JPH0655932B2 - Adhesive composition for decorative material and method of using the same - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an adhesive composition for decorative material and its use. More specifically, the present invention relates to an adhesive composition for a decorative material, which exhibits a high adhesive strength by curing for a short time and is excellent in waterproof property, and a method of using the same. In addition,
In this specification, the decorative material includes all elements such as tiles, stones, terrazzo, etc. that are attached as finishing materials or decoration materials to the surface of various building materials or panels such as PC plates, cement extruded boards, ALC plates, etc. It is a concept. Less than,
In the present specification, the present invention will be described by taking a tile, which is a typical decorative material, as an example.

[0002]

2. Description of the Related Art Recently, the demand for tiles has been increasing every year because the high quality and weight of tiles have been favored by the market. However, the production volume of the tile itself can meet the market demand due to the modernization of the tile manufacturing factory, but due to the lack of skilled workers to actually install the tile, it is not possible to meet such demand in terms of construction. There is a situation. In addition, the importance of on-site management is strongly emphasized as there is a risk of accidental stripping of tiles. In addition, the demand for PC and ALC plates is increasing with the recent demand for shorter construction period in the construction field.

For this reason, tile construction is being performed in the factory as a part of the panel production line, rather than on-site tile construction.

However, the conventionally used tile mortar for adhering tiles has been prepared in consideration of sticking tiles on a vertical surface because it is for on-site construction. That is, the composition is determined such that the tile mortar does not move downward by its own weight and does not move, that is, so-called "drip" does not occur. However, in the tile construction in the factory, it is completely meaningless to "do not sag" because the tiles on the horizontal surface are more lineable than the vertical surface, and on the contrary, it is difficult to spread on the surface, which is a negative factor. turn into.

In order to increase the panel productivity,
It is necessary to shorten the hardening and curing time of cement.

[0006]

DISCLOSURE OF THE INVENTION The present invention provides an adhesive composition having high fluidity and exhibiting high adhesive strength at an early stage, which is suitable for construction of tiles on concrete panels in a factory. The purpose is to do.

[0007]

In view of the above circumstances, the inventors of the present invention have earnestly studied an adhesive composition suitable for tile construction in a factory, and as a result, have used a phosphate ester as a diluent. The adhesive composition consisting of the epoxy resin composition and the cement mortar, which has a high flowability, exhibits high adhesive strength at an early stage, and is also excellent in waterproofness, and to complete the present invention. I arrived.

The adhesive composition for a decorative material of the present invention is an epoxy resin composition comprising (a) a main component composed of a bisphenol type epoxy resin and a non-reactive diluent of a phosphoric acid ester type, and a curing agent composed of polyamidoamine. 5 to 40% by weight, and (b) 95 to 60% by weight of a cement mixture consisting of cement, fine aggregate and water reducing agent.
Further, the method of using the adhesive composition for decorative material of the present invention is to apply the adhesive composition on a panel placed horizontally in the presence of water, and to apply the adhesive composition within the open time of the adhesive composition. The feature is that the material is pasted on the panel and then cured for a predetermined time.

[0009]

EXAMPLES The decorative adhesive composition of the present invention (hereinafter referred to as an adhesive) comprises an epoxy resin composition and a cement mixture. Of these, the epoxy resin composition is composed of a main agent and a curing agent.

The main component is composed of a bisphenol type epoxy resin and a phosphate ester-based non-reactive diluent.

A typical example of the bisphenol type epoxy resin which constitutes the main component is a resin formed from bisphenol A and epichlorohydrin. This bisphenol A
Type epoxy resin has an average molecular weight of about 340-400, 25
Viscosity at ℃ is about 50 ~ 200 poise, epoxy equivalent is about 170
Liquids of up to 230 are preferably used. Various bisphenol type epoxy resins such as bisphenol F type other than bisphenol A type epoxy resin can also be used.

The non-reactive diluent added to the main component is
The purpose of the present invention is to reduce the viscosity of the epoxy resin and make it easier to use, but in the present invention, a phosphate compound is used. Typical examples of the compound include trimethyl phosphate, triethyl phosphate, tributyl phosphate and the like.

In a general-purpose epoxy adhesive, a phthalate ester compound is generally used as the non-reactive diluent, but in an epoxy adhesive using this phthalate ester compound, When water enters the resin, the reaction between the resin and the curing agent does not proceed, and as a result, the curing of the resin is hindered. The phosphate ester-based diluent used in the present invention prevents curing inhibition due to water that has penetrated into the resin and allows sufficient curing of the resin even in an environment with water. Although its mechanism of action has not been elucidated, the phosphate ester reacts with the water that has entered the resin and is hydrolyzed, resulting in the consumption of water, and as a result, the reaction between the resin and the curing agent is affected by water. It is speculated to be avoidable.

