JP6388949B2 - Binder composition and binding method using the same - Google Patents

Description

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

  Glass cotton used as an incombustible heat insulating material is a material used for suppressing heat flow flowing from a high temperature to a low temperature, and is a heat insulating material having a thermal conductivity at room temperature of about 0.1 Kcal / mh ° C. or less. This is an artificial mineral fiber (MMMF) that is made by melting 6 types of glass materials in addition to silica sand at high temperature, fiberizing them using high-speed rotational force, and forming them into a certain shape. Fine fibers form continuous pores. doing. A product obtained by spraying a thermosetting resin into a fiber is molded into a form of a mat or a board and used as a heat insulating material, a heat insulating material, or a sound absorbing material.

  The binder applied to the non-combustible heat insulating material plays a role of preventing warpage and flexibility of glass fibers and the like, and also plays a role of increasing the tensile strength of the product. Also, since most glass fibers are manufactured in the form of mats or boards at high temperatures, the binder used must also have heat resistant properties.

  Conventionally, melamine-formaldehyde resin has usually been used as a binder used for collecting and matting non-combustible heat insulating materials such as glass cotton. However, such melamine-formaldehyde resin deteriorates the working environment by causing formaldehyde to flow out into the air when spraying on glass cotton, and a considerable amount of formaldehyde is generated during drying and curing in the atmosphere in the form of vapor. Has the disadvantage of being discharged. In addition, if formaldehyde generated during curing remains inside the glass cotton and is slowly released over time after construction and flows out into the indoor air, if inhaled by humans, it is the main cause of sick house syndrome Sometimes, it is not preferable.

  In the case of modern people, the time spent living in a building that is an artificial environment is 80% or more of the whole. Until recently, when formaldehyde is gradually accumulated in a room without being removed or diluted, the importance of the indoor air environment has been underestimated until recently, despite the fact that it can have a direct impact on the health of occupants. The actual situation is that no countermeasures are taken.

  The smell generated from formaldehyde is generally felt at 1 ppm, but some people sense it from a concentration of 0.05 ppm. In December 1980, the National Institute for Occupational Safety and Health (NIOSH) and the Occupational Health Administration (OSHA) recommended that formaldehyde should be treated as a carcinogen for occupational health. Usually, when the concentration of formaldehyde is 1 ppm or less, abnormal symptoms are observed in irritation of eyes, nose or throat, upper respiratory tract, etc., and if it is 5 ppm or less, severe asthma attacks are caused in asthmatic patients. In addition, symptoms such as cough, pressure on the lungs, head sensation or heart pulsation are observed at 20 ppm or less, and accumulation of pulmonary fluid or pulmonary inflammation is observed at a high concentration of 100 ppm or less. There is a risk of death.

  Therefore, the control of indoor air quality in major industrialized countries tends to be strengthened by the regulation and management of laws by related departments in the government and private organizations, and based on this, development of formaldehyde-compatible products is active worldwide. It has become.

  Therefore, a method such as Patent Document 1 characterized by curing by an ester reaction using a polysaccharide and a compound having a polyfunctional carboxylic acid functional group is currently being studied. However, the ester condensation reaction between a carboxylic acid and a hydroxyl group of a polysaccharide has a problem that the reaction rate is not fast, so that a sufficiently high temperature condition and a curing time must be provided. Patent Document 2 describes an adhesive having the same purpose, and is characterized by a condensation reaction between a neutralized polyfunctional acid compound and a reducing sugar. However, when ammonia or a volatile amine is used as a neutralizing agent, there may be a problem that it may volatilize at the time of curing to cause loss of raw materials and air pollution.

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

  The present invention relates to a binder composition and a binding method using the same, and an object thereof is to provide a method for binding a fibrous material using the binder composition.

The present invention relates to a binder composition and a binding method using the same.
As one example of the binder composition,
One or more amino compounds;
A carbohydrate; and an acid catalyst;
The amino compound provides a binder composition including one or more methanol groups bonded to a nitrogen atom.
In addition, as an example of a binding method using the binder composition,
Spraying a solution comprising an amino compound, a carbohydrate and an acid catalyst; and thermally curing the sprayed solution;
The amino compound provides a binding method using a binder composition containing one or more methanol groups bonded to a nitrogen atom.
The present invention also provides a fibrous material that is bound using the binder composition.
Furthermore, the present invention provides a fibrous material binding method using the binding method.

