JPH01197348A - Polymer concrete composition - Google Patents

Abstract

PURPOSE:To provide the title compsn. having excellent water-resistance, mechanical strength, dimensional stability and forming property, etc., by contg. ethylenic unsatd. monomer mixture having a specified compsn. thermoplastic resin and aggregate as essential component. CONSTITUTION:The ethylenic unsatd. monomer mixture contg. (A) partial ester of polyhydric alcohol (e.g., triethylene glycol) and (meth)acrylic acid, and (B) (meth)acrylic acid tert-butylcyclohexyl ester, in at least 5wt.% to the total monomer, respectively. As the monomer other than (A) and (B) components, styrene, methacrylate, etc., are exemplified. The polymer concrete compsn. is composed by contg. the ethylenic unsatd. monomer mixture, thermoplastic resin (e.g., polystyrene) and aggregate (e.g., silica sand), as essential component.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a polymer concrete composition comprising a resin component and an aggregate.

[Conventional technology]

BACKGROUND ART Polymer concrete (also referred to as resin concrete or resin mortar) compositions made by kneading aggregate with unsaturated polyester resin or epoxy resin have been known.

This type of composition provides concrete with superior mechanical strength, corrosion resistance, abrasion resistance, and frost resistance compared to cement, so it is used for surface repair and reinforcement of highways, bridges, dam revetments, etc. It is also used in acid-resistant tanks, gutter covers, terrazzo, cable burying structures, etc.

However, among the above-mentioned conventional polymer concrete compositions, those based on unsaturated polyester have the disadvantage that cracks are likely to occur in the cured product due to shrinkage and heat generation during curing. In addition, epoxy-based products have high viscosity, which causes poor kneading and molding workability, which tends to result in insufficient contact between aggregate and resin, and has disadvantages such as difficulty in defoaming entrained air. was there.

On the other hand, Japanese Patent Application Laid-Open No. 60-76 concerning the applicant's own prior invention
Publication No. 502 discloses an acrylic polymer concrete composition, that is, a partial ester of polyhydric alcohol and acrylic acid or methacrylic acid, in which a small amount of thermoplastic resin is blended to solve the above-mentioned drawbacks. discloses a composition obtained by kneading aggregate. This composition has excellent kneading and molding workability, and due to the polymerization and curing of the above partial ester, it has good adhesion between the resin component and the aggregate, and has good dimensional stability without cracks and good mechanical strength. It has the characteristic of applying polymer concrete.

[Problem to be solved by the invention]

However, according to subsequent research by the present inventors, the above-mentioned known acrylic polymer concrete compositions:
It has been found that the polymer concrete formed from this method has poor water resistance, and its mechanical strength may gradually decrease when exposed to rainwater or groundwater, and that improvements to this problem are strongly desired. did.

Therefore, the present invention has improved kneadability, molding workability, adhesion between the resin content in the cured product and aggregate, crack resistance, dimensional stability, and mechanical strength compared to unsaturated polyester-based and epoxy-based products. It is an object of the present invention to provide an acrylic polymer concrete composition which has further improved water resistance and has higher practical value, in addition to the above-mentioned characteristics of being able to satisfy all of the physical properties such as.

[Means to solve the problem]

As a result of intensive studies to achieve the above object, the present inventors found that the poor water resistance of the known acrylic polymer concrete compositions could be improved by improving the adhesion between the aggregate and the resin component. Due to the partial ester of polyhydric alcohol and acrylic acid or methacrylic acid to contribute,
In other words, we learned that this is due to the hydroxyl group contained within the molecule of this partial ester, and after further investigation based on this, we found that a specific ethylenically unsaturated monomer was used together with the partial ester. This solves the above water resistance problem, and in this case improves the characteristics of an acrylic polymer concrete composition, such as kneading properties, moldability, adhesion between the resin in the cured product and aggregate, and crack resistance. It has been found that various physical properties such as dimensional stability and mechanical strength are still maintained.

