JPS61205676A - Bonding joint material for brick construction - 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] The present invention relates to a room temperature curing adhesive joint material, and in particular a room temperature curing resin suitable for bonding shaped bricks together during brick construction. The present invention relates to an adhesive joint material for brick construction that has strong adhesive properties even at operating temperatures above the combustible temperature range.

[Conventional technology]

For example, long bricks such as the bottom bricks of an exchangeable converter 1
As shown in Figure 1, when brick supports are stacked vertically on hardware 2,
Even if the bricks are placed in close contact with each other during construction, if the joint mortar does not harden at room temperature or the adhesive strength is insufficient with conventional joint materials, the bricks' own weight and dimensional accuracy may be slightly affected. As shown in Figure 2, this variation caused variations in joint thickness and distortion in the arrangement of bricks, making it impossible to build as designed. If variations in joint thickness or distortion in the brick arrangement occur in this way, the bricks will be heated from multiple sides during operation.
At the same time, the thermal spalling tendency of the bricks is further exacerbated because adjacent bricks abut each other at points or lines due to thermal expansion. Therefore, in order to prevent thermal spalling of the bricks, it was necessary to construct the bricks in such a way that the bricks were in surface contact with each other.

Traditionally, joint mortar has generally been mixed with water, but for converter bricks whose main components are easily hydrated substances such as MgO and CaO, thermosetting phenol is used. A non-aqueous solution such as a resin is often used, and MgO-based powder is usually used as a filler in consideration of corrosion resistance to FeO.

When curing the phenol resin itself at room temperature, a weak acid such as an organic acid may be added, for example.

When acid is added to furan-based phenolic resin-MgO-based mortar, the MgO hardens first, and the hardening of the phenol resin is delayed, causing the phenol resin to separate and become unsuitable for practical use.On the other hand, if the filler in the mortar is From AQ20. If substituted with F, etc., the resin can be cured at room temperature by adding a weak acid, but the basicity is high and F
As a joint material for converter bricks that are subject to slag attack that contains a large amount of eO, AQ2 is recommended in terms of chemical corrosion resistance.
0. It was also not appropriate to replace it with

In addition, since the organic components of resins that cure at room temperature are combusted when heated, the adhesion between bricks at elevated temperatures and high temperatures in a high-temperature furnace such as a converter has not been sufficiently satisfactory.

[Problem that the invention seeks to solve]

As a countermeasure to this problem, conventionally, fillers such as clay minerals were added to epoxy resin as an adhesive that hardens at room temperature.
Bonding strength in a high temperature range was obtained by forming a ceramic bond at a temperature of 1000°C or higher.

However, in the case of joint materials in brick furnaces, only high temperatures are required in response to continuous temperature changes due to the temperature gradient between the working side and the shell side, which come into contact with the molten steel generated inside the bricks of the furnace body during use. In addition, it is necessary to maintain adhesive strength even in the intermediate temperature range of, for example, 300 to 1000°C, and the development of a means to solve this problem has been awaited.

The inventors of the present invention have conducted intensive studies to solve these problems with conventional adhesives, and as a result, have discovered a novel adhesive joint material for brick construction, which will be described below.

The object of the present invention is to provide a relatively fast-curing, room-temperature curing type that is made of a hydratable filler such as MgO or CaO and a non-aqueous solution, and that is free from temperature changes that occur in the furnace during use.
An object of the present invention is to provide an adhesive for brick construction that has excellent adhesive properties even at high temperatures (intermediate temperature range) and high temperatures (high temperature range).

[Means for solving problems]

The present invention includes a fire-resistant powder, an epoxy resin, a room-temperature curing agent,
The gist of this is an adhesive joint material for brick construction, which is made by mixing a sintering aid that develops adhesive strength in an intermediate temperature range and a sintering aid that develops adhesive strength in a high temperature range. be.

The present invention will be explained in detail below.

The adhesive joint material of the present invention is composed of a liquid part (epoxy resin and its curing agent) and a powder part, and the two are appropriately kneaded together in consideration of workability.

The liquid part is a so-called two-component epoxy resin.

The powder part acts as a so-called joint filler, and M is made with a sintering aid (binder) added according to high-temperature usage conditions.
gO, Cab, A1220. ．． Various refractory powders such as 5iOz+ZrO are used.

