KR101929591B1 - Binder composition and combining method using it - Google Patents

Abstract

The present invention relates to a binder composition and a laminating method using the same, and it is possible to provide a method for laminating a fibrous material using the binder composition. The binder composition according to the present invention hardly contains dangerous substances such as formaldehyde, It is possible to realize high water resistance and surface hardness of the processed product through economical curing conditions and a laminating method using the binder composition.

Description

[0001] The present invention relates to a binder composition and a binder composition,

The present invention relates to a binder composition and a laminating method using the same.

The glass surface used as fire-proof insulation material is a material used for suppressing the flow of heat flowing from a high temperature to a low temperature and is a thermal insulation material having a thermal conductivity at room temperature of about 0.1 Kcal / mh ° C or less. This is a man made mineral fiber (MMMF) which is formed by molding 6 kinds of glass raw materials at high temperature and forming them into a certain shape by using high speed rotation force. Fine fibers form continuous pores, It is used as a sound absorbing material. It is a heat insulation, insulation and sound absorbing material which is formed by molding a thermosetting resin into a fibrous product in the form of a mat or a board.

The binder applied to the fireproof insulation plays a role of preventing the bending property and the deflection of the glass fiber and the like and also enhancing the tensile strength of the product. Also, since most of the glass fibers are manufactured in a mat or a board form at a high temperature, the binder used must also have heat-resistant properties.

Conventionally, a melamine-formaldehyde resin has been conventionally used as a binder to be used for the surface of a fireproof thermal insulation material such as a glass surface and for matting. However, such a melamine-formaldehyde resin has a disadvantage in that when formaldehyde is sprayed on the glass surface, the formaldehyde is spilled out to worsen the working environment and a considerable amount of formaldehyde is generated during the drying and curing, and is discharged into the atmosphere in the form of vapor. In addition, since formaldehyde generated during curing remains in the glass surface, it is gradually released as time elapses after the application, and it is a major cause of sick house syndrome when a person is inhaled through the room air.

In the case of modern people, the time spent living in the indoor environment of the artificial environment is more than 80% of the whole, so that if the formaldehyde is not removed or diluted and accumulated gradually in the room, , The importance of the indoor air environment was evaluated to be low and there were few countermeasures against it

The odor from formaldehyde is generally felt at 1 ppm, but some people detect it at a concentration of 0.05 ppm. In December 1980, the National Institute for Occupational Safety and Health (NIOSH) and the Occupational Safety and Health Administration (OSHA) recommended that formaldehyde be treated as a carcinogen on occupational hygiene. If the concentration of formaldehyde is less than 1 ppm, it may cause irritation to eyes, nose or throat, or upper respiratory tract. If the concentration is below 5 ppm, severe asthma attacks may occur in asthmatic patients. At 20 ppm or less, symptoms such as coughing, pressure of the lungs, weight of the head, or accelerated heartbeat are raised. At high concentrations of less than 100 ppm, symptoms of lung accumulation or pulmonary inflammation complain, It can lead to death.

In this respect, the management of indoor air quality in major industrialized countries is undergoing legal regulation and management by government ministries and civilian organizations. As a result, the development of products for formaldehyde has become active worldwide.

Therefore, methods such as Korean Patent Laid-Open No. 1998-0043144, which is characterized in that the polysaccharide is cured by an ester reaction using a compound having a polyfunctional carboxylic acid functional group, has been studied, and it has been proposed that a carboxylic acid and a polysaccharide Ester condensation reaction with a hydroxyl group has a problem that a reaction speed is not high and a sufficient high temperature condition and a curing time have to be given. Korean Patent Laid-Open Publication No. 2008-0049012 describes an adhesive for the same purpose and is characterized in that the neutralized polyfunctional acid compound is subjected to a condensation reaction with a reducing sugar. If ammonia or volatile amine is used as the neutralizing agent, it may cause a loss of raw materials and air pollution due to volatilization during curing.

