JP2853954B2 - Resin concrete composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin concrete composition using a methacrylate resin as a binder.

[0002]

Prior art and its problems Resin concrete is
In general, it is used mainly as a secondary product or repair material for factories, taking advantage of its high strength, excellent water tightness, chemical resistance, and abrasion resistance. Because of the lack of stability,
At present, the application of on-site construction to structures is still at the trial stage. However, focusing on these advantages, it is very unlikely that resin concrete will be applied to important structures such as marine / deep underground structures and structures that require chemical resistance to sulfates. Seems to be expensive.

[0003] The 3rd Annual Conference of Concrete Engineering Annual Conference (1981), pp. 233-236, "Mechanical Properties of Poly (methyl methacrylate) Concrete" discloses a resin concrete composition using a methacrylate resin as a binder. ing. Also, Concrete Engineering Annual Paper 9-
1 (1987) pp. 271 to 276, "Basic research on resin mortar using methyl methacrylate"
A resin mortar composition using a methacrylate resin as a binder is disclosed.

A number of studies have been made on methacrylate-based resin concrete, but most of the studies are based on basic research on the composition of resin, and the mixing and mixing of resin concrete are supposed to be carried out on site. ,
It is a fact that there is hardly any practical research that is examining implantation.

[0005]

The object of the present invention is to use a low-viscosity methacrylate resin as a binder and to study the composition thereof, and as a result, have invented a resin concrete having good workability.

Accordingly, an object of the present invention is to provide a resin concrete composition having the same consistency as cement concrete.

[0007]

The present invention relates to a resin concrete composition comprising a methacrylate resin, a filler and an aggregate, wherein (1) the composition contains 6 to 8 methacrylate resins.
(2) the volume ratio of the methacrylate resin to the filler is 2.4 or less; and (3) JIS A
The slump value measured by a method based on 1101 (method for slump test of concrete) is in the range of 12 to 21 cm.

[0008]

DETAILED DESCRIPTION OF THE INVENTION The present invention will be specifically described below. For the resin concrete of the present invention, generally used aggregates such as sand, gravel, crushed stone, and blast furnace slag aggregate can be used. In the case of resin concrete, these aggregates are contained in the composition at 76 to 86% by weight.

In the present invention, the methacrylate resin serving as a binder is a homopolymer of a methacrylate monomer or a copolymer of a combination of two or more methacrylate monomers, or a methacrylate monomer and the methacrylate monomer. It is mainly composed of a copolymer of a monomer and another copolymerizable monomer.

Examples of the methacrylate monomers include methyl methacrylate, ethyl methacrylate, n
-Butyl methacrylate, isobutyl methacrylate,
Examples thereof include t-butyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, and lauryl methacrylate. In the present invention, those containing methyl methacrylate as a main component are preferable.

Other monomers copolymerizable with the methacrylate monomer include, for example, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, Acrylate monomers such as lauryl acrylate; ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, Hexylene glycol di (meth) acrylate, 2,2-bis [4- (meth) acryloyloxyphenyl] propane, 2,2-bis [4- (meth) acryloyloxy Cyclohexyl] propane,
2,2-bis [3- (meth) acryloyloxy-2-
[Hydroxypropoxyphenyl] propane, trimethylolpropane tri (meth) acrylate, pentaerythritol tera (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and other polyfunctional (meth) acrylate monomers; dimethyl maleate, diethyl maleate Maleate ester monomers such as catenate, di-n-butyl maleate, di-t-butyl maleate, diisobutyl maleate; dimethyl fumarate, diethyl fumarate, di-n-butyl fumarate;
Fumaric acid ester monomers such as di-t-butyl fumarate and diisobutyl fumarate; and vinyl monomers such as styrene and vinyl toluene. These monomers are used alone or in combination of two or more.

