JPH05311094A - Water-based primer - Google Patents

Abstract

PURPOSE:To obtain a water-based primer which can satisfactorily cure on and adhere to a wet concrete surface and is excellent in workability and safety by mixing an emulsion of polysulfide-modified epoxy resin of a specified structure with a water-dispersible polyamine or polyaminoamide. CONSTITUTION:The primer is obtained by mixing an emulsion of a polysulfide- modified epoxy resin of the formula (wherein R1 and R3 are each an organic group containing a disphenol skeleton; and R2 is an organic group containing sulfur) with a water-dispersible polyamine or polyaminoamide in a mixing ratio of desirably 2-200 pts.wt., more desirably 5-100 pts.wt., to 100 pts.wt.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an aqueous primer,
In particular, it relates to a water-based primer for concrete that adheres well to water-wet concrete or uncured concrete and is excellent in safety and environmental conservation.

[0002]

2. Description of the Related Art Concrete requires long-term curing to be completely dried even after being hardened. In particular, concrete that has been hardened and cured when the humidity is high, or concrete floors on the basement floor, earthen concrete, concrete on spring pits or water tanks, or concrete that has been cast on an impermeable layer such as an iron plate, will not dry. Have difficulty. Even if the surface of the concrete appears to be dry, the water content inside the concrete is often quite high. If you apply an adhesive or floor covering when the concrete is not sufficiently dried,
In many cases, the adhesive strength is greatly reduced, causing peeling and deformation.

When applying an adhesive or a coating floor material in a state where concrete is not completely dried, a primer is used as an undercoat to maintain adhesive strength and prevent peeling or deformation. .. As such a primer, one containing an epoxy resin is considered.

A primer containing an epoxy resin has an excellent effect of reinforcing the concrete surface and improves the dustproof property and abrasion resistance of the underlying surface. Particularly, the primer containing the polysulfide-modified epoxy resin reduces the permeation of moisture, gas, and oils from the concrete surface, and has a strong adhesive force not only on the concrete dry surface but also on the concrete wet surface. However, since the polysulfide-modified epoxy resin generally has a high resin viscosity, it is difficult to apply it as a primer by itself.

Therefore, when a polysulfide-modified epoxy resin is used as a primer, it is necessary to reduce the viscosity by adding an organic solvent such as toluene, xylene and ketones to improve workability.

However, organic solvents such as toluene, xylene, and ketones are flammable and may enter the human body through the respiratory tract or skin to cause health problems. Especially in a room with no windows, a basement, a clean room, etc. where ventilation and ventilation conditions are poor, it is necessary to perform mechanical ventilation and pay attention to the health management of workers.

Therefore, the workability is improved by reducing the viscosity without using an organic solvent such as toluene, xylene, and ketones, and even when the concrete is wet, it strongly adheres to the concrete to shorten or omit the drying time of the concrete. There is a demand for a primer which is capable of enhancing the concrete surface reinforcing effect, improves the dustproof property and abrasion resistance of the underlying surface, and can reduce the permeation of moisture, gas and oils from the concrete surface.

Therefore, the object of the present invention is to harden and adhere well to the concrete surface even when the concrete is wet, and the viscosity becomes low even without the use of an organic solvent, so that workability, safety and environmental conservation are achieved. It is to provide an excellent water-based primer.

[0009]

As a result of intensive studies in view of the above object, the present inventors have found that a polysulfide modified epoxy resin emulsion having a specific structure and a polyamine or polyaminoamide dispersible in water. The present invention has been found out that the water-based primer obtained by mixing the above is hardened and adheres well to the concrete surface even when the concrete is wet with water, and is excellent in safety and environmental conservation, and has arrived at the present invention.

That is, the aqueous primer of the present invention is
(A) The following general formula:

[Chemical 2] (However, R ₁ and R ₃ are organic groups containing a bisphenol skeleton, and R ₂ is an organic group containing a sulfur atom.), And a modified epoxy resin emulsion containing a polysulfide modified epoxy resin, (B) A water-dispersible polyamine or polyaminoamide is contained.

