KR102420583B1 - Aqueous binder composition and fibrous materials using the same - Google Patents

Abstract

The present invention relates to an aqueous binder composition and a fibrous material to which the same is applied. It's about materials.

Description

Aqueous binder composition and fibrous material applied thereto {Aqueous binder composition and fibrous materials using the same}

The present invention relates to an aqueous binder composition and a fibrous material to which the same is applied.

As a binder for bonding fibrous materials such as glass wool and rock wool, phenol formaldehyde resin (PFR), which is inexpensive and has excellent physical properties, has been mainly used. However, the phenol formaldehyde resin emits formaldehyde, a carcinogen, during the manufacturing process and even after construction, and unreacted phenol, a toxic substance, continuously leaks to the external environment and may adversely affect it.

In order to improve this, Korean Patent Registration No. 240044 discloses an adhesive containing pullulan and saccharides derived from natural substances as main components, and a molded product containing the same. However, the adhesive disclosed in this patent cannot secure sufficient physical properties such as water resistance because the degree of curing is too low to be used as a binder for bonding fibrous materials.

US Patent Publication No. 2012-0133073 discloses an adhesive use of melanoidin and polyester polymer obtained by reacting molasses and polyacid at high temperature. However, molasses has a disadvantage in that it is difficult to constantly manage the types and contents of the components due to the characteristics of the raw material itself.

Korean Patent Laid-Open No. 1999-0037115 discloses a binder composition that is cured by esterification using a compound having a hydroxyl group and a polyfunctional carboxylic acid functional group of a polysaccharide. However, the ester condensation reaction has a problem in that the reaction rate is slow, and a sufficient high temperature condition and curing time must be given to obtain a desired reaction rate.

Korean Patent Laid-Open No. 2008-0049012 discloses an adhesive comprising a Maillard reactant of a neutralized polyfunctional acid compound and a reducing sugar. However, this adhesive has disadvantages in that it is difficult to obtain sufficient strength after curing at a high temperature, and water-soluble brown low molecular weight compounds are eluted when immersed in water. In addition, when cutting a product obtained by applying the binder to inorganic fibers such as glass wool or mineral wool, lint is generated on the cut surface and a process for removing it is additionally required.

It is an object of the present invention to provide an aqueous binder composition that exhibits excellent physical properties while being cheaper than the conventional phenol formaldehyde resin used for bonding fibrous materials.

In order to achieve the above object, one aspect of the present invention provides an aqueous binder composition comprising a reducing sugar, an amino acid, a hydrolysis-condensation product of a metal alkoxide compound, and an ionic compound including a cationic metal of divalent or higher.

In addition, another aspect of the present invention provides a fibrous material bound by the aqueous binder composition.

The aqueous binder composition of the present invention is inexpensive compared to conventional phenol formaldehyde resins, does not emit toxic substances such as formaldehyde or phenol, and is eco-friendly. indicates

Hereinafter, the present invention will be described in detail.

1. Aqueous Binder Composition

One aspect of the present invention provides an aqueous binder composition.

The aqueous binder composition includes a reducing sugar, an amino acid, a hydrolysis-condensation product of a metal alkoxide compound, and an ionic compound containing a divalent or higher cation metal.

The reducing sugar serves to improve the fiber focusing power and strength of the aqueous binder composition. The reducing sugar refers to an aldose or ketose sugar that has an aldehyde or can have an aldehyde structure by isomerization.

Specifically, as the reducing sugar, monosaccharides or disaccharides such as glucose, maltose, fructose, galactose, lactose, cellobiose, gentiobiose, and rutinose may be used alone or in combination, but is not limited thereto.

The solid content of the reducing sugar contained in the aqueous binder composition of the present invention may be 40 to 95 parts by weight based on 100 parts by weight of the total solid content of the reducing sugar and the amino acid, and as another example, 60 to 90 parts by weight may be used. If the content is less than 40 parts by weight, the hardness of the cured product formed from the binder composition may be reduced, and if it exceeds 95 parts by weight, the stability of the composition and the degree of curing of the cured product may be deteriorated.

The amino acid serves to impart fiber bundling power, water resistance and flexibility of the aqueous binder composition. The amino acid may be a compound having at least one amino group and at least one carboxyl group in one molecule.

