KR102024067B1 - Water glass-based hybrid adhesives for wooden flooring and manufacturing method thereof - Google Patents

Abstract

One example of the present invention is an adhesive in the form of a composition comprising water glass, an epoxy resin and a coupling agent, wherein the coupling agent is present in a state in which it is bound to silicon dioxide (SiO ₂ ) present in the water glass and has a polymer form of an amino silane monomer. It provides a water glass-based adhesive adhesive for attaching wood flooring. The adhesive according to the present invention contains more water glass than the epoxy resin, so when used as an adhesive for building finishing materials, it is possible to minimize the emission of volatile organic compounds (VOC) and is environmentally friendly. In addition, the adhesive according to the present invention can favorably adhere different substrates even when the surface of the substrates to be attached is irregular or the gap between the substrates is large. Therefore, the adhesive according to the present invention is very useful when constructing a building finish made of another material such as wood or synthetic resin on one surface of a building such as a concrete floor surface having a large gap or irregular surface. Furthermore, it is excellent in thermal conductivity and can improve the thermal efficiency of an ondol floor.

Description

Eco-friendly water-based adhesive for attaching wood flooring and its manufacturing method {Water glass-based hybrid adhesives for wooden flooring and manufacturing method

The present invention relates to an adhesive and the like, and more particularly, it is possible to attach different substrates well even when the surface of the wood to be adhered to is environmentally friendly and the adherend or the gap between the substrates is good, and the heat transfer efficiency is excellent. It relates to a water glass-based adhesive for attaching wood flooring material and a method of manufacturing the same.

The building finishing material refers to a general building interior and exterior materials, and is a building material attached to the inner wall, floor, and outer wall of a building such as tiles, floors, and stone panels to perform unique functions. Such building finishing materials are attached to the inner wall, floor, and outer walls of the building, respectively, and perform additional functions such as appearance beauty, heat insulation, and waterproofing, and thus are essential building materials. In this case, an adhesive for building is used to attach a building finishing material made of another material such as wood or synthetic resin to an inner wall, a bottom surface, and an outer wall of a building made of glass, metal, or concrete. In particular, the adhesives used to attach building flooring floors to cement mortared floors have different properties between cement mortared floors and flooring floors, so they must have good adhesion to both the substrate and the flooring. .

Conventionally used ondol flooring adhesives are classified into organic adhesives based on epoxy resins, acrylic resins or urethane resins, and inorganic adhesives based on silicates such as sodium silicate and potassium silicate. In general, organic adhesives contain volatile organic compounds (VOCs) such as formaldehyde and organic solvents (toluene, xylene). When released into the air, they cause air pollution and water pollution. Ingestion may cause headache, dizziness, vomiting or irritation of the airways that is harmful to the human body. In particular, formaldehyde, which occurs when constructing building finishing materials using organic adhesives, causes severe chemical smell and is becoming a culprit of sick house syndrome. In addition, organic adhesives have a problem in that the adhesive surface is destroyed by repeated heating and cooling due to poor heat resistance or weather resistance. On the other hand, inorganic adhesives are widely used in fields requiring high heat resistance, chemical resistance, or waterproof because they have high thermal stability and do not cause harmful substances during adhesive application or drying, unlike organic adhesives. However, inorganic adhesives generally have a low drying speed, limited coating thickness, and low adhesive strength, so that they are difficult to use for building materials. Regarding the inorganic adhesive, Korean Patent No. 10-1240667 (prior art 1) discloses a raw material mixture of liquid sodium silicate and activated kaolin, soda feldspar, calcium carbonate, asbestos-free talc, aluminum hydroxide, titanium dioxide and magnesia, A mixture of an aqueous thickener-based modified SBR (styrene butadiene rubber), or at least one additive of modified acrylic resin or modified polyurethane resin or modified latex, modified EVA (Ethylene Vinyl Acetate) to enhance water resistance and adhesive strength. Inorganic adhesive compositions are disclosed. In addition, the inorganic adhesive composition disclosed in the prior art 1 is 40 to 60% by weight of the liquid sodium silicate, 15 to 25% by weight of the active kaolin, 5 to 10% by weight of the soda feldspar, the carbonic acid based on 100% by weight of the raw material mixture 5-10 wt% of calcium, 5-10 wt% of the asbestos-free talc, 1-5 wt% of the aluminum hydroxide, 1-5 wt% of the titanium dioxide and 1-5 wt% of the magnesia, and then the additive 2 to 7% by weight and 0.1 to 0.3% by weight of the acrylic thickener is added and characterized in that the second mixture. However, the inorganic adhesive disclosed in the prior art contains various raw materials such as activated kaolin, soda feldspar, calcium carbonate, asbestos-free talc, aluminum hydroxide, titanium dioxide and magnesia as essential components, and thus, have problems in securing or managing raw materials. As a result, it is economically inferior, and the increase in adhesive strength due to the addition of modified polymer resin is insufficient for use in building materials. Therefore, there is still a need for the development of adhesives for building materials with high adhesive strength, eco-friendliness, and further economic efficiency.

In order to secure eco-friendliness and excellent adhesion in relation to adhesives for building finishing materials, a study of mixing water glass and epoxy resins has recently been conducted. For example, the Republic of Korea Patent No. 10-1600819 (prior art 2) is an adhesive in the form of a composition comprising 6 to 14 parts by weight of epoxy resin and 4 to 9 parts by weight of a silane coupling agent based on 100 parts by weight of water glass, the composition Adhesives for attaching building finishes are disclosed in which the weight ratio of epoxy resin to silane coupling agent is 1: 1 to 3: 1 and the silane coupling agent is amino silane. Typically, when attaching ondol flooring to a cement mortar-treated floor surface, the cement mortar-treated floor surface has a large gap between the floor material and the floor surface because the surface is very irregular. The adhesive for building finishing materials disclosed in the prior art 2 has a relatively low viscosity, which limits the thickness of the coating film, which is suitable when the gap between the flooring material and the floor surface is small. However, when the gap between the flooring material and the floor surface is large, the adhesive strength is significantly reduced. There is.

In order to solve the problems of the prior art of the present invention, an object of the present invention is environmentally friendly, and at the same time it is possible to adhere different substrates well even when the surface of the substrates to be attached is irregular or the gap between the substrates is large. It is to provide an eco-friendly water glass-based adhesive for attaching wood flooring and a method of manufacturing the same.

In addition, another object of the present invention is to provide an adhesive having improved thermal conductivity in consideration of the case where the adhesive is applied to the building floor surface such as ondol.

The water glass-based adhesive for attaching wood flooring according to an embodiment of the present invention is a composition comprising water glass, an epoxy resin, and a coupling agent, wherein the coupling agent is present in the state of being bonded to silicon dioxide (SiO ₂ ) present in the water glass and amino silane. It has a polymer form of the monomer and comprises 5 to 30 parts by weight of the thermally conductive powder relative to 100 parts by weight of the composition.

The water glass is sodium (Na ₂ O) 5 ~ 20% by weight, silicon dioxide (SiO ₂₎ by 20 to 40 may include water (H ₂ O) on a weight% and the remaining amount, the epoxy resin is bisphenol A oxide Epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bisphenol A novolac type epoxy resins, bisphenol F novolac type epoxy resins, glycidylamine type epoxy resins, terminal amine modified epoxy resins, and the like can be used.