Korean Patent Publication No. 1998-0043144 Korean Patent Publication No. 2008-0049012

The present invention relates to a binder composition and a laminating method using the same, and a method for laminating a fibrous material using the binder composition.

The present invention relates to a binder composition and a laminating method using the same.

As one example of the binder composition,

At least one amino compound;

carbohydrate; And

Acid catalyst,

The amino compound may provide a binder composition comprising at least one methanol group bonded to a nitrogen atom.

As an example of the laminating method using the above-mentioned binder composition,

Spraying a solution comprising an amino compound, a carbohydrate and an acid catalyst; And

Thermally curing the sprayed solution,

The amino compound may provide a laminating method using a binder composition comprising at least one methanol group bonded to a nitrogen atom.

Further, the present invention can provide a fibrous material that is laminated using the binder composition.

In addition, the present invention can provide a method for laminating fibrous materials using the laminating method.

The binder composition according to the present invention hardly contains hazardous materials such as formaldehyde and has economical curing conditions. Through the laminating method using the binder composition, it is possible to improve the properties such as high water resistance and surface hardness of the processed product Can be implemented.

The present invention relates to a binder composition and a laminating method using the same, and as one example of the binder composition,

At least one amino compound;

carbohydrate; And

Acid catalyst,

The amino compound may provide a binder composition comprising at least one methanol group bonded to a nitrogen atom.

Specifically, the binder composition may be a water-dispersible binder composition that does not release formaldehyde, which is a toxic substance that has been a problem in the prior art, and can be cured at low temperatures.

The amino compound may include at least one compound represented by any one of the following general formulas (1) to (5).

[Chemical Formula 1]

(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

In the above Formulas 1 to 5,

R ₁ to R ₁₈ are each independently selected from the group consisting of hydrogen, a methylol group, an alkoxy group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms, and an amino group,

At least one of R ₁ to R ₁₈ is a methylol group,

n is an integer of 1 to 5;

For example, a method of reacting the active hydrogen of the amino compound with formaldehyde by a method comprising at least one methanol group bonded to the nitrogen atom of the amino compound can be used.

At this time, the content of the active hydrogen reacted with the formaldehyde may be 15 to 90 mol% based on 100 mol% of the total active hydrogen contained in the amino compound. For example, the active hydrogen content may be from 15 to 80 mol%, from 20 to 60 mol%, or from 30 to 50 mol%. Within the range of the active hydrogen content, the amount of formaldehyde emission can be lowered, and high hardness can be achieved after curing.

Specifically, in the above Chemical Formulas 1 to 5, the methylol group linked to nitrogen can be cured at a low temperature with a hydroxyl group, a carboxyl group and / or an aldehyde, and through this, the binder composition can be cured at a low temperature.

The binder composition may have a thermal curing temperature of 150 ° C to 250 ° C. For example, the thermosetting temperature may be 150 to 220 캜, 160 to 200 캜 or 160 to 180 캜. Within the above range, the binder composition can be cured at a low temperature and can have a higher economical efficiency than a composition which is cured using existing high temperatures.

Based on 100 parts by weight of the entire binder composition,

10 to 90 parts by weight of the at least one amino compound;

5 to 80 parts by weight of the carbohydrate; And

And 0.1 to 10 parts by weight of the acid catalyst.

The amino compound is not particularly limited and includes, for example, urea having at least one methanol group bonded to a nitrogen atom, ethylene urea having at least one methanol group bonded to a nitrogen atom, ethylene oxide having at least one methanol group bonded to a nitrogen atom Urea, and a melamine having at least one methanol group bonded to a nitrogen atom. Specifically, the amino compound may be 1-hydroxymethylurea, 1,1-bis (hydroxymethyl) urea, 1,3-bis (hydroxymethyl) urea, 1,1,3- (Hydroxymethyl) urea, 1-hydroxymethyl-4-hydroxyethylene urea, 1-hydroxymethyl-5-hydroxyethylene urea Dihydroxymethyl-4-hydroxyethylene urea, dihydroxymethyl-4,5-dihydroxyethylene urea, methylol melamine, dimethylol Melamine, trimethylol melamine, and hexamethylol melamine. [0040] The term " a "

For example, the amino compound may be 25 to 70 parts by weight or 30 to 50 parts by weight based on 100 parts by weight of the entire binder composition. Within this range, the amount of formaldehyde released may be lowered, have.

