JPH08198654A - Quick-hardening cement-epoxy composition - Google Patents

Abstract

PURPOSE: To provide a cement-epoxy compsn. not causing phase separation at the time of mixing the cement-epoxy compsn. contg. bisphenol type epoxy resin as a polymer component with water. CONSTITUTION: This quick-hardening cement-epoxy compsn. contains 100 pts.wt. cement, 1-40 pts.wt. water-soluble epoxy resin, 1-80 pts.wt. bisphenol type epoxy resin and 1-50 pts.wt. curing agent.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fast-curing cement-epoxy composition, and more specifically, it does not cause layer separation even when mixed with water, and has curability, compressive strength and bending strength. , A cement-epoxy composition containing a bisphenol-based epoxy resin as a polymer component, which is capable of producing concrete having excellent adhesiveness and water permeability.

[Prior art and problems to be solved]

In recent years, a polymer cement composition containing a thermosetting epoxy resin as a polymer component has been widely studied, and among the epoxy resins, a bisphenol type is widely used (Japanese Patent Laid-Open No. 3-69538). Gazette).
Cement hydrates when it is hardened, but bisphenol epoxy resin has poor hydrophilicity, so when a polymer cement composition containing a bisphenol epoxy resin as a polymer component is mixed with water, it is separated into two layers. It had drawbacks.

In addition, concrete using a polymer cement composition containing a bisphenol epoxy resin as a polymer component is not excellent in curability, adhesiveness and water permeation resistance due to the above-mentioned layer separation, and therefore has compressive strength and bending strength. There was a problem that it was too small.

Therefore, an object of the present invention is to provide a cement composition which does not cause layer separation when a cement-epoxy composition containing a bisphenol epoxy resin as a polymer component is mixed with water. Another object of the present invention is to provide a cement-epoxy composition containing, as a polymer component, a bisphenol epoxy resin having excellent curability, compressive strength, bending strength, adhesiveness and water permeability when concrete is manufactured. It is in.

[0005]

Means for Solving the Problems As a result of intensive studies by the present inventors, the above object was obtained by adding a water-soluble epoxy resin having surface activity to a polymer cement composition containing a bisphenol epoxy resin as a polymer component. Has been achieved.

That is, the present invention comprises 100 parts by weight of cement,
The present invention provides a fast-curing cement-epoxy composition containing 1 to 40 parts by weight of a water-soluble epoxy resin, 1 to 80 parts by weight of a bisphenol type epoxy resin, and 1 to 50 parts by weight of a curing agent. .

The present invention also provides a fast-curing cement-epoxy composition, which comprises the above composition optionally containing a curing accelerator.

The cement used in the fast-curing cement-epoxy composition of the present invention is any cement that can be industrially used. These cements can be used alone or in a mixture of two or more kinds. Good.

Examples of the above-mentioned cement include ordinary Portland cement, early-strength Portland cement, ultra-early-strength Portland cement, sulfate resistant Portland cement, moderate heat Portland cement, white Portland cement, ultra-fast Portland cement, etc., expansion. Cement, acidic phosphate cement, self-hardening cement, lime slag cement, blast furnace cement, high sulfate slag cement, fly ash cement, keens cement, pozzolan cement, alumina cement, calcium aluminate, and mixtures thereof. .

It is preferable to use a mixture of Portland cement and alumina cement and / or calcium aluminate as the cement, and the weight ratio of the Portland cement and the alumina cement (Portland cement / alumina cement) is preferably. Is 1/1 to 25/1, more preferably 1/1 to 5 /
It is 1. By using the above range, the cement can be hardened in a short time.

The above-mentioned Portland cement is industrially called so-called Portland cement, such as ordinary Portland cement, early-strength Portland cement, ultra-early-strength Portland cement, sulfate resistant Portland cement, moderate heat Portland cement, and white Portland cement. All of them are included, and even if they are used alone, 2
You may mix and use 1 or more types.

Examples of the above-mentioned alumina cement include
For example, 12CaO / 7Al₂O₃, CaO / Al₂O ₃, CaO / 2Al₂O₃,
5CaO / 3Al₂O₃ , 3CaO / Al₂O₃, 11CaO ・ 7Al₂O₃・ Ca
F₂, 2CaO / SiO₂, 11CaO ・ 7Al₂O₃・ CaF₂, 4CaO / Al₂O₃
・ Fe₂O₃, 4CaO / 3Al₂O₃・ 2F, 4CaO ・ 3Al₂O₃・ SO₃Etc.
It may be composed of single or mixed components. Also,
Examples of the calcium aluminate include CaO.
2Al₂O₃, CaO / Al₂O₃, 3CaO / Al₂O₃ , 12CaO / 7Al₂O₃
 , 3CaO / 3Al₂O₃・ CaF₂, 11CaO / 7Al₂O₃・ CaF₂Etc.
It may include one or a mixture of components.

