface drying properties such as cobalt octylate, cobalt naphthenate, and linseed oil fatty acid cobalt. Cobalt soap having Further, as the curing initiator, manganese octylate, nickel octylate, vanadium octylate, copper octylate, manganese naphthenate, nickel naphthenate, vanadium naphthenate, copper naphthenate, cobalt acetylacetonate, manganese acetylacetonate, Nickel acetylacetonate, vanadium acetylacetonate and the like are known, but in the present invention, they may be used in combination with (C) fatty acid cobalt for the purpose of improving the properties of the obtained cured product.

  In the present invention, in addition to the components (A) to (C), it is essential to contain (D) a basic compound. As a result of various studies to promote the curing of conventionally known acrylic cured product compositions, the present inventors have surprisingly found that alkali metal or alkaline earth metal hydroxides or 1,8-diazabicyclo [5]. , 4,0] undecene-7 or in the presence of calcium oxide and water, the compositions (A) to (C) are found to cure rapidly. The reason why this phenomenon occurs is not clear, but the inventor promoted the generation of free cobalt ions by the presence of the basic compound, and catalyzed the curing reaction of the compositions (A) to (C). I think it is influencing.

In other words, the present inventors have found that when a specific basic substance is added to an acrylic two-material curing composition using cumene hydroperoxide and fatty acid cobalt as a radical generator, the curing time is remarkably increased. Discovered and reached the present invention. The presence of a specific basic substance does not work on cumene hydroperoxide, but it reacts with fatty acid cobalt to produce highly active cobalt ions, so that cumene hydroperoxide is instantly decomposed to a high concentration It is estimated that the active radicals are generated. The generation of this high concentration of active radicals causes the acrylic liquid composition to rapidly polymerize and cure at a high rate. And when a basic substance reacts with fatty acid cobalt, it is presumed that the reaction of liberating cobalt ions by replacing the basic substance with cobalt is involved.
Furthermore, it is known that the curing rate of the acrylic two-part curable composition using cumene hydroperoxide and fatty acid cobalt as radical generators is extremely reduced when moisture is added. Is mainly a modification of fatty acid cobalt, which is also the cause of delayed hardening in rainy weather such as concrete. In the present invention, when calcium oxide is blended, even if the composition contacts or mixes with moisture, the calcium oxide immediately changes to calcium hydroxide and exhibits the effect of promoting the hardening. is.

The first of the present invention is a fast-curing composition containing (D) a basic compound in addition to the composition containing (A) to (C). As described above, it is considered that the composition consisting of (A) to (C) is rapidly cured under the free cobalt ions that are promoted by the presence of the basic compound (D), and free cobalt ions Examples of the basic compound that promotes the generation of (D) include various hydroxides including alkali metals and alkaline earth metals, 1,8-diazabicyclo [5,4,0] undecene-7, Examples include carbonates, bicarbonates, oxides, and organic compounds of various metals that can react with water to show the same effect, and all of them should be used as long as they do not impair the effects of the present invention. Can do.
The inventor further conducted various experiments. For example, alkali metal hydroxide, carbonate, bicarbonate such as lithium hydroxide, lithium carbonate, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, Although it has an effect on curing, it has been found that the obtained cured product has strong deliquescence and is not necessarily free of problems in practice. Under such circumstances, in the present invention, as the basic compound (D), calcium hydroxide, 1,8-diazabicyclo [5,4,0] undecene-7 described below, and calcium oxide and water are used. Sharing is preferably selected.
Examples of a group of (D) basic compounds used in the present invention include alkaline earth metal hydroxides such as beryllium hydroxide, calcium hydroxide, magnesium hydroxide, and strontium hydroxide, which are used alone. They may be combined or combined. In particular, calcium hydroxide is preferable because it is inexpensive and easily available. The blending amount of the alkaline earth metal hydroxide of the basic compound is less than 2 parts by mass with respect to 100 parts by mass of the compositions (A) to (C), and the effect of shortening the curing time is insufficient. Cases are likely to occur, and when it exceeds 20 parts by mass, the rapid curing time does not change greatly, so 2 to 20 parts by mass is preferably selected.
Another group of the basic compound (D) is an organic compound, but it is easy to use in a liquid state and easily obtains a transparent cured product, so that 1,8-diazabicyclo [5,4,0] undecene-7 is used. Is preferably selected. With respect to the amount of 1,8-diazabicyclo [5,4,0] undecene-7 added, it is preferably 2 to 10 parts by weight with respect to 100 parts by weight of the compositions (A) to (C). With respect to the amount of 1,8-diazabicyclo [5,4,0] undecene-7 added, if it is less than 2 parts by mass, the curing rate cannot be sufficiently increased, and if it exceeds 10 parts by mass, it can be uneconomical. This is because the water resistance of the cured product is somewhat lowered, which is not preferable.