In the present invention, the methacrylate resin may be used in combination with one of the above-mentioned methacrylate monomers, a copolymer comprising two or more thereof, or a methacrylate monomer. If necessary, other components may be contained in addition to the copolymer with other monomers. Other components include, for example, plasticizers such as di-2-ethylhexyl phthalate, di-n-octyl phthalate, tricresyl phosphate, and di-2-ethylhexyl adipate; oxygen barrier agents such as paraffin wax; Agent; a trace amount of a polymerization inhibitor for stabilizing the monomer; or a polymer or copolymer of the above-mentioned methacrylate-based monomer or acrylate-based monomer.

Conventionally, the methacrylate resin is blended in the resin concrete composition in an amount of 9 to 25% by weight, but in the present invention, it is usually 6 to 8% by weight, preferably 6.5 to 7.5% by weight. %. This is 6% by weight
If it is less than 8%, the workability is deteriorated. On the other hand, if it exceeds 8% by weight, material separation easily occurs.

In the present invention, the mixing ratio of the methacrylate resin and the filler is extremely important, and the volume ratio of the methacrylate resin to the filler must be 2.4 or less. That is, this resin / filler ratio is 2.4.
In the following cases, there is no occurrence of material separation or resin outflow.

As the filler of the present invention, heavy calcium carbonate, alumina, fly ash, blast furnace slag, aluminum hydroxide, clay, talc, kaolin and the like can be used, and heavy calcium carbonate and alumina are particularly preferred. . In the resin concrete of the present invention, the filler is blended in the composition at 8 to 16% by weight.

The resin concrete composition of the present invention comprises
It is necessary that the slump value measured by a method based on SA 1101 (slump test method for concrete) is in the range of 12 to 21 cm. If the slump value exceeds this value, material separation tends to occur, while if the slump value is less than the above value, the workability of the composition becomes poor. The slump value is preferably in the range of 13 to 19 cm.

The resin concrete according to the present invention contains, as a main component, a methacrylate resin compound containing a methacrylate monomer which is a component of the methacrylate resin and / or another monomer, and is compounded as required. After the polymerization catalyst is dissolved in a liquid formulation containing other components, the filler and the aggregate are mixed, and the mixture is cured by reaction to produce the mixture.

Examples of the polymerization catalyst include a polymerization initiator such as an organic peroxide and an azo compound, or a redox polymerization catalyst which is a combination of a polymerization initiator and an accelerator. When only a polymerization initiator is used as a polymerization catalyst, the resin composition can be cured by heating. When a redox polymerization catalyst is used as the polymerization catalyst, curing can be performed at room temperature or at a temperature near room temperature.

Examples of the organic peroxide include dibenzoyl peroxide, dicumyl peroxide, diacetyl peroxide, dicapryl peroxide, dilauroyl peroxide, distearoyl peroxide, t-butyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide and the like. No.

Examples of the azo compound include azobisisobutyronitrile, dimethylazobisisobutyrate and the like.

Examples of the redox polymerization catalyst include a combination of the above organic peroxide with a tertiary amine, a ferrous salt, a mercaptan, a naphthenate, or a combination of a persulfate and sodium hydrogen sulfite. Is mentioned.

Examples of the tertiary amine include aniline, N, N-dimethylaniline, N, N-dimethyl-
p-Toluidine, N, N-di (hydroxyethyl) -p
-Toluidine, N, N-di (hydroxyethyl) -m-
Toluidine, N, N-di (β-hydroxypropyl)-
p-Toluidine and the like can be mentioned. In particular, when the methacrylate resin composition contains methyl methacrylate as a main component, it is preferable to use a redox polymerization catalyst comprising a combination of an organic peroxide and a tertiary amine.

The amount of the polymerization catalyst used is about 0.1 to 10% by weight with respect to the methacrylate resin when the polymerization initiator is used alone, and when the redox polymerization catalyst is used, the above-mentioned polymerization catalyst is used. Further, an accelerator is added at a ratio of 0.1 to 5% by weight to the ratio of the polymerization initiator used.

