KR20080097721A - Water-borne epoxy adhesive for laminated floating flooring floor - Google Patents

Abstract

A two-part aqueous epoxy adhesive composition for ondol(korean hypocaust) floor is provided to improve workability and storage stability by using a self-emulsified epoxy resin reacting the epoxy resin and surfactant and water, and to make the adhesive composition be environment-friendly and human affinitive by suppressing the discharge of a volatile organic compound and poisonous material. A two-part aqueous epoxy adhesive composition for ondol(korean hypocaust) floor comprises a main material(a) and a hardener(b). The main material comprises (i) a self-emulsified epoxy resin 20~40 parts by weight; (ii) water 10~30 parts by weight as a diluted solvent; (iii) sieved pigments 30~60 parts by weight used for filling and texture reinforcement; (iv) a compound 0.1-1 parts by weight based on polyethersiloxane and polyether in which the organic volatile component is not detected, as a antifoaming agent; (v) an aqueous dispersant 0.1-1 parts by weight of polycarboxylic acid type; and (vi) silica (SiO2) 0.1-1 parts by weight. The hardener comprises (i) a hydrophile self-emulsified epoxy resin 20~40 parts by weight; (ii) water 10~30 parts by weight as a diluted solvent; (iii) sieved pigments 30~60 parts by weight used for filling and texture reinforcement; (iv) a compound 0.1-1 parts by weight based on polyethersiloxane and polyether in which the organic volatile component is not detected, as a antifoaming agent; (v) an aqueous dispersant 0.1-1 parts by weight of polycarboxylic acid type; (vi) silica (SiO2) 0.1-1 parts by weight; and (vii) 4-cyclohexene-1,2-dibutyl carboxylic acid, dibutyl ester(C16H26O4) 1~10 parts by weight added for the workability improvement.

Description

Water-borne Epoxy Adhesive for Laminated Floating Flooring Floor}

The present invention relates to a water-based epoxy adhesive composition for ondol floors, and in detail, the self-emulsifying epoxy resin reacted with an epoxy resin and a surfactant and water (H ₂ O) completely excluding alcohol are used to improve workability and storage stability. It prevents volatile organic compounds and harmful wool emissions during or after construction, which facilitates the construction of workers and prevents side effects due to inhalation of harmful substances. The human-friendly advantage and the surfactant reacted with epoxy also participate in the curing reaction with the curing agent, so that the surfactant does not move to the surface layer after curing, so it does not emit pollutants and has excellent adhesion to moisture-containing and almost all adherends. There is an advantage.

For example, conventionally developed aqueous and water-soluble adhesives are disclosed in Korean Unexamined Patent Publication No. 2005-117387, Korean Unexamined Patent Publication No. 2005-044990, Korean Unexamined Patent Publication No. 2005-047004, and Japanese Unexamined Patent Publication No. 2005-336333. In addition to this type, this type of surfactant causes a decrease in water resistance and adhesion as the surfactant moves to the surface layer, and there is a part that cannot release harmful substances.

Ondol flooring water-based adhesive currently used in Korea is a type to add a surfactant to the epoxy resin (acrylic emulsion or vinyl acetate emulsion, alcohol, water is used in combination. In this type, as the surfactant moves to the surface layer after curing, it causes water resistance and adhesive strength, and there is a part that can not exclude the emission of harmful substances, and also harmful to the environment and harmful to human body due to the emission of volatile organic compounds by using alcohol. There is a side effect of inhaling the worker. On the other hand, if alcohol is not used, there is a problem that the workability does not come out of storage stability due to stability problems.

In order to solve the above problems, the present invention uses only self-emulsifying epoxy resin and water (H ₂ O) reacted with an epoxy resin and a surfactant to improve workability and storage stability, thereby improving volatile organic compounds and It is an object of the present invention to provide a two-component aqueous epoxy adhesive composition for ondol flooring that is environmentally friendly and human-friendly by suppressing the discharge of harmful substances.