  Since the binder composition according to the present invention contains almost no dangerous substance such as formaldehyde and has an economical curing condition, a product processed by the binding method using the binder composition has high water resistance. Further, physical properties such as surface hardness can be realized.

The present invention relates to a binder composition and a binding method using the same, and as an example of the binder composition,
One or more amino compounds;
A carbohydrate; and an acid catalyst;
The amino compound provides a binder composition including one or more methanol groups bonded to a nitrogen atom.

  Specifically, the binder composition may be a water-dispersible binder composition that hardly releases formaldehyde, a toxic substance that has been regarded as a problem in the past, and can be cured at a low temperature.

  The amino compound may contain one or more compounds represented by any one of the following formulas (1) to (5).

Wherein 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 or more of R _{1 to} R ₁₈ is a methylol group;
n is an integer of 1-5. )

  For example, for the amino compound containing one or more methanol groups bonded to a nitrogen atom, a method in which active hydrogen of the amino compound is reacted with formaldehyde can be used.

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

  Specifically, in the above formulas (1) to (5), the methylol group bonded to nitrogen can be cured with a hydroxy group, a carboxy group and / or an aldehyde at a low temperature. Thereby, low temperature hardening of a binder composition is attained.

  The binder composition has a thermosetting temperature of 150 ° C to 250 ° C. For example, the said thermosetting temperature is 150 to 220 degreeC, 160 to 200 degreeC, or 160 to 180 degreeC. Since the binder composition can be cured at a low temperature within the above range, it has high economic efficiency as compared with a composition cured using a conventional high temperature.

The present invention is based on 100 parts by weight of the entire binder composition.
10 to 90 parts by weight of the one or more amino compounds;
5 to 80 parts by weight of the carbohydrate; and 0.1 to 10 parts by weight of the acid catalyst.

  The type of amino compound is not particularly limited. For example, urea having one or more methanol groups bonded to a nitrogen atom, ethylene urea having one or more methanol groups bonded to a nitrogen atom, or methanol group bonded to a nitrogen atom. It includes one or more compounds selected from the group consisting of ethylene hydroxide having one or more and melamine having one or more methanol groups bonded to nitrogen atoms. Specifically, the amino compound includes 1-hydroxymethylurea, 1,1-bis (hydroxymethyl) urea, 1,3-bis (hydroxymethyl) urea, 1,1,3-tri (hydroxymethyl) urea, 1- (hydroxymethyl) ethylene urea, 1,3-bis (hydroxymethyl) ethylene urea, 1-hydroxymethyl-4-hydroxyethylene urea, 1-hydroxymethyl-5-hydroxyethylene urea, 1-hydroxymethyl-4, A compound selected from the group consisting of 5-dihydroxyethylene urea, dihydroxymethyl-4-hydroxyethylene urea, dihydroxymethyl-4,5-dihydroxyethylene urea, methylol melamine, dimethylol melamine, trimethylol melamine, and hexamethylol melamine; U Comprising one or more of.

  For example, the content of the amino compound is 25 to 70 parts by weight or 30 to 50 parts by weight based on 100 parts by weight of the entire binder composition. High hardness can be realized.

  The kind of the carbohydrate is not particularly limited, and may be a water-soluble or water-dispersible carbohydrate containing one or more of monosaccharides, disaccharides, oligosaccharides and polysaccharides. For example, the carbohydrate includes one or more of an aldehyde group, a hydroxy group, a carboxy group, and an amino group. Thereby, condensation curing reaction with the amino compound which is a binder composition, a carbohydrate, and an acid catalyst can be accelerated | stimulated. For example, the content of the carbohydrate is 15 to 60 parts by weight or 25 to 50 parts by weight based on 100 parts by weight of the whole binder composition, and within the above range, high stability of the binder composition is realized. It is possible to prevent the degree of curing and the coating film hardness from being lowered during curing.