The water-soluble epoxy resin used in the fast-curing cement-epoxy composition of the present invention is not particularly limited as long as it is an epoxy resin which is soluble in water, and a particularly preferable one is-(O-R ¹ ). It is an epoxy resin having a polyalkylene glycol chain represented by _m − as an essential structure. Here, R ¹ is one or more alkyl groups selected from the group consisting of an ethylene group, a propylene group and a butylene group, and may be linear or branched. Or a mixture thereof. Further, the polyalkylene glycol chain may be any of single polymerization, block polymerization, random polymerization, or a mixture thereof. Further, m is 5 to 50, preferably 10
~ 30.

The water-soluble epoxy resin has an epoxy ring (oxirane ring) at the end of its structure, and preferably has 2 to 6 epoxy rings. The epoxy equivalent of the water-soluble epoxy resin is preferably 100 to 2000, more preferably 200.
~ 1000.

As the water-soluble epoxy resin, Those having a structure represented by in the molecule can also be preferably used. Here, R ¹ and m are as described above. X is one or more atoms selected from the group consisting of carbon, nitrogen, oxygen and sulfur.

That is, an epoxy resin having a structure having the above polyalkylene glycol chain and an organic group having an ester bond, a urethane bond, a carbonic acid bond or a thiocarbonic acid bond is included. Among these, preferred is a compound in which X is carbon, that is, a compound having an ester bond. The water-soluble epoxy resin having an ester bond can be produced by reacting a polyalkylene glycol, a polyvalent carboxylic acid and a polyol polyglycidyl ether.

The polyalkylene glycol used in the above production is as described above, and among them, polyethylene glycol is preferable.

Examples of the polycarboxylic acid used in the above production include phthalic acid, trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid, maleic acid, tetrahydrophthalic acid, alkyl-substituted tetrahydrophthalic acid and succinic acid. , Alkyl-substituted succinic acid, hexahydrophthalic acid, alkyl-substituted hexahydrophthalic acid,
Examples thereof include nadic acid, alkyl-substituted nadic acid, adipic acid, azelaic acid, and their anhydrides.

The polyol polyglycidyl ether used in the above production is a polyglycidyl ether of a polyhydric alcohol. Examples of the polyhydric alcohol include, for example, neopentyl glycol, trimethylolethane, trimethylolpropane, pentaerythritol,
Examples thereof include dipentaerythritol, tripentaerythritol, and their polyalkylene glycol adducts and caprolactone adducts. To the above polyhydric alcohol,
The addition of epihalohydrin (eg epichlorohydrin) produces the polyol polyglycidyl ether.

The above water-soluble polyol polyglycidyl ether has an epoxy ring (oxirane ring) at the end of its structure.
Those having 2 to 6 epoxy rings are particularly preferable. The epoxy equivalent of the polyol glycidyl ether is preferably 100 to 2000, more preferably 200 to 1000.

The bisphenol type epoxy resin used in the composition of the present invention has a bisphenol type structure represented by the following formula in its structure. (In the formula, R ³ and R ⁴ represent a hydrogen atom, a halogen atom, an alkyl group, and a halogenated alkyl group, Ph is a phenyl group, and one or more halogen atoms, an alkyl group, and a halogenated alkyl group. It may be a phenyl group substituted with a group)). It also includes hydrogenated phenyl groups.
Among them, bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F
Type epoxy resin, bisphenol AF type epoxy resin and the like are particularly preferable in terms of excellent physical strength such as compressive strength and bending strength.

The contents of the water-soluble epoxy resin and the bisphenol type epoxy resin used in the present invention are
With respect to 100 parts by weight of cement, the content of the water-soluble epoxy resin is 1 to 40 parts by weight, preferably 5 to 15 parts by weight,
The content of the bisphenol type epoxy resin is 1 to 80 parts by weight, preferably 12 to 35 parts by weight, and the total amount of both is preferably 3 to 100 parts by weight, more preferably 5 to 100 parts by weight.
50 parts by weight, most preferably 10 to 50 parts by weight.
If the total amount of both is less than 3 parts by weight, the physical strength of the epoxy resin cannot be expressed, and if it exceeds 100 parts by weight, the curing rate of the cement may be remarkably slowed. Therefore, the above range is preferable.

