JPH02150455A - Resin composition for hydraulic silicate material - Google Patents

Abstract

PURPOSE:To obtain a composition having improved performances such as increased curing rate in moisture states and the strength after being cured by using a crosslinking polymerizable monomer, a curing polymerizable monomer containing a polymer to be crosslinked, a hydraulic silicate material and a surfactant. CONSTITUTION:The objective composition is composed of (A) a thermosetting resin composition of a polymerizable monomer crosslinking type, containing a polymerizable monomer for crosslinking and a polymer to be crosslinked, (B) a hydraulic silicate material containing CaO and SiO2, (C) water and (D) an anionic and/or nonionic surface active agent wherein the component D is 0.1 to 8wt.% based on the total of component A and component C. The proportion of individual components is A=5 to 30 pts.wt., B=3 to 50 pts.wt. and C=1 to 25 pts.wt., further optionally aggregate =50 to 80 pts.wt.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a hydraulic silicate material resin composition, and particularly improves the performance of polymer concrete and resin concrete, such as the curing speed in a wet state and the strength of the cured product. Regarding improvements to.

[Conventional technology]

Conventionally, there are two types of concrete compositions using polymeric materials. One of them is SBR latex and EVA in general cement concrete compositions.
One is so-called polymer cement concrete, which contains a polymer dispersion for mixing with cement, such as an emulsion, and the other is concrete, which uses only polymers such as epoxy resin, polyester resin, and methyl methacrylate resin as a binder. This is what is called resin concrete, which is made by bonding materials together.

The former has advantages such as excellent adhesion to cement concrete and ease of construction on site. However, the drawbacks include that it takes a long time to develop strength and that the strength is generally low. On the other hand, resin concrete has the advantage that it hardens quickly and takes only a short time to develop strength. However, since only resin is used as the binding material, it is expensive. In addition, it is difficult to use in wet conditions; for example, if the composition contains 1.0% or more water, curing will be significantly inhibited, making it impossible to use aggregates such as ordinary river sand, and drying There is a problem that only the bone [o] can be used.

[Problem to be solved by the invention]

In order to solve these drawbacks, Japanese Patent Application Laid-Open No. 58-848
No. 13 proposes that an aqueous composition system consisting of an unsaturated polyester resin, water, aggregate, etc. contains a substance that will become a component of cement.

According to this, the drawbacks of polymer cement concrete and resin concrete described above can be eliminated. However, one of the problems with this method is that it is a reverse phase emulsion containing water in the resin, and since this emulsion is simply formed by mechanical mixing, the water will not last longer than the resin. is in a state where it is easy to separate and cannot maintain an emulsified state stably for a long time.

Therefore, when the ratio of water to resin increases, a separation phenomenon occurs in the composition. As a specific blending ratio, if the water/resin ratio exceeds 35%, the phase structure of the emulsion will be destroyed. Furthermore, since the resin and water separate in this way, the physical properties of the cured composition are low and vary widely, and the surface is likely to suffer from poor curing.

(Means for Solving the Problems) In order to solve the above-mentioned problems, the present invention provides: (bl) a silicate material containing CaO, SiO2, (c1 water and (dl) containing at least an anionic and/or nonionic surfactant, and component (d) containing (al Hydraulic silicate material resin, characterized in that it is contained in a proportion of 0.1 to 8% by weight based on the total of the crosslinking polymerizable polymer and crosslinked polymer of the components and the total of component (e). The present invention provides a composition.In this case, aggregate may be included, and component (a) is such that the crosslinking polymerizable monomer accounts for 30 to 60% by weight in the total of the crosslinking polymerizable monomer and the polymer to be crosslinked. %, and the mountain) components are C for CaO' and 5iQ2.
aO is 45 to 70% by weight, SiO is 15 to 30% by weight, and (al component 5 of these components (a) and (b)
-30 parts by weight, (5 to 40 parts by weight of BL component, further 1 to 20 parts by weight of component (e), and preferably 50 to 85 parts by weight of aggregate, and further the type of aggregate. composition for polymer concrete, by selecting
It can be made into a composition for mortar.

Next, the present invention will be explained in detail.

In the present invention, the polymerizable thermosetting resin composition includes at least a polymerizable monomer for crosslinking and a crosslinked polymer, and the thermosetting resin composition is a polymerizable monomer crosslinked thermosetting resin composition using an unsaturated polyester as the crosslinking polymer. Polymerizable monomers using vinyl ester resin as a crosslinked polymer, crosslinked thermosetting vinyl ester resin compositions, etc. may be mentioned.

The polymerizable crosslinked thermosetting unsaturated polyester resin composition preferably used in the present invention is α.

