JPS6146019B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing resin concrete made of polyurethane resin and aggregate. Conventionally, mortar or concrete using inorganic cement has drawbacks such as insufficient mechanical strength, acid resistance, and waterproofing properties. To overcome these problems, resin concrete, which is made of synthetic resins such as unsaturated polyester resins and epoxy resins and aggregates, has been used in various fields as it has excellent mechanical strength and chemical properties. However, polyester resins have drawbacks such as curing shrinkage of the resin, generation of cracks due to heat generation, and poor alkali resistance. Epoxy resins have excellent mechanical strength and chemical resistance, but have the major drawbacks of poor impact resistance and low-temperature curing properties, as well as being expensive. On the other hand, resin concrete using polyurethane resin has excellent mechanical strength and impact resistance, but because it contains water and active isocyanate groups, it is susceptible to moisture contained in aggregate or active hydrogen group-containing compounds. The reaction generates carbon dioxide gas, which causes foaming, and the reality is that it is hardly used despite its excellent physical properties. Therefore, due to this problem of foaming, not only the workability such as moisture control of the aggregate is poor, but also the performance of the obtained resin concrete is not sufficient and there is a drawback that it lacks uniformity. For this reason, it cannot be used particularly as a thick molded product or resin concrete with a high resin content, and its waterproof properties are also poor, so there are significant restrictions on its field of application. The inventors of the present invention have conducted extensive research to eliminate the essential drawback of foaming of resin concrete using polyurethane resin, and have found that by using a specific aggregate, an excellent resin concrete that does not foam can be produced. The present inventors have discovered that the following can be obtained, and have completed the present invention. That is, the present invention provides for the production of resin concrete by blending (A) a polyisocyanate compound, (B) an active hydrogen group-containing compound, and (C) aggregate. A hydrolyzable group-containing organic silane compound-coated aggregate is coated with an organic silane compound without heating, and the aggregate is coated with the above-mentioned (A) polyisocyanate compound and (B) active hydrogen group-containing compound. The present invention relates to a method for producing resin concrete, which is characterized by mixing under heating. In producing resin concrete by blending aggregate with a liquid resin consisting of a polyisocyanate compound and an active hydrogen group-containing compound, the present invention provides an organic metal compound containing a hydrolyzable group consisting of a silane compound on the surface of the aggregate. This method is characterized by using aggregate coated without heating, and by blending the above-mentioned components without heating. The hydrolyzable group-containing organometallic compound used herein refers to compounds that are well known as reinforcing fillers for plastics such as glass fibers, coupling agents for surface treatment of powder fillers, and the like. However, in the case of resin concrete, the mixing ratio of liquid resin and aggregate is usually 1:10 to 1:1.
Because the blending ratio of 1 and aggregate is large, it is impractical to coat the surface of this aggregate with a coupling agent for surface treatment in terms of processing costs, and there have been no cases where this treatment has been carried out to date. Ta. Furthermore, the conventional surface treatment method using a coupling agent involves reacting with the silanol groups of glass fibers by heat treatment at, for example, about 110° C. after coating the surface, and this method achieves the effect as a coupling agent. In the present invention, a hydrolyzable group-containing organosilane compound is added to and mixed with aggregate containing a small amount of moisture, and the foaming phenomenon caused by moisture in the aggregate is suppressed by surface coating and blending without heating. This was completely prevented, and was made based on the findings that were first made clear through experiments by the inventors. Moreover, if aggregate coated with this hydrolyzable group-containing organosilane compound is heat-treated at 110°C, the objective of the present invention, which is to prevent foaming, cannot be achieved. , it is considered to be a new system that is completely different from conventional processing mechanisms. The present invention will be specifically explained below. Examples of the polyisocyanate compound used in the method of the present invention include tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, polymethylene polyphenyl isocyanate, xylylene diisocyanate, cyclohexane phenylene diisocyanate, chlorophenylene diisocyanate, naphthalene-1, 5-diisocyanate, xylylene-
