KR100789109B1 - A mixing ratio and manufacturing method of a water soluble epoxy 2 componant adhesives for ceramic tiles - Google Patents

Abstract

A two pack type water-soluble epoxy resin-based adhesive composition for a ceramic tile is provided to improve water fastness, heat resistance, adhesive strength and curing velocity, to reduce the uncuring at a low temperature and to enhance environmental friendliness. A two pack type water-soluble epoxy resin-based adhesive composition comprises a base which comprises 30-40 wt% of a water-soluble epoxy resin, 0.05-0.1 wt% of a dispersant, 0.1-0.5 wt% of a preservative, 0.1-0.5 wt% of a thickener, 0.05-0.1 wt% of a pH controller, 0.3-1.0 wt% of a silane coupling agent, 45-60 wt% of a filler, and 5-15 wt% of a diluting solvent; and a curing part which comprises 10-20 wt% of a water-dispersible polyamine-based curing agent, 0.05-0.1 wt% of a dispersant, 0.1-0.5 wt% of a preservative, 0.3-1.0 wt% of yellow soil, 0.05-0.1 wt% of a pH controller, 0.01-0.1 wt% of an antifoaming agent, 60-70 wt% of a filler, and 10-20 wt% of a diluting solvent.

Description

Composition of adhesive for two-component water-soluble epoxy resin-based porcelain tiles {A mixing ratio and manufacturing method of a water soluble epoxy 2 componant adhesives for ceramic tiles}

The present invention is a two-component water-soluble epoxy resin-based porcelain tile adhesive that significantly improves the problems caused by water resistance, heat resistance, curing speed, especially uncured at low temperatures, the construction of the crimping method It has excellent workability and construction quality, and it is an environmentally friendly and human-friendly tile adhesive that hardly detects formaldehyde and volatile organic compounds (VOCs) that are harmful to humans because it does not use formaldehyde or organic solvents. .

There are two types of tile adhesives currently widely used, one of which is an organic tile adhesive and the other is an organic / inorganic mixed adhesive mainly composed of hydraulic polymer cement. Among them, the organic tile adhesive is excellent in workability as a one-component paste, but vulnerable to water, and it takes a long time to cure due to hardening of the natural drying method, and it may smell the chemicals of the adhesive for a long time, and it may interfere with the subsequent process. It is possible to use the site is very limited. That is, it can be used only on the inner wall of the building, which can be protected from moisture, and can be used only on new buildings that are less affected by the curing time. There is a water-soluble tile adhesive of Korea Patent Application No. 2003-0015565 and an aqueous emulsion adhesive for ceramic tile adhesion excellent in water resistance and adhesion of Patent No. 10-0510324, and an oil-based adhesive for ceramic tile of Patent No. 2001-0100102. Water-soluble tile adhesives are excellent in water resistance and alkali resistance, and the main component is an acrylic emulsion with a high solid content, which maintains the adhesive strength during the immersion test in dry water and alkali water. It is a tile adhesive whose use is limited to the bathroom and kitchen wall except home shower booth, and the aqueous emulsion adhesive for ceramic tile adhesion with excellent water resistance and adhesion of the registered patent 10-0510324 is mainly composed of abietin acid. Natural rosin in the molecular chain with epoxide or amide After producing rubber modified rosin by reacting with low molecular weight liquid rubber, it is vulnerable to adhesives for tiles and long-term water resistance strength and curing time by using it. The adhesive may have good water resistance, but may have an adverse effect on the environment and the human body by using an organic solvent, which is very difficult to use indoors. In addition, the organic-inorganic mixed adhesive mainly composed of hydraulic polymer cement has a short open time for attaching tiles, a high possibility of poor construction quality due to water mixing at the construction site, and contaminates the environment due to dust generation. have. Therefore, excellent construction quality, such as long-term water resistance, heat resistance, curing speed, open time, and research on environmentally friendly and human-friendly tile adhesives without using formaldehyde and organic solvents are urgently needed.

In order to overcome the problems of the prior art as described above, the present invention is designed to enable tile adhesion of walls and floors using a water-soluble epoxy resin and a water-dispersible polyamine-based curing agent as the main raw materials containing hydrophilicity in the molecule and dispersed in water. . It has excellent construction quality such as long-term water resistance, heat resistance, curing speed, and open time. It is environmentally friendly without using formaldehyde and organic solvents, and is human-friendly. The present invention provides a method for producing a two-component water-soluble epoxy resin-based porcelain tile adhesive, which enables tile construction of exterior walls and floors, and is divided into a main portion and a hardener portion.