Produced by polycondensation of β-unsaturated dibasic acid or its acid anhydride, aromatic saturated dibasic acid or its anhydride, and glycols, and optionally contains an aliphatic or alicyclic saturated dibasic acid as the acid component. 30 to 80 parts by weight of unsaturated polyester produced in combination with 70 to 70 parts by weight of α,β-unsaturated monomer
Examples include those obtained by dissolving in 20 parts by weight. In addition, the polymerizable seven-mer crosslinked thermosetting vinyl ester resin composition refers to an unsaturated polyester whose terminal end is modified with vinyl, and an epoxy resin skeleton (epoxy resin) whose terminal end is modified with vinyl. Examples include those obtained by dissolving α,β-unsaturated monomers.

In addition to a curing catalyst and a curing accelerator, a thickener, a filler, a shrinkage reducing agent, etc. may be added to these as necessary, and the addition of a curing catalyst and a curing accelerator is particularly preferred.

Examples of α, β unsaturated dibasic acids or their acid anhydrides used in unsaturated polyester synthesis include maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, chlormaleic acid, and esters thereof. Aromatic saturated dibasic acids or their acid anhydrides include phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, nitrophthalic acid, tera esters, etc., and aliphatic or alicyclic saturated dibasic acids. Examples include oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, glutaric acid, hexahydrophthalic anhydride, and esters thereof, each of which may be used alone or in combination.

In addition, as glycols, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,3-butanediol, 1.4-7
'Tandiol, 2-methylpropane-1,3-diol, neopentyl glycol, triethylene glycol, tetraethylene glycol, 1,5-bentanediol, l,6-hexanediol, bisphenol^, hydrogenated bisphenol A1 ethylene glycol carbonate , 2,2-di(4-hydroxypropoxydiphenyl)propane, etc., which can be used alone or in combination, but oxides such as ethylene oxide and propylene oxide can also be used in the same way. Furthermore, polycondensates such as polyethylene terephthalate can also be used as part of the glycols and acid components.

The α,β-unsaturated monomers used in proportion to the polymerizable monomer for crosslinking include styrene, vinyltoluene, α-methylstyrene, chlorostyrene, dichlorostyrene, vinylnaphthalene, ethyl vinyl ether lylate, ethyl acrylate, and methyl. Examples include vinyl monomers or vinyl oligomers that can be crosslinked with unsaturated polyesters such as vinyl compounds such as methacrylate, acrylonitrile, and methacrylonitrile, and allyl compounds such as diallyl phthalate, diallyl fumarate, diallyl succinate, and triallyl cyanurate. , used alone or in combination, -Styrene is used for boat fishing.

The ratio of the crosslinking polymerizable monomer to the total of the crosslinking polymerizable monomer and proportion-linked polymer mixture is preferably 30 to 60% by weight, and the preferable viscosity of the crosslinking polymerizable monomer and crosslinked polymer mixture is 0.5 ~20 poise, more preferably 0.5~5 poise. When the viscosity is high, it becomes difficult to knead with other components described below, and when the viscosity is low, the components are likely to separate.

It is also preferable that the polymerizable seven-mer crosslinked thermosetting resin composition contains a curing agent to accelerate its curing, and examples thereof include organic peroxides.

Specifically, known ones such as diacyl peroxide type, peroxy ester type, hydroperoxide type, dialkyl peroxide type, ketone peroxide type, peroxyketal type, alkyl perester type, and percarbonate light are used. It is selected appropriately depending on the crosstalk conditions, curing temperature, etc.

The amount added is a commonly used amount, preferably 0.01 to 4 parts by weight based on 100 parts by weight of the total amount of the crosslinking polymerizable monomer and the crosslinking polymer.

Of course, the above curing agents may be used in combination.

It is also preferable to include a curing accelerator in the polymerizable monomer crosslinked thermosetting resin composition, which includes metal soaps such as cobalt naphthenate, cobalt octenoate, vanadyl octenoate, copper naphthenate, and naphthenate. Examples include barium, and metal chelate compounds include vanadyl acetylacetate, cobalt acetylacetate, and iron acetylacetonate. In addition, the amines include dimethylaniline, Nn-diethylaniline, n-dimethylparatoluidine, N-ethylmetatoluidine, triethanolamine, metatoluidine, diethylenetriamine,
Examples include pyridine, phenylmorpholine, piperidine, and jetanolaniline.

The amount added is usually 0.1 to 3 parts by weight per 100 parts by weight of the total amount of the polymerizable polymer for crosslinking and the polymer to be crosslinked.In the present invention, amine accelerators are preferred. The agent may be added in advance or may be added at the time of use.