When using a redox polymerization catalyst,
A tertiary amine or the like, which is an accelerator, is previously dissolved in a liquid composition containing a methacrylate-based monomer and / or a methacrylate resin compound containing other monomers as a main component. Immediately before kneading with the aggregate and the filler, a polymerization initiator such as a peroxide is dissolved to initiate a reaction. Of course, a commercially available methacrylate-based liquid formulation in which the accelerator is previously blended may be used. Further, in the present invention, a method of dissolving the polymerization initiator in the liquid formulation in advance and dissolving the accelerator immediately before kneading with the aggregate, or a method of adding the polymerization initiator and the accelerator immediately before kneading. You can use it.

[0025]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail with reference to embodiments.

Composition of Resin Concrete [Materials Used] (1) Methacrylate Resin A commercially available methyl methacrylate-based liquid resin was used.
This liquid resin is made of methyl methacrylate (hereinafter referred to as MMA).
Sometimes abbreviated. ) As a main component, a polymerization accelerator (tertiary aromatic amine), a crosslinkable monomer (polyfunctional methacrylate), and a small amount of a polymerization inhibitor (Mitsui Petrochemicals ( Co., Ltd., Silical R17D and Silical R17DLV).

In the present embodiment, polymethyl methacrylate (hereinafter sometimes abbreviated as PMMA) is added to increase the viscosity in order to smoothly progress the polymerization reaction of the liquid resin. Here, a type in which PMMA is separately added as a bead-shaped powder (hereinafter referred to as “resin A”) and a type in which PMMA is dissolved and contained in a liquid resin in advance (manufactured by Mitsui Petrochemicals Co., Ltd., Silal R17K and Silal R17KL)
V, hereinafter referred to as resin B. ) Were used.

As the polymerization initiator, commercially available benzoyl peroxide (manufactured by NOF Corporation, Niper FF, 50% diluted product) was used (hereinafter sometimes abbreviated as BPO).

(2) Filler Heavy calcium carbonate (average particle size: about 4 μm, specific gravity: 2.7)
0) and alumina (average particle size about 4 μm, specific gravity 3.9)
5) were used.

(3) Aggregate Crushed stone from Tonohara (Gmax 20 mm, specific gravity of surface dryness 2.71, specific gravity of absolute dryness 2.69, FM 6.90) as coarse aggregate, and mixed silica sand (No. 3 and 6) as fine aggregate No .: Absolute specific gravity 2.60)
And Tenryu-produced land sand (surface dry specific gravity 2.61, absolute dry specific gravity 2.58.
FM 2.45). In addition, these aggregates were used in a substantially dry state.

[Kneading] Table 1 shows the combination of fine aggregate and filler.
And the formulations as shown in Table 2 were performed. Table 2
In the above, the resin / filler ratio indicates a volume ratio of the methacrylate resin to the filler. As a kneading method,
After putting in the aggregate, knead it for 1 minute, and put it in 2-3 minutes after putting in the liquid resin.
Kneaded for minutes.

The amount of the polymerization initiator was 6.5% by weight of the unit resin, and the polymerization initiator was mixed with the resin 30 seconds before charging the resin.

When resin A was used as the liquid resin, a small amount of PMMA was used as a part of the fine aggregate.

[0034]

[Table 1]

[0035]

[Table 2] Composition Table Composition No. Unit Amount (% by weight ) s / a Resin / resin filler Fine aggregate Coarse aggregate ( % ) Filler ratio 1-1 7.2 12.1 35.5 45.2 46.0 1.67 1-2 5.2 8.7 37.9 48.2 〃 1.67 1-3 6.5 11.1 36.2 46.2 〃 1.66 1-4 6.9 11.6 35.9 45.6 〃 1.66 1-5 7.7 10.6 28.5 53.2 35.8 2.03 2-1 6.7 15.2 34.4 43.7 46.0 1.80 2-2 7.6 12.5 35.1 44.8 〃 2.48 2-3 7.2 12.6 35.3 44.9 〃 2.35 3 7.2 10.6 36.2 46.0 〃 1.90 4 6.7 15.2 34.4 43.7 〃 1.80 5-1 7.5 13.9 35.5 43.2 〃 2.20 5-2 7.5 13.9 35.5 43.2 〃 2.20

Performance Evaluation [Test Method] Performance evaluation was performed separately for fresh and hardened products.