That is, the present invention has been completed based on the above knowledge, and its gist is A) the following a)
component 1 and component a2; a+) partial ester of polyhydric alcohol and acrylic acid or methacrylic acid; 8 g) tert-butylcyclohexyl acrylate or tert-butylcyclohexyl methacrylate, respectively, at least 5% by weight of the total monomers. B) a thermoplastic resin; and C) aggregate as essential components.

[Structure and operation of the invention]

As the ethylenically unsaturated monomer mixture of component A in the present invention, in addition to using the above-mentioned al component and a2 component as essential components, if necessary, for the purpose of improving kneadability and physical properties of the cured product, etc. Other ethylenically unsaturated monomers copolymerizable with these can be used.

The a1 component, which is one of the essential components, is a partial ester of polyhydric alcohol and acrylic acid or methacrylic acid, and has at least one free hydroxyl group in its molecule, so it can be used as a resin in hardened concrete. It greatly contributes to improving the adhesion between the aggregate and the aggregate, and also gives good results in imparting various physical properties such as mechanical strength.

Such partial esters include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, l.3-propanediol, l.
4-butanediol, 1,3-butanediol, 1,6
- Monoester or diester (3
(in the case of a polyhydric alcohol with a valence of 5 or more), triester (in the case of a polyhydric alcohol with a valence of 5 or more), and tetraester (in the case of a polyhydric alcohol with a valence of 5 or more). Further, as partial esters other than these, for example, ethan glycidyl ether diacrylate or dimethacrylate, bisphenol A diglycidyl ether diacrylate or dimethacrylate, etc. can be used. .

Particularly preferred among these partial esters are those using trihydric or higher polyhydric alcohols such as glycerin, trimethylolpropane, and pentaerythritol.Among these, partial polyhydric esters of diester or higher, that is, those containing acryloyl in the molecule, are particularly preferable. group or methacryloyl group to 2
Partially polyvalent esters having at least 100% polyester are most desirable in order to obtain a cured product with high strength.

Another essential ingredient is a! Acid component, acrylic acid
ert-butylcyclohexyl ester or tert-butylcyclohexyl methacrylate ester,
The synthesis method is not particularly limited, although one synthesized by a normal esterification reaction of tert-butylcyclohexyl alcohol and acrylic acid or methacrylic acid can be used.

Since this Al component contains an alicyclic lipophilic group in its molecule, it imparts good internal water properties to the cured product, and as a result, the decrease in water resistance caused by the Al component is greatly suppressed. . In addition, unlike low molecular weight unsaturated monomers such as styrene and methyl methacrylate, this ag acid component is mostly odorless, so it is difficult to use when kneading polymer concrete compositions or during construction. It has the advantage that there is no risk of harming the working environment.

The above-mentioned al+at acid component as an essential component, the ethylenically unsaturated monomer mixture of component A may be composed only of these components, or as mentioned above, other ethylene copolymerizable with these components may be used. A sexually unsaturated monomer may be used in combination. In these usage modes, a1 component and a
The amount of each acid component used should be at least 5% by weight based on the total monomers, preferably in the range of 10 to 80% by weight based on the total monomers. good. Further, when using the above-mentioned partial polyhydric ester of trihydric or higher polyhydric alcohol as the a1 component, it is particularly desirable that the polyhydric ester accounts for 5 to 95% by weight of the total monomers. By using the amount within such a range, very good results can be obtained in improving various physical properties and water resistance of the cured product.

al+ a! used as an optional component Various other ethylenically unsaturated monomers that can be copolymerized with the acid component can be used, but it is better to avoid the use of styrene, methyl methacrylate, etc., which cause odor, as much as possible. Of course, it can be used in small amounts.

Examples of preferable ethylenically unsaturated monomers include polyhydric esters obtained by completely esterifying polyhydric alcohols similar to those in component a with acrylic acid or methacrylic acid, as well as lauryl alcohol. , acrylates or methacrylates of monohydric alcohols such as cetyl alcohol, stearyl alcohol, oleyl alcohol, phenol, benzyl alcohol, diacrylates or dimethacrylates of bisphenol A polyethylene glycol, diacrylates or dimethacrylates of bisphenol A polypropylene glycol, etc. .