The hydraulic silicate material containing CaO and SiO2 used in the present invention includes Ca045 to 70% by weight, S
Contains 15 to 30% by weight of iO2, and if these do not add up to 100%, other components such as Al2O3, Fe2O3,
Examples include those containing MgO1S03 and the like, and a representative example thereof is Portland cement. Other early strength,
Various Portland cements such as ultra-early strength, moderate heat, and sulfate resistant can also be used. Mixed cements, such as blast furnace cement, silica cement, and fly ash cement, can also be used.

Additionally, special cements such as white cement, alumina cement, oil well cement, colloidal cement, rapid hardening cement, high sulfate slag cement, geothermal cement, etc. can also be used.

The order of mixing the cement and other components may be as follows: first, water may be mixed with water and then mixed with a mixture of the crosslinking polymerizable top layer and the crosslinked polymer τ, or the cement and the crosslinking polymerizable top layer and the crosslinking polymer τ may be mixed together. It is also possible to mix the mixture of crosslinked polymers and add water to it, whichever is fine.

The water used in the present invention may be commonly used tap water, well water, seawater, water containing sulfates, etc., and is preferably based on the Architectural Institute of Japan, Construction Standard Specifications and Explanations JASS 5.
This water is suitable for reinforced concrete construction.

The aggregate used in the present invention refers to sand, gravel, crushed stone, and other similar materials containing silica as a main component. There are two types of particle size: fine aggregate, which passes 85% or more by weight through the 51111 sieve, and coarse aggregate, which passes 85% or more by weight through the 5-tsuru sieve. A mixture is preferable; a composition using only fine aggregate as an aggregate with cement etc. becomes mortar, whereas a composition using only coarse aggregate or a mixture of coarse aggregate and fine aggregate with cement etc. is generally used as a composition for concrete. become.

Aggregates include natural aggregates and artificial aggregates. The former includes river gravel/river sand, mountain gravel/mountain sand, and sea gravel/sea sand. 1j!
They are processed materials using rocks, clay, industrial by-products, etc. as raw materials, and include crushed stone/crushed sand, silica sand, slag crushed stone/crushed sand, artificial lightweight aggregate, etc.

Further, fine powder used as a filler may be used in combination with a part of the aggregate. Examples of the filler include known ones such as clay, alumina powder, silica powder, talc, barium sulfate, silica powder, glass beads, glass peas, mica, aluminum hydroxide, cellulose, agarite, and astronomical stone chips. .

Various fibers can be mixed into the composition of the present invention in order to improve strength, prevent cracking, impart conductivity, and provide other functions. Specifically, there are metal fibers, glass fibers, organic fibers, asbestos fibers, carbon fibers, aramid fibers, and the like.

The surfactant used in the present invention is an anionic surfactant and/or a nonionic surfactant.

Examples of anionic acids include carboxylic acid salts such as fatty acid soaps, N-
Amino acid salts such as acylsarcosine salts and N-acylalanine salts, alkanesulfonates, α-olefinsulfonates (AO5'), dialkylsulfosuccinates, alkylbenzenesulfonates, alkylnaphthalenesulfonates, N-acyl- Dulphonate salts such as N-methyl taurine salts, alkyl sulfate salts, polyoxyethylene alkyl ether sulfate salts, polyoxyethylene alkyl phenyl ether sulfate salts, sulfuric acid ester salts such as fatty acid monoglyceride sulfate salts, alkyl phosphate esters There are salts and phosphate ester salts such as polyoxyethylene alkyl ether phosphate ester salts.

Nonionic types include polyoxyethylene alkyl ether, methoxypolyoxyethylene alkyl ether,
Polyoxyethylene series such as polyoxyethylene alkyl phenyl ether, polyethylene glycol fatty acid ester, polyoxyethylene alkylamine, polyoxyethylene alkyl thioether, polyoxyethylene polyoxypropylene copolymer (Pluronic), sorbitan fatty acid ester, polyoxyethylene Sorbitan fatty acid ester, glycerin fatty acid ester, polyoxyethylene glycerin fatty acid ester, pentaerythritol fatty acid ester, propylene glycol monofatty acid ester, polyoxyethylene propylene glycol monofatty acid ester, polyoxyethylene sorbitol fatty acid ester, sucrose fatty acid ester, etc. There are polyhydric alcohol types, fatty acid alkylolamides, alkylamine oxides, etc.