(1) Fresh JIS A 1101 (Slump test method for concrete) and
Slump and air volume were measured in accordance with JIS A 1128 (Test method based on pressure of air volume of concrete not yet solidified (air chamber pressure method)).

[0038] Resin concrete generally has the advantage that the curing time is short, but an appropriate pot life is required when assuming on-site construction. Therefore, the time-dependent change of the slump (5 minutes after mixing the polymerization initiator (immediately after kneading)
And 10 minutes after 10 minutes have elapsed)
We decided to evaluate the pot life. In addition, each time slump was measured, reworking was performed.

(2) At the time of curing In order to examine the relationship between the pot life and the strength characteristics at the time of curing, a diameter of 10 cm ×
After preparing a cylindrical specimen having a height of 20 cm and air-curing for 7 days in a room at 20 ± 2 ° C., JIS A 1182 and JIS
A compression strength test and a split tensile strength test were performed in accordance with A 1185 (compression strength test method and tensile strength test method for polyester resin concrete). Further, at the time of the compressive strength test, the static elastic modulus was also measured.

Further, in order to confirm the strength development due to the material age, immediately after kneading, a cylindrical specimen having a diameter of 10 cm and a height of 20 cm was prepared and mixed with a polymerization initiator 2 hours after the polymerization initiator was added.
After a lapse of time and at 1, 3, 7, 14, and 28 days of the material age, the compressive strength test was performed. The specimens were air-dried in a room at 20 ± 2 ° C. until a prescribed age. The removal time is
All specimens on which the strength test was performed after 1 day of the material age were all on the 1st day of the material age, and those subjected to the strength test before that were demolded immediately before the test.

[Test Results] Table 3 shows the test results for each of the above formulations. In the column of "Evaluation" in Table 3, excellent ones are given in consideration of the results of visual observation of material separation resistance and fluidity in addition to the consistency such as slump value.
A mark, a good one is indicated by a circle, and a bad one is indicated by a cross.

[0042]

TABLE 3 Test results formulation No. Slump air amount compressive strength tensile strength static modulus rating (cm) (%) (kgf / cm 2) (kgf / cm 2) (kgf / cm 2) 1-1 18.5 1.4 371 51 1.34 × 10 ⁵ ○ 1-2 1.0 2.1 389 55 1.77 × 10 ⁵ × 1-3 17.5 1.6 363 51 1.40 × 10 ⁵ ○ 1-4 18.5 1.2 357 53 1.38 × 10 ⁵ ○ 1-5 22.0-- − − × 2-1 19.0 1.4 496 81 2.07 × 10 ⁵ ○ 2-2 16.5 0.9 459 77 1.84 × 10 ⁵ × 2-3 19.5 0.9 504 81 2.15 × 10 ⁵ ○ 3 17.0 1.2 407 60 1.32 × 10 ⁵ ○ 4 16.5 0.9 521 87 2.15 × 10 ⁵ ◎ 5-1 18.5 1.1 876 110 2.91 × 10 ⁵ ◎ 5-2 19.5 1.1 910 114 2.95 × 10 ⁵ ◎

Looking at the test values at the time of freshness,
o.1-2 has an extremely small slump value,
And No.2-2 caused material separation. However, in other formulations, although the slump values of formulations No. 3 and No. 4 using land sand as fine aggregate are slightly smaller, no material separation of resin and aggregate was observed, and cement The same consistency as concrete was obtained.