As said amino silane monomer, N-2 (aminoethyl) 3-aminopropylmethyldimethoxysilane, N-2 (aminoethyl) 3-aminopropyltrimethoxysilane, N-2 (aminoethyl) 3-aminopropyltri Ethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl- 3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, 3-aminopropylmethyldiethoxysilane, 3-aminopropyl-tris (2- Methoxy-ethoxy-ethoxy) silane, N-methyl-3-aminopropyltrimethoxysilane, triaminopropyl-trimethoxysilane and the like can be used.

The content of the water glass may be 50 to 90% by weight based on the total weight of the composition, the content of the epoxy resin may be 5 to 20 parts by weight per 100 parts by weight of water glass.

On the other hand, the coupling agent may be 2 to 10 parts by weight per 100 parts by weight of water glass.

As the thermally conductive powder, aluminum nitride, boron nitride, volume-expanded graphite, silver, iron, aluminum, copper, or the like can be used.

 The composition may further include an epoxy resin curing agent, and the epoxy resin curing agent may include ethylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, p-xyl Rendiamine, m-xylenediamine, 1,5-diaminonaphthalene, m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-di Aminodiphenylethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenylether, 1,1-bis (4-aminophenyl) cyclohexane, 4,4'-diaminodiphenyl Sulfone, bis (4-aminophenyl) phenylmethane, 4,4'-diaminodicyclohexane, 1,3-bis (aminomethyl) cyclohexane, dicyandiamide, and the like can be used. The content of the epoxy resin curing agent in the composition is water glass-based adhesive for attaching wood flooring, characterized in that 20 to 60 parts by weight per 100 parts by weight of epoxy resin.

According to an aspect of the present invention, there is provided a method of preparing a water glass-based adhesive for attaching a wooden flooring material, by adding an amino silane monomer to water glass and reacting at 60 to 150 ° C. for 10 to 240 minutes to include a water-glass-coupling agent-inorganic hybrid. Forming a mixture; And adding an epoxy resin and a thermally conductive powder to the first mixture and mixing to form a second mixture.

According to another aspect of the present invention, there is provided a method of preparing a water glass-based adhesive for attaching a wood flooring to a water glass, by adding an amino silane monomer to water glass and reacting at 60 to 150 ° C. for 10 to 240 minutes to include a water-glass-coupling agent-inorganic hybrid. Forming a mixture; And adding and mixing an epoxy resin, a thermally conductive powder, and an epoxy resin curing agent to the first mixture to form a second mixture.

The water-glass-coupling agent constituting the hybrid coupling agent is present in a state combined with a silicon dioxide (SiO ₂₎ present in the water glass and has a polymeric form of amino silane monomer.

The adhesive according to the present invention contains more water glass than the epoxy resin, so when used as an adhesive such as wood flooring, it is possible to minimize the emission of volatile organic compounds (VOC) and is environmentally friendly. In addition, the adhesive according to the present invention can favorably adhere different substrates even when the surfaces of the substrates to be attached are irregular or the gaps between the substrates are large.

Therefore, the adhesive according to the present invention is very useful when constructing a building finish made of wood, such as wood flooring on one side of the building, such as concrete floor surface having a large gap or irregular surface.

In addition, the adhesive according to the present invention includes a thermally conductive powder, when the wood floor is attached to the ondol, it is possible to maximize the thermal efficiency of the ondol.

1 is a photograph showing the phase stability of the adhesive prepared in Preparation Example 1, Figure 2 is a photograph showing the phase stability of the adhesive prepared in Preparation Example 2, Figure 3 is a phase stability of the adhesive prepared in Preparation Example 3 It is a photograph showing, Figure 4 is a photograph showing the phase stability of the adhesive prepared in Preparation Example 4.
Figure 5 is a photograph showing the state of the adhesive prepared in Preparation Example 5, Figure 6 is a photograph showing the state of the adhesive prepared in Preparation Example 6, Figure 7 is a photograph showing the state of the adhesive prepared in Preparation Example 7 8 is a photograph showing a state of the adhesive prepared in Preparation Example 8, FIG. 9 is a photograph showing a state of the adhesive prepared in Preparation Example 9, and FIG. 10 is a photograph showing a state of the adhesive prepared in Preparation Example 10 11 is a photograph showing a state of the adhesive prepared in Preparation Example 11, FIG. 12 is a photograph showing a state of the adhesive prepared in Preparation Example 12, and FIG. 13 shows a state of the adhesive prepared in Preparation Example 13 It is a photograph.
14 shows a state when the adhesive prepared in Preparation Example 23 is applied to a wooden substrate and dried, and FIG. 15 shows a state when the adhesive prepared in Preparation Example 26 is applied to a wooden substrate and dried will be.
Figure 16 shows the surface state of the mortar substrate and the wood substrate peeled off when measuring the adhesive strength of the adhesive prepared by Preparation Example 23, Figure 17 is a mortar substrate peeled off when measuring the adhesion strength of the adhesive prepared by Preparation 26 And the surface state of the wood substrate, Figure 18 shows the surface state of the mortar substrate and the wood substrate peeled off when measuring the adhesive strength of the adhesive prepared in Preparation Example 27.

Hereinafter, the present invention will be described in detail with reference to the accompanying drawings.

One aspect of the present invention relates to an eco-friendly water glass-based adhesive that can adhere different substrates well even when the surface of the wood flooring or mortar to be attached at the same time is irregular or the gap between the substrates is large.

Adhesive according to an embodiment of the present invention has the form of a composition comprising a water glass, an epoxy resin and a coupling agent, the composition may be added a thermally conductive word for improving heat transfer. In addition, the adhesive according to an embodiment of the present invention preferably has the form of a composition comprising a water glass, an epoxy resin, a coupling agent, an epoxy resin curing agent.

 Hereinafter, the adhesive according to an example of the present invention will be described by dividing the components.

water glass

Water glass, which is one component of the adhesive according to one embodiment of the present invention, serves to make the adhesive have a predetermined adhesive strength with respect to one surface of a building made of glass, concrete, or a metallic material. Water glass is the most widely used inorganic compound among water-soluble silicates, and generally includes a material represented by the following Chemical Formula 1.

[Formula 1]

M ₂ O-nSiO ₂ -H ₂ O (M is an alkali metal, n is a number from 1-8)

The water glass represented by Chemical Formula 1 is an aqueous solution of an alkali silicate salt obtained by melting silicon dioxide and an alkali metal. Examples of the alkali silicate salt included in the water glass include Na ₂ O.SiO ₂ , K ₂ O.SiO ₂ , and Li ₂ O. SiO ₂ and the like.

In the present invention, the water glass is not limited to a kind thereof if it includes the material represented by the formula (1), but in consideration of the adhesive strength of the adhesive, the ease of bonding with the amino silane monomer, commercial availability, etc. Contains the substance to be displayed.

[Formula 2]

Na ₂ O-nSiO ₂ -xH ₂ O

The water glass including the material represented by Chemical Formula 2 is composed of unit components such as sodium oxide (Na ₂ O), silicon dioxide (SiO ₂ ), and water (H ₂ O). In addition, commercial specifications of the water glass including the material represented by the formula (2) include KS-1, KS-2, KS-3, KS-4. In addition, the water glass used in the present invention is preferably 5 to 20% by weight of sodium oxide (Na ₂ O), 20 to 40% by weight of silicon dioxide (SiO ₂ ) in consideration of the adhesive strength of the adhesive, the ease of bonding with the amino silane monomer, etc. % And the residual amount of water, more preferably 8 to 12% by weight of sodium oxide (Na ₂ O), 25 to 32% by weight of silicon dioxide (SiO ₂ ) and the remaining amount.