When explaining the two-component water-soluble epoxy resin-based ceramic tile adhesive according to the present invention in detail.

The present invention is divided into the main portion and the curing agent portion with respect to the whole composition,

(1) Topics

30-40 wt% water-soluble epoxy resin, 0.05-0.1 wt% dispersant, 0.1-0.5 wt% preservative, 0.1-0.5 wt% thickener, 0.05-0.1 wt% ph regulator, 0.3-1.0 wt% silane It has a composition containing a coupling agent, 45-60 weight% filler, and 5-15 weight% dilution solvent.

(2) Curing agent

10-20 wt% water-dispersed polyamine curing agent, 0.05-0.1 wt% dispersant, 0.1-0.5 wt% preservative, 0.3-1.0 wt% ocher, 0.05-0.1 wt% ph regulator, 0.01-0.1 wt% Antifoaming agent, 60 to 70% by weight of filler, and 10 to 20% by weight of diluent.

Water-soluble epoxy resin refers to a resin that has an epoxide functional group in the molecule, and has a hydrophilic functional group which can be emulsified and dispersed in water, and its use may vary depending on molecular weight or equivalent weight. The most basic resin of water-soluble epoxy resin is Bis-Phenol A-type epoxy resin and Novolac, Brome, Rubber, and Urethane modified resins, but it has excellent storage stability and high crosslinking density after curing, and is excellent in mechanical and chemical properties. A low equivalent resin having a molecular weight of about 200 to 700 so as to exhibit adhesive strength, the particle size of which is smaller than 1 μm, the solid content is 70 to 90% by weight, and an epoxy equivalent of 100 to 350 g / eq bisphenol A type epoxy resin is used. It is desirable to.

The dispersant functions to evenly disperse the solids in the composition, and a product of BYK, which is a block copolymer solution of a polymer having a pigment affinity group, is used.

As the preservative, benzoic acid, silicic acid, formalin and the like can be used. However, formalin is very irritating to humans and should be avoided if possible. Water-soluble epoxy resin-based porcelain tile adhesives use natural products to improve their thickening and adhesion. Therefore, when the temperature and humidity are high in summer, they may be deteriorated and deteriorated by microorganisms, so an appropriate amount of preservative must be added.

Thickeners are used to maintain high viscosity and to have excellent phoxotropy properties that show flowability when subjected to external forces. However, if the amount of thickener used is large, workability and water resistance deteriorate due to water absorption, so be careful. As a thickener, a salt salt of an acrylic resin is usually used.

The pH control agent uses a strong base such as ammonium hydroxide as the pH of the whole composition.

The silane coupling agent is classified into amino, epoxy, acrylic, vinyl and other silane coupling agents. The silane coupling agent contains a hydrolyzable group such as an alkoxy group and an organic functional group such as an epoxy to help the organic material and the inorganic material to be bonded to each other. Epoxy-based silane coupling agent of 3-Glycidoxypropyltrimethoxysilane is used.

The filler uses calcium carbonate (CaCO ₃ ) or silica sand, it is used to maintain the proper particle size in the product to shorten the drying time, to maintain workability, preferably oil absorption (25 ± 3) ml / 100g Calcium carbonate with average particle size (8 ± 2) ㎛ and pot weight (0.7 ± 0.1) g / mL is used.

Water is used as the diluting solvent. Water should be used with caution as the change in viscosity is remarkable even with small amounts of water.

Epoxy resin alone can not exhibit the physical properties, it is possible to cure only by using an epoxy resin curing agent, excellent physical properties. Polyamines, polyamides, acid anhydrides, etc. are mainly used as epoxy resin curing agents, but the curing agent for water-soluble epoxy resins has a hydrophilic group in the molecule and is dispersed in water, and has good compatibility with water-soluble epoxy resins to increase the crosslinking density. A water-soluble polyamine-based curing agent having a solid content of 70 to 90% by weight and active hydrogen equivalent weight of 80 to 100 g / eq can be used.

Ocher is used to improve the eco-friendly performance of the product and to express the color of the curing agent. It has a particle size of 0.02 to 0.05 mm and contains coarse and neutral dust. The porosity is about 60% and the density is 1.5. g / cm 3, specific gravity is 2.7 on average, and the chemical composition of ocher is 50 to 60% by weight of silica (SiO ₂ ), 8 to 12% by weight of alumina (Al ₂ O ₃ ), and 2 to 4% by weight of iron oxide ( III) (Fe ₂ O ₃ ), 0.8-1.1 wt% iron (II) (FeO), about 0.5% wt titanium dioxide (TiO ₂ ) and manganese oxide (MnO), 4-16 wt% lime (CaO ), 2 to 6% by weight of magnesium oxide (MgO) or the like, and generally composed of commercially available products.