2,2'-diisocyanate, isopropylbenzene-2,4-diisocyanate, addition reaction product of polypropylene glycol or triol with tolylene diisocyanate, trimethylolpropane 1
An example is an addition reaction product between mol and 3 mol of tolylene diisocyanate. Next, as active hydrogen group-containing compounds, ethylene glycol, propylene glycol, 1,4-
Low molecular weight polyols such as butanediol, glycerin, trimethylolpropane, 1,2,6-hexanetriol, pentaerythritol, ethylenediamine, 4,4'-methylene-bis-2-chloroaniline, 4,4'-methylene-bis Examples include polyether polyols such as a propylene oxide adduct of bisphenol A obtained by addition polymerizing an amine compound such as -2-ethylaniline, or a low-molecular polyol or an amine compound with an alkylene oxide such as ethylene oxide or propylene oxide. Furthermore, it is a condensation polymer of polyhydric alcohols such as ethylene glycol, propylene glycol, and 1,4-butanediol and polybasic acids such as phthalic acid, maleic acid, malonic acid, succinic acid, adipic acid, and terephthalic acid. polyester polyol having hydroxyl groups,
Acrylic polyols, castor oil, tall oil, etc. may also be mentioned. There are also liquid rubbers having active hydrogen groups such as hydroxyl groups, amino groups, imino groups, carboxyl groups, and mercapto groups at the molecular ends. These liquid rubbers have a number average molecular weight of 500 to 25,000.
diene polymers and copolymers having 4 to 12 carbon atoms, and furthermore, these diene monomers and α- having 2 to 22 carbon atoms
There are copolymers with olefinic addition polymerizable monomers. Specifically, polybutadiene homopolymer, polyisoprene homopolymer, butadiene-
Examples include isoprene copolymer, butadiene-styrene copolymer, butadiene-acrylonitrile copolymer, butadiene-2-ethylhexyl acrylate copolymer, butadiene-n-octadecyl acrylate copolymer. These various polyisocyanate compounds and active hydrogen group-containing compounds can be used not only as individual compounds in combination, but also as a mixture of multiple compounds, taking into consideration the performance, purpose of use, workability, etc. of resin concrete. You can also do it. The blending ratio of the polyisocyanate compound and the active hydrogen group-containing compound is preferably in the range of 0.8 to 2.0 in terms of equivalent ratio of NCO group to active hydrogen (NCO group/active hydrogen).
It is preferably determined in the range of 1.0 to 1.8, particularly preferably 1.3 to 1.6. In the present invention, a plasticizer, process oil, organic solvent, etc. can be used in the liquid resin in order to reduce the viscosity of the composition. In this case, plasticizers include dioctyl phthalate, dibutyl phthalate, and dihexyl phthalate, process oils include aromatic, naphthenic, and paraffinic low-viscosity oils, and organic solvents include industrial gasoline, kerosene, Examples include toluene and benzene. Further, if necessary, an unsaturated group-containing polymerizable monomer may be added together with a polymerization reaction initiator for the purpose of reducing the viscosity and further improving the performance of the resulting resin concrete. As the polymerizable monomer, styrene, vinyl acetate, vinyl chloride, acrylic acid, etc. may be used alone or in a mixture thereof. As the polymerization initiator, peroxides such as benzoyl peroxide, methyl ethyl ketone peroxide, and kyumene hydroperoxide are selected in consideration of the reactivity of the polymerizable monomer, curing conditions, and the like. In the method of the present invention, after the liquid resin composition described above is mixed uniformly, aggregate prepared separately from this is mixed. A feature of the present invention is that aggregate coated with an organic silane compound containing a hydrolyzable group without heating is used as the aggregate, and such aggregate is coated with the polyisocyanate compound and active hydrogen groups without heating. It is in the process of blending with the contained compounds. Here, "without heating" means that no heat treatment that would cause a reaction with the silanol groups of the glass fibers is performed. Therefore, in the present invention, such heat treatment is not performed at all during aggregate coating or blending. The aggregates used here include various types of sand such as silica sand (for example, No. 3, No. 4, and No. 7), river sand, and crushed stone (2 to 5 mm), which may be used alone or mixed with various types of sand. things are used. These aggregates have a low moisture content, for example 1% by weight,