The content of water glass in the adhesive according to an embodiment of the present invention is relatively large compared to the epoxy resin, specifically, the environmental friendliness of the adhesive, the adhesive strength of the adhesive to the glass, concrete or metal surface and compatibility with other components, etc. It is preferably 50 to 90% by weight, more preferably 60 to 90% by weight, most preferably 75 to 88% by weight based on the total weight of the adhesive composition when considered.

Epoxy resin

Epoxy resin, which is a component of the adhesive according to an embodiment of the present invention, serves to make the adhesive have a predetermined adhesive strength with respect to a building finish made of a hydrophobic material or an organic material such as wood or synthetic resin.

In the present invention, the epoxy resin is not particularly limited as long as it has at least two functional groups. The functional group contained in the epoxy resin includes an epoxy group or an amine group derived from an epoxy group. Examples of the epoxy resin used in the present invention include bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, bisphenol A novolac epoxy resin, Bisphenol F novolak type epoxy resin, alicyclic epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, hydantoin type epoxy resin, isocyanurate type epoxy resin, aliphatic chain epoxy resin, terminal amine And modified epoxy resins, and one of these may be used alone or in combination of two or more thereof. In connection with the terminal amine-modified epoxy resin, the present invention includes the contents disclosed in US Pat. Nos. 3331548, 6,294,73 and 60,401. For example, terminal amine-modified epoxy resins can be prepared by reacting an epoxy resin with aromatic diamines such as m-phenylenediamine, p-phenylenediamine, methylenedianiline, xylene diamine, diamine pyridine, and the like. have. In addition, the epoxy resin used by this invention may be halogenated and may be hydrogenated.

In the present invention, the epoxy resin is bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol A novolac in consideration of adhesive strength to the hydrophobic material or organic material of the adhesive, ease of bonding with the silane coupling agent, etc. It is preferable that it is 1 or more types chosen from the group which consists of a type | mold epoxy resin, a bisphenol F novolak-type epoxy resin, a glycidylamine type | mold epoxy resin, and a terminal amine modified epoxy resin, and is a bisphenol-A type epoxy resin and a glycidylamine type | mold epoxy It is more preferable that it is at least 1 type selected from the group which consists of resin and terminal amine modified epoxy resin. In addition, in the present invention, the epoxy resin may be in solid form or in liquid form, or may be a combination of solid form and liquid form. In addition, the epoxy resin in the present invention may have an epoxy equivalent of 100 ~ 1500 g / eq, it is preferable to have an epoxy equivalent of 150 ~ 800 g / eq, more preferably having an epoxy equivalent of 150 ~ 400 g / eq desirable.

In the adhesive according to an embodiment of the present invention, the content of the epoxy resin is relatively small compared to water glass, and in particular, the eco-friendliness of the adhesive, the adhesion to the hydrophobic material or the organic material of the adhesive, and compatibility with other components are to be considered. It is preferable that it is 5-20 weight part per 100 weight part of water glass, It is more preferable that it is 6-18 weight part, It is most preferable that it is 8-18 weight part.

Coupling agent

Coupling agent, one component of the adhesive according to an embodiment of the present invention increases the compatibility between the inorganic component and the epoxy resin contained in the water glass to ensure the phase stability of the adhesive and at the same time increases the viscosity of the adhesive to increase the adhesion It serves to facilitate the adhesion of the ashes.

In the adhesive according to an embodiment of the present invention, the coupling agent is present in a state in which it is bonded with silicon dioxide (SiO ₂ ) present in water glass and has a polymer form of an amino silane monomer. In addition, in the adhesive according to an embodiment of the present invention, the coupling agent and the silicon dioxide (SiO ₂ ) present in the water glass may be a hydrogen bond or a covalent bond. General silanes used as coupling agents have a structure in which four chains are bonded to silicon atoms, at least one chain contains an alkoxy group, and at least one chain contains a mercapto group, a vinyl group, an epoxy group, an amino group, a methacryl group, Functional groups such as phenyl group and the like. In the present invention, a silane in which at least one chain includes an alkoxy group and at least one chain includes an amino group among general silanes used as coupling agents is referred to as amino silane. In the present invention, silane having one silicon atom and at least one chain containing an alkoxy group and at least one chain comprising an amino group is referred to as an amino silane monomer.

In the adhesive according to an embodiment of the present invention, the amino silane monomer constituting the coupling agent is not limited as long as it is commonly used in the art, for example, N-2 (aminoethyl) 3-aminopropylmethyldi Methoxysilane, N-2 (aminoethyl) 3-aminopropyltrimethoxysilane, N-2 (aminoethyl) 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltri Ethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2- Aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, 3-aminopropylmethyldiethoxysilane, 3-aminopropyl-tris (2-methoxy-ethoxy-ethoxy) silane, N-methyl-3-amino At least one selected from the group consisting of propyltrimethoxysilane and triaminopropyl-trimethoxysilane Can be. In the adhesive according to an embodiment of the present invention, the coupling agent may be composed of a polymer of one amino silane monomer, or may be composed of a polymer of two or more amino silane monomers, and the phase stability of the adhesive and the adhesive strength of the adhesive, etc. In consideration of the above, it is more preferable that the polymer is an amino silane monomer having one or two amino groups. Preferred amino silane monomers with one amino group are 3-aminopropyltrimethoxysilane. Preferred amino silane monomers having two amino groups include N-2 (aminoethyl) 3-aminopropylmethyldimethoxysilane, N-2 (aminoethyl) 3-aminopropyltrimethoxysilane, N-2 ( Aminoethyl) 3-aminopropyltriethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, and the like.

In the adhesive according to an embodiment of the present invention, the content of the coupling agent is preferably 2 to 10 parts by weight, more preferably 3 to 8 parts by weight, based on the phase stability of the adhesive, adhesive strength, ease of application, and the like. , 4 to 5.5 parts by weight is most preferred. When the content of the coupling agent in the adhesive according to an embodiment of the present invention is less than 3 parts by weight per 100 parts by weight of water glass, there is a fear that the effect of the addition of the coupling agent is insignificant, and when the content of the coupling agent exceeds 5.5 parts by weight, the viscosity of the adhesive is too large to be applied. There is a fear not.

In the adhesive according to an embodiment of the present invention, the weight ratio of the epoxy resin to the coupling agent is preferably 1: 0.05 to 1: 0.6, more preferably 1: 0.1 to 1: 0.5, in consideration of the phase stability and adhesive strength of the adhesive. Most preferably, 1: 0.25 to 1: 0.45.

Epoxy resin curing agent

Adhesive according to an embodiment of the present invention may preferably further comprise an epoxy resin curing agent to promote the curing of the epoxy resin. The epoxy resin curing agent is not particularly limited as long as it has at least two functional groups capable of curing reaction with an epoxy group in the molecule, for example, amine-based curing agent whose functional group is an amino group, phenol-based curing agent whose functional group is a hydroxyl group, The acid anhydride type hardening | curing agent etc. whose functional group is a carboxyl group are mentioned, It is preferable that it is an amine type hardening | curing agent or a phenol type hardening | curing agent, and it is more preferable that it is an amine type hardening | curing agent.