As the antifoaming agent inhibits foaming, commercially available products such as conventional nonionic oil in water type (O / W) emulsions such as polyether-siloxane copolymers containing hydrophobic silica may be used.

Hereinafter, the configuration and the effect of the present invention will be described in more detail as compared to commercialized products.

The present invention is divided into the main portion and the curing agent portion with respect to the whole composition,

(1) Topics

30-40 wt% water-soluble epoxy resin, 0.05-0.1 wt% dispersant, 0.1-0.5 wt% preservative, 0.1-0.5 wt% thickener, 0.05-0.1 wt% ph regulator, 0.3-1.0 wt% silane It has a composition containing a coupling agent, 45-60 weight% filler, and 5-15 weight% dilution solvent.

(2) Curing agent

10-20 wt% water-dispersed polyamine curing agent, 0.05-0.1 wt% dispersant, 0.1-0.5 wt% preservative, 0.3-1.0 wt% ocher, 0.05-0.1 wt% ph regulator, 0.01-0.1 wt% Antifoaming agent, 60 to 70% by weight of filler, and 10 to 20% by weight of diluent.

(Example: Preparation of adhesive for two-component water-soluble epoxy resin-based porcelain tiles)

Example

As the preparation of the two-component water-soluble epoxy resin ceramic tile adhesive, the main portion and the hardener portion were uniformly mixed in a 1: 1 ratio to prepare an adhesive composition for the two-component water-soluble epoxy resin ceramic tile.

[Manufacture process]

(1) Topics

1) 0.05 to 0.1 wt% of a ph regulator is added to a 5 to 15 wt% dilution solvent and mixed for 2 to 3 minutes.

2) 30-40 wt% water-soluble epoxy resin, 0.05-0.1 wt% dispersant, 0.1-0.5 wt% preservative, 0.1-0.5 wt% thickener, 0.3-1.0 wt% silane coupling agent in order to the mixer Add and mix for about 5 minutes each.

3) Add 0.1 to 0.5% by weight of a thickener into the mixer and mix for about 5 minutes.

4) After confirming that the thickener is mixed, 45 to 60% by weight of the filler is placed in the mixer and mixed for about 15 to 20 minutes.

5) After mixing, check the dispersion and pack it in a container.

(2) Curing agent

1) 0.05 to 0.1% by weight of a ph regulator is added to 10 to 20% by weight of a diluting solvent and mixed for 2 to 3 minutes.

2) 10-20 wt% water-dispersed polyamine curing agent, 0.05-0.1 wt% dispersant, 0.1-0.5 wt% preservative, 0.3-1.0 wt% ocher, 0.01-0.1 wt% defoamer in order Add and mix for about 5 minutes each.

3) After confirming that the mixture was mixed, 60 to 70% by weight of the filler was placed in the mixer and mixed for about 15 to 20 minutes.

4) After mixing, check the dispersion and pack it in a container.

(Comparative example: product which is commercially available and sold)

Comparative Example 1

Serafix PC-7000D of SANGGOM Co., Ltd., a type III (product used in an area not affected by water and hot water after being attached to a dried base), was used as an adhesive for a synthetic resin emulsion-type porcelain tile.

Comparative Example 2

Serafix PC-7000S of Ssangbear Co., Ltd., a type II (product used in an area affected by water and hot water intermittently after being attached to a dried ground), was used as an adhesive for a resin emulsion porcelain tile.

Comparative Example 3

Dryfix I of Twin Bear Co., Ltd., an organic / inorganic mixed adhesive based on hydraulic polymer cement, was used.

In order to confirm the effect of the present invention, the properties of the water-soluble epoxy resin-based porcelain tile adhesive prepared as described above were measured according to the measurement method shown in Table 3 below.

[How to measure]

The measurement method was quoted by the Korean Industrial Standards (KS), and when the Korean Industrial Standards (KS) did not indicate a measurement method, a generalized measurement method was used.

General conditions of the test are as follows.

-Preparation of samples and test specimens shall be done in standard condition unless otherwise specified. Standard condition means the standard condition (temperature 20 ± 2 ° c, humidity 65 ± 10%) specified in KS L0006.