The carbohydrate is not particularly limited and may be a water-soluble or water-dispersible carbohydrate including at least one of monosaccharides, disaccharides, oligosaccharides and polysaccharides. For example, the carbohydrate may include at least one of an aldehyde group, a hydroxyl group, a carboxyl group, and an amino group. As a result, the condensation curing reaction with the amino compound, the carbohydrate and the acid catalyst as the binder composition can be promoted. For example, the carbohydrate may be 15 to 60 parts by weight or 25 to 50 parts by weight based on 100 parts by weight of the entire binder composition. Within the above range, the carbohydrate can realize high stability of the binder composition, It is possible to prevent the decrease in the hardness of the coating film.

The acid catalyst is not particularly limited and may be, for example, an organic or inorganic compound containing at least one of carboxylic acid, sulfonic acid and phosphoric acid, and the acid catalyst may be neutralized selectively using alkali. For example, the acid catalyst may be used in an amount of 0.5 to 7 parts by weight or 1 to 5 parts by weight based on 100 parts by weight of the entire binder composition, and within the above range, the stability of the binder composition is not impaired and curing can be promoted .

In addition, the binder composition may further include other additives, and the other additives may include at least one of a water repellent agent, an antirust agent, a dustproof oil, a buffer, and a coupling agent. The type of the water repellent agent, rust preventive agent, dustproof oil, buffering agent and coupling agent is not particularly limited, and the rustproofing agent can be added to prevent corrosion of the equipment, and the dustproof oil can prevent scattering of particles generated during the manufacturing process of the binder composition Or < / RTI > In addition, the buffer may be added to adjust the pH of the binder composition, and the coupling agent may be added to improve the adhesion of the fibrous substrate to the binder composition.

Further, the present invention can provide a laminating method using the above-mentioned binder composition. As an example,

Spraying a solution comprising an amino compound, a carbohydrate and an acid catalyst; And

The binder composition may be laminated through thermal curing the sprayed solution,

The amino compound may include at least one methanol group bonded to a nitrogen atom.

For example, a binder composition in the form of an aqueous phase containing an amino compound, a carbohydrate and an acid catalyst may be sprayed onto the fibrous material, and the fibrous material and the binder composition may be laminated by thermal curing.

At this time, the kind of the amino compound, the carbohydrate and the acid catalyst and the thermosetting temperature may be the same as described above.

Further, the present invention can provide a fibrous material that is laminated using the binder composition. For example, the fibrous material may comprise a collection of short fibers, such as glass and rock surfaces. By compounding the binder composition with the fibrous material, a fibrous material having excellent surface hardness and water resistance can be produced, which can be used as a material of a heat insulating material and the like to improve physical properties.

In addition, the present invention can provide a method for laminating fibrous materials using a laminating method using the binder composition. The laminating method may be the same as described above, and may be, for example, a laminating method in which a binder composition is sprayed onto a fibrous material and thermally cured at a low temperature.

Hereinafter, the present invention will be described in more detail by way of examples and the like. The embodiments of the present invention are intended to be illustrative of the invention and are not intended to limit the scope of the invention.