The said amine type hardening | curing agent has C2-C20 aliphatic polyamines, such as ethylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, diethylenetriamine, and triethylenetetramine; p-xylenediamine, m-xylenediamine, 1,5-diaminonaphthalene, m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4 '-Diaminodiphenylethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenylether, 1,1-bis (4-aminophenyl) cyclohexane, 4,4'-di Aromatic polyhydric amines such as aminodiphenyl sulfone and bis (4-aminophenyl) phenylmethane; Alicyclic polyamines such as 4,4'-diaminodicyclohexane and 1,3-bis (aminomethyl) cyclohexane; And dicyandiamide or the like, and aromatic polyhydric amines are preferred in consideration of the adhesive strength of the adhesive, the phase stability of the adhesive, and the like, and 4,4'-diaminodiphenylmethane, 4,4'-diamino Diphenyl ethane, 1, 5- diamino naphthalene and p-phenylenediamine are more preferable.

A phenol resin, a phenol aralkyl resin (having a phenylene skeleton, a diphenylene skeleton etc.), a naphthol aralkyl resin, a polyoxystyrene resin etc. are mentioned as said phenol type hardening | curing agent. As a phenol resin, Resol type phenol resins, such as an aniline modified resol resin and a dimethyl ether resol resin; Novolak-type phenol resins such as phenol novolak resin, cresol novolak resin, tert-butylphenol novolak resin, and nonyl phenol novolak resin; Special phenol resins, such as a dicyclopentadiene modified phenol resin, a terpene modified phenol resin, and a triphenol methane type resin, etc. are mentioned, As a polyoxystyrene resin, poly (p-oxystyrene) etc. are mentioned.

The acid anhydride-based curing agent may be methylhexaxaphthalphthalic anhydride, methyltetrahydrophthalic anhydride, methyl anhydride (Methyl-5-norbornene-2,3-dicarboxylic anhydride), hexahydrophthalic anhydride, tetrahydroanhydride. Phthalic acid, dodecyl succinic anhydride, phthalic anhydride, succinic anhydride, maleic anhydride, pyromellitic anhydride, trimellitic anhydride and the like.

In the adhesive according to an embodiment of the present invention, the content of the epoxy resin curing agent is preferably 20 to 60 parts by weight per 100 parts by weight of epoxy resin, and more preferably 30 to 50 parts by weight in consideration of the adhesive strength of the adhesive and the ease of forming the coating film of the adhesive. desirable. In addition, the content of the curing agent in the adhesive according to an embodiment of the present invention may be represented by the total amount of functional groups capable of curing reaction with the epoxy group. For example, in the present invention, the amount of the epoxy resin curing agent is usually 0.5 to 1.5 times, preferably 0.9 to 1.1 times the total amount of the functional groups capable of curing reaction with the epoxy groups in the curing agent, relative to the total amount of the epoxy groups in the epoxy resin. This is used.

additive

1. Thermal conductive additive

The adhesive according to an embodiment of the present invention is a wood flooring adhesive, which is often applied to wood to be attached on the underfloor, in consideration of this, an additive for improving the thermal conductivity of the adhesive may be considered. Through the introduction of such additives, the thermal efficiency of the ondol can be improved. Thermally conductive additives that can be used include aluminum nitride (AIN), boron nitride (BN), volumetric expanded graphite; Fine metal powders, such as silver, iron, aluminum, and copper, are mentioned. The content of such thermally conductive additives varies depending on the type of work to be adhered to the wood flooring or the intention to work. However, 5 to 30 parts by weight relative to 100 parts by weight of the adhesive may be mixed and used in the adhesive.

2. Other additives

Adhesive according to an embodiment of the present invention is a silica powder, such as fused crushed silica powder, fused spherical silica powder, crystalline silica powder, secondary agglomerated silica powder as other additives; Fillers such as titanium dioxide, aluminum hydroxide, talc, clay, mica, glass fiber and alumina; Curing accelerators such as triphenylphosphine, 1,8-azabicyclo [5.4.0] -7-undecene, and 2-methylimidazole; Coloring agents such as carbon black; Low stress components such as silicone oil and silicone rubber; It may further include an antioxidant. In addition, the adhesive according to an embodiment of the present invention may optionally further include a diluent liquid to adjust rheological properties such as viscosity of the adhesive or the like to improve dispersibility of the constituents as other additives. In the present invention, the diluent liquid may be selected from water, alcohol, various known organic solvents, and the like, and more preferably water in terms of ensuring environmental friendliness of the adhesive according to the present invention.

In the adhesive according to an embodiment of the present invention, the content of the additive may be selected within a range that does not impair performance such as compatibility of water glass and epoxy resin in the adhesive, adhesive strength of the adhesive, coating workability of the adhesive, and coating film formation of the adhesive. have. For example, the content of the other additives in the adhesive according to an embodiment of the present invention may be 1 to 10 parts by weight, and 2 to 8 parts by weight, per 100 parts by weight of water glass.

Viscosity of adhesive

The viscosity of the adhesive according to one embodiment of the present invention is preferably 5,000 to 50,000 centipoise (cetipoise), based on room temperature, considering the ease of application and coating film forming ability, and the like, and is 7,500 to 40,000 centipoise (cetipoise) More preferably, it is most preferable that it is 10,000-35,000 centipoise.

One aspect of the present invention relates to a method for producing a water-based adhesive for attaching wood flooring which can adhere different substrates well even when the surface of the substrates to be attached to the environment and at the same time is irregular or the gap between the substrates is large. Water glass, epoxy resin, coupling agent, epoxy resin curing agent in the manufacturing method of the adhesive according to the present invention are the same as the above-described details, and will not be described.

Method of preparing an adhesive according to an embodiment of the present invention comprises the steps of adding an amino silane monomer to water glass and reacting at 60 ~ 150 ℃ for 10 to 240 minutes to form a first mixture comprising a water-glass-coupling agent organic-inorganic hybrid; And adding an epoxy resin to the first mixture and mixing to form a second mixture. In addition, the method for producing an adhesive according to another embodiment of the present invention is to add an amino silane monomer to the water glass and reacted for 10 to 240 minutes at 60 ~ 150 ℃ to form a first mixture comprising a water-glass-coupling agent organic-inorganic hybrid step; And adding an epoxy resin and an epoxy resin curing agent to the first mixture and mixing to form a second mixture. In addition, the method for producing an adhesive according to another embodiment of the present invention is to add an amino silane monomer to the water glass and reacted for 10 to 240 minutes at 60 ~ 150 ℃ to form a first mixture comprising a water-glass-coupling agent organic-inorganic hybrid step; And adding an epoxy resin to the first mixture and mixing to form a second mixture. And adding an epoxy resin curing agent to the second mixture and mixing to form a third mixture.