-Materials used for sample and test should be left in the standard room for 24 hours before manufacturing.

-Adhesives should be stirred well when testing.

Materials and tools used for the test are as follows.

-Materials and tools used for the test shall be in accordance with Table 1 below.

TABLE 1

-The applicator used for the test shall be a standard comb. However, combs specified by the manufacturer may be used. The thickness shall be 0.8 ± 0.2 mm.

-The adhesive surface of the iron strip used for the manufacture of the test specimen shall be 40 × 40 mm.

(1) Ease of kneading termination confirmation

The main body and the curing agent are collected on a plate glass having a thickness of about 300 × 300 mm and a thickness of about 3 mm at a ratio of about 1: 1 to a total of about 200 to 300 g, and kneaded for about 3 minutes so as to be sufficiently uniform with a spatula. Visually confirm that the kneading finish and color are clear (KS L 1593).

(2) adhesive strength

Adhesive strength test method is as follows.

1) Test material: Test material is as follows.

a) background material

The base material is mortar plate, 70 × 70mm in size and 20mm in thickness. Clean the surface to avoid dust and other foreign matter.

b) ceramic tile

Porcelain tiles (hereinafter referred to as tiles) are those cut into 40 × 40 mm size in advance.

2) Preparation of test body: The production of test body is as follows.

a) application of adhesive

For the application of adhesive to the base material, insert 5 pieces of base plate without gaps on the flat surface of the iron application frame of KS L 1593 without gaps, take the appropriate amount of adhesive and apply it with a standard comb. When applying the adhesive, attach the tape specified in KS A1527 to the base material so that the butterfly covers 7mm, put the appropriate amount of adhesive on it, apply it with a thickness of 3mm using a spatula, etc. It is set up at °, and it is pulled in front of itself at once at both speeds, and the adhesive is evenly applied with 5 substrates. The tape is peeled off slowly after applying the adhesive.

b) tile attachment

In principle, after 20 minutes after applying the adhesive, the ceramic tile cut to 40 × 40 mm size is placed in the center of the base material coated with adhesive, and then the weight of 1kg is placed on it for about 30 seconds. Remove and cure for 7 days.

c) device of iron sheet

Between 4 and 6 days of curing, the iron strips from KS L 1593 are adhered to the tile with epoxy resin adhesive or the like in a standard state. (When preparing the test specimen, the surface of the tile may be roughened with sand paper, etc.).

3) Treatment of test body: The processing of test body is as follows.

a) hot water immersion

After curing at low temperature, cure in a constant temperature bath according to Table 2 below.

b) Repetition of drying and submersion

After curing at low temperature, cure according to Table 2 below. Drying is done in a constant temperature and humidity room and immersed in water.

c) dry and wet repetition

After high humidity curing, cure according to Table 2 below and dry in a constant temperature room. Wetting is done in a constant temperature and humidity room.

d) alkali soaking

After standard curing, cure according to Table 2 below. Immerse in saturated calcium hydroxide solution.

e) thermal aging

After standard curing, cure in a constant temperature room according to Table 2 below.

f) low temperature curing

After curing at low temperature, cure in a constant temperature room according to Table 2 below.

TABLE 2

4) Adhesive strength test

a) tester

The tester is a tensile tester whose breakdown load is 15-85% of the tester capacity, and the tension rate can be adjusted to 3 mm / min.

b) adhesive strength

After curing the test body, the adhesive strength is installed in the tester using a jig, the tensile test is performed at a tensile speed of 3 mm / min, and the maximum load until breaking is recorded and the broken state is recorded. Tensile tests are also done immediately after completion of curing. Test specimens subjected to dry, wet, repeated curing and heat aging curing shall be left to stand for 24 hours in a standard condition.

c) How to find the adhesive strength

Adhesion strength is calculated by the following equation.

Adhesion strength is expressed by the average value of 5 specimens.

d) broken status record

Observe the broken surface, visually measure the broken area representing the maximum area, and mark the broken area. In addition, test specimens broken at the interface between iron and tile are retested according to the number of specimens, and are expressed as the average value of the five specimens in combination with the previous figures. (KS L 1593)

(3) heat resistance

Two tiles are bonded to each other up and down 10 mm, and the standard cured specimen is almost vertically attached to a 60 ° C thermostat, and a weight of 4.5 kg is placed on one tile and left for 24 hours. If the tile is not peeled off and falls off, pass (KS L 1593).