Manufacturing example  One: Urea - Formaldehyde Resin 1  Produce

340 g of formaldehyde (37%) and 126 g of Urea were placed in a synthetic four-necked flask equipped with a thermometer and a stirrer and stirred at room temperature while blowing nitrogen gas. Then, it was confirmed that the liquid phase was clean and 0.8 g of caustic soda (20% aqueous solution) was added. Then, the pH value was confirmed to reach 8 to 9 levels, and the temperature was slowly raised to 80 占 폚. After maintaining at this temperature for 2 hours, the temperature was lowered to room temperature and diluted with 232 g of distilled water. As a result, a urea-formaldehyde resin having a solid content of 36% and a pH of 8.26 was obtained. Here, the total molar equivalent ratio of formaldehyde to the urea was confirmed to be 2: 1.

Manufacturing example  2: Urea - Formaldehyde Resin 2  Produce

511 g of formaldehyde (Formaline (37%)) and 126 g of Urea were placed in a synthetic four-necked flask equipped with a thermometer and a stirrer and stirred at room temperature while blowing nitrogen gas. After confirming that the liquid phase was clean, 1.0 g of caustic soda (20% aqueous solution) was added. Then, the pH value was confirmed to reach 8 to 9 levels, and the temperature was slowly raised to 80 占 폚. After the temperature was maintained at the above temperature for 2 hours, the temperature was lowered to room temperature and diluted with 238 g of distilled water. As a result, a urea-formaldehyde resin having a solid content of 36% and a pH of 8.31 was obtained. Here, the ratio of the total molar equivalents of formaldehyde to the urea was found to be 3: 1.

Example  One

350 kg of urea-formaldehyde resin composition obtained in Production Example 1, 310 kg of molasses (80%), 30 kg of citric acid (98%), 3800 kg of distilled water, silicone water repellent (SI1420Z-KCC) 2 kg and 3 kg of Dust Oil-Govi Garo 217S were added and stirred with a stirrer for 30 minutes to prepare a binder composition. The solid content of the prepared binder was found to be about 9%.

Example  2

350 kg of urea-formaldehyde resin composition obtained in Production Example 1, 310 kg of maltose (83%), 30 kg of citric acid (98%), 3800 kg of distilled water, silicone water repellent (SI1420Z- kg and 3 kg of Dust Oil-Govi Garo 217S were added and stirred with a stirrer for 30 minutes to prepare a binder composition. The solid content of the prepared binder was found to be about 9%.

Example  3

350 kg of the urea-formaldehyde resin composition obtained in Production Example 2, 274 kg of glucose (91%), 30 kg of citric acid (98%), 3800 kg of distilled water, ) And 3 kg of dust oil (Dust Oil-Govi Garo 217S) were charged and stirred with a stirrer for 30 minutes to prepare a binder composition. The solid content of the prepared binder was found to be about 9%.

Example  4

161 kg of dihydroxymethyl-4,5-dihydroxyethylene urea (DMDHEU), 214 kg of maltodextrin (99%), diammonium sulfate (99% ), 30 kg of distilled water, 3800 kg of silicone water repellent agent (SI1420Z-KCC) and 3 kg of dust oil (Dust Oil-Garo 217S) were stirred and stirred with a stirrer for 30 minutes to prepare a binder composition. The solid content of the prepared binder was found to be about 9%.

Example  5

88 kg of hexamethylol melamine (Cymel303), 266 kg of dextrin, 50 kg of citric acid (98%), 3800 kg of distilled water, 2 kg of silicone water repellent (SI1420Z-KCC) Dust Oil-Garo 217S), and the mixture was stirred with a stirrer for 30 minutes to prepare a binder composition. The solid content of the prepared binder was found to be about 9%.

Example  6

151 kg of the urea-formaldehyde composition obtained in Production Example 2, 211 kg of glucose (D-glucose (91%)), 211 kg of acrylic acid resin (KCC HW7002A, solid content 40%), 3800 kg of distilled water, ) And 3 kg of dust oil (Dust Oil-Garo 217S) were added and stirred with a stirrer for 30 minutes to prepare a binder composition. The solids content of the prepared binder was about 9%.