In the adhesive production method of the present invention, the step of adding an amino silane monomer to water glass and reacting at 60 to 150 ° C. for 10 to 240 minutes to form a first mixture including a water glass-coupling agent organic-inorganic hybrid comprises silicon dioxide of water glass ( The amino silane monomer is primarily bonded to SiO ₂ ), and the coupling or polymerization between the silane monomers is induced to form a coupling agent. Accordingly, the coupling agent constituting the water glass-coupling agent hybrid is present in the state of being bonded with silicon dioxide (SiO ₂ ) present in the water glass and has a polymer form of an amino silane monomer. In addition, the amino silane monomer is N-2 (aminoethyl) 3-aminopropylmethyldimethoxysilane, N-2 (aminoethyl) 3-aminopropyltrimethoxysilane, N-2 (aminoethyl) 3-amino Propyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N- Phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, 3-aminopropylmethyldiethoxysilane, 3-aminopropyl-tris ( 2-methoxy-ethoxy-ethoxy) silane, N-methyl-3-aminopropyltrimethoxysilane and triaminopropyl-trimethoxysilane; one or more selected from the group consisting of 3-aminopropyltri It is preferable that it is methoxysilane. In addition, the reaction temperature of the step of forming the first mixture in the adhesive production method of the present invention is preferably 70 ~ 120 ℃, more preferably 80 ~ 110 ℃. Further, the reaction time of the step of forming the first mixture in the adhesive production method of the present invention is preferably 30 to 180 minutes, more preferably 50 to 150 minutes. In addition, the amount of the amino silane monomer added in the step of forming the first mixture in the adhesive production method of the present invention is preferably 2 to 10 parts by weight, more preferably 3 to 8 parts by weight, 4 to 4 parts by weight of water glass. Most preferably, it is 5.5 parts by weight.

In addition, the amount of the epoxy resin added in the step of forming the second mixture in the production method of the present invention is preferably 5 to 20 parts by weight per 100 parts by weight of water glass. In addition, the amount of the epoxy resin curing agent added in the step of forming the second mixture or the third mixture in the manufacturing method of the present invention is preferably 20 to 60 parts by weight per 100 parts by weight of the epoxy resin.

Specific technical features or usage amounts of the components, which are not described in the preparation method of the adhesive according to the present invention, refer to the above-described contents in the adhesive portion.

Hereinafter, the present invention will be described in more detail with reference to Examples. However, the following examples are only intended to clearly illustrate the technical features of the present invention, and do not limit the protection scope of the present invention.

I. First experiment: compatibility test between water glass and epoxy resin

The inventors of the present invention tested the compatibility of water glass and epoxy resin to develop an adhesive comprising water glass and epoxy resin.

Specifically, the water-glass in a mixer (standard: KS-3 call; component ratio: Na ₂ O 9 ~ 10 wt%, SiO ₂ 28 ~ 30% by weight and the remaining amount is mulim) and was added to the epoxy resin and mixed to prepare an adhesive The phase stability of the adhesive was observed.

Table 1 shows the blending components and blending ratios of the adhesive including water glass and an epoxy resin.

Adhesive Manufacturing Example Adhesive Compounding Components and Mixing Ratios Water glass content (g)
Epoxy resin Content (g) Kinds Product Name and Manufacturer Preparation Example 1 20 5 Bisphenol A liquid epoxy resin YD-128 (Kukdo Chemical) Preparation Example 2 20 5 Bisphenol A solid epoxy resin YD-011 (Kukdo Chemical) Preparation Example 3 20 5 Bisphenol F type liquid epoxy resin YDF-170 (Kukdo Chemical) Preparation Example 4 20 5 Urethane Modified Liquid Epoxy Resin UME-330 (Kukdo Chemical)

1 is a photograph showing the phase stability of the adhesive prepared in Preparation Example 1, Figure 2 is a photograph showing the phase stability of the adhesive prepared in Preparation Example 2, Figure 3 is a phase stability of the adhesive prepared in Preparation Example 3 It is a photograph showing, Figure 4 is a photograph showing the phase stability of the adhesive prepared in Preparation Example 4. As shown in Figures 1 to 4, both water glass and epoxy resin are incompatible regardless of the type of epoxy resin. Adhesives comprising them were phase separated.

II. Second experiment: screening test of silane coupling agent to improve compatibility of water glass and epoxy resin

In the first experiment, when only the water glass and the epoxy resin were mixed to prepare the adhesive, the compatibility of the water glass and the epoxy resin was poor and the phase of the adhesive was separated. In order to improve the compatibility of water glass and epoxy resin, the inventor of the present invention added various silane coupling agents to prepare an adhesive, and observed the stability of the phase, etc. to select a silane coupling agent candidate suitable for adhesive preparation. The details are as follows.

1. Preparation of an adhesive comprising a silane coupling agent

Preparation Example 5.

20 parts by weight of water glass (standard: KS-3; component ratio: 9 to 10% by weight of Na ₂ O, 28 to 30% by weight of SiO ₂ and the balance is water) and 3-mercaptopropyltrime as a silane coupling agent The mixture was prepared by adding 0.5 parts by weight of methoxysilane (3-Mercaptopropyltrimethoxysilane; product name: KBM-803; manufacturer: Shinetsu, Japan) and stirring for about 5 minutes at a temperature of about 100 rpm at room temperature. Thereafter, 5 parts by weight of bisphenol A liquid epoxy resin (product name: YD-128; manufacturer: Kukdo Chemical, Korea) was added to the mixture, and stirred at a speed of about 100 rpm at room temperature for about 30 minutes to prepare an adhesive.

Preparation Example 6.

2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane [2- (3,4-Epoxycyclohexyl) ethyltrimethoxysilane; Product Name: KBM-303; Manufacturer: Shinetsu, Japan] except that the adhesive was prepared under the same conditions and methods as in Preparation Example 5.

Preparation Example 7.

Adhesives under the same conditions and methods as in Production Example 5, except that 3-methacryloxy propyltrimethoxysilane (Product Name: KBM-503; Manufacturer: Shinetsu, Japan) was used as the silane coupling agent. Was prepared.

Preparation Example 8.

An adhesive was prepared under the same conditions and methods as in Preparation Example 5, except that phenyltrimethoxysilane (Product Name: KBM-103; Manufacturer: Shinetsu, Japan) was used as the silane coupling agent.

Preparation Example 9.

As a silane coupling agent, vinyl tris (2-methoxyethoxy) silane; Product Name: Silquest A-172; Manufacturer: Momentive, USA] except that the adhesive was prepared under the same conditions and methods as in Preparation Example 5.

Preparation Example 10

As a silane coupling agent, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane [N- (2-aminoethyl) -3-aminopropyltrimethoxysilane; Product Name: KBM-603; Manufacturer: Shinetsu, Japan] except that the adhesive was prepared under the same conditions and methods as in Preparation Example 5.

 Preparation Example 11.

Except for using 3-glycidoxypropyltrimethoxysilane (Product Name: KBM-403; Manufacturer: Shinetsu, Japan) as the silane coupling agent, the adhesive was prepared under the same conditions and methods as in Preparation Example 5. Prepared.

Preparation Example 12

An adhesive was prepared under the same conditions and methods as in Preparation Example 5, except that octyltriethoxysilane (trade name: Silquest A-137; manufacturer: Momentive, USA) was used as the silane coupling agent.

Preparation Example 13.

An adhesive was prepared under the same conditions and methods as in Preparation Example 5, except that methyltrimethoxysilane (Product Name: KBM-13; Manufacturer: Shinetsu, Japan) was used as the silane coupling agent.

2. Observation of phase stability of adhesive

Figure 5 is a photograph showing the state of the adhesive prepared in Preparation Example 5, Figure 6 is a photograph showing the state of the adhesive prepared in Preparation Example 6, Figure 7 is a photograph showing the state of the adhesive prepared in Preparation Example 7 8 is a photograph showing a state of the adhesive prepared in Preparation Example 8, FIG. 9 is a photograph showing a state of the adhesive prepared in Preparation Example 9, and FIG. 10 is a photograph showing a state of the adhesive prepared in Preparation Example 10 11 is a photograph showing a state of the adhesive prepared in Preparation Example 11, FIG. 12 is a photograph showing a state of the adhesive prepared in Preparation Example 12, and FIG. 13 shows a state of the adhesive prepared in Preparation Example 13 It is a photograph.