Further, the weight ratio of the contents of the water-soluble epoxy resin and the bisphenol type epoxy resin (water-soluble epoxy resin / bisphenol type epoxy resin) is from the viewpoint of the emulsion stability of the two mixed epoxy resins. , Preferably 1/9 to 6/4, more preferably 1/9 to
It is 4/6.

As the curing agent used in the fast-curing cement-epoxy composition of the present invention, all those generally used as curing agents for epoxy resins can be used, but in particular, aliphatic polyamine type curing agents and aliphatic polymethylene are used. A diamine-based curing agent, an alicyclic polyamine-based curing agent, an aliphatic polyamine-based curing agent containing an aromatic ring, an aromatic diamine-based curing agent, or a modified amine-based curing agent obtained by modifying these, and a polymercaptan-based curing agent, etc. It can be preferably used.

As the above-mentioned aliphatic polyamine-based curing agent,
For example, diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), iminobispropylamine (DPT)
A), bis (hexamethylene) triamine, 1,3,6
-Trisaminomethylhexane (TMAH) and their derivatives.

Examples of the aliphatic polymethylenediamine-based curing agent include trimethylhexamethylenediamine (TMD), polyetherdiamine, diethylaminopropylamine (DEAPA) and their derivatives.

As the alicyclic polyamine-based curing agent,
For example, menthenediamine (MDA), isophoronediamine (IPD), bis (4-amino-3-methylcyclohexyl) methane, N-aminoethylpiperazine (A
EP), 1,3-bis (aminomethyl) cyclohexane (1,3BAC) and their derivatives.

Examples of the aliphatic polyamine-based curing agent containing an aromatic ring include, for example, metaxylylenediamine (MXD).
A) or this derivative etc. are mentioned.

Examples of the aromatic diamine-based curing agent include metaphenylenediamine (MPDA), diaminodiphenylmethane (DDM), diaminodiphenylsulfone (DDS) and derivatives thereof.

Further, as the curing agent, the above polyamines, polyol polyglycidyl ether and / or
Alternatively, a polyamine compound obtained by reacting a polyalkylene oxide diglycidyl ether can also be suitably used. As the polyol polyglycidyl ether as used herein, the same compounds as described above are used. Further, the polyalkylene oxide diglycidyl ether referred to here is
It is a diglycidyl compound of polyalkylene oxide. Furthermore, it is a preferred method to use the above amine-based curing agent after diluting it with water beforehand.

As the above-mentioned polymercaptan type curing agent,
Examples include esters of mercaptopropionic acid with polyhydric alcohols such as dipentaerythritol and trimethylolpropane.

The content of the above-mentioned curing agent is such that the equivalent ratio to epoxy (epoxy equivalent / active hydrogen equivalent of amine) is 0.9 to.
Cement 100 is preferred, preferably 1.1
1 to 50 parts by weight, preferably 2 to 20 parts by weight
Parts by weight. If the content of the curing agent is less than 1 part by weight, the curing reaction of the epoxy resin will be insufficient, and if it exceeds 50 parts by weight, the amine will be in excess and the physical strength will be low.

The fast-curing cement-epoxy composition of the present invention may further contain water, and the content of water is preferably 1 to 100 parts by weight of cement.
70 parts by weight, more preferably 20 to 50 parts by weight.
Within the above content range, the strength of the cement increases as the amount of water decreases, and the flowability improves as the amount of water increases.
If the above content is less than 1 part by weight, it is not realistic, and
If it exceeds 70 parts by weight, there is a problem in physical strength.

The quick-curing cement-epoxy composition of the present invention may contain a water-soluble epoxy resin, a bisphenol type epoxy resin and a curing agent which are essential constituents, as well as a usual epoxy resin. The epoxy resin that can be used here refers to all resins having one or more epoxy rings (oxirane rings) in the structure. Typical examples include glycidyl ether type epoxy resins, cycloaliphatic epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, and heterocyclic epoxy resins.

Examples of the glycidyl ether type epoxy resin include novolac type epoxy resin, brominated epoxy resin, polyalkylene glycol type epoxy resin and the like.