In addition, the above a, component, a2 structure, and the ethylenically unsaturated monomer copolymerizable with these may be used alone or in combination of two or more.

The thermoplastic resin of component B in the present invention includes esters of monohydric alcohols having 1 to 20 carbon atoms and acrylic acid or methacrylic acid, acrylic acid, methacrylic acid, glycidyl methacrylate, acrylonitrile, styrene, polyalkylene glycol monoacrylate. Alternatively, there are homopolymers, random polymers, block polymers, graft copolymers, etc. of various monomers such as methacrylate and vinylpyrrolidone.

This B component plays an important role in improving the adhesion between the aggregate and the resin component and obtaining a high-strength cured product, but it also plays an important role in maintaining good physical properties such as dimensional stability. In addition, it is desirable that the composition completely dissolves, partially dissolves, or swells in the ethylenically unsaturated monomer mixture of component A. Therefore, the type, molecular weight, composition ratio, etc. of component B should be appropriately selected depending on the type, composition, ratio, etc. of component A.

As the aggregate of component C in the present invention, silica sand, gravel,
Coarse and fine aggregates such as crushed stone, clay, talc, mica, asbestos, walrus night, calcium silicate, feldspar powder, acid clay, sericite, glass powder, slate powder, shirasu, calcium carbonate, barium carbonate , magnesium carbonate, dolomite, barium sulfate, calcium sulfate, magnesium hydroxide, aluminum hydroxide, alumina, antimony oxide, magnesia, titanium oxide, zinc white,
Fine fillers such as white carbon, synthetic silicates, amorphous silica, diatomaceous earth, molybdenum sulfide, graphite, wood flour, pulp flour, potassium titanate, Portland cement, alumina cement, etc. can be used in combination.

The composition of the aggregate should generally be 20-80% by weight of coarse aggregate, 10-70% by weight of fine aggregate, and 5-50% by weight of fine filler, and the particle size of the coarse/fine aggregate. It is preferable to have a particle size structure in which the ratio and the particle size ratio of fine aggregate/fine filler are each 10 times or more.

The polymer concrete composition of the present invention has the above-mentioned ethylenically unsaturated monomer mixture as component A, the thermoplastic resin as component B, and the aggregate as component C as essential components. A radical polymerization initiator or various known additives such as a polymerization accelerator, pigments, decorative gravel, glass fibers and metal fibers for improving strength may be blended with the radical polymerization initiator.

Among the above essential components, A and B components are resin components, and the mutual usage ratio of these components is such that the weight ratio of component A/component B is in the range of 99/l to 85/15. preferable. If the amount of component B in the resin component is too small, the dimensional stability and other physical properties of the cured product are likely to be impaired. There is also a risk of causing a decrease in physical properties.

In addition, in order to obtain polymer concrete with high dimensional stability and mechanical strength, the aggregate of component C, which is another essential component, is combined with A, which is a resin component.

The total amount of N5 to 40 of component B is % by weight, particularly preferably 6 to 3
It is preferable that the proportion of the C component aggregate is 95 to 60% by weight, particularly preferably 94 to 70% by weight, relative to 0% by weight.

There are no particular restrictions on the method of curing the polymer concrete composition of the present invention, and various methods using light, heat, high-energy radiation, etc. can be applied.

During curing, it is preferable to use a radical polymerization initiator such as an organic peroxide, an inorganic peroxide, a nitrile compound, an azo compound, a diazo compound, and a sulfinic acid compound, or a radical polymerization initiator together with a polymerization accelerator.