The present invention will be described in detail below. The water-based primer of the present invention contains a polysulfide-modified epoxy resin emulsion having a specific molecular structure, and a water-dispersible polyamine or polyaminoamide.

The polysulfide-modified epoxy resin is represented by the following general formula (1).

[Chemical 3]

(R ₁ and R ₃ in the above general formula (1) are organic groups containing a bisphenol skeleton, and R ₂ is an organic group containing a sulfur atom.)

Examples of the organic groups R ₁ and R ₃ containing the bisphenol skeleton include bisphenol A type epoxy resin, bisphenol AD type epoxy resin, halogenated bisphenol A type epoxy resin, and bisphenol F.
Examples thereof include those having a molecular structure similar to that of the epoxy resin of the type, halogenated bisphenol F type epoxy resin and the like, or those having a similar molecular structure.

The polysulfide skeleton R ₂ in the general formula (1) is represented by the following general formula (2). (−R ₄ −S _m ) _n− (2)

In the above general formula (2), the average content m of S is in the range of 1 to 3, preferably 1.5 to 2.5.
Is. Furthermore, the range of the average content n of the polysulfide skeleton is 1 to 50, preferably 2 to 30. When the average content n of the polysulfide skeleton is less than 1, it becomes the same as that of a usual bisphenol type epoxy resin, and when n exceeds 50, the viscosity becomes high and it becomes difficult to use.

In the above general formula (2), R ₄ is an organic group such as an alkylene group or an ether bond-containing alkylene group, which may have a substituent such as an OH group or a COOH group. The number is 1-30. Examples of such R ₄ include the following.

-(CH ₂ ) _a -,-(CH ₂ OC
_{H 2) a -, - (} CH 2 CH 3 CH) a - (CH 2 C
_{H (OH) CH 2) a} -, - (C 2 H 4 OCH 2 OC 2 H
₄ ) _a- (however, a is 1 or more, preferably an integer of 1 to 6).

Specific examples of R ₂ are preferably those having —SS— (disulfide bond), and particularly, the following chemical formula
Those shown in (3) are preferable. _{- (C 2 H 4 OCH 2} OC 2 H 4 -SS) n - ··· (3) ( where, n is an integer from 1 to 50, preferably 2 to 30
Is an integer. )

A commercially available product of such a polysulfide-modified epoxy resin is FL manufactured by Toray Thiokol Co., Ltd.
EP-10, FLEP-50, FLEP-60, FLE
P-80 etc. can be mentioned.

In the present invention, in addition to the polysulfide-modified epoxy resin, general epoxy resins (bisphenol A type epoxy resin, bisphenol A
D type epoxy resin, halogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, halogenated bisphenol F type epoxy resin, etc.) may be blended. In this case, it is preferable that the total amount of the epoxy resin is 100% by weight and the proportion of the polysulfide-modified epoxy resin is 30% by weight or more. If the amount of the polysulfide-modified epoxy resin is smaller than this, the desired effect cannot be obtained. Particularly, it is more preferable that the polysulfide-modified epoxy resin is 60% by weight or more and the general epoxy resin is less than 40% by weight.

A surfactant is used to emulsify the polysulfide-modified epoxy resin as described above, but in the present invention, it is particularly preferable to use a nonionic surfactant.

Examples of the nonionic surfactant used in the present invention include polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene dodecyl phenyl ether, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether. , Sorbitan monolaurate, sorbitan monostearate, etc., and those having an HLB value in the range of 8 to 18 are preferable. These nonionic surfactants are
They may be used alone or in combination of two or more depending on the case.

In the present invention, the phase inversion emulsification method is preferably used as the emulsification method for obtaining the emulsion. That is, a W / O type emulsion is obtained by first adding a small amount of water to an oil component (polysulfide-modified epoxy resin-containing organic solvent) to which a surfactant has been added and mixing. Next, water is gradually added to invert the phase to finally obtain an O / W type emulsion.