  In the present invention, calcium oxide cannot release free cobalt ions by itself, but is a substance that promotes the generation of free cobalt ions for the first time when it coexists with water. Alkaline earth metal oxides such as magnesium oxide, strontium oxide, and beryllium oxide have similar properties. Among these, calcium oxide is preferably selected because it is inexpensive and easy to use without toxicity or radioactivity. About the addition amount of a calcium oxide, 2-20 mass parts is preferable with respect to 100 mass parts of compositions of (A)-(C). Here, regarding the addition amount of calcium oxide, if it is less than 2 parts by mass, the curing rate cannot be sufficiently increased, and if it exceeds 20 parts by mass, the rapid curing time does not change greatly.

  Regarding the amount of water added when calcium oxide is used, it may be 32 parts by mass with respect to 100 parts by mass of calcium oxide. This is because calcium oxide and water react in equimolar amounts to form calcium hydroxide. Actually, the composition with calcium oxide added has a long pot life, but rapidly hardens on wet surfaces. This is a very beneficial property.

  In the present invention, (B) cumene hydroperoxide and (C) fatty acid cobalt are preferably two-material mixed in two different materials. (B) Cumene hydroperoxide and (C) fatty acid cobalt are present in two different materials, and when the two materials are brought into contact with each other, curing starts rapidly, and curing can be completed in a short time. It can be applied to various purposes.

  In the present invention, powder aggregate can also be added. Any powdered aggregate can be used as long as it is other than the substance corresponding to the radical polymerization inhibitor. For example, as an inorganic material, glassy balloon, shirasu balloon, ceramic powder, ceramic balloon, glass powder, short fiber glass, silica powder, ultrafine silica, alumina powder, mica powder, ceramic powder, cinnabar sand, sand, rock powder , Magnesia powder, calcium carbonate powder, silicon carbide powder, silicon nitride powder, aluminum nitride powder, carbon powder, kaolin clay, dry clay mineral powder, ferrite powder, dry diatomaceous earth powder, etc. Etc. As organic filler, synthetic polymer powder, for example, polyethylene powder, polypropylene powder, rubber powder, plastic balloon, nylon powder, plastic short fiber powder, silicone rubber powder, crosslinked acrylic powder, crosslinked polystyrene powder, grafted with vinyl monomer Polymerized rubber particle powder, polyester powder, Teflon (registered trademark) powder, polyvinyl alcohol powder, polyvinyl butyral powder, polycarbonate powder, epoxy resin powder, cured epoxy resin powder, etc. And paraffin waxes, organic natural polymer compounds, such as wood flour, rice bran powder, rice husk powder, walnut shell powder, starch, wheat flour, oat shell powder, cellulose powder, and the like. Further, if necessary, a colorant such as a pigment or a dye may be added, and powdered aggregates may be used alone or in combination according to the purpose.

<(A) Production of organic peroxide-containing acrylic liquid composition>
1000 g of calcium carbonate powder (light coal char powder manufactured by Toyo Flour & Chemical Co., Ltd.), 200 g of 2-hydroxyethyl methacrylate (light ester HO manufactured by Kyoeisha Chemical Co., Ltd.), 400 g of dicyclopentenyloxyethyl methacrylate (QM-657 manufactured by Rohm and Haas) 400 g of 1,2 polybutadiene modified dimethacrylate (TE-2000 manufactured by Nippon Soda Co., Ltd.), 15 g of N, N-di (2-hydroxyethyl) -P-toluidine, 6 g of paraffin wax (manufactured by Nippon Seiki Co., Ltd.), silane coupling 1.5 g of an agent (Nihon Unica Co., Ltd. A-174) and 0.3 g of hydroquinone (reagent) were added and heated to 65 ° C. with stirring and mixing to dissolve the paraffin wax and then cooled to 25 ° C. Next, 20 g of cumene hydroperoxide (Nippon Yushi Co., Ltd. Park Mill H80) was added and mixed with stirring to obtain (A) an organic peroxide-containing acrylic liquid composition.