According to the results of the strength test, the composition using land sand as the fine aggregate has higher strength than the composition using mixed silica sand, but there is no significant difference. On the other hand, the difference in strength development depending on the type of filler is quite large, and the blend No. 2-1 and No. 4 using alumina as the filler
Has a compressive strength of 30 even though the amount of resin unit is smaller than the formulations No.1-1 and No.3 using heavy calcium carbonate.
%, And a value about 50% larger in split tensile strength. Further, the ratio of the split tensile strength to the compressive strength is also increased.

Table 4 shows the measured values of the slump, the compressive strength and the change in static elasticity of the compound No. 5-1 with the polymerization initiator over time.

[0046]

[Table 4]

FIG. 1 is a graph of the data in Table 4. As for the slump, a significant slump loss occurs when the elapsed time reaches 40 minutes, and the initial consistency cannot be obtained clearly. You can see that. In addition, the compression strength shows almost the same value until 20 minutes have elapsed, but the value of the specimen manufactured after 30 minutes has decreased by about 10%. However, the static elasticity coefficient hardly changed regardless of the elapsed time, and poor curing did not occur.

In consideration of the above-mentioned change with time of the slump and the state of the development of the compressive strength, the pot life for maintaining the required performance of the resin concrete of the present invention is 20 to 30 minutes after mixing the polymerization agent. It is believed that there is.

FIG. 2 shows the relationship between the material age and the compressive strength in the above formulation No. 5-2. Although the compressive strength at the age of 7 days showed a slightly small value, almost 100 days at 1 day of age.
% Compression strength is obtained. However, there is a tendency for the strength to increase slightly even after the first day of timber age. In addition, with respect to the compressive strength at the age of 28 days, about 80% (774 kgf / cm ² ) 2 hours after mixing the polymerization initiator and about 90% (879 kg
f / cm ² ), indicating that high strength was obtained at an early stage.

[0050]

The resin concrete of the present invention has the same consistency as cement concrete, and has good workability. Therefore, the present invention has extremely high practicality in on-site construction of a structure requiring strong water-tightness, chemical resistance, wear resistance and the like.

Further, the above excellent consistency is as follows:
Since the composition of the present invention can be obtained by using a general aggregate and reducing the amount of resin compared to the conventional one, it can be said that the composition of the present invention also has economical merits.

[Brief description of the drawings]

FIG. 1 is a graph showing measured values of slump, compressive strength and static elasticity of a composition No. 5-1 after mixing with a polymerization initiator, with time.

FIG. 2 is a graph showing the relationship between material age and compressive strength in Formulation No. 5-2.

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Masanori Kuromoto 1043 Shimoyama, Onigakubo, Tsukuba-shi, Ibaraki Pref. 1 Inside Kumagaya Gumi Technical Research Institute (72) Inventor Hideki Koyama Oji-Kiga, Tsukuba-shi, Ibaraki 1043 Shimoyama, Kubota 1 Inside Kumagaya Gumi Technical Research Institute Co., Ltd. (72) Inventor Yasushi Yamada 61-2, Waki, Waki-machi, Kuga-gun, Yamaguchi Prefecture Inside Mitsui Petrochemical Industry Co., Ltd. (72) Inventor Goro Sugaya Tokyo 3-39-10 Yushima, Bunkyo-ku Mitsui Petrochemical Products Co., Ltd. (56) References JP-A-62-174215 (JP, A) JP-A-1-141185 (JP, A) JP-A 63-25253 ( JP, A) JP-A-60-76502 (JP, A) JP-A-57-92564 (JP, A) JP-A-61-247653 (JP, A) JP-A-63-154304 (JP, A) Hei 4-224149 (JP, A) (58) key Fields examined (Int. Cl. ⁶ , DB name) C04B 26/06 C04B 14/02 C08F 2/44

Claims (1)

(57) [Claims] 1. A resin concrete composition comprising a methacrylate resin, a filler and an aggregate, wherein (1) the composition contains 6 to 8% by weight of a methacrylate resin, and (2) a methacrylate resin based on the filler. And (3) a slump value measured by a method in accordance with JIS A 1101 (test method for concrete slump) in the range of 12 to 21 cm. Concrete composition.