Specifically, the amino acids are glycine, alanine, valine, leucine, isoleucine, threonine, serine, cysteine, methionine, aspartic acid, asparagine, glutamic acid, diiodotyrosine, lysine, arginine, histidine, phenylalanine, tyrosine, tryptophan, proline, oxy Proline, glutamine, etc. may be used alone or in combination, but is not limited thereto.

The solid content of the amino acid contained in the aqueous binder composition of the present invention may be 5 to 60 parts by weight based on 100 parts by weight of the total solid content of the reducing sugar and the amino acid, and as another example, 10 to 40 parts by weight may be used. If the content is less than 5 parts by weight, the stability of the composition and the degree of curing of the cured product may be deteriorated, and if it exceeds 60 parts by weight, the hardness of the cured product formed from the binder composition may be reduced.

According to one embodiment of the present invention, in order to increase the solubility of the amino acid in water, some or all of the amino group (eg, 20 to 100 equivalent% of the amino group included in the amino acid, in another example 30 to 100 equivalent%) An amino acid neutralized with an acid is preferably used. Examples of the acid used for neutralization of amino acids include sulfuric acid, phosphoric acid, carboxylic acid, organic sulfonic acid, and the like, and as the form, an acid compound in the form of a monomer, a dimer, a trimer, an oligomer, or a polymer can be used without limitation. In some cases, it may be used in a neutralized form with an amine compound or ammonia. Preferably, an acid compound having a high boiling point having a boiling point of 300° C. or higher (eg, 300-500° C.) under conditions of room temperature and pressure (ie, 25° C., 1 atm) described later may be used.

The reducing sugar and the amino acid are obtained through hydrolysis or fermentation process of starch, molasses, etc. collected from plants, and there is no need to worry about the depletion of resources. In addition, it can be eco-friendly because it does not contain or generate toxic substances such as phenol and formaldehyde in the manufacturing process or final product of a product using the aqueous binder composition.

The hydrolysis-condensation product of the metal alkoxide compound serves to improve strength and heat resistance of the aqueous binder composition. The hydrolysis-condensation product of the metal alkoxide compound is a product obtained by hydrolyzing a mixture of at least one alkoxy silane compound containing a tetrafunctional or more alkoxy silyl group and at least one alkoxy silane compound containing one or more organic functional groups. can For example, the hydrolysis-condensation product of the alkoxide compound may be a silica sol compound including an organic functional group. For example, a mixture of two different types of compounds and an alkoxysilane compound including an organic functional group among the alkoxysilane compounds including a tetrafunctional or higher alkoxy silyl group may be used, and different types of alkoxysilane compounds including an organic functional group may be used. A mixture of two types of compounds and an alkoxysilane compound containing a tetrafunctional or more alkoxysilyl group may be used, and a mixture of an alkoxysilane compound containing a tetrafunctional or more alkoxysilyl group and an alkoxysilane compound containing an organic functional group may be used. have.

The alkoxysilane compound containing the tetrafunctional or higher alkoxy silyl group is tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetraisobutoxysilane and One selected from the group consisting of bis(triethoxysilyl)ethane or a mixture thereof may be used.

The alkoxy silane compound including the organic functional group may be an alkoxy silane compound including an organic functional group selected from the group consisting of an unsaturated double bond, a glycidyl group, an amino group, an ureido group, and an isocyanate group.

For example, the alkoxy silane compound containing the organic functional group is vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxy Propyltrimethoxysilane, γ-acryloxypropyltriethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-aminopropyltrime Toxysilane, N-β-(aminoethyl)-γ-aminopropyltriethoxysilane, vinylmethyldimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-acryloxypropylmethyldimethoxysilane, γ- Glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-ureidopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, γ One selected from the group consisting of -isocyanatopropyltrimethoxysilane and γ-isocyanatopropyltriethoxysilane or a mixture thereof may be used.