Examples of organic peroxides include methyl ethyl ketone peroxide, 1,1-bis(tert-butylperoxy)cyclohexanone, tert-butyl hydroperoxide,
Cumene hydroperoxide, diisopropylbenzene hydroperoxide, di-tert-butyl peroxide, tert-butyl cumyl peroxide, dicumyl peroxide, lauroyl peroxide, benzoyl peroxide, diisopropyl peroxycarbonate, di-
n-propyl peroxycarbonate, tert-butyl peroxy acetate, tert-butyl peroxy butyrate, tert-butyl peroxy bivalate,
Examples include tert-butylperoxylaurate, tert-butylperoxybenzoate, tert-butylperoxyisopropyl carbonate, and the like.

Inorganic peroxides include hydrogen peroxide, ammonium persulfate, potassium persulfate, etc., and nitrile compounds include 2,2-azobisisobutyronitrile, 2,2-
Examples include azobisvaleronitrile. In addition, examples of azo compounds and diazo compounds include diazoaminobenzene,
Examples of sulfinic acid compounds include p-)luenesulfinic acid, p-
Examples include sodium toluenesulfinate and propylsulfinic acid.

Examples of polymerization accelerators include amines such as N-N-dimethyl para-toluidine, N-N-dimethylaniline, tri-n-butylamine, and 2-N-ethylanilinoethanol;
Examples include inorganic compounds such as sodium bisulfite, sodium sulfite, and ferrous sulfate, and metal complexes such as nickel, cobalt, and manganese.

The amounts of these radical polymerization initiators and polymerization accelerators are o, ooi to 20 parts by weight, respectively, based on 100 parts by weight of the ethylenically unsaturated monomer mixture as component A and the thermoplastic resin as component B. parts, preferably 0.05 to 15 parts by weight.

Next, a method for obtaining a cured polymer concrete using the polymer concrete composition of the present invention will be described with reference to typical examples.

First, as resin components, a predetermined amount of an ethylenically unsaturated monomer mixture of component A containing components a, component and a2, and a thermoplastic resin of component B are mixed. Next, the mixture is divided into portions, and predetermined amounts of the radical polymerization initiator and the polymerization accelerator are added to one portion and the other portion, respectively, and dissolved therein.

Next, the resin component to which the above-mentioned radical polymerization initiator and polymerization accelerator have been added and a predetermined amount of aggregate adjusted to a predetermined composition are quickly kneaded. After kneading, pour into the mold. An exothermic reaction occurs and hardens in a few minutes to tens of minutes.
Polymer concrete is obtained. A kneading machine such as a mixer can be used to mix the resin component and the aggregate, and a machine such as a vibrator can also be used to pour the mixture into a mold.

〔Effect of the invention〕

The polymer concrete composition of the present invention includes the above-mentioned A and B.
By using a specific resin component, it has excellent kneading properties with aggregate and molding workability, and provides handling properties equivalent to those of cement concrete compositions.

In addition, the polymer concrete that is cured with this material has a low shrinkage rate during curing, has excellent dimensional stability with no clumps, and has high strength with good adhesion between the resin component and the aggregate. Moreover, it has excellent water resistance, so there is little risk of gradual decline in mechanical strength even if exposed to rainwater.

Furthermore, the polymer concrete composition of the present invention has the advantage that it has low odor during kneading and there is no risk of harming the working environment of the actual concrete construction. Regarding this point, it should be noted that the conventional unsaturated polyester resins described above emit a significant odor because a large amount of styrene is used for the dissolution and reactivity of the resin. Similarly, epoxy-based products have a pronounced odor due to resin diluents, etc. Therefore, these conventional polymer concrete compositions are not suitable for use in closed spaces such as gymnasiums, warehouses, and basements. , deterioration of the working environment due to odors becomes a major problem.

On the other hand, in the present invention, the resin component has the above-mentioned A and B.
By using the above-mentioned al+ 82 component as an essential component as the A component which is a monomer mixture, that is, the a and component have extremely low odor similar to the partial ester of the a1 component. Therefore, when these resin components and aggregates are mixed together, there is no problem of odor as in the past, and therefore there is no particular concern that the working environment will be harmed even when used in the above-mentioned closed state.