As shown in FIG. 5, when the mercapto group-containing silane was used as the silane coupling agent, gelation proceeded by the reaction between the respective components, and the applicability required for the adhesive was greatly deteriorated. 6 to 9 and 13, in the case of using a cyclic epoxy group-containing silane, a methacrylate group-containing silane, a phenyl group-containing silane or a low molecular weight alkyl group-containing silane as the silane coupling agent, It has been shown that float is formed in the adhesive without improving compatibility. On the other hand, when the amino group-containing silane, the linear epoxy group-containing silane and the high molecular weight alkyl group-containing silane are used as shown in Figs. 10 to 12, the compatibility between the water glass and the epoxy resin is remarkably improved, and phase separation does not occur in the adhesive. It has been shown to maintain a suitable viscosity.

III. Third Experiment: Preparation and Properties of Adhesives Using Silane-Based Coupling Candidates

In the second experiment, an amino group-containing silane, a linear epoxy group-containing silane, and a high molecular weight alkyl group-containing silane were selected as candidates for the silane coupling agent to improve the compatibility of water glass and epoxy resin. Evaluated.

1. Preparation of Adhesive

Preparation Example 14.

Water glass in the mixer (standard: KS-3 call; component ratio: Na ₂ O 9 ~ 10 wt%, SiO ₂ 28 ~ 30% by weight and the remaining amount is mulim) 95 parts by weight of a silane coupling agent N- (2- aminoethyl ) -3-aminopropyltrimethoxysilane [N- (2-aminoethyl) -3-aminopropyltrimethoxysilane; Product Name: KBM-603; Manufacturer: Shinetsu, Japan] 1.9 parts by weight of the mixture was added and stirred at a rate of about 100 rpm at room temperature for about 5 minutes to prepare a mixture. Thereafter, 3.1 parts by weight of a bisphenol A liquid epoxy resin (product name: YD-128; manufacturer: Kukdo Chemical, Korea) was added to the mixture, and stirred at a speed of about 100 rpm at room temperature for about 30 minutes to prepare an adhesive.

Preparation Example 15

90 parts by weight of water glass (standard: KS-3; component ratio: 9 to 10% by weight of Na ₂ O, 28 to 30% by weight of SiO ₂ and the balance is water) and N- (2-aminoethyl as silane coupling agent ) -3-aminopropyltrimethoxysilane [N- (2-aminoethyl) -3-aminopropyltrimethoxysilane; Product Name: KBM-603; Manufacturer: Shinetsu, Japan] The mixture was prepared by adding 3.8 parts by weight and stirring for about 5 minutes at a speed of about 100 rpm at room temperature. Then, 6.2 parts by weight of bisphenol A liquid epoxy resin (product name: YD-128; manufacturer: Kukdo Chemical, Korea) was added to the mixture, and stirred at a speed of about 100 rpm at room temperature for about 30 minutes to prepare an adhesive.

Preparation Example 16

Water glass in the mixer (standard: KS-3 call; component ratio: Na ₂ O 9 ~ 10 wt%, SiO ₂ 28 ~ 30% by weight and the remaining amount is mulim) 85 parts by weight of a silane coupling agent N- (2- aminoethyl ) -3-aminopropyltrimethoxysilane [N- (2-aminoethyl) -3-aminopropyltrimethoxysilane; Product Name: KBM-603; Manufacturer: Shinetsu, Japan] The mixture was prepared by adding 5.6 parts by weight and stirring for about 5 minutes at a speed of about 100 rpm at room temperature. Thereafter, 9.4 parts by weight of bisphenol A liquid epoxy resin (Product Name: YD-128; Manufacturer: Kukdo Chemical, Korea) was added to the mixture, and stirred at a speed of about 100 rpm at room temperature for about 30 minutes to prepare an adhesive.

Preparation Example 17

80 parts by weight of water glass (standard: KS-3; component ratio: 9-10 wt% of Na ₂ O, 28-30 wt% of SiO ₂ , and the balance is water) and N- (2-aminoethyl as silane coupling agent ) -3-aminopropyltrimethoxysilane [N- (2-aminoethyl) -3-aminopropyltrimethoxysilane; Product Name: KBM-603; Manufacturer: Shinetsu, Japan] 7.5 parts by weight was added and the mixture was prepared by stirring for about 5 minutes at a speed of about 100 rpm at room temperature. Then, 12.5 parts by weight of a bisphenol A liquid epoxy resin (product name: YD-128; manufacturer: Kukdo Chemical, Korea) was added to the mixture, and stirred at a speed of about 100 rpm at room temperature for about 30 minutes to prepare an adhesive.

Preparation Example 18

Water glass in the mixer (standard: KS-3; component ratio: 9-10 wt% of Na ₂ O, 28-30 wt% of SiO ₂ , and the balance is water) 85 parts by weight and N- (2-aminoethyl as silane coupling agent ) -3-aminopropyltrimethoxysilane [N- (2-aminoethyl) -3-aminopropyltrimethoxysilane; Product Name: KBM-603; Manufacturer: Shinetsu, Japan] The mixture was prepared by adding 3.8 parts by weight and stirring for about 5 minutes at a speed of about 100 rpm at room temperature. Thereafter, 11.2 parts by weight of bisphenol A liquid epoxy resin (product name: YD-128; manufacturer: Kukdo Chemical, Korea) was added to the mixture, and stirred at a speed of about 100 rpm at room temperature for about 30 minutes to prepare an adhesive.

Preparation Example 19

Water glass in the mixer (standard: KS-3; component ratio: 9-10 wt% of Na ₂ O, 28-30 wt% of SiO ₂ , and the balance is water) 85 parts by weight and N- (2-aminoethyl as silane coupling agent ) -3-aminopropyltrimethoxysilane [N- (2-aminoethyl) -3-aminopropyltrimethoxysilane; Product Name: KBM-603; Manufacturer: Shinetsu, Japan] 7.5 parts by weight of the mixture was added and stirred at a rate of about 100 rpm at room temperature for about 5 minutes to prepare a mixture. Thereafter, 7.5 parts by weight of bisphenol A liquid epoxy resin (product name: YD-128; manufacturer: Kukdo Chemical, Korea) was added to the mixture, and stirred at a speed of about 100 rpm at room temperature for about 30 minutes to prepare an adhesive.

Preparation Example 20

Water glass (standard: KS-3; component ratio: 9 to 10% by weight of Na ₂ O, 28 to 30% by weight of SiO ₂ and remaining amount of water) 85 parts by weight and 3-glycidoxypropyl tree as silane coupling agent 5.6 parts by weight of methoxysilane (3-glycidoxypropyltrimethoxysilane; product name: KBM-403; manufacturer: Shinetsu, Japan) was added and stirred at room temperature at a rate of about 100 rpm for about 5 minutes to prepare a mixture. Thereafter, 9.4 parts by weight of bisphenol A liquid epoxy resin (Product Name: YD-128; Manufacturer: Kukdo Chemical, Korea) was added to the mixture, and stirred at a speed of about 100 rpm at room temperature for about 30 minutes to prepare an adhesive.