In the case of a mixture of the alkoxysilane compound including the tetrafunctional or more alkoxysilyl group and the alkoxysilane compound including the organic functional group, the molar ratio is preferably 80:20 to 10:90, more preferably 30:70 to 70: It can be 30 days. If the content of the alkoxysilane compound including the organic functional group is lower than the above range, there may be a problem in that mechanical properties such as strength and water resistance are inferior due to lack of coupling between the organic component and the silica sol component in the composition. When the content of the alkoxysilane compound containing the organic functional group is higher than the above range, the crosslinking density of the hydrolysis-condensation product of the metal alkoxide compound decreases as the content of the alkoxysilane containing the tetrafunctional or higher alkoxysilyl functional group decreases. There is a problem of being inferior.

The solid content of the hydrolysis-condensation product of the metal alkoxide compound included in the aqueous binder composition of the present invention may be 5 to 250 parts by weight, for example, 8 to 150 parts by weight, based on 100 parts by weight of the total solid content of the reducing sugar and the amino acid, As another example, 10 to 100 parts by weight may be used. If the content is less than 5 parts by weight, there is a problem in that mechanical properties such as tensile strength, hardness and cutting workability and heat resistance stability of the final molded product are lowered, and if it exceeds 250 parts by weight, the final molded product is easily broken due to excessive hardness increase. , there is a problem in that the binding force of the final molded product (eg, fibrous material) is inferior.

The ionic compound containing the divalent (eg, 2 to 7) or higher cationic metal serves to increase the crosslinking density through metal coordination bonds in the aqueous binder cured product to improve strength and water resistance.

Since the aqueous binder composition of the present invention is in the form of an aqueous solution or aqueous dispersion before being applied to a fibrous material to be described later, it is preferable that the aqueous solubility of the ionic compound containing the divalent or higher cation metal is high. Specifically, a divalent or higher cation metal complex compound having a water solubility of 5 wt% or more (eg, 5-50 wt%) may be preferably used. If the water solubility of the divalent or higher cationic metal complex is too low, the metal complex does not dissolve well in the preparation of the binder aqueous solution, so that it does not exhibit sufficient curing performance, or a water-insoluble chelate is formed before spraying the fibrous material to lose the adhesive function. can

The ionic compound is in a form in which a cationic metal having a divalent or higher value is ionically bonded to an anion of an organic acid or an inorganic acid. Examples of the metal include at least one selected from the group consisting of Co, Cu, Ni, Cd, Mn, Mg, Zn, Fe, Al and Zr, and examples of the anion of the organic acid or inorganic acid include a halogen anion, sulfuric acid and at least one selected from the group consisting of anions, carbonate anions, phosphate anions, nitrate anions, thiocyanate anions and organic acid anions. Also, preferably, for the purpose of preventing corrosion of equipment, for pH control, water solubility improvement, and stability of the adhesive solution, the divalent or higher cationic metal complex may further include an ammonium salt, and may be in the form of a hydrate or an aqueous solution.

Specific examples of the divalent or higher cationic metal complexes usable in the present invention include ammonium cobalt (II) thiocyanate, ammonium cobalt (II) sulfate, ammonium cobalt (II) phosphate, ammonium copper (II) sulfate, ammonium copper (II) Carbonate, Ammonium Nickel(II) Sulfate, Ammonium Nickel(II) Phosphate, Ammonium Manganese(II) Sulfate, Ammonium Manganese(III) Diphosphate, Ammonium Manganese(II) Phosphate, Ammonium Zinc(II) Sulfate, Ammonium Zinc(II) phosphate, ammonium zinc(II) carbonate, ammonium iron(II) sulfate, ammonium iron(III) sulfate, ammonium iron(III) citrate, ammonium iron(II) phosphate, ammonium iron(III) phosphate, ammonium aluminum(III) At least one selected from the group consisting of sulfate, ammonium aluminum (III) phosphate, ammonium aluminum (III) carbonate, ammonium zirconium (IV) sulfate, ammonium zirconium (IV) phosphate and ammonium zirconium (IV) carbonate and hydrates thereof However, the above example is not intended to limit the type of the metal complex compound that can be used in the present invention. That is, various divalent or higher cation metals may combine with various types of anions to form a water-soluble compound, all of which may be included in the scope of the present invention.