As the main ingredient of the liquid part used in the present invention, epoxy is used. Epoxy resins are well-known compounds having at least two epoxy groups in one molecule, and include glycidyl epoxy resins and non-glycidyl epoxy resins6. For example, among glycidyl epoxy resins, glycidyl ethers include bisphenol A diglycidyl ether.

diglycidyl ether of resorcinol, diglycidyl ether of halogenated bisphenol A, diglycidyl ether of bisphenol F, diglycidyl ether of butanediol, diglycidyl ether of polypropylene glycol, triglycidyl ether of glycerin,
Examples of glycidyl esters include triglycidyl ether of trihydroxyphenylpropane and glycidyl ether of phenol borac resin.

Examples include phthalic acid glycidyl ester, diglycidyl ester of lyluic acid dimer, and examples of the glycidyl amines include N-glycidylaniline, glycidyl ether of P-aminophenol, and glycidylamine. Furthermore, non-glycidyl epoxy resins include epoxidized polyolephane, epoxidized soybean oil, and vinyl tsuku. Examples include hexene dioxide.

Further, as the upper curing agent used in the present invention, a polyamine curing agent is suitable. Polyamine-based curing agents are known as polyamines having two or more amino groups or modified products thereof. As polyamines, resinous polyamines include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dimethylaminopropylamine, diethylaminopropylamine, xylylenediamine, N-aminoethylpiperazine, 1,3-bisaminomethylcyclohexane, isophoronediamine, etc. can be,
Examples of aromatic polyamines include metaphelene diamine and diaminodiphenylmethane. However, when aromatic polyamines are used, a curing catalyst such as carboxylic acid or tertiary amine is required since these do not harden at room temperature. Modified products of the polyamines include amine adducts, which are addition reaction products with other compounds such as epoxy resins, acrylic compounds, and phenolic resins;
Examples include polyamide resins that are condensates with dicarboxylic acids such as dimer acids and fatty acids, and monocarboxylic acids.

Although polysulfite resin is another room-temperature curing epoxy resin curing agent, it does not cure sufficiently by itself, so it is desirable to use it in combination with other polyamine curing agents.

In the case of MgO, natural magneside, seawater magnesia, sintered magnesia, etc. may be cited as raw materials for the fire-resistant powder that is mixed with such two-component epoxy resin and acts as a joint agent. ni, Cab, Sin,
, AQ20. , ZrO.

It is also possible to use one type or a mixture of two or more types of refractory powders such as . When used as a refractory powder, these are used as raw materials, pulverized, blended in particle size, and used with the particle size composition changed depending on the required joint thickness.

In order to ensure strength at 300 to 1000°C, such a refractory powder is coated with alkali silicate or the like.

Additives such as phosphate compounds, and a suitable amount of sintering aids such as clay minerals that help form a ceramic bond at temperatures above 1000''C are added.

In addition, the two-component epoxy resin may contain a curing accelerator, a reactive diluent represented by a monoexoxy compound, as necessary.
Non-reactive diluents such as solvents and plasticizers, and anti-settling agents that prevent fillers from settling.

Anti-sag agents and the like may also be added.

The room-temperature curing adhesive of the present invention described above is composed of an epoxy resin, a room-temperature curing agent, and a refractory powder material to which a sintering aid has been added, and these can be used by kneading appropriate amounts of each at the brick construction site. be able to.

〔Example〕

EXAMPLES The present invention will be explained in more detail by examples below, but the present invention is not limited to the following examples unless it exceeds the gist thereof.

Examples 1 to 4 Bricks were bonded using the adhesive shown in Table 1, and the coating properties and
The curability and adhesion were tested and as shown in Table 1, the coating properties were good, the curability (room temperature curability) was no problem in terms of time, and the adhesive strength was also extremely good. Got the results.

Comparative Example 1 is the formulation of Example 1 or 2 in which only the clay as a high temperature sintering aid and the clay as an intermediate temperature range sintering aid are removed, and Comparative Example 3 is the same as in Example 1 or 2. This is the formulation in which only the phosphate compound, which is an intermediate temperature range sintering aid, is removed. Bricks were bonded using the adhesives of each comparative example, and the coating properties, curability, and adhesion when cured at room temperature and 1500°C x 4 hrs were the same as in Example 1 or 2.
The hot adhesion properties were tested and compared under the following conditions and after heating at 500°C for 4 hours.