The blending ratio of the bisphenol type epoxy resin and the non-reactive diluent varies depending on the type of the diluent, but 3 to 40 parts of the diluent is added to 100 parts of the bisphenol type epoxy resin (weight part, the same applies hereinafter). It is preferably used in the range. If the proportion of the diluent exceeds the above range, there is a problem that the strength of the cured product decreases, while if it is less than the above range, there is a problem that the water in the composition system inhibits the curing, which is not preferable.

The curing agent used in the epoxy resin composition is composed of one or more polyamidoamines.

The polyamidoamine has a molecular weight of about
A low molecular weight polyamidoamine of about 200 to 800 is preferably used. Although various kinds of amines are known as a curing agent, the polyamide amine is used in the present invention in view of the length of open time, relatively large blending ratio, and relatively low viscosity. The polyamidoamine may be used in one kind, but since it has solubility in water, it is preferable to use two or more kinds in consideration of the viscosity balance of the composition and the strength balance of the cured product. Specific compounds include reaction products of a linoleic acid dimer and an ethylenediamine derivative.

The ratio of the curing agent to be used is preferably in the range of 30 to 100 parts by weight with respect to 100 parts by weight of the main agent. If the amount of the curing agent exceeds the above range, the adhesive strength can be maintained, but the strength is lowered and the heat resistance is also deteriorated. On the other hand, if the amount is less than the above range, the strength of the cured product will be high but the adhesive force will be insufficient.

It is preferable to add a tertiary amine as a curing aid to the curing agent. The tertiary amine has the functions of accelerating the curing and improving the adhesive strength to the adherend (base and tile) after the curing. Further, by increasing the amount of the tertiary amine, it is possible to accelerate the curing and further improve the adhesive strength.

As the tertiary amine, compounds which have been conventionally used as a curing accelerator for epoxy resins, such as dimethylbenzylamine, imidazoles and n-AE, are used.
One or two or more such as P can be used.
The mixing ratio of the polyamidoamine and the tertiary amine varies depending on the types of the polyamidoamine and the tertiary amine, but the tertiary amine is used in the range of about 1 to 10 parts per 100 parts of the epoxy resin. If the proportion of the tertiary amine exceeds the above range, there is a problem that the water resistance is lowered and the strength is lowered.

The cement mixture in the present invention is a mixture of cement such as early strength Portland cement, ordinary Portland cement, white Portland cement and fine aggregate and a water reducing agent. The mixing ratio of the fine aggregate is not particularly limited in the present invention, but usually cement 100
The range is 50 to 200 parts for fine aggregate.

Since the adhesive of the present invention is mainly intended for tile installation on a horizontal surface, it requires high fluidity. Therefore, it is possible to provide fluidity by increasing the amount of water. As a general concept of mortar, it is said that the mortar strength develops faster when a large amount of water is retained in the mortar system. However, in the present invention, since the epoxy resin and the polyamidoamine are contained in the composition, the presence of 2.5 times (by weight) or more water of these resin components is disadvantageous in that the strength development is delayed and the adhesive strength is lowered. Therefore, in the adhesive of the present invention, an appropriate amount of a water reducing agent (fluidizing agent) is added to the cement mixture in order to reduce the amount of water used while having high fluidity.

As the water reducing agent used in the present invention, an amino resin such as a sulfonated melamine type, for example, Melment manufactured by Showa Denko KK, Sikament FF manufactured by Nippon Sika Co., Ltd., P-300 manufactured by Hoechst Synthetic Co., Ltd. is used.

Conventionally, casein is generally used as a water reducing agent for mortar. However, casein is not suitable because it tends to delay the hardening of mortar on the one hand and adversely affects the rapid hardening property which is the object of the present invention. On the other hand, the amino resin-based water reducing agent is characterized in that it does not delay the hardening of the mortar, and conversely tends to accelerate the development of strength. The water reducing agent is used in an amount of 0.5 to 5 parts per 100 parts of cement, particularly preferably 1.5 parts.
The range is up to 2.5 copies. If it is less than the above range, there is almost no flow effect and the water content must be increased, and if it exceeds the above range, the mortar working water tends to float on the surface (material separation) and the flow effect decreases, resulting in adhesion to tiles. There is a problem of inhibiting sex.