The apparatus used for mixing is preferably a shaft stirrer having a rotary blade, a homogenizer, a homomixer, a colloid mill and the like. The emulsification temperature is preferably in the range of 10 to 80 ° C. More preferably, it is in the range of 30 to 50 ° C.

The amount of the surfactant added is preferably 100 parts by weight or less, and more preferably 100 parts by weight with respect to 100 parts by weight of the polysulfide-modified epoxy resin (polysulfide-modified epoxy resin + in the case of other epoxy resins, the total of both). Is about 5 to 20 parts by weight.

In order to obtain an emulsion having excellent stability, it is effective to add a water-miscible organic solvent capable of dissolving the surfactant used. When such a water-miscible organic solvent is added, the surfactant can be efficiently dispersed in the oil component, so that the W / O (oil-in-water) type emulsion generated in the initial phase inversion emulsification can be easily generated. .. This W / O
The water dispersed in the type emulsion crushes the oil from the inside at the phase inversion stage achieved by adding more water, so the particles of the O / W type emulsion obtained are very fine. Will be things. As a result, it is considered that an emulsion having excellent stability can be obtained.

Examples of water-miscible organic solvents include monoalcohols such as methanol, ethanol and butanol,
Polyhydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propylene diol, 1,4-butane diol, glycerin, acetone, dimethyl sulfoxide, N, N-dimethylformamide, tetrahydrofuran, dioxane, etc. Is. In the emulsification, these water-miscible organic solvents may be used alone or, in some cases, two or more kinds may be used in combination. When a water-miscible organic solvent is added, the amount of addition should be 1
The amount is preferably 100 parts by weight or less, more preferably 30 to 70 parts by weight, based on 00 parts by weight.

In the present invention, the polysulfide-modified epoxy resin emulsion obtained as described above is mixed with water-dispersible polyamines or polyaminoamides as a curing agent.

Examples of such polyamines include modified aliphatic polyamines (for example, "Adeka Hardener EH-027" and "Adeka Hardener EH-220" manufactured by Asahi Denka Co., Ltd.,
"ADEKA HARDNER EH-227" and "ADEKA HARDNER EH
-230 ", Daito Kuraru J-166 manufactured by Daito Sangyo Co., Ltd.
6 "," Daito Clar X-1777A "and" Daito Clar X-2392 "," Laccamide "manufactured by Dainippon Ink and Machinery Co., Ltd.
"WH-036-S", "Fuji Cure # 5420" manufactured by Fuji Kasei Kogyo Co., Ltd.
”, Mitsui Petrochemical Industry Co., Ltd.“ Epomic Q-611 ”,
"Epicure 3012" and "Epicure XD-358" manufactured by Yuka Shell Epoxy Co., Ltd.), modified alicyclic polyamine
(For example, Daito Sangyo Co., Ltd. "Daitokuraru X-132
1 ", Fuji Kasei Kogyo Co., Ltd." Fujicure FXD-822 "etc.), modified polyamine (for example, Daito Sangyo Co., Ltd." Daitokural U-4075 "," Daitokural I-1199 ",
"Daitokural I-4036", "Daitokuraru X-973
"," Daito Clar X-1301S ",""Daito Clar X
-1942 "," Daitokuraru X-1840 "and" Daitokuraru X-2733 ", Fuji Chemical Co., Ltd." Fujicure # 500 "
1 "and" Fujicure E-1604 "," React CA-101 "and" React CA-102EM "manufactured by Sanyo Kasei Co., Ltd.," Epomate N-001 "and" Epomate QX- "manufactured by Yuka Shell Co., Ltd.
2 "," Epomate B-002W "," Epicure 3255 ", and" Epicure SE-11 ").

Examples of polyaminoamides include "Adeka Hardener EH-20" manufactured by Asahi Denka Kogyo Co., Ltd.
3 "," ADEKA HARDNER EH-204 "," ADEKA HARDNER EH-303 "," ADEKA HARDNER EH-321 "," ADEKA HARDNER EH-331 "and" ADEKA HARDNER EHE-360 ",
Examples include “Tomade # 238” and “Tomade # 225ND” manufactured by Fuji Kasei Kogyo Co., Ltd.