The present invention relates to a two-component aqueous epoxy adhesive composition for ondol floor, the composition of which is a) i) bisphenol A epoxy resin equivalent 180-220 (g / eq), viscosity 8,000-15,000 (cps, at25 ℃) liquid resin 90 to 95% by weight of reactive surfactant added with an amine group, 5 to 10% by weight of polyetheramine having a molecular weight of about 2,000, a polypropylene oxide to polyethylene oxide mole ratio of 8:25 and an amine value of 95 at 130 ° C. 20 to 40 parts by weight of the self-emulsifying epoxy resin obtained by reacting for 2 hours; Ii) 10 to 30 parts by weight of water as a diluting solvent for fluidity control; Iii) 30 to 60 parts by weight of extender pigments used for filling and reinforcing properties; Iii) 0.1 to 1 parts by weight of a compound system based on polyether siloxane and polyether in which organic volatile matter is not detected as an antifoaming agent; Iii) 0.1 to 1 parts by weight of an aqueous dispersant in the form of a polycarboxylic acid mainly used for sieving pigment dispersions; Iii) 1 part of a main composition containing 0.1 to 1 parts by weight of silica (SiO ₂ ) system mainly added for thixotropic and sedimentation prevention; and b) amine value (mg KOH / g) 220 to 310, viscosity (cps, at25). 50 to 70% by weight of polyamide having 2,500 to 50,000, 10 to 30% by weight of diethylenetriamine having a molecular weight of 103, equivalent to 180 to 220 (g / eq), viscosity 8,000 to 15,000 (cps, at 25 ° C), After reacting 5 to 10% by weight of phosphorus bisphenol-A epoxy resin at 130 ° C for 1 hour, 2 to 5% by weight of reactive surfactant added with viscosity (cps, at25 ° C) 700 and ethylene oxide 30 mol (mol) 15 to 25 parts by weight of a hydrophilic self-emulsifying curing agent obtained by secondary reaction at 130 ° C. for 1 hour by adding thereto; Ii) 10 to 30 parts by weight of water as a diluting solvent for fluidity control; Iii) 30 to 60 parts by weight of extender pigments used for filling and reinforcing properties; Iii) 0.1 to 1 parts by weight of a compound based on polyether siloxane and polyether in which organic volatile matter is not detected as an antifoaming agent; Iii) 0.1 to 1 parts by weight of an aqueous dispersant in the form of a polycarboxylic acid mainly used for sieving pigment dispersions; Iii) 0.1 to 1 parts by weight of silica (SiO ₂ ) system mainly added for thixotropic and sedimentation prevention; V) 1 part of a curing agent composition containing 1 to 10 parts by weight of 4-cyclohexene-1,2-dibutylcarboxylic acid, dibutyl ester, and (molecular formula C16H26O4) added to improve workability. It relates to a two-component aqueous epoxy adhesive composition for environmentally friendly ondol floors.

Hereinafter, the present invention will be described in detail.

In the present invention, the bisphenol-A epoxy resin used in the subject of the aqueous epoxy adhesive composition for ondol floor is used as a main component in the reaction with a reactive surfactant. Commercially available epoxy resins which are generally useful for adherents are often referred to as liquid resins and solid resins. Important solid epoxy resins on the market have an epoxy equivalent weight (EEW) of at least about 450. Epoxy resins with much higher equivalents can be used, but the resins used in the amine cured adhesives have an equivalent weight of 1,000 or less.

When the equivalent is larger, the resulting crosslinking density becomes too low to obtain the desired physical properties. Commercially available liquid epoxy resins have an equivalent weight of about 250 or less, more commonly about 200 or less. They have a much slower drying rate than solid epoxy resins, but can obtain a coating film having a very high crosslink density, so that the present invention can be used to obtain useful workability and easy viscosity.

In the present invention, the composition required for synthesizing the self-emulsifying epoxy resin is a) i) bisphenol A epoxy resin equivalent 180-220 (g / eq), the viscosity of 8,000-15,000 (cps, at25 ℃) to use a liquid resin Desired viscosity 9,000 ~ 18,000 (cps, at25 ℃) and physical properties can be obtained, and the amount of use is correlated with reactive surfactant, and when used over 95% by weight, the self emulsifying power is lowered, and when used at 90% by weight or less, there is no problem. have.