In the adhesive of the present invention, the ratio of the epoxy resin composition as the component (a) and the cement mixture as the component (b) varies depending on the surface condition of the material to be adhered and the like, but usually the component (a) is 5 to 5%. 40%, preferably 9 to 20%, and the component (b) is used in the range of 95 to 60%, preferably 91 to 80%. If the component (a) is less than the above range, it is not sufficient in terms of early development of adhesive strength, high adhesive strength, and waterproofness, and if the component (a) exceeds the above range, the cured composition becomes flammable. And the adhesive strength and the strength of the cured product decrease remarkably, which is not preferable.

The adhesive of the present invention is used by mixing the epoxy resin composition and the cement mixture in the presence of water. The amount of water added is generally in the range of 30 to 50 parts per 100 parts of cement. If the amount is less than the above range, sufficient water cannot be secured for the hydration reaction of cement, curing failure may occur, and the fluidity which is the object of the present invention may not be obtained, which is not preferable. On the other hand, when the amount exceeds the above range, a large amount of water is contained in the composition system of the present invention, which delays the development of strength and reduces the adhesive strength, which is not preferable.

The mixture obtained by adding water to the above-mentioned adhesive composition of the present invention can obtain high strength and waterproofness from an early stage which are not found in conventional adhesives. Conventionally, cement was sometimes mixed with epoxy resin, but in that case, the cement was treated as a filler. In other words, it was only an aggregate and gave only the same effect as calcium carbonate and sand. This is because the conventional epoxy adhesive has never considered mixing water.

However, since the phosphoric acid ester compound is used as the diluent for the epoxy resin composition in the adhesive of the present invention, it becomes possible to mix water, and as a result, the cement is cured to obtain the strength and strength of the cement. The adhesive strength can be exerted.

On the other hand, when viewed from the tile mortar side, by mixing the epoxy resin composition, it is possible to develop high adhesive strength with waterproofness and curing for a short time which have not been hitherto known.

In short, when a normal epoxy adhesive and mortar are mixed, the water for the hydration reaction of cement inhibits the reaction between the epoxy resin and the curing agent. In this respect, it can be said that the mortar and the epoxy-based adhesive are mutually incompatible materials, but in the present invention, by adopting the above-mentioned configuration, these incompatible materials are bound to each other to obtain a high-quality tile mortar. Could be realized.

Next, a method for producing the adhesive of the present invention and a method for using the same will be described.

First, the main component and the curing agent constituting the epoxy resin composition are weighed in predetermined amounts and uniformly kneaded. Then, the cement mixture obtained by previously measuring and mixing predetermined amounts of cement, fine aggregate and water reducing agent is added to the epoxy resin composition. Water is added to the mixture and kneaded. In this case, it is preferable to add about half the amount and knead first, and then add the remaining water so that the epoxy resin is uniformly dispersed in the mortar and not kneaded at once. . Further, it is also possible to mix a mixture of the main component and the curing agent that make up the epoxy resin composition, and a mixture of water and a cement mixture. In this way, the adhesive of the present invention can be obtained. An appropriate device such as a mortar mixer can be used for kneading.

Next, the method of using the adhesive prepared as described above will be described by taking the case of attaching a tile to a panel as an example.

First, the PC plate or AL to which the adhesive should be applied
Clean the surface of the panel such as C plate, and then apply the adhesive evenly to a thickness of 2 to 6 mm on the panel surface placed horizontally using a roller, spatula, and trowel. The tile is then attached to the surface of the panel within the open time of the adhesive (usually 15-30 minutes at room temperature). After the tiles have been attached, curing is performed for about 3 hours, and then tile jointing is performed, and then curing is performed for about 1 to 2 days after completion of the jointing. With conventional tile mortar, it usually takes about 10 to 28 days to develop strength, but with the adhesive of the present invention, the product can be shipped in a curing period of only about one day, thus improving panel productivity. It becomes possible.

Next, the adhesive of the present invention will be described based on Examples, but the present invention is not limited to such Examples as a matter of course.

Example 1 Bisphenol A type liquid epoxy resin 80 having a molecular weight of about 400
Parts and 20 parts of triethyl phosphate as a diluent, 45 parts of polyamidoamine having a molecular weight of about 600 as a hardening agent and 5 parts of dimethylbenzylamine as a hardening aid are added.
The mixture was mixed and stirred for 5 minutes with a mortar mixer. Then, 1500 parts of a cement mixture prepared by mixing 1000 parts of powder cement, 1000 parts of silica sand and 20 parts of Melment made by Showa Denko KK as a water reducing agent were mixed. Then, 200 parts of water was added to the mixture and stirred for 5 minutes, and 100 parts of water was further added and stirred for 5 minutes to prepare an adhesive composition.