As for the type of surfactant to be added, it is preferable to use it according to the ratio of water/(polymerizable 7-mer/cross-linked polymer for cross-linking).If it is an oil-in-water type, an anionic type is preferable, and a non-ionic type is preferable. The HLB value is preferably 10 to 20. In addition, in the case of a water-in-oil type in which the total amount of the polymerizable monomer for crosslinking and the crosslinked polymer is large, a nonionic type having an HLB of 4 to 9 is more preferable than an anionic type.

The composition of the present invention obtained in this way includes water ~ (polymerizable monomer for crosslinking and partially crosslinked polymer), water ~ silicate material, and silicate material ~ (polymerizable monomer for crosslinking and partially crosslinked polymer). By adding a surfactant, each prefecture becomes very uniform, resulting in a composition with less separation.

As an evaluation method, a breathing test method based on JISA1123 can be used.

In order to improve various performances of the composition of the present invention, such as weather resistance, flame retardance, water resistance, chemical resistance, electrical properties, and mechanical properties such as strength, various commonly known additives are mixed in advance. Alternatively, it may be added at the time of use.

The composition ratio of each constituent component of the composition of the present invention is 5 to 30 parts by weight of the polymerizable 7-mer crosslinked thermosetting resin composition and 3 to 50 parts by weight of the hydraulic silicate material such as the cement composition. Parts by weight, preferably 5 to 40 parts by weight, 1 to 25 parts by weight of water,
Preferably 5 to 20 parts by weight, and preferably 50 to 85 parts by weight of aggregate. If the proportion of hydraulic silicate material is less than 3 parts by weight, the balance of the curing system of the composition of the present invention will be disrupted;
It becomes easy to separate. Furthermore, if the proportion is more than 50 parts by weight, the viscosity of the composition of the present invention becomes high, which causes problems in the kneading process, and the fluidity becomes extremely poor, making subsequent operations difficult. If the water content is more than the above-mentioned ratio, the water will tend to separate, and if it is less, the curing of the hydraulic silicate material will be insufficient.

Further, the amount of the surfactant used in the present invention is in the range of 0.1 to 8% based on the total amount of the polymerizable monomer for crosslinking, the polymer to be crosslinked, and the total amount of water. Addition amount is 0.
If it is less than 1%, a decrease in breathing occurs and the dispersibility deteriorates. In addition, the strength also decreases. If it is more than 8%, the dispersibility effect remains the same, but there is no favorable effect of its inclusion.

On the contrary, it has the disadvantage that the water resistance deteriorates significantly.

The composition of the present invention thus obtained can be applied to civil engineering, architectural fields, and other uses.

For example, by taking advantage of its quick construction properties, adhesives can be used for adhesion of PC slopes, tile adhesion, concrete pouring, embedding of anchor bolts, etc.; ), it can be used as a paving material or repair material for elevated bridges, parking lots, race tracks at airports, etc.

Chemical factories, laboratories, etc. floors, waste liquid ditches, electric field baths, hot spring baths, etc., using heat resistance, chemical resistance, etc. to prevent corrosion, concrete roof slabs, and other waterproofing materials, and various types of presses that take advantage of strength. Cast products, such as block manholes for communications, gas, and electricity, FRP, reinforcing pipes and panels, U-shaped gutters, gutter lids, segments for shield construction, sidewalk boards, high-strength piles, decorative terrazzo (artificial marble) ), sinks, simple underground storage, prefabricated panels and frames for geomagnetic observation, etc.

Furthermore, since the composition of the present invention has very strong separation resistance in liquid, it can also be used as resin concrete for underwater construction.

Furthermore, the hydraulic silicate material resin composition of the present invention can also be used as a paint. In this case, aggregate may not be used. The paint also contains a primer and has good curing and adhesion to wet surfaces.

〔Example〕

Examples 1-15, Comparative Examples 1-6 First, a polymerizable 7-mer crosslinked thermosetting unsaturated thermosetting resin composition was produced as follows.

■ Composition A: 3.15 mol of propylene glycol, 1 mol of orthophthalic acid
．． 5 mol, Fumar M 1.5 mol, and toluhydroquinone so ppm were heated and condensed at 200 to 205°C, and the acid value was 2.
The reaction was terminated when the temperature reached 6, and an unsaturated polyester was synthesized. 35 parts by weight of a styrene monomer was stirred and dissolved in 65 parts by weight of the resin to produce a composition which was a polymerizable monomer crosslinked thermosetting unsaturated polyester resin composition.