Comparative Example  One

404 kg of distilled water, 1,500 kg of distilled water, 2 kg of silicone water repellent (SI1420Z-KCC) and 3 kg of Dust Oil-Garo 217S (phenol / formaldehyde resin (KCC manufactured CAC00112, solid content 42%, formaldehyde / phenol molar ratio = And the mixture was stirred with a stirrer for 30 minutes to prepare a binder composition. The solid content of the prepared binder was found to be about 9%.

Comparative Example  2

A binder composition was prepared from the materials disclosed in Korean Patent Laid-Open No. 2008-0049012 (Example 1).

Specifically, 158 kg of glucose (91%), 44 kg of citric acid (98%), 2000 kg of distilled water, 50 kg of ammonia water (25%), 2 kg of silicone water repellent (SI1420Z- 3 kg of Dust Oil-Govi Garo 217S was added and stirred with a stirrer for 30 minutes to prepare a binder composition. The solid content of the prepared binder was found to be about 9%.

Experimental Example

The binder compositions prepared in Examples 1 to 6 and Comparative Examples 1 and 2 were measured for water resistance, formaldehyde emission, disintegration rate, tensile strength, recovery rate and mold resistance. The measurement results are shown in Table 1 below.

The experimental conditions are as follows.

1) Specimen Manufacturing

The high-temperature glass fibers were passed through a spinner to be fiberized at a rate of 2100 kg / hr, and the binder prepared in Examples 1 to 6 and Comparative Examples 1 and 2 was applied to glass fibers coming down to the housing face at a rate of 47 L / After spraying in an amount, the glass surface insulation material was obtained through a drying process. The prepared glass surface was sampled at 100 mm (width) x 100 mm (length) x 50 mm (thickness).

2) Water resistance measurement conditions

The water resistance was measured by a basic 48 hour test, and the time taken to completely sink into the beaker was measured. The grade of water resistance is bad when it is close to 0, and better when it is close to 5.

3) Formaldehyde emission measurement conditions

The formaldehyde emission was measured by HPLC (liquid chromatography), and the chamber air was collected on the 7th day after the specimen was left in the small chamber according to the small chamber method. The specific test method was tested by the method set by the Korea Air Cleaning Association (Korea), and the result was judged on the 7th day.

4) Conditions for measuring the decomposition rate

For the determination of the disintegration rate, four specimens were prepared with a width of 1.5 cm and a width of 10 cm. The weights were weighed before measurement, and the fabricated samples were placed in a crushing rate meter, and the samples were shaken back and forth, right and left at a speed of 1 m / min. The total measurement time was based on 10 minutes per sample, and the weigher was automatically stopped and weighed. The equation of disintegration rate was calculated as [(weight before measurement, weight after measurement) - 1] x 100, and the notation is expressed in%.

5) Tensile strength measurement conditions

For measuring the tensile strength, 3 specimens were fabricated with a width of 4 cm. The tensile rod was placed shorter than the length of the specimen, and the specimen was fixed horizontally to the tensile rod. The tensile strength tester was set at a speed of 15 mm / min, and the rod display was zeroed and then operated. The average value was measured by measuring the maximum load displayed after the test machine stopped automatically.

6) Conditions for measuring the recovery rate

 A glass surface sample of 10 m (width) x 1 m (length) x 0.05 m (thickness) was prepared, rolled in roll form and stored at room temperature for 8 weeks, Respectively.

7) Fungal resistance measurement conditions

The fungus resistance was measured by observing the fungal growth rate of the specimen for 1 month according to ASTM G21-09 test method.