The obtained adhesive composition was applied onto a concrete plate (300 mm × 300 mm) whose surface had been cleaned beforehand using a gold iron. The coating thickness of the adhesive was about 2 mm.

Then, a porcelain mosaic tile (45 mm × 45 mm) was stuck on the panel within the open time (about 10 minutes) of the applied adhesive. After fully striking the tiles with a hammer pattern, they were cured for about 48 hours.

The adhesive strength of the tiles of the obtained panel was measured by the Kenken test method. Standard time (Temperature 20 ℃,
The adhesive strength at a humidity of 65%) is 22 kg as an average value of 5 samples.
f / cm ² , and the adhesive strength when immersed in water at a temperature of 20 ° C for 7 days was also 20 kgf / cm ² on average.

The waterproofness of the obtained adhesive was confirmed by using the device shown in FIG. In Figure 1, (1) is
It is a concrete plate of 300 mm × 300 mm × 30 mm (length × width × thickness), and the adhesive (2) according to this example is applied to the surface of the concrete plate so as to have a thickness of 3 mm and cured for 7 days ( The temperature was 20 ° C. and the humidity was 65%). Then, the cylinder (3) was set as shown in FIG. 1, the contact part was sealed with a sealing material (4) so that water did not leak, and then distilled water was added to a height of 20 cm. To prevent water from evaporating, put a stopper (5) on the top surface and leave it in a temperature-controlled room for 1.
3,5,24, and 48 hours later by measuring the water-reducing amount, a water permeation rate per unit area than its water reducing weight, water permeation rate (ml / cm ²⁾
= Amount of water reduction (ml) ÷ contact area (cm ² ) The results are shown in Table 1. From Table 1, it can be seen that the adhesive of this example does not allow water to permeate at all and has extremely high waterproofness.

[0040]

[Table 1]

Comparative Example 1 Tile mortar as an adhesive [1000 parts of cement, 1000 of sand
Parts, water retention agent (methyl cellulose) 3 parts, ethylene-vinyl acetate copolymer emulsion (solids 100 parts, water 500
Part)] was used in the same manner as in Example 1 to attach tiles.

[0042] The adhesive strength of the tiles was subjected to the same tests as in Example 1, 5 kgf / cm ² at Time was 0 kgf / cm ² in water immersion. A waterproof test was conducted in the same manner as in Example 1. The results are shown in Table 1, and water permeation was recognized around 24 hours.

Comparative Example 2 Tile mortar as an adhesive (1000 parts of cement, 1000 of sand)
Parts, water retention agent (methyl cellulose) 3 parts, water 600 parts) were used in the same manner as in Example 1 to apply tiles.

When the same test as in Example 1 was conducted on the adhesive strength of the tile, it was 0 kgf / cm ² even when immersed in water as a standard of 0 kgf / cm ² . A waterproof test was conducted in the same manner as in Example 1. The results are shown in Table 1, and water permeation was recognized after 3 hours.

[0045]

As described above, according to the adhesive of the present invention, a mixture of an epoxy resin using a phosphoric acid ester system as a diluent and a cement mortar containing a water reducing agent is used. Since high fluidity is obtained at the time of construction, the construction is facilitated, and sufficient adhesive strength can be obtained early after construction so that the production period of the production line can be shortened. Further, since the epoxy resin is mixed with the mortar, it is possible to obtain waterproofness which is not available in conventional mortar.

[Brief description of drawings]

FIG. 1 is an explanatory diagram of an apparatus used for a waterproof property test in Examples and Comparative Examples.

[Explanation of symbols]

 1 Concrete board 2 Adhesive 3 Cylinder 4 Sealant 5 Stopper

Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location C08K 5/521 NLB 7242-4J // (C04B 28/02 24:24)

Claims (3)

[Claims] 1. An epoxy resin composition comprising 5 to 40% by weight of (a) a main component comprising a bisphenol type epoxy resin and a non-reactive phosphate-based diluent, and a curing agent comprising a polyamidoamine, and (b) ) An adhesive composition for decorative material, which comprises 95 to 60% by weight of a cement mixture containing cement, fine aggregate and a water reducing agent. 2. An epoxy resin composition comprising 4 to 35% by weight of (a) a main agent comprising a bisphenol type epoxy resin and a non-reactive phosphate ester diluent and a curing agent comprising polyamidoamine, and (b) ) An adhesive composition for decorative material, which comprises 96 to 65% by weight of cement mortar consisting of cement, water, fine aggregate and a water reducing agent. 3. The adhesive composition for decorative material according to claim 2 is applied to a panel placed horizontally, the decorative material is attached to the panel, and then cured for a predetermined time. Adhesion method for decorative materials.