Conversely, the amount of surfactant used is less than 5% by weight of its own emulsification power, while when used more than 10% by weight of over-emulsification has no price competitiveness.

When using less than 20 parts by weight of the self-emulsified epoxy amount obtained above, the desired physical properties are not obtained, and when it is used more than 40 parts by weight, the price is not competitive.

Ii) When water is used at 10 parts by weight or less as a diluting solvent, the viscosity is too high. When it is used at 30 parts by weight or more, the viscosity decreases, causing pigment settling and water separation.

체) Constitutional pigments used for filling and reinforcing properties may use talc, cray, barium lactate, etc., but there are problems such as sedimentation, workability, etc., and price competitiveness is low. Calcium carbonate is useful and has no filling effect when used at 30 parts by weight or less, and there is a deterioration of the coating film when used at 60 parts by weight or more.

Iii) Antifoaming agent is applied to environment-friendly products. Polyether siloxane and polyether-based compounds which are not detected in organic volatiles are used. There is a problem of poor adhesion.

분산) Dispersant that is mainly used for dispersing pigments has no dispersing effect when added to 0.1 parts by weight or less, and does not help product shelf life. .

Iii) Silica (SiO2), which is mainly added to thixotropy and sedimentation prevention, has a problem that the sedimentation prevention effect is weak when used at 0.1 parts by weight or less, and the flowability is deteriorated when it is used at 1 part by weight or more.

1 part of the main composition described above is suitable for the viscosity of 3,000 ~ 8,000 (cps, at25 ℃) considering the bone formation, mixing, workability, storage.

b) iii) When the polyamide resin is used at 50 wt% or less during the first reaction during the self-emulsifying curing agent synthesis, the price is not competitive and collapse occurs in bone formation.When it is used at 70 wt% or more, it does not receive water softly. There is a problem of not saving.

When less than 10% by weight of diethylenediamine is used, the final viscosity of the self-emulsifying epoxy is high, and when used at 30% by weight or more, there is a problem that the bone collapses, poor physical properties, and the gloss disappear.

Bisphenol-A epoxy resin does not reach the desired viscosity when used in less than 5% by weight, disadvantageous in terms of price, there is a problem that the viscosity is excessively attached when used in more than 10% by weight.

In the second reaction, the reactive emulsifier is less than 2% by weight of the self-emulsifying power and when used more than 5% by weight of the excess emulsification leads to property inhibition.

The self-emulsifying agent obtained above has an amine value (mgKOH / g) of 260 to 380 and a viscosity of about 5,000 to 18,000 (cps, at25 ° C). It is destroyed. If it is used more than 25 parts by weight, the curing speed is increased, but the coating film becomes soft in final properties.

Ii) When water is used at 10 parts by weight or less as a dilution solvent for controlling fluidity, the viscosity is excessively high. When it is used at 30 parts by weight or more, the viscosity decreases, causing pigmentation and water separation. .

Ⅲ) Constitutional pigments used for filling and reinforcing properties may use talc, cray, barium lactate, etc., but there are problems such as sedimentation, workability, etc., and price competitiveness is low in the present invention. Calcium is useful and there is no filling effect when used at 30 parts by weight or less and there is a deterioration of the coating film when used at 60 parts by weight or more.

Iii) Antifoaming agent is applied to eco-friendly products. Polyether siloxane and polyether-based compounds that can not detect organic volatiles are used. When it is added at 0.1 parts by weight or less, the antifoaming effect is low. There is a problem of poor adhesion.

분산) Dispersant that is mainly used for dispersing pigment pigment has no dispersing effect when added to 0.1 parts by weight or less, and does not help product shelf life, and when added to 1 part by weight or more, there is a problem of collapsing in bone formation. .

Iii) Silica (SiO2), which is mainly added to thixotropy and sedimentation prevention, has a problem that the sedimentation prevention effect is weak when used in an amount of 0.1 parts by weight or less and the flowability is poor when used in an amount of 1 part by weight or more.