Examples of the above-mentioned cycloaliphatic epoxy resin include epoxy resins having cycloaliphatic group such as cyclohexene oxide group, tricyclodecene oxide group and cyclopentene oxide group. Alicyclic diepoxy acetal type , Alicyclic diepoxy adipate type, alicyclic diepoxy carboxylate type, vinylcyclohexene dioxide type and the like.

Examples of the glycidyl ester type epoxy resin include diglycidyl ester phthalate epoxy resin, tetrahydrophthalic acid diglycidyl ester type epoxy resin, hexahydrophthalic acid diglycidyl ester type epoxy resin, diglycidyl-p-oxybenzoic acid. Examples thereof include acid type epoxy resins and dimer acid glycidyl ester type epoxy resins.

Examples of the glycidyl amine type epoxy resin include tetraglycidyl diaminodiphenylmethane (TGDDM) type epoxy resin, triglycidyl paraaminophenol (TGPAP) type epoxy resin, triglycidyl metaaminophenol (TGMAP) type epoxy resin, diglycidyl. Aniline (DGA) type epoxy resin, diglycidyl toluidine (DGT) type epoxy resin, tetraglycidyl metaxylylenediamine (TG
MXA) type epoxy resin, diglycidyl tribromoaniline type epoxy resin, tetraglycidyl bisaminomethylcyclohexane type epoxy resin and the like.

Examples of the above heterocyclic epoxy resin include hydantoin type epoxy resin, triglycidyl isocyanurate (TGIC) type epoxy resin and the like.

In the present invention, it is preferable to use a glycidyl ether type epoxy resin from the viewpoint of hydrolysis resistance, physical strength and easiness of production. Such an epoxy resin can be used in an appropriate amount as long as the effect of the present invention is not impaired, but the amount used is preferably 10 to 50 parts by weight, more preferably 5 to 15 parts by weight with respect to 100 parts by weight of cement. Is.

The fast-curing cement-epoxy composition of the present invention may further contain a curing accelerator in order to accelerate the curing reaction of the water-soluble epoxy resin and the bisphenol type epoxy resin. As the above-mentioned curing accelerator, any of those usually used as a curing accelerator for epoxy resins can be used, but in particular, imidazoles, tertiary amines and the like can be mentioned, and among them, tertiary amines are preferably used.

The tertiary amine means an amine having three carbon atoms bonded to a nitrogen atom, and examples thereof include linear tertiary amine, benzyldimethylamine, monodimethylaminomethylphenol, bisdimethylaminomethylphenol, Trisdimethylaminomethylphenol, tetramethylguanidine, triethanolamine, alkyl-te
rt-monoamine, triethylenediamine, N, N'-dimethylpiperazine, 1,8-diazabicyclo (5,4,
0) Undecene-7 (DBU) and the like.

The content of the curing accelerator is preferably 1 to 20 parts by weight, more preferably 3 to 15 parts by weight, based on 100 parts by weight of the epoxy resin. In the present invention,
When a curing accelerator is used, the epoxy group in the epoxy resin self-polymerizes, so the content of the curing agent may be relatively small, for example, about 1 to 20 parts by weight.

Other additives may be added to the fast-curing cement-epoxy composition of the present invention as long as the effects of the present invention are not impaired. Examples of the additive include calcium 2-ketogluconate, milk casein,
Set retarders such as sodium citrate and sodium potassium tartrate, slaked lime, limes such as dolomite plaster,
Admixture for granulated blast furnace slag, AE such as alkyl sulphate, polyoxyethylene alkyl phenyl ether, etc.
And water reducing agents such as ligninsulfonic acid.

If necessary, an aggregate can be mixed with the fast-curing cement-epoxy composition of the present invention. Examples of the aggregate include silica sand, sand, gravel and the like.

[0046]

The present invention will be described in more detail with reference to the following examples. However, the invention is not limited to these examples.

[Examples 1 to 10 and Comparative Examples 1 to 3] <Materials Used in Examples and Comparative Examples> Materials used in Examples and Comparative Examples are as follows.

Water-soluble epoxy resin-1: Obtained by reacting the acid group of the half ester obtained by reacting polyethylene glycol (molecular weight 1000) with hexahydrophthalic anhydride with trimethylolpropane triglycidyl ether by a conventional method. 4 functional epoxy resin (epoxy equivalent 5
00).

Water-soluble epoxy resin-2: Bifunctional epoxy resin obtained by reacting glycidol with a prepolymer obtained by reacting polyethylene glycol (molecular weight 1000) with tolylene diisocyanate (epoxy equivalent 76
0).