In the present invention, the amount of polyamines or polyaminoamides used varies somewhat depending on the type of polyamines or polyaminoamides used, but it is usually 2 to 200 parts by weight based on 100 parts by weight of the polysulfide-modified epoxy resin emulsion. It is preferably 5 parts by weight, more preferably 5 to 100 parts by weight. By using the polyamines or polyaminoamides in such a range, the reaction between the polysulfide-modified epoxy resin emulsion and the polyamines or polyaminoamides becomes more complete, and the adhesive strength becomes stronger.

The water-based primer of the present invention is obtained by mixing a polysulfide-modified epoxy resin emulsion with water-dispersible polyamines or polyaminoamides. If necessary, water can be added to adjust to a desired concentration.

Such an aqueous primer of the present invention can be applied even when the concrete is not sufficiently dried, and strongly adheres to the concrete. Further, since the water-based primer of the present invention does not need to contain an organic solvent such as toluene, xylene, and ketones, it is not flammable, and there is no concern that it may enter the human body through the respiratory tract or skin and cause health problems.

[0035]

As described above, the water-based primer of the present invention is
It comprises a polysulfide-modified epoxy resin emulsion and water-dispersible polyamines or polyaminoamides. The water-based primer thus obtained has good chemical resistance and adhesiveness that the polysulfide-modified epoxy resin has, and also has an extremely good affinity for wet concrete due to the effect of emulsification, and strongly adheres to the surface. To do. Further, the water-based primer of the present invention has a low viscosity and thus has good workability,
It is excellent in safety and environmental protection because it contains no organic solvent.

[0036]

The present invention will be described in more detail by the following examples. The polysulfide-modified epoxy resin emulsion used in each of the examples described below was synthesized by the following two methods.

Synthesis Example 1 100 parts by weight of a polysulfide-modified epoxy resin (FLEP-10 manufactured by Toray Thiokol Co., Ltd.) and a nonionic surfactant (Neugen EA-produced by Dai-ichi Kogyo Seiyaku Co., Ltd.)
157) 5 parts by weight and 20 parts by weight of water are mixed, and the mixture is stirred and mixed with a homogenizer at 5000 rpm for about 3 minutes to obtain W /
An O type emulsion was obtained. Subsequently, when water addition and stirring were repeated until the total amount of added water reached 100 parts by weight, phase inversion occurred and an O / W type polysulfide-modified epoxy resin emulsion was obtained. The appearance of the emulsion immediately after emulsification was good, and the average particle size of the epoxy resin particles in the emulsion was 2.0 to 3.0 μm.

Synthetic Example 2 100 parts by weight of a polysulfide-modified epoxy resin (FLEP-60 manufactured by Toray Thiokol Co., Ltd.) and a nonionic surfactant (Neugen EA-produced by Dai-ichi Kogyo Seiyaku Co., Ltd.).
157) 20 parts by weight, 10 parts by weight of ethylene glycol, and 20 parts by weight of water were mixed, and stirred and mixed at 5000 rpm for about 3 minutes with a homogenizer to obtain a W / O type emulsion. Subsequently, when water addition and stirring were repeated until the total amount of added water reached 100 parts by weight, phase inversion occurred and an O / W type polysulfide-modified epoxy resin emulsion was obtained. The appearance of the emulsion immediately after emulsification was good, and the average particle size of the epoxy resin particles in the emulsion was 2.0 to 3.0 μm.

Example 1 100 parts by weight of the polysulfide-modified epoxy resin emulsion obtained in Synthesis Example 1 and a modified aliphatic polyamine (Adeka Hardener EHE-22 manufactured by Asahi Denka Co., Ltd.)
0) 10 parts by weight were mixed to prepare an aqueous primer.

With respect to this water-based primer, the adhesion on the wet surface of concrete and the state of coating film after curing were evaluated by the following methods.