V) 4-cyclohexene-1, 2-dibutyl carboxylic acid dibutyl ester added to improve the workability is added 1 to 10 parts by weight according to the season to control the surface drying time. One part of the curing agent composition described above has a viscosity of 3,000 to 8,000 (cps, at25 ° C.) in consideration of bone formation, mixing, workability, and storage properties.

The present invention relates to a two-component aqueous epoxy composition for ondol flooring, which is composed of a) a main composition and b) a curing agent composition and is used in a 1: 1 weight ratio.

Hereinafter, preferred embodiments are provided to help understanding of the present invention, but the following examples are merely to illustrate the present invention, and the following embodiments of the present invention are not limited thereto.

EXAMPLE

Examples 1-5

Bisphenol A type epoxy resin YD-128 (Kukdo Chemical) 93% by weight of liquid resin and 7% by weight of polyetheramine (reactive surfactant with amine groups, molecular weight of about 2,000, polypropylene oxide to polyethylene oxide mol) After preparing a self-emulsifying epoxy resin obtained by reacting the ratio of 8:25 and the amine number 95) at 130 ° C. for 2 hours, 72 wt% of G-5022 (Kukdo Chemical) and 20 wt% of diethylenetriamine were used as a polyamide in the curing agent. , 5% by weight of bisphenol A type epoxy resin YD-128 (Kukdo Chemical) was first reacted at 130 ° C. for 1 hour, and then 3% by weight of reactive surfactant (viscosity (cps, at25 ° C.) 700, ethylene oxide 30 mol) The hydrophilic self-emulsifying hardener obtained by the addition and secondary reaction at 130 degreeC for 1 hour is prepared.

Using the self-emulsifying epoxy resin and the self-emulsifying curing agent resin obtained above, an aqueous epoxy adhesive composition for ondol floor was prepared according to the components and composition ratios as shown in Table 1 below.

Table 1

Table 2 shows the adhesive composition and the tensile strength of the adhesive composition prepared according to Examples 1 to 5 after curing for 5 days at room temperature using marble and plywood as an adhesive. It is shown as the general physical properties.

Table 2

Table 3 shows the results of testing the composition of Example 1 (subject: curing agent = 1: 1 weight ratio) by the indoor air quality process test method.

Table 3

As a result of Table 3, it can be confirmed that there is almost no emission of organic compounds and no harmful substances.

Table 4 shows the results of testing whether the composition ( Example : curing agent = 1: 1 weight ratio) of Example 1 contains a heavy metal to be regulated.

Table 4

As a result of Table 4 , it can be seen that the aqueous epoxy adhesive composition does not contain harmful heavy metals .

(Comparative Example 1)

In Example 1, the volatile volatiles detected in the 9-13 minutes were analyzed by gas chromatograph using ethyleneamine in the self-emulsified curing agent resin composition using triethylene tetraamine (Figure 1) and diethylenetriamine (Figure 2), respectively. The result table is shown graphically.

(Figure 1)

(Figure 2)

As a result of the gas chromatograph analysis, diethylene triamine was found to be free of volatiles in the ninth to thirteenth component.

(Comparative Example 2)

In Example 1, the diluent is changed to methyl alcohol, and the other composition is the same, and is shown in Table 5 by comparing general physical properties.

Shear adhesion strength test in (Comparative Example 2) is the average value measured three times after five days after bonding marble and plywood.

Standard condition: Shear bond strength test after 5 days of adhesion.

Water resistance test: test after leaving for 24 hours in water at 60 ℃, left for 1 hour at room temperature.

Heat resistance test: Test after leaving for 1 hour at room temperature after leaving for 24 hours in an oven at 60 ℃.

Table 5

(Comparative Example 2) As a result, it was confirmed that the present invention showed sufficient adhesive strength without using alcohol, and on the other hand, it provided sufficient working time considering the surface drying time.

Eco-friendly two-component water-based epoxy adhesive composition for ondol floor according to the present invention is environmentally friendly and does not have odor during construction because it does not use toxic substances, alcohol and formaldehyde, improving work efficiency and no harmful emissions after construction, thereby improving indoor air quality. It is human-friendly and has the effect of reducing environmental pollutants. In addition, in the workability, the existing alcohol-type water-based adhesive has an inconvenience of having to work within a short time because the surface drying time is too fast during the construction of ondol floor, whereas the aqueous epoxy adhesive composition developed in accordance with the present invention is considered in consideration of the ondol floor construction process. By providing sufficient surface drying time, the workability was improved to facilitate the operator's work. On the other hand, the ondol floor coating material had permeability and thixotropy suitable for the variation of cement mortar and plywood, and the difference in absorbency. Improved workability and adhesion, such as sex, bone formation.