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 1 Comparative Example 2 Water resistance 5 4 4 5 4 4 5 4 Formaldehyde
Emission
(mg / m ² · hr) 0.001 0.002 0.004 0.001 0.005 0.001 0.035 0 Disintegration rate (%) 0.6 0.8 0.6 0.5 1.0 0.9 0.5 1.8 The tensile strength
(kg _f / cm ²⁾ 0.25 0.22 0.23 0.26 0.22 0.2 0.25 0.2 Restoration rate (%) 100 or more 100 or more 100 or more 100 or more 100 or more 100 or more 100 or more 100 or more mold
Resistance Great Great Great Great Great Great Great Great

Referring to Table 1, the glass surface insulation material containing the binder composition according to the present invention had a level of formaldehyde emission close to zero as compared with the phenol / formaldehyde binder (Comparative Example 1), and had a disintegration rate, water resistance, tensile strength, Were comparable to phenol binder levels. In particular, it was confirmed that the water resistance and the mechanical properties were generally superior to those of the binder not containing formaldehyde (Comparative Example 2), and particularly, the disintegration rate was low.

Claims (12)

At least one amino compound; carbohydrate; And an acid catalyst,
The amino compound includes at least one methylol group bonded to a nitrogen atom,
Wherein the mixture does not comprise a compound comprising a phenolic group.
The method according to claim 1,
Wherein the amino compound is at least one compound represented by any of the following formulas (1) to (5):
[Chemical Formula 1]

(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

In the above Formulas 1 to 5,
R ₁ to R ₁₈ are each independently selected from the group consisting of hydrogen, a methylol group, an alkoxy group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms, and an amino group,
Any one of R ₁ to R ₄ , any one of R ₅ to R ₈ , any one of R ₉ to R ₁₀ , any one or more of R ₁₁ to R ₁₂ , and any one of R ₁₃ to R ₁₈ Is a methylol group,
n is an integer of 1 to 5;
The method according to claim 1,
Wherein the binder composition has a thermal curing temperature of from 150 캜 to 250 캜.
The method according to claim 1,
Based on 100 parts by weight of the total binder composition,
10 to 90 parts by weight of at least one amino compound;
5 to 80 parts by weight of carbohydrates; And
0.1 to 10 parts by weight of an acid catalyst.
The method according to claim 1,
The at least one amino compound is selected from urea having at least one methylol group bonded to a nitrogen atom, ethylene urea having at least one methylol group bonded to a nitrogen atom, ethylene urea having at least one methylol group bonded to a nitrogen atom, A melamine having at least one methylol group bonded to a nitrogen atom, and at least one compound selected from the group consisting of melamine having at least one methylol group bonded to a nitrogen atom.
The method according to claim 1,
The at least one amino compound may be,
(Hydroxymethyl) urea, 1 - (hydroxymethyl) urea, 1- (hydroxymethyl) urea, Methylene) ethylene urea, 1,3-bis (hydroxymethyl) ethylene urea, 1-hydroxymethyl-4-hydroxyethylene urea, 1-hydroxymethyl- 4,5-dihydroxyethylene urea, dihydroxymethyl-4-hydroxyethylene urea, dihydroxymethyl-4,5-dihydroxyethylene urea, methylol melamine, dimethylol melamine, trimethylol melamine, and Hexamethylolmelamine, and hexamethylolmelamine. The binder composition according to claim 1,
The method according to claim 1,
The carbohydrate includes at least one of monosaccharides, disaccharides, oligosaccharides and polysaccharides.
The method according to claim 1,
Wherein the acid catalyst is an organic or inorganic compound containing at least one of carboxylic acid, sulfonic acid and phosphoric acid.
The method according to claim 1,
The binder composition further comprises at least one of a water repellent agent, an antirust agent, a dustproof oil, a buffer, and a coupling agent.
Spraying a solution comprising a mixture of an amino compound, a carbohydrate and an acid catalyst; And
Thermally curing the sprayed solution,
The amino compound includes at least one methylol group bonded to a nitrogen atom,
Wherein the mixture does not comprise a compound comprising a phenolic group.
A fibrous material laminated using the binder composition of any one of claims 1 to 9.
A method for laminating fibrous materials using the method of claim 10.