Preparation Example 21

Water glass (standard: KS-3; component ratio: 9 to 10% by weight of Na ₂ O, 28 to 30% by weight of SiO ₂ and the balance is water) 85 parts by weight and octyltriethoxysilane as silane coupling agent Product Name: Silquest A-137 Manufacturer: Momentive, USA) 5.6 parts by weight was added and the mixture was stirred at room temperature at a rate of about 100 rpm for about 5 minutes to prepare a mixture. Thereafter, 9.4 parts by weight of bisphenol A liquid epoxy resin (Product Name: YD-128; Manufacturer: Kukdo Chemical, Korea) was added to the mixture, and stirred at a speed of about 100 rpm at room temperature for about 30 minutes to prepare an adhesive.

2. Evaluation of Physical Properties of Adhesives

The adhesive prepared in Preparation Examples 14 to 21 was applied to both surfaces of a metal substrate having a surface area of 95 mm 2, and dried for about 24 hours to prepare a specimen. Thereafter, the tensile tester (product name: LLOYD LR30K +; manufacturer: LLOYD INSTRUMENT LTD., GK) was used to measure the maximum tensile load and adhesive strength of the specimen, and the results are shown in Table 2 below. In addition, a specimen was prepared using only water glass as a control, and its maximum tensile load and adhesive strength were measured.

Classification of Adhesives Used in Specimen Preparation Tensile load (N) Bond strength (N / mm2) Preparation Example 14 125 1.32 Preparation Example 15 203 2.14 Preparation Example 16 400 4.21 Preparation Example 17 120 1.26 Preparation Example 18 295 3.10 19 in manufacturing 280 2.95 Preparation Example 20 86 0.90 Preparation Example 21 67 0.71 Water glass only use 50 0.53

As shown in Table 2, when the linear epoxy group-containing silane (Production Example 20) or the high molecular weight alkyl group-containing silane (Production Example 21) is used as the silane coupling agent, the compatibility between the water glass and the epoxy resin was greatly improved, but the adhesive strength of the adhesive was improved. Was found to be very poor. On the other hand, when using an amino group-containing silane as a silane coupling agent (Preparation Examples 14 to 19) showed an appropriate level of adhesion at various content ratios, in particular, the amino group-containing silane content of 4 to 8% by weight and epoxy resin It was found that the adhesive strength of the adhesive having a content of 6-12 wt% was very good.

Ⅳ. Fourth Experiment: Preparation and Properties of Adhesives through Deformation of Silane Coupling Agents

In the third experiment, the use of an amino group-containing silane as the silane coupling agent and the preparation of the adhesive by controlling the content of the amino group-containing silane and the content of the epoxy resin can improve the compatibility of water glass and the epoxy resin and improve adhesion. It was confirmed. However, since the evaluation of the physical properties of the adhesive prepared in the third experiment was made by attaching the metal substrate to the metal substrate, it does not reflect the adhesive properties when the building finishing material, in particular, the building floor material is attached to the cement floor. In general, the cement floor to which the building flooring is attached has a predetermined range of surface roughness, so that an irregular gap of about 1 to 2 mm exists between the floor surface and the flooring. Since the adhesive prepared in Preparation Examples 14 to 19 is made of water glass, a silane coupling agent, and an epoxy resin, the volume of the adhesive is reduced in the solidification process by evaporation of water when it is used to attach the building flooring to the cement floor. As a result, they are driven to the edges of the adhesive surface and the hollow surface is generated, which ultimately results in uneven adhesion and deterioration of adhesion.

Accordingly, the inventors of the present invention prepared an adhesive by reacting amino silane in the monomer form used as a silane coupling agent with water glass in advance, and evaluated the adhesive strength and viscosity of the adhesive.

1. Preparation of Adhesive

Preparation Example 22.

100 parts by weight of water glass (standard: KS-3; component ratio: 9 to 10% by weight of Na ₂ O, 28 to 30% by weight of SiO ₂ and the balance is water) and 3-aminopropyltrimethoxysilane as an amino silane monomer (3-aminopropyltrimethoxysilane; Product Name: KBM-903; Manufacturer: Shinetsu, Japan) Add 3.5 parts by weight and stir for 90 minutes at 90 ° C at a speed of about 90rpm for the reaction between water glass and amino silane and the reaction between amino silanes. A mixture was prepared which comprises a waterglass-coupling agent hybrid in which the polymer of the amino silane monomer acts as the coupling agent and the coupling agent is in the form bound to the silicon dioxide present in the waterglass. Thereafter, 13 parts by weight of a bisphenol A liquid epoxy resin (product name: YD-128; manufacturer: Kukdo Chemical, Korea) was added to the mixture, and stirred at a speed of about 90 rpm at room temperature for about 30 minutes to prepare an adhesive.

Preparation Example 23

Preparation Example 22 and 3 except that the amino silane monomer 3-aminopropyltrimethoxysilane (Product Name: KBM-903; Manufacturer: Shinetsu, Japan) was changed to 4.0 parts by weight instead of 3.5 parts by weight. Adhesives were prepared in the same conditions and in the same manner.

Preparation Example 24

Preparation Example 22 and 3 except that the amino silane monomer 3-aminopropyltrimethoxysilane (Product Name: KBM-903; Manufacturer: Shinetsu, Japan) was changed to 4.6 parts by weight instead of 3.5 parts by weight. Adhesives were prepared in the same conditions and in the same manner.

Preparation Example 25.

Preparation Example 22 and 3 except that the amino silane monomer 3-aminopropyltrimethoxysilane (Product Name: KBM-903; Manufacturer: Shinetsu, Japan) was changed to 5.2 parts by weight instead of 3.5 parts by weight. Adhesives were prepared in the same conditions and in the same manner.

Preparation Example 26

100 parts by weight of water glass (standard: KS-3; component ratio: 9 to 10% by weight of Na ₂ O, 28 to 30% by weight of SiO ₂ and the balance is water) and 3-aminopropyltrimethoxysilane as an amino silane monomer (3-aminopropyltrimethoxysilane; Product Name: KBM-903; Manufacturer: Shinetsu, Japan) Add 4.0 parts by weight and stir for 90 minutes at 90 ° C. at a speed of about 90 rpm to allow the reaction between water glass and amino silane and the reaction between amino silanes. A first mixture was prepared which induces and comprises a waterglass-coupling agent hybrid, in which the polymer of the amino silane monomer acts as a coupling agent and the coupling agent is in the form bound to silicon dioxide present in the waterglass. Thereafter, 13 parts by weight of a bisphenol A liquid epoxy resin (product name: YD-128; manufacturer: Kukdo Chemical, Korea) was added to the first mixture, and stirred at a speed of about 90 rpm at room temperature for about 30 minutes to prepare a second mixture. . Thereafter, 4.7 parts by weight of 4,4'-diaminodiphenylmethane (DDS; manufacturer: sigma-aldrich, USA), which is an amine curing agent, was added to the second mixture, and stirred at a speed of about 90 rpm at room temperature for about 30 minutes for adhesive. Was prepared.

Preparation Example 27

Water glass in the mixer (standard: KS-3 call; component ratio: Na ₂ O 9 ~ 10 wt%, SiO ₂ 28 ~ 30% by weight and the remaining amount is mulim) 100 parts by weight of amino silane monomer is 3-aminopropyltrimethoxysilane (3-aminopropyltrimethoxysilane; product name: KBM-903; manufacturer: Shinetsu, Japan) 3.5 parts by weight were added and stirred at room temperature at a rate of about 90 rpm for 90 minutes to prepare a mixture. Thereafter, 13 parts by weight of a bisphenol A liquid epoxy resin (product name: YD-128; manufacturer: Kukdo Chemical, Korea) was added to the mixture, and stirred at a speed of about 90 rpm at room temperature for about 30 minutes to prepare an adhesive.