  100 g of (A) produced above was taken in a polyethylene cup, and 5 g of slaked lime powder (Kanto Chemical Co., Inc., reagent calcium hydroxide) was added and mixed. Subsequently, when 1 g of cobalt octylate (Octolife Co12 manufactured by Shinto Chemical Co., Ltd.) was added and mixed in an atmosphere of 25 ° C., heat was generated after 1 minute, and curing occurred after 1 minute and 40 seconds.

  It mixed with the same mixing | blending, and it apply | coated to the high-strength concrete surface immediately, and joined the steel jigs of the adhesive surface 40mm x 40mm. After 30 minutes, the concrete was broken at 8.2 MPa as a result of measuring the strength with a Kenken type tensile tester.

<Production of (B) Curing Initiator-Containing Acrylic Liquid Composition>
1000 g of calcium carbonate powder (light coal char powder manufactured by Toyo Flour & Chemical Co., Ltd.), 200 g of 2-hydroxyethyl methacrylate (light ester HO manufactured by Kyoeisha Chemical Co., Ltd.), 400 g of dicyclopentenyloxyethyl methacrylate (QM-657 manufactured by Rohm and Haas) 1, 400 g of 1,2-polybutadiene modified dimethacrylate (TE-2000 manufactured by Nippon Soda Co., Ltd.) and 6 g of paraffin wax (manufactured by Nippon Seiki Co., Ltd.) were heated to 65 ° C. with stirring and mixing to dissolve the paraffin wax. To 25 ° C. Next, 100 g of cobalt octylate (Octo Co12 manufactured by Shinto Fine Co., Ltd.) was added and mixed by stirring to obtain (B) a curing initiator-containing acrylic liquid composition.

  100 g of (A) produced in Example 1 was taken in a polyethylene cup, and 10 g of slaked lime powder (Kanto Chemical Co., Inc., reagent calcium hydroxide) was added and mixed. Next, when 100 g of (B) was added and mixed in an atmosphere at 25 ° C., the mixture was cured after 2 minutes.

<Production of (C) Curing Initiator-Containing Powdered Composition>
500 g of No. 6 silica sand, 500 g of No. 7 silica sand and 0.01 g of white titanium 3 g carbon black were put into a small universal mixer and premixed at 100 rpm for 1 minute. The oil absorption of this mixture was about 18. Next, a mixed solution of 10 g of 2-hydroxyethyl methacrylate (Kyoeisha Chemical Co., Ltd. light ester HO) and cobalt octylate (Octolife Co12 manufactured by Shinto Fine Chemical Co., Ltd.) was added and mixed for 5 minutes to start curing (C) An agent-containing powder composition was obtained.

  200 g of (A) produced in Example 1 and 20 g of slaked lime powder (Kanto Chemical Co., Inc., reagent calcium hydroxide) were added to and mixed with the polypropylene balls. Next, when 500 g of (C) was added and mixed with a spoon, it easily became an uncured mortar, and was cured into a mortar with heat generation after 1 minute 30 seconds in an atmosphere at 25 ° C.

  It mixed with the same mixing | blending, and it apply | coated to the high-strength concrete surface immediately, and joined the steel jigs of the adhesive surface 40mm x 40mm. After 30 minutes, the concrete was destroyed at 8.4 MPa as a result of measuring the strength with a Kenken type tensile tester.

  200 g of Example 1 (A) cooled in an atmosphere of 5 ° C., 500 g of Example 3 (C), and 20 g of slaked lime were mixed at 5 ° C. ambient temperature, and 5 mm on a paving stone cooled in a −30 ° C. refrigerator. As a result of application to the thickness, it was hardened after about 8 hours, and the paving stone concrete was destroyed by a kenken type tensile strength of 5.4 MPa.

  To polypropylene balls, 200 g of (A) produced in Example 1 and 2.0 parts by weight of 1,8-diazabicyclo [5,4,0] undecene-7 (Kanto Chemical Co., Ltd., reagent) were added and mixed. Next, when 500 g of (C) was added and mixed with a spoon, it easily became an uncured mortar, and cured into a mortar with heat generation after 2 minutes in an atmosphere at 25 ° C.

