JPH04106178A - two-component adhesive - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed Description of the Invention] [Field of Industrial Application] This invention relates to an adhesive for bonding and integrating a hydraulic matrix such as concrete or plaster to steel plates, stone, concrete, FRP, wood, etc. .

[Conventional technology]

A matrix (such as concrete or plaster) that hardens by a hydration reaction is applied to existing architectural and civil engineering structures, such as structures made of steel plates, synthetic resin plates with reinforcing materials, and wood. When joining (hydraulic matrix) or when composing a composite material of steel plates, stones, etc. and hydraulic matrix, head studs, angles, etc. are planted on the existing steel plate, etc., and concrete, etc. is poured on top. It is common to set As a special example,
There is a technique in which a polymer cement mixed with polymers such as SBR and EVA is applied onto a steel plate to a thickness of 10 to 30 mm, and then concrete is poured and hardened to integrate the cement. In addition, when synthesizing unsaturated polyester resin concrete for cement concrete, a technology is known to improve adhesion by applying an adhesive containing a specified vinyl ester resin to the required parts of the cement concrete. (Japanese Unexamined Patent Publication No. 56-55667).

This method ensures integration by intervening a vinyl ester resin that has shorter gel tiles than the unsaturated polyester resin. Apply a pouring adhesive containing epoxy resin to the underside of the floor slab,
A technique is also known in which a mesh-like reinforcing material is fixed thereon using the adhesive force of an adhesive, and then a cement mortar is further coated (Japanese Patent Application Laid-Open No. 62-253807). As a result, the adhesive acts as a buffer against the difference in expansion and contraction between the floor slab and the cement mortar, thereby preventing the cement mortar from peeling off.

[Problem to be solved by the invention]

Installing studs or angle members on a steel plate requires construction such as welding, which poses an economical problem, and at the same time has the disadvantage that the base is limited to materials such as steel plates. In addition, such a joining method has the disadvantage that local stress is generated due to point or angle line joining using a stand. Another drawback is that adhesive strength cannot be achieved unless the amount of poured concrete is thick enough. On the other hand, when using polymer cement, it has been pointed out that its adhesive strength is not so high and there are problems with the ease of application. The method of applying a vinyl ester resin adhesive on a cement concrete structure and pouring unsaturated polyester resin concrete on top of it is: ■ poor workability, ■ difficult to mix, and requires a lot of effort such as cleaning the mixer. , ■High cost.

Furthermore, in the method of applying epoxy resin to the lower surface of the floor slab, it is used to bond mesh-like reinforcing material, not as an adhesive for cement mortar.

The present invention was devised in view of the current situation, and can be applied to a wide range of materials without causing problems such as local stress generation.
The object of the present invention is to provide an adhesive that has high adhesive strength and is easy to apply, regardless of the thickness of the hydraulic matrix.

[Means to solve the problem]

As a result of intensive studies to solve the above problems, the present inventors found that
The present invention has been completed based on the discovery that this object can be achieved by using a two-component adhesive consisting of a bisphenol A epoxy resin having a specific epoxy equivalent and a polyamide amine having a specific amine conversion rate.

That is, in the present invention, 1150 to 300 g/epoxy
A matrix that is cured by a hydration reaction, whose main ingredient is bisphenol A type epoxy resin, has active hydrogen that reacts with epoxy groups, and uses a water-soluble polyamine, polyamidoamine, or one or more modified products thereof as a curing agent. A two-component adhesive for bonding metal plates, stone, concrete, FRP, wood, etc., and a mixture of this base agent and hardening agent are applied to the metal plate, stone, concrete, FRP, wood, etc., and the mixture is applied to the coated surface. A matrix material that hardens through a hydration reaction is placed before the adhesive hardens. An integrated product of a metal plate, stone slab, concrete, FRP, wood, etc. and a matrix that hardens through a hydration reaction. This relates to a manufacturing method.

A bisphenol A type epoxy resin having an epoxy equivalent of 150 to 300 g/eq is used as the main resin.

As the main agent, bisphenol A type, bisphenol F diglycidyl ether (BF), brominated bisphenol A type, etc. are used, but bisphenol A type is most preferred in terms of versatility and economy.

However, BP resin has a lower viscosity than B^ resin and has the advantage of being less likely to crystallize even at low temperatures.

If the epoxy equivalent is less than 150 g/eq, the viscosity of the base resin will be too low and the reactivity will be low, resulting in low adhesive strength. On the other hand, if it exceeds 300, the viscosity becomes too high and diffusion into the uncured hydraulic matrix becomes poor, resulting in a decrease in adhesive strength.