The content of the ionic compound containing the divalent or higher cationic metal included in the aqueous binder composition of the present invention may be 0.1 to 5 parts by weight, for example, 0.1 to 3 parts by weight, based on 100 parts by weight of the total solid content of the reducing sugar and the amino acid. Part by weight may be used, and as another example, 0.1 to 1 part by weight may be used. If the content is less than 0.1 parts by weight, complex formation by coordination with other organic binder compositions may be insufficient, and physical properties such as water resistance of the product may be deteriorated. As the ionic substances remain, it may also adversely affect the physical properties of the product.

The aqueous binder composition of the present invention may further include a high boiling point acid compound having a boiling point of 300° C. or higher (eg, 300-500° C.) at room temperature and atmospheric pressure (ie, 25° C., 1 atm). These high boiling point acid compounds can be used to increase the solubility of amino acids in water and also to increase the curing reaction rate in the high-temperature baking process after spraying on the fibrous aggregate. It is preferable that a boiling point is 300 degreeC or more. Examples of the high boiling point acid compound include sulfuric acid, phosphoric acid, carboxylic acid, organic sulfonic acid, and the like, and as the form, an acid compound in the form of a monomer, a dimer, a trimer, an oligomer, or a polymer may be used without limitation. In some cases, it may be used in a neutralized form with an amine compound or ammonia.

When the high boiling point acid compound is included in the aqueous binder composition of the present invention, the content may be 0.1 to 10 parts by weight based on 100 parts by weight of the total solid content of the reducing sugar and the amino acid, for example, 0.1 to 5 parts by weight may be used. and, as another example, may be 0.1 to 3 parts by weight. If the content is less than 0.1 parts by weight, non-curing may occur and the physical properties of the cured product may be deteriorated, and if the content is more than 10 parts by weight, a brittle cured product may occur.

In addition to the above components, the aqueous binder composition of the present invention may optionally further include one or more additives as needed within a range capable of achieving the object of the present invention. Useful additional additives include a water repellent to increase the water resistance of the fibrous aggregate, a rust preventive to prevent corrosion of equipment, a dustproof oil to lower the dust generation rate of the product, a buffer to adjust the pH, and a coupling agent to improve adhesion. However, the present invention is not limited thereto, and additives commonly used in the art may be used. There is no particular limitation on the amount of these additional additives, for example, based on 100 parts by weight of the total solid content of the reducing sugar and the amino acid, each additive may be used in the range of 0.1 to 10 parts by weight, but is not limited thereto.

Water (industrial water, groundwater, process water, etc.) is used as a diluent for uniformly applying the above components to the fibrous material, and the solid content thereof is reduced as needed by 2 to 50% by weight, preferably 5 to 20% by weight ( That is, the content of water may be adjusted to 50-98% by weight, preferably 80-95% by weight) based on 100% by weight of the total roll of the composition. If the amount of water as a diluent is too large, energy for volatilizing the water is consumed excessively. On the contrary, if the amount of water is too small, the binder composition is not well applied on the fibrous material, and as a result, the binder content in the product is unnecessarily high, which is undesirable.

When the binder composition of the present invention is heat-treated at a temperature of, for example, 120° C. or higher, the Maillard reaction that occurs in the Amadori intermediate between the aldehyde group of the reducing sugar and the amine group of the amino acid, the amide reaction between the carboxylic acid group of the amino acid and the amine group, and the hydroxyl group of the reducing sugar Various curing reactions with high crosslinking density, such as an ester reaction between an amino acid and a carboxylic acid group, a coordination bond between a metal ion and an organic functional group, a condensation reaction between a metal oxide and an alkoxysilane, and a crosslinking reaction between an alkoxysilane and an organic functional group, occur. and, through this, a water-insoluble polymer is formed, so that it can be used as an adhesive having very excellent physical properties such as water resistance and mechanical strength.

The pH of the binder composition of the present invention is not particularly limited, but when the equipment for manufacturing inorganic fiber products is designed with general carbon steel instead of stainless material, it is preferable to adjust the pH to a basic atmosphere in order to minimize equipment corrosiveness. In the case of the pH adjusting agent used, it is preferable to use volatile ammonia or amines that do not affect the physical properties of the product, and the range is preferably between pH 6-10, more preferably 7-9. If the pH is lower than this, corrosiveness to iron equipment increases, and if the pH is high, volatile ammonia or amine smell may become a problem during binder manufacture.