(4) slip resistance

An 8 mm asbestos slate (flexible plate) is cut into a size of 200 x 500 mm, and a 5 mm rod is attached to both ends of the short sides with an epoxy resin adhesive. The surface should be clean to prevent dust and other foreign matters from being attached. Use 100mm square ceramic tile without backing. Application of the adhesive to the substrate is performed by taking an appropriate amount of the adhesive and using a spatula or the like on the substrate with a thickness of about 3 mm. The standard comb is then angled at 60 ° and pulled out at once at both speeds to remove any remaining adhesive. The direction of combing is two places parallel and perpendicular to the long side of the base material. Within 5 minutes after the application of the adhesive, the tile is placed on the base material coated with the adhesive, and the weight of 5 kg is placed on the substrate for about 30 seconds. Then, the weight is removed and marked with ink in the center of the test specimen. Stand upright. After 24 hours, the slip length at the baseline is measured with a scale of 0.05 mm or more. (KS L 1593)

(5) Housework time and attachable time

Pot life and attachable time shall be the longest time satisfying the standard bond strength (KS L 1593).

(6) Appearance

The adhesive collected for the test is opened in a bright place and inspected for color and foreign matters.

(7) viscosity

Examples using the RVT viscometer are spindele No. Comparative example at T-E, rpm 5.0 is spindele No. It was measured at T-F, rpm 2.5.

(8) Long-term water resistant adhesive strength

Using the material of (1), (2), prepare the specimen by the method of 2), cure for 24 hours at 20 ± 2 ℃, immerse in water for 6 months, take it out after 6 months, and immediately Adhesion strength shall be measured according to the method of testing the adhesion strength of 4).

(9) low temperature curing adhesive strength

Using the material of (1), (1), prepare specimens by the method of (2), cure at -5 ± 1 ° C for 7 days, and then apply the adhesive strength according to the test method of 4). Measure.

(10) 24 hours curing adhesive strength

Surface treatment of urethane and non-absorbing tile to the material of (2) 1) and the mortar plate of the same material as that of the item 1) were used as the test base plate, and the test piece was prepared by the method of (2) 2). After 24 hours curing at ± 2 ℃. Adhesion strength shall be measured according to the method of Adhesion Strength Test of 4).

TABLE 3

As shown in the results, all the physical properties of the examples were superior to the comparative examples. In particular, the comparative example is given a curing time of at least seven days, while the adhesive strength is expressed, the embodiment can be seen that all the adhesive strength is excellent after 24 hours. In addition, it can be seen that the comparative example does not cure at the water-resistant adhesive strength and low-temperature cure adhesive strength, whereas the embodiment exhibits sufficient adhesive strength by curing.

The two-component water-soluble epoxy resin-based porcelain tile adhesive according to the present invention has significantly improved the problems of water resistance, heat resistance, adhesive strength, curing speed, and in particular, uncured at low temperature, which are disadvantages of conventional ceramic tile adhesives. It is possible to install the product, which makes the workability and construction quality very excellent. Therefore, there is an effect that the contractor and the occupant can escape from the damage caused by the poor tile adhesion, there is also the effect of expanding the use of the tile by completely solving the conventional use of the tile. In addition, it is an environmentally friendly and human-friendly product that hardly detects formaldehyde and volatile organic compounds (VOCs) that are harmful to humans because it does not use formaldehyde and organic solvents. It is effective to prevent unpleasantness and pollution from toxic and to enjoy comfortable construction and healthy living.

Claims (1)

The main portion is 30 to 40% by weight of water-soluble epoxy resin, 0.05 to 0.1% by weight dispersant, 0.1 to 0.5% by weight preservative, 0.1 to 0.5% by weight thickener, 0.05 to 0.1% by weight ph regulator, 0.3 to 1.0% by weight Silane coupling agent, 45 to 60% by weight of filler, 5 to 15% by weight of diluent solvent, the curing agent portion of 10 to 20% by weight of water-based polyamine curing agent, 0.05 to 0.1% by weight of dispersant, 0.1 to 0.5% by weight of Preservatives, 0.3 to 1.0% by weight ocher, 0.05 to 0.1% by weight ph regulator, 0.01 to 0.1% by weight antifoaming agent, 60 to 70% by weight filler, 10 to 20% by weight diluent , Manufactured porcelain tile adhesive for gypsum board, ALC dry tile and concrete wet surface, allowing for tile construction of interior and exterior walls and floors, and two-component water-soluble epoxy resin ceramics divided into main and hardener parts Composition of the adhesive for vaginal tiles.