A suitable viscosity for the adhesive is 5 to 100 voids (20°C). If the viscosity is less than 5 poise, the viscosity is too low and it is difficult to apply to a predetermined thickness, while if it exceeds 100 poise, the adhesive will not diffuse into the uncured hydraulic matrix and the adhesive strength will not improve. A reactive diluent, a diluent, a modifier, a reinforcing agent, etc. can be added to the main ingredient, but care must be taken regarding the amount of hardening agent added and the skin irritation of the diluent.

When using a reactive diluent, the content of bisphenol A type epoxy resin in the base resin is 30 to 100%, preferably 50 to 100%.

A water-soluble amine having active hydrogen that reacts with an epoxy group is used as a curing agent. If the curing agent is not water-soluble, it will not diffuse into the uncured hydraulic matrix and the bond strength will not improve. Examples of such water-soluble amines include polyamide amines, aromatic polyamines, aliphatic polyamines, and One or more types of modified products can be mentioned.

A reaction accelerator, a reinforcing agent, a plasticizer, a modifying agent, etc. can be added to the curing agent. The content of the amine in the curing agent is 2
It is 0-100%, preferably 40-100%.

The two-component adhesive of the present invention is used for manufacturing composite members used for architectural members, civil engineering members, and the like.

One side of the composite member is metal plate, stone, concrete, FRP
, wood, etc. Examples of metal plates include steel plates, stainless steel plates, titanium plates, and the like.

In these cases, the adhesive surface is cleaned prior to applying the adhesive. This treatment may be carried out according to a known method depending on each of the above-mentioned materials. For example, in the case of a steel plate, blasting treatment, acid treatment, etc. can be carried out depending on its condition. It is preferable to apply a primer to the adhesive surface before applying the adhesive.

In the case of a metal plate, the appropriate thickness of the primer is about 30 to 200 pm. Adhesive is a mixture of base agent and curing agent and applied to the adhesive surface. The mixing ratio of the base resin and curing agent should be determined so that sufficient strength can be obtained by curing, and the amine equivalent/
A suitable epoxy equivalent ratio is about 0.5 to 2. next,
Figure 1 shows the results of measuring the adhesive strength with different blending ratios of three types of base ingredients and two types of curing agents.

The measurement method was to apply an adhesive containing a mixture of a main agent and a hardening agent to a 120 x 130 x 12 m steel plate, glue a 50 mm x 100 mm mortar with a bolt embedded on top of it, and then pull the embedded bolt upward. , was determined from the tensile force required for peeling.

In the figure, the triangle marks indicate the case where a water-soluble fatty acid-modified polyamide amine with an amine value of 235 g/equivalent and a viscosity of 60 to 120 voids (20″C) is used as the curing agent, and the circle mark indicates the case where the amine value is 265 g/equivalent. /equivalent viscosity is 100-200
The cases in which a water-soluble fatty acid-modified polyamide amine of Poise (25°C) is used are shown. In both circles and triangles, white is the main ingredient and the epoxy equivalent is 217.
Bisphenol A type epoxy resin with a viscosity of 9 to 14 poise (25°C) at 5 g/equivalent, and semi-black with a viscosity of 18 to 20 poise (25”) at an epoxy equivalent of 218 g/equivalent.
C) bisphenol A type epoxy resin, and the black one has an epoxy equivalent of 325 g/equivalent and a viscosity of 20 to 80
The case where Boyes (25°C) bisphenol is used is shown in each case. As shown in this figure, it can be seen that sufficient adhesive strength can be obtained if the mixing ratio of the main agent and curing agent is amine equivalent/epoxy equivalent of 0.5 or more. It can also be seen that the lower the viscosity of the base agent, the higher the adhesive strength. The appropriate amount of adhesive to be applied to the adhesive surface is about 0.1 to 2 mm. The application method can be carried out according to known methods.
Brush application, roller application, spray application, etc. can be used.

The other part of the composite member is a hydraulic matrix such as concrete, mortar, masonry wax, etc. The uncured hydraulic matrix must be cast before the adhesive hardens. After casting, the uncured hydraulic matrix is cured by conventional methods to obtain a composite member.