2. fibrous ingredient

Another aspect of the present invention provides a fibrous material bound by the aqueous binder composition.

Examples of the fibrous material include, but are not limited to, inorganic fibers (eg, rock wool, glass wool, ceramic fibers, etc.) or short fiber aggregates such as fibers obtained from natural and synthetic resins.

The aqueous binder composition may be used in an amount of 2 to 15% by weight based on the total weight of the fibrous material. If the content of the aqueous binder composition is less than 2% by weight, there is a problem in that the fiber binding force is lowered and the strength of the final product is inferior. can be done

Specifically, the fibrous material may be formed by spraying 2 to 15% by weight of the aqueous binder composition onto the fibrous material, and thermosetting the sprayed fibrous material with the aqueous binder composition to form a bound fibrous material.

At this time, the heat treatment temperature for curing is 120 ° C. or higher (for example, 120-300 ° C, 150-250 ° C for another example) is suitable. Dust generation can be a problem.

Hereinafter, the present invention will be described in more detail through examples. However, these examples are only for helping the understanding of the present invention, and the scope of the present invention is not limited to these examples in any sense.

[Production Example]

Preparation Example 1: Hydrolysis-condensation product of metal alkoxide compound

147 kg of glucose (D-glucose, solid content: 91% by weight), 30 kg of acetic acid, and 412 kg of distilled water were put into a mixing vessel capable of increasing the temperature, and then stirred at 25 ° C. to 30 ° C. for 30 minutes to dissolve the input. After completion of dissolution, a mixed solution of 512 kg (2,458 mol) of tetraethoxysilane (TEOS) and 249 kg (1,055 mol) of γ-glycidoxypropyltrimethoxysilane (Silquest A-187, Momentive Performance Materials) was placed in a mixing container for 10 minutes. was put in. Then, after maintaining stirring for 30 minutes, the temperature was raised to 60±2° C., and the maturation reaction was performed under stirring conditions for an additional 2 hours. The solid content of the final product was about 42% by weight. The solids content of the hydrolysis-condensation product of the metal alkoxide compound in the final product was 33% by weight.

Preparation Example 2: Hydrolysis-condensation product of metal alkoxide compound

155 kg of glucose (D-glucose; solid content: 91% by weight), 28 kg of acetic acid, and 374 kg of distilled water were put into a mixing vessel capable of increasing the temperature, and then stirred at 25 to 30° C. for 30 minutes to dissolve the input. After completion of dissolution, a mixture of 332 kg (1,593 mol) of tetraethoxysilane (TEOS) and 376 kg (1,593 mol) of γ-glycidoxypropyltrimethoxysilane (Silquest A-187, Momentive Performance Materials) was placed in a mixing container for 10 minutes. was put in. Then, after maintaining stirring for 30 minutes, the temperature was raised to 60±2° C., and the maturation reaction was performed under stirring conditions for an additional 2 hours. The solid content of the final product was about 48% by weight. The solid content of the hydrolysis-condensation product of the metal alkoxide compound in the final product was 36% by weight.

[Example]

Example 1

Glucose to a solid content of 192.3 kg, solid lysine neutralized with sulfuric acid to a solid content of 68.6 kg, ammonium aluminum (III) sulfate hydrate (AASD) 2.5 kg and distilled water 2083 kg in a mixing vessel was added, and stirred for 30 minutes with a stirrer to prepare a uniform mixed solution. After that, the hydrolysis-condensation product of the metal alkoxide compound prepared in Preparation Example 1 was added so that the solid content was 29.6 kg, stirred for 10 minutes, and then 3.2 kg of a silicone water repellent (KCC-SI1402Z) was added and an additional 10 minutes. A binder composition was prepared by stirring. The binder composition prepared as described above had a solid content of about 12% by weight.

Examples 2 to 8

A binder composition was prepared by applying the mixing ratios in Table 1 below in the same manner as in Example 1. The binder compositions of Examples 2 to 8 prepared as described above had a solid content of about 12±1% by weight.

Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Distilled water (kg) 1984 1,886 1,786 2,093 2014 1935 1,855 D-glucose (kg) 149.0 115.0 63.0 191.9 149.0 106.1 63.2 L-lysine (kg) 52.9 37.2 22.5 68.6 52.9 37.24 22.54 AASD(kg) 2.5 2.5 2.5 2.5 2.5 2.5 2.5 Preparation Example 1 (kg) 88.9 177.5 207.1 - - - - Preparation Example 2 (kg) - - - 29.5 88.6 147.6 206.6 Silicone water repellent (kg) 3.2 3.2 3.2 3.2 3.2 3.2 3.2

[Comparative example]

Comparative Example 1: Preparation of binder using phenol/formaldehyde resin

404 kg of phenol/formaldehyde resin (manufactured by KCC), 3020 kg of distilled water, 2 kg of water repellent (KCC-SI1402Z) and 3 kg of anti-vibration oil (Garo217S) were put into a mixing container and stirred with a stirrer for 30 minutes to prepare a binder. The solid content of the prepared binder was about 12% by weight.

Comparative Example 2: Preparation of a binder using polycarboxylic acid (Example 1 of Korean Patent Application Laid-Open No. 2008-0049012)

Glucose (D-glucose; solid content: 91 wt%) 158 kg, citric acid (solid content: 98 wt%) 44 kg, ammonia water (25%) 50 kg, distilled water 3800 kg, water repellent (KCC-SI1402Z) 2 kg, and dustproof oil (Garo217S) ) 3 kg was put into a mixing container and stirred with a stirrer for 30 minutes to prepare a binder. The solid content of the prepared binder was about 4.5%.

Comparative Example 3: Preparation of natural component binder without hydrolysis-condensation product of metal alkoxide compound

Glucose (D-glucose; solid content: 91 wt%) 96 kg, solid lysine (L-lysine) neutralized with sulfuric acid (solid content: 98 wt%) 35 kg, ammonium aluminum (III) sulfate hydrate (AASD) 1 kg, silicone water repellent (KCC) -SI1402Z) 1.5 kg and distilled water 870 kg were put into a mixing container and stirred with a stirrer for 30 minutes to prepare a binder. The solid content of the prepared binder was about 12% by weight.

[Experimental example]

Experimental Example: Binding of Fibrous Materials Using Binder

Each of the binders prepared in Examples 1 to 8 and Comparative Examples 1 to 3 was applied to the glass fibers descending into the collecting chamber while passing high-temperature glass water through the spinner and fiberizing it at a rate of 2100 kg/hr per hour, 47 L/min. After spraying positively, a glass surface insulating material was obtained through a drying process.

Experiments of the following items were performed on each glass surface prepared as described above.

water resistance

After preparing a glass surface sample of 100 mm (horizontal) x 100 mm (length) x 50 mm (thickness), a basic 48-hour water resistance test was performed. The time it takes for the sample to sink completely was measured by floating the sample in a beaker containing fresh water. Water resistance ratings indicate that the closer to 0, the worse, and the closer to 5, the better. The experimental results are shown in Tables 2 and 3 below.

submersible

After preparing a glass surface sample of 100mm (horizontal) x 100mm (length) x 50mm (thickness), a basic 72-hour immersion test was performed. The color change was measured for 72 hours by completely immersing the sample in a 2L beaker filled with fresh water. At this time, the degree of color change according to the concentration was objectively quantified. In the water permeability rating, the closer to 0, the worse, and the closer to 5, the better. The experimental results are shown in Tables 2 and 3 below.

Formaldehyde emission

After leaving the specimen in the small chamber according to the small chamber method, the chamber air was collected on the 7th day, and the collected air was analyzed by HPLC (liquid chromatography). The specific test method followed the method set by the Air Cleaning Association (KS M ISO 16000, KS M 1998), and the result was determined on the 7th day. The experimental results are shown in Tables 2 and 3 below.