Evaluation Method (1) Measurement of Adhesion to Wet Surface of Concrete A commercial sidewalk board made of concrete was immersed in water for 24 hours.
The wet sidewalk board made of concrete was taken out from the water, the surface water was wiped off with a waste cloth, and the above water-based primer was applied. The lower half of the concrete sidewalk was immersed in water and cured at 20 ° C for 5 days. A metal adapter (4 × 4 cm) was attached to the cured resin surface with an adhesive, and the adhesive strength to the concrete wet surface was measured by a Kenken-type adhesive strength tester to evaluate the concrete wet surface adhesiveness. (2) Evaluation method of coating film state after curing The state of the coating film after curing of the above water-based primer was visually judged and evaluated.

Table 1 shows the results of evaluation of the wet surface adhesiveness of the water-based primer and the state of the coating film after curing, together with the formulations and proportions.

Example 2 100 parts by weight of the polysulfide-modified epoxy resin emulsion obtained in Synthesis Example 2 and a modified aliphatic polyamine (Adeka Hardener EH-02 manufactured by Asahi Denka Co., Ltd.)
7) 43 parts by weight was mixed to prepare an aqueous primer.
Table 1 shows the results of evaluating the adhesion of the water-based primer to the concrete on the wet surface and the state of the coating film after curing in the same manner as in Example 1, together with the formulations and proportions.

Example 3 100 parts by weight of the polysulfide-modified epoxy resin emulsion obtained in Synthesis Example 2 and a modified aliphatic polyamine (manufactured by Daito Sangyo Co., Ltd., Daito Clar I-4036) 2
6 parts by weight were mixed to prepare an aqueous primer. Table 1 shows the results of evaluating the adhesion of the water-based primer to the concrete on the wet surface and the state of the coating film after curing in the same manner as in Example 1, together with the formulations and proportions.

Example 4 100 parts by weight of the polysulfide-modified epoxy resin emulsion obtained in Synthesis Example 2 and a modified aliphatic polyamine (Daito Clar I-4036 manufactured by Daito Sangyo Co., Ltd.) 2
6 parts by weight and 50 parts by weight of water were mixed to prepare an aqueous primer. Table 1 shows the results of evaluating the adhesion of the water-based primer to the concrete on the wet surface and the state of the coating film after curing in the same manner as in Example 1, together with the formulations and proportions.

Example 5 100 parts by weight of the polysulfide-modified epoxy resin emulsion obtained in Synthesis Example 2 and polyaminoamide (Adeka Hardener EH-331 manufactured by Asahi Denka Co., Ltd.) 19
By mixing with parts by weight, an aqueous primer was prepared. Table 1 shows the results of evaluating the adhesion of the water-based primer to the concrete on the wet surface and the state of the coating film after curing in the same manner as in Example 1, together with the formulations and proportions.

Comparative Example 1 For comparison, a bisphenol A type epoxy resin emulsion (EPE-041T manufactured by Asahi Denka Co., Ltd.) 10
0 parts by weight and modified aliphatic polyamine (Asahi Denka Co., Ltd.)
Manufactured by Adeka Hardener EHE-027) (75 parts by weight) was mixed to prepare an aqueous primer. Table 1 shows the results of evaluating the adhesion of the water-based primer to the concrete on the wet surface and the state of the coating film after curing in the same manner as in Example 1, together with the formulations and proportions.

Comparative Example 2 For comparison, 100 parts by weight of a polysulfide-modified epoxy resin (FLEP-60, manufactured by Toraythiocol Co., Ltd.) and a modified aliphatic polyamine (Daito Clar X-2392, manufactured by Daito Sangyo Co., Ltd.) were used. 28 parts by weight and 20 parts by weight of xylene / butanol (3/1) were mixed to prepare a solvent-based primer. Table 1 shows the results of evaluation of the adhesion of the solvent-based primer to the concrete on the wet surface and the state of the coating film after curing in the same manner as in Example 1, together with the formulations and proportions.