A composite member bonded with the adhesive of the present invention has a great feature of high adhesive strength. Figure 2 shows the results of a comparison of the adhesive strength between the product of the present invention and various conventional products. The measurement method was to apply various commercially available adhesives to the surface of the steel plate according to the directions for use, and 30 minutes later, concrete was poured.
The adhesive strength was measured after 1 day. Adhesive A is 5B
R - A three-component mixture of acrylic modified latex, blast furnace cement, and blast furnace slag, B is a one-component acrylic emulsion (polymer cement for waterproofing), and C is a two-part mixture of acrylic emulsion and weather-resistant cement. D is a two-part warm-up type of siloxane crosslinking acrylic resin, and E is a two-part warm-up type of epoxy-polyamide resin. In the figure, the ○ mark indicates the adhesive strength between the concrete and the steel plate. Note that the △ mark indicates the adhesive strength when steel plates are bonded together with each adhesive, and the mouth mark indicates the adhesive strength obtained by bonding the steel plate and the hardened concrete plate. Second
As shown in the figure, the adhesive strength between steel plate and concrete when conventional adhesives are used is only about 1 to 6 kgf/cd. On the other hand, the adhesive strength between steel plates using a three-component mixture type is as high as 35 to 45 kgf/d, and even when bonding a hardened concrete plate and steel plate, a two-component heating type using epoxy-polyamide resin has a bond strength of 19 to 24 kgf/d. /cii. These results suggest that the bonding mechanism is different between the case of hardening after pouring and the case of bonding between solid materials.

The product of the present invention uses epoxy as the main ingredient, and
g/eq, viscosity 9 to 14 voids (25°C), water-soluble polyamide amide (molecular weight 10
00, viscosity 50-100 poise) was used.

Needless to say, other laminated materials may be further laminated on the composite member obtained above.

[Effect]

By using a relatively low-viscosity bisphenol A epoxy resin and a water-soluble curing agent, adhesive strength is expected to increase as the adhesive is appropriately diffused and impregnated into the uncured hydraulic matrix and cured. It will be done.

〔Example〕

Example 1 A bisphenol A type epoxy resin (rEP-4520TXJ, manufactured by Asahi Denka Kogyo) having an epoxy equivalent of 217.5 g/equivalent and a viscosity of 9 to 14 voids (25°C) was used as the base resin. To 100 parts by weight of the main resin, 60 parts by weight of a water-soluble fatty acid-modified polyamide amine (rEH-2Q6J, Asahi Denka Kogyo product) with an amine value of 235 g/equivalent and a viscosity of 50 to 100 voids (25'C) was added as a curing agent. Add and mix well.

Grid#100. SIS, Sa 2
．． 5) Then treated with phosphoric acid. The above-mentioned kneaded material was coated on the surface with a bar coater to a thickness of 500 Jrm. Immediately, a mortar of 1 part cement: 2 parts sand: 0.5 water was placed on top of the mold using a φ50 x 100 ann mold and cured for 21 days at 20''C with heating cloth to obtain a composite member.

The adhesive strength between the mortar and steel plate of this composite member was measured and was found to be 26.8 kg/c1i! Met.

Example 2 The main ingredient was 60 parts by weight of ADEKA EP-4520Tx, which is the same as in Example I, and a diluent and an aromatic epoxy resin reactive diluent (Ciba Geigy) to lower the viscosity to enable spray coating. 40 parts by weight of DYO23) and t! A test piece was prepared in the same manner as in Example 1 using 61 parts by weight of H-206. The adhesive strength of this product was 20.6 kg/C1N.

〔Effect of the invention〕

By using the adhesive of the present invention, the adhesive can be applied to the adhesive surface without planting stud angle materials, etc.
A composite member with high adhesive strength can be manufactured simply by placing an uncured hydraulic matrix thereon.

[Brief explanation of drawings]

Figure 1 is a graph showing the relationship between the mixing ratio and adhesive strength of various combinations of base agents and curing agents with different viscosities, etc., and Figure 2 shows the results of measuring the adhesive strength of various commercially available adhesives. It is a graph.

Claims (2)

[Claims] (1) Main material is bisphenol A type or F type epoxy resin with an epoxy equivalent of 150 to 300 g/eq, and is cured with water-soluble polyamine or polyamidoamine having active hydrogen that reacts with epoxy groups, or one or more modified products thereof. A two-component adhesive that bonds a matrix that hardens through a hydration reaction with metal plates, stone, concrete, FRP, wood, etc. (2) Applying a mixture of the main agent and hardening agent according to claim (1) to a metal plate, stone, concrete, FRP, wood, etc.,
A matrix material that hardens through a hydration reaction is placed on the applied surface before the adhesive hardens. Manufacturing method of integrated product