The tensile strength

Three measurement samples were prepared each having a size of 4 cm in width. The tensile bar was positioned shorter than the length of the sample, and the sample was fixed to the tensile bar so as to be horizontal, and then the sample was tightened to the support bar so as to be vertical. The speed of the tensile strength tester was set to 15 mm/min, and after zeroing the load display, it was operated. After the tester stops automatically, the displayed maximum load is measured and the average value is taken. The experimental results are shown in Tables 2 and 3 below.

dust rate

Four measurement samples were prepared each having a width of 1.5 cm and a width of 10 cm. After weighing the weight before measurement, the sample was placed in a dust rate meter and shaken back and forth at a speed of 1 m/min. The total measurement time was based on 10 minutes per sample, and after the tester stopped automatically, the weight of the sample was measured. Dust rate = [(Weighing weight after measurement / Weighing weight before measurement) 1]*100 The dust rate was calculated and expressed as %. The experimental results are shown in Tables 2 and 3 below.

recovery rate

A glass surface sample of 10 m (horizontal) × 1 m (length) × 0.05 m (thickness) was prepared, wound in a roll form and stored at room temperature for 8 weeks, and then released to the original state to confirm the thickness change. The experimental results are shown in Tables 2 and 3 below.

fungal resistance

The mold resistance was measured by observing the mold growth rate on the specimen for 1 month according to the ASTM G21-09 test method. The experimental results are shown in Tables 2 and 3 below.

Heat resistance, high temperature (1,000℃) exposure mass retention (%)

Each binder composition was applied on a glass plate and exposed at 230±10° C. for 15 minutes to obtain a cured binder product after drying and curing. The heat-resistance properties of the thus-obtained solid binder cured product were confirmed through a thermogravimetric analyzer. As for the test temperature condition, the mass retention rate of the cured binder was measured by raising the temperature at a rate of 10°C per minute from the initial 20°C to the final 1,000°C. In general, the higher the mass retention rate (%) at high temperature, the better the heat resistance. have. The test results are shown in Tables 2 and 3 below.

Item Example One 2 3 4 5 6 7 8 water resistance 5 5 5 5 5 5 5 5 submersible 5 5 5 5 5 5 5 5 Formaldehyde emission 0 0 0 0 0 0 0 0 Tensile strength (kgf/㎠) 0.32 0.3 0.23 0.2 0.34 0.32 0.28 0.24 Dust rate (%) 0.6% 0.5% 0.6% 0.6% 0.5% 0.5% 0.5% 0.5% Restoration rate (%) 100%
More than 100%
More than 100%
More than 100%
More than 100%
More than 100%
More than 100%
More than 100%
More than fungal resistance Great Great Great Great Great Great Great Great heat resistance
(mass retention rate) 6.8% 11.8% 21.2% 32.7% 7.3% 12.5% 23.8% 35.3%

Item comparative example One 2 3 water resistance 5 3 4.5 submersible 5 2 4 Formaldehyde emission 0.035 0 0 Tensile strength (kgf/㎠) 0.25 0.2 2.3 Dust rate (%) 0.5% 1.8% 0.5 Restoration rate (%) 100% or more 100% or more 100% or more fungal resistance Great Great Great heat resistance
(mass retention rate) 2.6% 0.4% 0.8%

Claims (6)

reducing sugar,
amino acid,
hydrolysis condensates of metal alkoxide compounds and
An aqueous binder composition comprising an ionic compound comprising a divalent or higher cationic metal,
The hydrolysis-condensation product of the metal alkoxide compound is a condensed product after hydrolysis of a mixture of at least one alkoxysilane compound containing a tetrafunctional or higher alkoxysilyl group and at least one alkoxysilane compound containing an organic functional group,
The organic functional group will include a glycidyl group, the aqueous binder composition. The method according to claim 1,
An aqueous binder composition comprising 5 to 250 parts by weight of a solid content of a hydrolysis-condensation product of a metal alkoxide compound based on 100 parts by weight of the total solid content of the reducing sugar and the amino acid. delete The method according to claim 1,
The hydrolysis-condensation product of the metal alkoxide compound is an aqueous binder composition in which the alkoxysilane compound containing the tetrafunctional or higher alkoxysilyl group and the alkoxysilane compound containing the organic functional group are mixed in a molar ratio of 80:20 to 10:90. A fibrous material bound using the aqueous binder composition according to any one of claims 1, 2, and 4. 6. The method of claim 5,
The aqueous binder composition is 2 to 15% by weight of the fibrous material.