It is preferable to use 0.5% by weight or less. The mixing ratio of these aggregates and liquid resin composition is
The ratio is arbitrarily determined depending on the use, moldability, workability, etc., but is usually in the range of 10:1 to 1:1, preferably 8:1 to 3:1. In the method of the present invention, the hydrolyzable group-containing organic silane compound used to coat the aggregate is a silane compound having a hydrolyzable group such as methoxy, ethoxy, isopropyl, or chloro. Examples of organic silane compounds having such a hydrolyzable group include vinyltrichlorosilane, vinyltriethoxysilane, vinyl-tris(β-methoxyethoxy)silane, γ-methacryloxypropyltrimethoxysilane, and β-(3-methoxyethoxysilane). ，
4-epoxycyclohexyl)-methyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, γ-ureidopropyl Triethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, β-mercaptoethyltriethoxysilane, N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane, N-(β- aminoethyl)-aminomethyltrimethoxysilane,
There are silane compounds such as N-(β-aminoethyl)-γ-amino-β-methylpropyltrimethoxysilane. Among these organic silane compounds, aminosilane compounds, especially those having an amino group and an imino group, such as N-β-(aminoethyl)-γ-
Aminopropyltrimethoxysilane and N-β-
(Aminoethyl)-γ-aminopropylmethyldimethoxysilane is effective in preventing foaming of the resin concrete of the present invention. The amount of the hydrolyzable group-containing organic silane compound added to the aggregate is in the range of 0.01 to 2% by weight, preferably 0.05 to 1% by weight. The amount to be added is appropriately determined in consideration of the water content of the aggregate, the mixing ratio of the aggregate and the liquid resin composition, and the like. Further, when water is contained in the liquid resin, it is preferable to add a large amount in consideration of the water content. In the method of the present invention, 110
Since it was not heat-treated to a temperature of around 100°C, it is thought that its function as a normal coupling agent was quite different. This is also evident from the fact that foaming cannot be prevented by heat-treating the aggregate at 110°C, as mentioned above. In the method of the present invention, a commonly used urethane catalyst is added to lower the reaction curing temperature and shorten the reaction curing time. These catalysts include:
Metal compounds such as stannous chloride, di-n-butyltin dilaurate, dibutyltin diacetate, dibutyltin sulfide, ferric chloride, iron acetylacetonate, cobalt naphthenate, bismuth nitrate, lead oleate, antimony trichloride, Examples include triethylamine and tetramethylbutanediamine. The amount of these catalysts added is usually 0.001 to 2.0 parts by weight, preferably 0.001 to 2.0 parts by weight, per 100 parts by weight of the liquid resin composition.
It ranges from 0.1 to 1.0 parts by weight. The required amount of the catalyst to be added is determined depending on the use of the resin concrete, workability, etc., and is usually added and mixed into the liquid resin composition excluding the polyisocyanate compound. In the method of the present invention, in addition to the above-mentioned aggregates, conventional fillers such as calcium carbonate, talc, clay, calcium oxide, calcium hydroxide, magnesium oxide, magnesium hydroxide, calcium sulfate, cements such as Portland cement, Asbestos, glass fibers, synthetic fibers, metal fibers, pulp, etc. may be added alone or in a mixture if necessary. The aggregate-containing liquid resin composition obtained as described above has a pot life of about 10 to 100 minutes at room temperature,
Depending on the selection of catalyst and the amount added, curing is completed in 3 to 4 hours to form resin concrete. The resulting resin concrete has excellent bending strength,
It has bending deflection, compressive strength, and impact strength.
Moreover, conventionally, even if the moisture content of aggregate was kept low,
It was very difficult to increase the ratio of liquid resin in the combination of aggregate and liquid resin, but as will be clear from the later examples, by using the technology of the present invention, it was possible to increase the ratio of liquid resin to 1:1. Resin concrete that does not cause foaming can be obtained even when mixed. As detailed above, the resin concrete obtained by the method of the present invention not only has excellent mechanical strength, chemical resistance, and waterproofness, but also can be used to create blistering-free products with any composition.