The adhesion mentioned above is excellent in adhesion to moisture-containing adherend (mortar cement plywood) by reacting a reactive surfactant to an epoxy resin to obtain a self-emulsifying epoxy having a hydrophilic polymer chain so as to basically come out in the present invention. It is also considered that there is a ripple effect that can accelerate the universality of eco-friendly products by applying the present invention to the field of civil engineering and construction.

Mankind has achieved great results as a result of efforts to improve the quality of life, but the environmental pollution that results from it poses a serious threat to the quality of life. Among them, volatile organic compounds (VOCs) and harmful air pollutants are a problem, and the government is putting a lot of budget and manpower to reduce them.

Therefore, when the present invention is applied, emissions of volatile organic compounds and harmful air substances can be reduced, resulting in a change in social awareness by suppressing disease occurrence factors caused by indoor air quality pollution, which has a large economic saving effect and is a social problem. The ripple effect will be great.

Claims (1)

A) Bisphenol A type epoxy resin equivalent to 180 ~ 220 (g / eq), 90 ~ 95% by weight of liquid resin with viscosity 8,000 ~ 15,000 (cps, at25 ℃) and amine group. Self-emulsifying epoxy resin obtained by reacting 5 to 10% by weight of a polyetheramine having a molecular weight of about 2,000, a polypropylene oxide to a polyethylene oxide molar ratio of 8:25 and an amine value of 95 as a reactive surfactant at 130 ° C for 2 hours. 20 to 40 parts by weight; Ii) 10 to 30 parts by weight of water as a diluting solvent for controlling fluidity; i) 30 to 60 parts by weight of extender pigment used for filling and reinforcing properties; i) Polyether siloxane and polyether in which organic volatiles are not detected with an antifoaming agent. 0.1 to 1 parts by weight of a compound-based compound based on the present invention; (iii) 0.1 to 1 parts by weight of an aqueous dispersant in the form of a polycarboxylic acid mainly used for dispersing pigments; 1 part of the main composition containing 0.1 to 1 parts by weight of SiO ₂ ) system, and b) 50 to 70% by weight of polyamide having an amine value (mg KOH / g) 220 to 310 and a viscosity (cps, at 25 ° C) of 2,500 to 50,000, 10 to 30% by weight of diethylene triamine having a molecular weight of 103, and an equivalent of 180 Viscosity (cps, at25 ° C) 700 after first reacting at 220 ° C (g / eq), viscosity 8,000-15,000 (cps, at 25 ° C), and 5-10% by weight of phosphorus bisphenol A epoxy resin at 130 ° C for 1 hour 15 to 25 parts by weight of a hydrophilic self-emulsifying curing agent obtained by adding 2 to 5% by weight of a reactive surfactant added with 30 mol (mol) of ethylene oxide, followed by secondary reaction at 130 ° C. for 1 hour; Ii) 10 to 30 parts by weight of a diluent solvent for fluidity control; i) 30 to 60 parts by weight of extender pigments used for filling and reinforcing properties; (Iii) 0.1 to 1 part by weight of a compound based on polyether siloxane and polyether in which organic volatile matter is not detected as an antifoaming agent; Iii) 0.1 to 1 parts by weight of an aqueous dispersant in the form of a polycarboxylic acid mainly used for sieving pigment dispersions; iii) 0.1 to 1 parts by weight of silica (SiO ₂ ) system mainly added for thixotropic imparting and sedimentation prevention; V) 1 part of a curing agent composition containing 1 to 10 parts by weight of 4-cyclohexene-1,2-dibutylcarboxylic acid, dibutyl ester, and (molecular formula C16H26O4) added to improve workability. Epoxy adhesive composition for eco-friendly ondol flooring.