Water-soluble epoxy resin-3: Diglycidyl ether of polyethylene glycol (molecular weight 1000) (epoxy equivalent 587).

Bisphenol A type epoxy resin: ADEKA RESIN EP-4100 [Epoxy equivalent 190 manufactured by Asahi Denka Kogyo KK].

Amine curing agent-1: ADEKA HARDNER EH
-040-1 [modified aliphatic polyamine manufactured by Asahi Denka Kogyo KK, solid content 40%, active hydrogen equivalent 187].

Amine curing agent-2: ADEKA HARDNER EH
-217 [modified aliphatic polyamine manufactured by Asahi Denka Kogyo Co., Ltd.
Solid content 100% active hydrogen equivalent 40].

Polymercaptan curing agent: ADEKA HARDNER EH-317 [Asahi Denka Kogyo KK, solid content 100
% SH equivalent 145].

Curing accelerator: ADEKA HARDNER EHC-3
0 [tertiary amine catalyst manufactured by Asahi Denka Kogyo Co., Ltd.].

Setting retarder: sodium potassium tartrate

<Test Method> The materials and proportions of the cement composition are shown in Table 1 (Examples 1 to 10) and Table 2 (Comparative Example 1 to 1).
It is shown in 3). Using the materials shown in Table 1 and Table 2, according to the following test methods, a curability test, a compression test, a bending test,
An adhesion test and a water permeation resistance test were conducted.

(Curing Property Test) The time when the cement composition started to harden and the time when the cement composition ended were measured.

(Compression test) The compression test was performed according to JIS R5201.

(Bending test) The bending test was carried out according to JIS R5201.

(Adhesion test) As shown in FIG. 1, 40 × 4
The test material 14 was filled in the mortar 12 of 0 × 160 mm to form the test piece 10, and the adhesive strength between the mortar and the test material was determined according to the bending test of JIS R5201.

(Water permeation resistance test) A jig 20 having cracks 27 through which water 29 passes from the lower part to the upper part of the concrete 22 as shown in FIG. 2 was prepared, and the test material 26 was applied to the concrete to a thickness of 1 mm. After daily curing, pressurized water (5 kgf / cm ² ) was passed through. The water permeability from the surface of the test material was confirmed.

The results of the curing test, compression test, bending test, adhesion test and water permeation resistance test are shown in Tables 1 and 2. Regarding the results of the water permeation resistance test, those with no water permeation are indicated by ⊚ and those with water permeation are indicated by x.

[0064]

[Table 1]

[0065]

[Table 2]

[0066]

The quick-setting cement-epoxy composition of the present invention can prevent layer separation when mixing water and cement. Further, concrete using the fast-curing cement-epoxy composition of the present invention is excellent in curability, compressive strength, bending strength, adhesiveness and water permeability.

[Brief description of drawings]

FIG. 1 is a diagram showing a method of an adhesion test performed in the present invention.

FIG. 2 is a diagram showing a method of a water permeability test performed in the present invention.

[Explanation of symbols]

 10 Method of Filling Test Material in Adhesion Test 12 Mortar 14 Test Material 20 Permeability Test Jig 22 Concrete 24 Test Material Application Surface 26 Test Material 27 Crack 28 Pressure Gauge 29 Pressurized Water

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Claims (5)

[Claims] 1. Cement 100 parts by weight, water-soluble epoxy resin 1-40 parts by weight, bisphenol type epoxy resin 1
-80 parts by weight, and 1 to 50 parts by weight of a curing agent, a fast-curing cement-epoxy composition. 2. The cement comprises portland cement and alumina cement and / or calcium aluminate, and the weight ratio of the portland cement to the alumina cement (Portland cement / alumina cement) is 1/1 to 25/1. The fast-setting cement-epoxy composition according to claim 1. 3. The fast-curing cement-epoxy composition according to claim 1, which further comprises 1 to 20 parts by weight of a curing accelerator. 4. The total content of the water-soluble epoxy resin and the bisphenol-type epoxy resin is 3 to 100 parts by weight, and the weight ratio of the water-soluble epoxy resin and the bisphenol-type epoxy resin (water-soluble epoxy Resin / bisphenol type epoxy resin) is 1/9 to 6/4, The rapid hardening cement-epoxy composition according to any one of claims 1 to 3. 5. The fast-curing cement-epoxy composition according to claim 1, which further comprises 1 to 70 parts by weight of water.