This solves an important problem with polyurethane resin concrete. Therefore, in addition to general flooring materials, flooring materials that require chemical resistance and corrosion resistance, the foundations of machines such as pumps in chemical factories, compaction rollers, mold materials, etc., and especially materials that harden quickly at room temperature. Outdoor applications that require waterproofing and corrosion resistance, such as roads,
This will expand the use of resin concrete in a wide range of civil engineering and architectural fields, including joints in bridges, roofs, etc. Hereinafter, the present invention will be explained in detail with reference to Examples. Example 1 and Comparative Example 1 A resin concrete mixture was prepared by mixing components A, B, and C according to the following mixing conditions, and a 50 mm × 25 mm
It was filled into a mold of ×50 mm (height). The degree of blistering caused by foaming on the open surface of the mold at the end of curing of this resin concrete was measured. The results are shown in Table 1.

【table】

[Table] In addition, the blended composition of Example 1 (1) was
It was filled into a 160mm mold. After curing, remove from the mold,
Physical properties were measured after 7 days and the following results were obtained. Density 1.9 g/cm ³ Bending strength 130 Kg/cm ² Bending deflection (100 mm between fulcrums) 6 mm Compressive strength 190 Kg/cm ² Falling ball impact strength ^*3 ＞100 cm *3 A 1 Kg steel ball is placed on top of the sample from a height of 40 cm. Drop it and repeat this 50 times. If the sample does not break, increase the drop height by 10 cm and repeat 50 times. Strength is displayed based on the test height and number of times the sample breaks. Example 2 The degree of blistering was measured using the same method as in Example 1 (1) except that the amount of N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane treated with respect to silica sand was changed. The following is shown. Amount of processing agent added Blister (mm) 0 8.8 0.1 3.8 0.3 2.2 0.4 0 0.5 0 Example 3 N-β-(aminoethyl)- used in Example 1(1)
Using silica sand treated with 0.5% by weight of γ-aminopropyltrimethoxysilane and varying the resin:silica sand ratio from 1:6 to 1:1, the degree of blistering was measured in the same manner. No blisters were observed in this case either. Example 4 The degree of blistering was measured in the same manner using a resin:silica sand ratio of 1:7 and varying the amount of N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane treated.The results are as follows. Shown below. Amount of treatment agent added Blister (mm) 0 3.6 0.1 0.2 0.2 0 Example 5 A resin concrete composition was prepared according to the following formulation and filled into a mold of 50 mm x 25 mm x 50 mm (height). The degree of blistering caused by foaming on the open surface of the mold at the end of curing of this resin concrete was measured. As a result, no blisters were observed (0 mm).

【table】

[Table] (silica sand with a moisture content of 0.25% by weight and 0.5% by weight of N-
(treated with β-(aminoethyl)-γ-aminopropyltrimethoxysilane) Note that blisters may occur when untreated silica sand is used.
It was 9.2mm.

Claims (1)

[Claims] 1. In producing resin concrete by blending (A) a polyisocyanate compound, (B) an active hydrogen group-containing compound, and (C) aggregate, the aggregate is hydrolyzed as the component (C). Using a hydrolyzable group-containing silane compound-coated aggregate coated with a hydrolyzable group-containing organic silane compound without heating, and combining the aggregate with the above-mentioned (A) polyisocyanate compound and (B) active hydrogen group-containing compound. A method for producing resin concrete characterized by mixing without heating. 2 The hydrolyzable group-containing organic silane compound is vinyltrichlorosilane, vinyltriethoxysilane, vinyllutris(β-methoxyethoxy)silane, γ-methacryloxypropyltrimethoxysilane, β-(3,4 epoxycyclohexyl)-
Methyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β-(aminoethyl)-
γ-aminopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, β-mercaptoethyltriethoxysilane, N-β-(aminoethyl)-γ -aminopropylmethyldimethoxysilane, N-(β-aminoethyl)-aminomethyltrimethoxysilane and N-(β-aminoethyl)-
The manufacturing method according to claim 1, wherein the compound is one kind of compound selected from the group consisting of γ-amino-β-methylpropyltrimethoxysilane.