Comparative Examples 1 or 2 and 3 excluding the sintering aid as shown in Table 1
Although good results were obtained in terms of coating properties, curing properties, and adhesiveness when cured at room temperature as in Examples 1 and 2, in terms of adhesive strength after heating at elevated temperatures, it was compared with Examples. A significant decrease in strength was observed. This is because a ceramic bond is not formed by each sintering aid that is suitable for each firing temperature, and it is clear from these results that the sintering aid, which is an essential component of the adhesive of the present invention, is highly effective. be.

The coating method was determined based on the results of the 11JL Festival regarding workability and sagging when the mixed adhesive was applied to bricks using a trowel. Curability was measured at 25° C. as the time until the bonded bricks no longer peeled off when pulled by hand. Also, the adhesiveness.

After curing the bonded bricks at 25°C for 3 days, J
According to IS-A-6024, the bending strength of the adhesive 4 between the bricks was measured at the position shown in FIG. 3 (a = 4a++, b = 12an).

In this case, the brick 3 which is the test specimen is 4 am x 4 a
A 12 dll rectangular parallelepiped, bending test 10 m
/ min conditions.

The adhesion (heating) was measured by heating the test specimens tested for adhesion at 1500°C for 4 hours for -1 and 500°C for 4 hours for medium 2, and then cooling them to room temperature.

1) Epicron 855: Diglycidyl ether of bisphenol A general-purpose low viscosity type (Dainippon Ink Co., Ltd. 11) 2) Laccamite EA-: Boryamide resin, filling 233
Modified (Dainippon Ink Co., Ltd. IIri 3) Laccamite TD-: Polyamide resin, low viscosity 950
degree, high strength type (Dainippon Ink Co., Ltd. iB)
) 4) Laccamite WH-: modified aliphatic polyamine, 10
8 Low viscosity, high strength type (manufactured by Dainippon Ink Co., Ltd.) 5) Carplex: Fine powder silicic acid, anti-sag agent (manufactured by Shionogi & Co., Ltd.) Example 5 Replacement bottom for 85TON top-bottom blowing converter Magnesia lime long bricks (150mm x 150 x 500mm)
) was constructed using the same adhesive as in Example 3.

As a result of the construction, we used a room-temperature curing adhesive for the joints, so the joints maintain a predetermined thickness and harden at room temperature, allowing the bricks to firmly adhere to each other and move when external forces are applied, such as when transporting the construction. Kotona〈The problems of the past have been completely resolved.

In addition, the variation in brick joints, which was an average of ±1.5 mm with the conventional phenol resin adhesive, was improved to an average of ±0.5 mm by the present invention. In addition, after heating operation, the movement of the bricks due to thermal expansion can be evenly distributed to each joint, so the bricks receive heat only in one direction on the heat-receiving surface, reducing the tendency for thermal spalling. Greatly relieved and therefore.

The life of the furnace bottom bricks was improved by 1.4 times compared to the conventional phenol resin adhesive.

〔Effect of the invention〕

As detailed above, according to the adhesive joint material for brick construction of the present invention, it is possible to bond with sufficient strength at room temperature, the curing time is quick, and the coating properties and corrosion resistance are also good. In addition, workability can be adjusted arbitrarily using the top size of the grains of the joint material and the viscosity of the resin as main parameters, so it is possible to bond and build according to the thermal characteristics of non-adhesive materials such as bricks.

The adhesive material for brick construction of the present invention can withstand a wide range of operating temperature conditions from room temperature to high temperatures and is extremely useful industrially.

[Brief explanation of drawings]

Figure 1 is a side view illustrating how long bricks are stacked vertically, Figure 2 is a side view illustrating variations in joint thickness in the vertical stacking of Figure 1, and Figure 3 is the adhesive properties in Examples 1 to 3. FIG. 2 is a side view illustrating a test method.

Claims (1)

[Claims] (1) It is made by mixing fire-resistant powder with an epoxy resin, a room-temperature curing agent, a sintering aid that develops adhesive strength in the intermediate temperature range, and a sintering aid that develops adhesive strength in the high-temperature range. Adhesive joint material for brick construction.