■ Composition B 485 g of Ebicuron 850 (epoxy resin manufactured by Dainippon Ink & Chemicals ■) with an epoxy equivalent weight of 189 obtained by the reaction of bisphenol A and epichlorohydrin 1 215 g of methacrylic acid, 0.35 g of hydroquinone, and 2.1 g of triethylamine were added to 110 g. The temperature was raised to ℃ and the reaction was continued for 6 hours to obtain a vinyl ester resin with an acid value of 6. 300 g of styrene monomer was added to this to obtain Composition C, which is a polymerizable heptamer crosslinked thermosetting vinyl ester resin composition with an acid value of 4.

Using the resin composition obtained above and the materials shown in Table 1, hydraulic silicate material resin compositions having the compositions shown in each column of the same table were prepared.

For the compositions of Examples and Comparative Examples obtained in this way, a slump test was conducted to check the uniformity of the composition, a slump test was conducted to check the fluidity, and a surface hardening state test was performed to check the curing speed. A bending strength test was conducted to examine the cured strength, and the results are shown in Table 1.

The test method is as follows.

■ Breathing test The test was conducted according to JIS A 1123 concrete breathing test method.

■ Slump test The slump test method for polymer mortar according to JIS A 1173 was used.

■Surface hardening condition test: Non-tacky to the touch: ◎, sticky: ×, and the intermediate between them was expressed as Δ.

■ Bending strength test A test specimen was prepared based on the JIS-1181 polyester resin concrete strength test specimen mold.
Based on JIS A 1184 bending test method for polyester resin concrete.

In addition, the formulation in the table indicates @ part.

Table 1 (20 minutes or less) Table 1 (Continued) In the table, Noigen is a nonionic surfactant manufactured by Daiichi Kogyo Seiyaku n. Specifically, it is as follows.

Neugen EA70...Polyoxyethylene alkyl HL
B 8) Enyl Ether Neugen ET65
・Polyoxyethylene alkyl (HLB 6)
Ether Neugen EA142 - Polyoxyethylene octyl (HLB 14) Phenyl ether Also, the following are manufactured by Kao ■.

Emar 2F... Sodium lauryl sulfate (anion) Demol N... β-naphthalenesphonic acid morpholine condensate sodium salt (anion) Cortamine 24P - Lauryltrimethylammonium chloride (cation) Acetamine-24... Cationic surfactant Also, the following is an anionic surfactant manufactured by Nippon Zeon tn+.

Wharf 500 Polycarboxylic acid salt From the above results, the examples have a low pleating rate and a large slump, indicating that those that are uniformly dispersed also have excellent fluidity.

This is a great advantage when a pump or the like is used to transport the material during on-site construction.

In addition, the bending strength of the example was high, which indicates that it is a uniformly cured product.The example also has a good surface hardening condition (this indicates that the curing speed is fast even in a wet state). .

〔Effect of the invention〕

According to the present invention, the polymerizable heptamer crosslinked thermosetting resin composition and the hydraulic silicate are nonionic and/or
Alternatively, by using an anionic surfactant, a large amount of water can be stably retained, so a uniform composition can be obtained, and it can be easily transferred using a pump. However, the cured product can have great strength without any deterioration. In this way, it is possible to provide a composition that has both the good on-site workability of polymer concrete, the good adhesion to cement concrete, and the quick hardening and short time to develop strength of resin concrete. .

December O1, 1988

Claims (5)

[Claims] (1) (a) A curable polymerizable monomer crosslinked thermosetting resin composition containing at least a crosslinking polymerizable monomer and a crosslinkable polymer, and (b) a hydraulic silicate containing CaO and SiO_2. material, (c) water, (d) anionic and/or nonionic surfactant, and (d) component is the sum of the crosslinking polymerizable monomer and crosslinked polymer of component (a). Above (c
) A hydraulic silicate material resin composition, characterized in that it is contained in a proportion of 0.1 to 8% by weight based on the total amount of components. (2) The hydraulic silicate material resin composition according to claim 1, which contains aggregate. (3) In component (a), the polymerizable monomer for crosslinking accounts for 30 to 6 in the total of the polymerizable monomer for crosslinking and the polymer to be crosslinked.
0% by weight, component (b) is 45-70% by weight for CaO and SiO_2, and 15-3% by weight for SiO_2.
0% by weight, and (a) of these components (a) and (b)
) 5 to 30 parts by weight of the component, 5 to 40 parts by weight of the component (b), further 1 to 20 parts by weight of the component (c), and 50 to 85 parts by weight of the aggregate.
The hydraulic silicate material resin composition according to claim 2, characterized in that it is contained in a proportion of parts by weight. (4) The silicate material resin composition according to claim 2 or 3, which is a concrete composition containing at least coarse aggregate. (5) The hydraulic silicate material resin composition according to claim 2 or 3, which is a mortar composition containing fine aggregate as an aggregate.