〔Example〕

Next, examples of the present invention will be described in more detail. In addition, hereinafter, parts shall mean parts by weight.

Example 1 Component A: 10 parts of glycerol monomethacrylate (at
Acid component, 22 parts of glycerol dimethacrylate (at acid component, methacrylic acid t)
Component B: 75% by weight of methyl methacrylate and 25% by weight of tert-butyl methacrylate. 6 parts of a random copolymer with a number average molecular weight of ff 142.000 Component C: 460 parts of silica sand of 16 to 18 mesh
Mixture of 200 parts of silica sand of 00 mesh pass and 70 parts of calcium carbonate Of the above A, B, and C components, first mix A component and B component thoroughly, divide this into three equal parts, and then add to one side. 3 parts of benzoyl peroxide and 1 part of N.N-dimethylaniline were added to the other and mixed.

Next, these two solutions were mixed, and the aggregate of component C, which had been mixed in advance with a mixer, was quickly added thereto and kneaded for 2 to 3 minutes to obtain a polymer concrete composition.

This polymer concrete composition was immediately packed into test tubes with a diameter of 18N and molds with the size of 40IIIX, 40IIX, and 160 dragons, and after being vibrated for 2 minutes on a table-type vibrator, it was allowed to stand and harden.

After 24 hours, the cured product was heated at 105°C for 2 hours, and after cooling, a test piece with a diameter of 18 cranes and a length of 36++n was cut out from the test tube, and the compressive strength was measured. In addition, for the cured product taken out from the mold, first ASTM D-2566-
The curing shrinkage rate was measured according to 69, and then 10
A test piece the size of a Tsuru xiOn After a week, the weight increase rate due to water absorption and the surface condition were observed with the naked eye, and the water resistance was examined. In addition,
The surface condition was evaluated as △ if O1 was slightly swollen if it was the same as before the water absorption test, and × if it was whitened or softened.

The results of these tests were as shown in Table 1 below. In addition, the same table also describes the odor of the polymer concrete composition during kneading.

The odor was evaluated as 0 if there was almost no odor, and × if the odor was strong.

Examples 2 to 4P One type of polymer concrete composition was prepared in the same manner as in Example 1, except that the components listed in Table 1 were used as components A, B, and C. A curing test similar to that in Example 1 was conducted. The results were as shown in Table 1.

In Table 1, "Random copolymer of rMM and Mt-Bu in component B" is 75% by weight of methyl methacrylate.
and 25% by weight of tert-butyl methacrylate, a block copolymer of rs ty and MM" is a block copolymer of 50% by weight of styrene and 50% by weight of methyl methacrylate, rs ty "A block copolymer of 50% by weight of styrene and 5% vinyl acetate"
It is a block copolymer with 0% by weight. Moreover, MW is a number average molecular weight.

Comparative Examples 1 to 3 Three types of polymer concrete compositions were prepared in the same manner as in Example 1, except that those listed in Table 1 were used as components A, B, and C. A curing test similar to that in Example 1 was conducted. The results were as shown in Table 1. In addition, these comparative examples 1 to 3 are A
Component a, which is one of the essential components of the present invention, was not used as a component.

As is clear from the results in Table 1 above, the polymer concrete composition of the present invention provides polymer concrete with low shrinkage and high mechanical strength, as well as excellent water resistance.

Furthermore, it is clear that the polymer concrete composition of the present invention is also characterized by low odor during kneading.

Patent applicant: NOF Corporation

Claims (1)

[Claims] (1) A) The following a_1 component and a_2 component; a_1
) Partial ester of polyhydric alcohol and acrylic acid or methacrylic acid a_2) Ethylenically unsaturated monomer containing at least 5% by weight of acrylic acid tert-butylcyclohexyl ester or methacrylic acid tert-butylcyclohexyl ester, respectively, based on the total monomers A polymer concrete composition comprising: a mixture; B) a thermoplastic resin; and C) an aggregate as essential components.