  It mixed with the same mixing | blending, and it apply | coated to the high-strength concrete surface immediately, and joined the steel jigs of the adhesive surface 40mm x 40mm. After 30 minutes, the concrete was destroyed at 8.3 MPa as a result of measuring the strength with a Kenken type tensile tester.

<Production of Anhydrous Calcium Oxide-Containing Organic Peroxide-Containing Acrylic Liquid Composition>
800 g of calcium carbonate powder (light coal carbon powder manufactured by Toyo Flour & Chemical Co., Ltd.), 200 g of anhydrous calcium oxide powder (Kanto Chemical Co., Reagent), 200 g of 2-hydroxyethyl methacrylate (Kyoeisha Chemical Co., Ltd. Light Ester HO), dicyclopentenyl 400 g of oxyethyl methacrylate (QM-657 manufactured by Rohm and Haas), 400 g of 1,2 polybutadiene modified dimethacrylate (TE-2000 manufactured by Nippon Soda Co., Ltd.), 15 g of N, N-di (2-hydroxyethyl) -P-toluidine, 6 g of paraffin wax (Nippon Seiki Co., Ltd.), 1.5 g of silane coupling agent (A-174 manufactured by Nihon Unica Co., Ltd.) and 0.3 g of hydroquinone (reagent) are added and heated to 65 ° C. with stirring and mixing to paraffin. After dissolving the wax, it was cooled to 25 ° C. Next, cumene high B peroxide (NOF Corp. Percumyl H80) and stirred mixture was charged to 20g, to obtain a free calcium hydroxide blended organic peroxide-containing acrylic liquid composition.
<Compound curing adhesion test>
200 g of this anhydrous calcium oxide-containing organic peroxide-containing acrylic liquid composition was weighed into a polypropylene ball, and then charged with 500 g of (C) produced in Example 3 and mixed with a spoon, it was easily uncured. Mortar shape. When 5 ml of tap water was added thereto and mixed, the mixture was cured in a mortar shape with heat generation after 2 minutes in an atmosphere at 23 ° C.

It mixed with the same mixing | blending, and it apply | coated to the high-strength concrete surface immediately, and joined the steel jigs of the adhesive surface 40mm x 40mm. After 30 minutes, the concrete was destroyed at 8.3 MPa as a result of measuring the strength with a Kenken type tensile tester.
(Comparative Example 1)
100 g of (A) produced in Example 1 was taken into a polyethylene cup, and 0.5 g of cobalt octylate (Octlife Co12 manufactured by Shinto Chemical Co., Ltd.) was added and mixed in an atmosphere at 23 ° C., and 15 minutes were required for curing. did.
(Comparative Example 2)
500 g of (C) produced in Example 3 was added to 200 g of an organic peroxide-containing acrylic liquid composition (Example (A)) containing no anhydrous calcium oxide in Example 6 and mixed with a spoon. Then, it easily becomes an uncured mortar. When 5 ml of tap water was added and mixed, it hardened after about 3 hours in an atmosphere at 23 ° C. However, as a result of measuring the strength with a Kenken type tensile tester at this time, it peeled easily from the concrete interface. The strength was 0.1 MPa or less.

  INDUSTRIAL APPLICABILITY The present invention can be applied in various fields, for example, repairing a cross section of a concrete structure in a cold region, repairing a cross section in a tunnel, adjusting irregularities, repairing a road surface, repairing the shape of a concrete member such as a manhole, and anchoring.

Claims (3)

(A) a polymerizable acrylic liquid composition;
(B) cumene hydroperoxide;
(C) fatty acid cobalt;
(D) a basic compound;
And (D) the basic compound is calcium hydroxide, and (B) and (C) are composed of one material containing (B) and one material containing (C). A high-speed curable composition characterized by being a two-material composition composed of a material. (A) a polymerizable acrylic liquid composition;
(B) cumene hydroperoxide;
(C) fatty acid cobalt;
(D) a basic compound;
And (D) the basic compound is composed of calcium oxide and water, and (B) and (C) are composed of one material blended with (B) and one material blended with (C). A high-speed curable composition characterized in that it is a two-material composition composed of two materials. (A) a polymerizable acrylic liquid composition;
(B) cumene hydroperoxide;
(C) fatty acid cobalt;
(D) a basic compound;
(D) the basic compound is 1,8-diazabicyclo [5,4,0] undecene-7, and (B) and (C) are combined with (B) A high-speed curable composition characterized in that it is a two-material composition composed of two materials composed of one material containing (C).