2. Evaluation of Physical Properties of Adhesives

The adhesive strength of the adhesive prepared in Preparation Examples 22 to 27 was measured by the following method.

* Adhesive strength: adhesive mortar substrate (70mm in width, 70mm in thickness, 40mm in thickness) and flooring flooring (Fairy Tale floor) A wood substrate (40 mm wide, 40 mm long, 8 mm thick) was used as a lozenge. Thereafter, the adhesive prepared in Preparation Examples 22 to 27 was applied to one side of the wood substrate to a thickness of about 0.6 mm, and the mortar substrate and the wood substrate were wrapped so that the coated surfaces of the adhesive touched each other, and then, at room temperature for about 7 days. The specimen was left to stand. Then, the tensile strength of the specimen was measured using a tensile tester (product name: LLOYD LR30K +; manufacturer: LLOYD INSTRUMENT LTD., GK).

* Viscosity: The viscosity of the adhesive prepared in Preparation Examples 33 to 47 was measured by a cone & plate method using a rheometer (TA Instruments AR-2000).

Table 3 shows the adhesive strength and viscosity of the adhesive prepared in Preparation Examples 22 to 27. As shown in Table 4 below, the adhesive prepared by Preparation Examples 22 to 27 showed about 5 to 16 times higher adhesive strength than the adhesive prepared by Preparation 27.

Adhesive Manufacturing Example Bond strength (N / mm2) Viscosity 22 1.5 7,200 23 3.6 10,100 24 4.4 20,090 25 4.7 38,000 26 4.8 14,000 27 0.3 950

14 shows a state when the adhesive prepared in Preparation Example 23 is applied to a wooden substrate and dried, and FIG. 15 shows a state when the adhesive prepared in Preparation Example 26 is applied to a wooden substrate and dried will be. As shown in FIG. 14 and FIG. 15, the cured dry matter of the adhesive prepared by Preparation Example 26 was clearer than the cured dry matter of the adhesive prepared by Preparation Example 23.

In addition, Figure 16 shows the surface state of the mortar substrate and the wood substrate peeled off when measuring the adhesive strength of the adhesive prepared by Preparation Example 23, Figure 17 is peeled off when measuring the adhesive strength of the adhesive prepared by Preparation 26 The surface state of the mortar base material and the wood base material is shown, and FIG. 18 shows the surface state of the mortar base material and the wood base material peeled at the time of measuring the adhesive strength of the adhesive agent manufactured by Preparation Example 27. FIG. As shown in FIGS. 16 to 18, in the case of using the adhesive prepared in Preparation Example 27, the adhesive layer was sporadically unevenly formed at the interface between the mortar substrate and the wood substrate, and the adhesive prepared in Preparation Example 26 was used. An adhesive layer was formed continuously and uniformly at the interface between the mortar substrate and the wood substrate.

Although the present invention has been described through the above embodiments as described above, the protection scope of the present invention is not necessarily limited thereto, and various modifications can be made without departing from the scope and spirit of the present invention. Therefore, the protection scope of the present invention should be construed as including all embodiments falling within the scope of the claims appended to the present invention.

Claims (18)

A composition comprising water glass, an epoxy resin and a coupling agent,
The coupling agent is present in a bonded state with silicon dioxide (SiO ₂ ) present in the water glass, and has a polymer form of an amino silane monomer.
Water-based adhesive for attaching wood flooring material comprising 5 to 30 parts by weight of the thermally conductive powder relative to 100 parts by weight of the composition.
The method of claim 1, wherein the water glass is 5 to 20% by weight of sodium oxide (Na ₂ O), 20 to 40% by weight of silicon dioxide (SiO ₂ ) and the remaining wood, characterized in that containing water (H ₂ O) Water glass adhesive for flooring.
The epoxy resin of claim 1, wherein the epoxy resin is a bisphenol A epoxy resin, a bisphenol F epoxy resin, a bisphenol S epoxy resin, a bisphenol A novolac epoxy resin, a bisphenol F novolac epoxy resin, or a glycidylamine epoxy. Water-based adhesive for attaching wood flooring, characterized in that at least one member selected from the group consisting of a resin and a terminal amine-modified epoxy resin. The method of claim 1, wherein the amino silane monomer is N-2 (aminoethyl) 3-aminopropylmethyldimethoxysilane, N-2 (aminoethyl) 3-aminopropyltrimethoxysilane, N-2 (aminoethyl ) 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propyl Amine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, 3-aminopropylmethyldiethoxysilane, 3-amino At least one member selected from the group consisting of propyl-tris (2-methoxy-ethoxy-ethoxy) silane, N-methyl-3-aminopropyltrimethoxysilane and triaminopropyl-trimethoxysilane. Water glass-based adhesive for attaching wooden floors.
The water glass-based adhesive for attaching wood flooring according to claim 1, wherein the content of the water glass is 50 to 90% by weight based on the total weight of the composition.
The water glass-based adhesive for attaching wood flooring according to claim 1, wherein the content of the epoxy resin is 5 to 20 parts by weight per 100 parts by weight of water glass.
The water glass-based adhesive for attaching wood flooring according to claim 1, wherein the coupling agent is 2 to 10 parts by weight per 100 parts by weight of water glass.
The method of claim 1,
The thermally conductive powder is at least one powder selected from the group consisting of aluminum nitride, boron nitride, volume expansion graphite, silver, iron, aluminum, copper, water glass-based adhesive for attaching wood flooring.
The method of claim 1,
The composition is water glass-based adhesive for attaching wood flooring further comprises an epoxy resin curing agent.
The method of claim 8, wherein the epoxy resin curing agent is ethylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, p-xylenediamine, m-xyl Lendiamine, 1,5-diaminonaphthalene, m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, 4, 4'-diaminodiphenylpropane, 4,4'-diaminodiphenylether, 1,1-bis (4-aminophenyl) cyclohexane, 4,4'-diaminodiphenylsulphone, bis (4-amino Phenyl) phenylmethane, 4,4'-diaminodicyclohexane, 1,3-bis (aminomethyl) cyclohexane and dicyandiamide water glass system for attaching wood flooring, characterized in that at least one selected from the group consisting of glue.
The water glass-based adhesive for attaching wood flooring according to claim 8, wherein the content of the epoxy resin curing agent in the composition is 20 to 60 parts by weight per 100 parts by weight of the epoxy resin.
Adding an amino silane monomer to the water glass and reacting at 60 to 150 ° C. for 10 to 240 minutes to form a first mixture including the water glass-coupling agent organic-inorganic hybrid; And
Adding an epoxy resin and a thermally conductive powder to the first mixture and mixing to form a second mixture to prepare a wood flooring adhesive.
Adding an amino silane monomer to the water glass and reacting at 60 to 150 ° C. for 10 to 240 minutes to form a first mixture including the water glass-coupling agent organic-inorganic hybrid; And
And adding an epoxy resin, a thermally conductive powder and an epoxy resin curing agent to the first mixture and mixing the first mixture to form a second mixture.
delete delete delete delete The method of claim 13,
The addition amount of the epoxy resin curing agent is 20 to 60 parts by weight per 100 parts by weight of epoxy resin manufacturing method of the water glass-based adhesive for wood flooring.

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