Table 1 Example 1 Example 2 Example 3 Example 4 Composition of aqueous primer (parts by weight) Polysulfide-modified epoxy resin emulsion Emulsion of Synthesis Example 1 100 --- Emulsion of Synthesis Example 2-100 100 100 Bisphenol A type epoxy resin emulsion EPE-041T ----- Polysulfide modified epoxy resin FLEP-60 --- --- Water-dispersible polyamines and polyaminoamides ADEKA HARDNER EHE-220 10 --- ADEKA HARDNER EHE-027-43 − − ADEKA HARDNER EH-331 − − − − Daito Clar I-4036 − − 26 26 Daito Clar X-2392 − − − − Water − − − 50 Solvent xylene / butanol (3/1) − − − − Concrete wet interview Adhesion (kg / cm ² ) ⁽¹⁾ Tensile bond strength 17 23 25 24 Coating state after curing ⁽²⁾ ○ ○ ○ ○

Table 1 (continued) Example 5 Comparative Example 1 Comparative Example 2 Composition of water-based primer (parts by weight) Polysulfide-modified epoxy resin emulsion Emulsion of Synthesis Example 1 --- Emulsion of Synthesis Example 2 100 --- Bisphenol A Epoxy resin emulsion EPE-041T − 100 − Polysulfide modified epoxy resin FLEP-60 − − 100 Water-dispersible polyamines, polyaminoamides Adeka Hardener EH-220 − − − Adeca Hardener EHE-027 − 75 − Adeka Hardner EH -331 19 − − Daito Clar I-4036 − − − Daito Clar X-2392 − − 28 Water − − − Solvent Xylene / Butanol (3/1) − − 20 Adhesion to concrete wet surface (kg / cm ² ) ^{(1 )} Tensile adhesive strength 21 7 28 Coating state after curing ⁽²⁾ ○ × ○

Note) (1): After 5 days at 20 ° C. (2) ○: Hardened in a clear state ×: Hardened while still white and turbid

As is clear from Table 1, in Examples 1 to 5 using the water-based primer of the present invention, the adhesive strength to the concrete wet surface was large as compared with Comparative Example 1 in which the polysulfide-modified epoxy resin emulsion was not used, A clearer coating can be made. Further, Comparative Example 2 in which the polysulfide-modified epoxy resin was used without being emulsified had better adhesiveness to the concrete wet surface than Comparative Example 1, but Comparative Example 2 uses a solvent, so safety and environmental conservation From the point of view, it is not perfect. The water-based primer of the present invention is also excellent in this respect.

[0053]

As described in detail above, the water-based primer of the present invention contains the polysulfide-modified epoxy resin emulsion and the water-dispersible polyamines or polyaminoamides, and thus has the following great effects. Play.

(1) Since it contains a polysulfide-modified epoxy resin as a main component, it is excellent in chemical resistance, durability, toughness, concrete surface reinforcing effect, dustproofness and abrasion resistance.

(2) Moisture, gas from the concrete surface,
It has the effect of reducing the penetration of oils.

(3) Concrete that has been hardened and cured when the humidity is high, or concrete floors on the basement floor, soil concrete, spring pits and receiving pits, because it has strong adhesion to not only the concrete dry surface but also the concrete wet surface. It is also suitable for construction in places where it is difficult to dry concrete such as concrete on a water layer or concrete impermeable on a water impermeable layer such as an iron plate.

(4) Since no solvent or diluent is used,
It is not flammable and there is no risk of health hazard due to solvents. In particular, it can be installed in areas with poor ventilation, such as indoors without windows, basements, and clean rooms, and it excels in safety and environmental conservation.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI technical display location C09D 179/00 PLT 9285-4J

Claims (1)

[Claims] 1. (A) The following general formula: (However, R ₁ and R ₃ are organic groups containing a bisphenol skeleton, and R ₂ is an organic group containing a sulfur atom.) And a polysulfide-modified epoxy resin emulsion containing a polysulfide-modified epoxy resin. , (B) a water-dispersible polyamine or polyaminoamide, which is an aqueous primer.