  The kind in particular of the said acid catalyst is not restrict | limited, For example, it is an organic or inorganic compound containing 1 or more types in carboxylic acid, a sulfonic acid, and phosphoric acid. The acid catalyst can be selectively neutralized using an alkali. For example, the content of the acid catalyst is 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 the stability of the binder composition is inhibited within the above range. Curing can be promoted without doing so.

  In addition, the binder composition may further include an additive, and the other additive is one or more of a water repellent, a rust preventive, a dustproof oil, a buffer, and a coupling agent. including. The type of the water repellent, rust preventive, dustproof oil, buffer and coupling agent is not particularly limited, the rust preventive is added to prevent the equipment from corroding, and the dustproof oil is a process for producing the binder composition. It is added to prevent scattering of particles generated inside. Moreover, a buffering agent is added in order to adjust pH of a binder composition, and a coupling agent is added in order to improve the adhesive force of a fibrous base material and a binder composition.

The present invention also provides a binding method using the binder composition. As an example,
The binder composition can be bound through spraying a solution comprising an amino compound, a carbohydrate and an acid catalyst; and thermally curing the sprayed solution;
The amino compound may include one or more methanol groups bonded to a nitrogen atom.

  For example, a moisture-like binder composition containing an amino compound, a carbohydrate, and an acid catalyst can be sprayed onto the fibrous material, which can be thermoset to bind the fibrous material and the binder composition.

  At this time, the types of amino compound, carbohydrate, and acid catalyst and the heat curing temperature may be the same as those described above.

  The present invention also provides a fibrous material that is bound using the binder composition. The fibrous material includes, for example, an aggregate made of single fibers such as glass cotton and rock wool. By binding a binder composition to the fibrous material, it is possible to produce a fibrous material having excellent surface hardness and water resistance, which can be used as a material such as a heat insulating material to improve physical properties. it can.

  Moreover, this invention provides the binding method of the fibrous material using the binding method using the said binder composition. The binding method may be the same as described above. For example, the binding method may be a method in which a fibrous material is sprayed with a binder composition and thermally cured at a low temperature.

  Hereinafter, the present invention will be described in detail with reference to examples and the like. The embodiments of the present invention are only for the detailed description of the invention, and do not limit the scope of rights.

Production Example 1 Production of Urea-Formaldehyde Resin 1 340 g of formaldehyde (formalin 37%) and 126 g of urea were placed in a 4-neck flask for synthesis with a thermometer and a stirrer, and stirred at room temperature while blowing nitrogen gas. After confirming that the liquid phase was clean, 0.8 g of caustic soda (20% aqueous solution) was added. After confirming that the pH value reached the 8-9 level, the temperature was slowly raised to 80 ° C. After holding at this temperature for 2 hours, the temperature was cooled 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, it was confirmed that the total molar equivalent ratio of formaldehyde to urea was 2: 1.

Production Example 2 Production of Urea-Formaldehyde Resin 2 511 g of formaldehyde (formalin 37%) and 126 g of urea were placed in a 4-neck flask for synthesis equipped with a thermometer and a stirrer, and stirred at room temperature while introducing nitrogen gas. After confirming that the liquid phase was clean, 1.0 g of sodium hydroxide (20% aqueous solution) was added. After confirming that the pH value reached the 8-9 level, the temperature was slowly raised to 80 ° C. After holding at this temperature for 2 hours, the temperature was cooled 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, it was confirmed that the total molar equivalent ratio of formaldehyde to urea was 3: 1.

Example 1
350 kg of urea-formaldehyde resin composition obtained in Production Example 1, 310 kg of molasses (Molaces 80%), 30 kg of citric acid (98% of citric acid), 3800 kg of distilled water, 2 kg of silicone water repellent (SI1420Z-KCC) and dustproof oil 3 kg of (Dust Oil-Govi Garo 217S) was added and stirred with a stirrer for 30 minutes to produce a binder composition. It was confirmed that the produced binder had a solid content of about 9%.

Example 2
350 kg of urea-formaldehyde resin composition obtained in Production Example 1, 310 kg of maltose (Maltose 83%), 30 kg of citric acid (98% of citric acid), 3800 kg of distilled water, 2 kg of silicone water repellent (SI1420Z-KCC) and dustproof oil 3 kg of (Dust Oil-Govi Garo 217S) was added and stirred with a stirrer for 30 minutes to produce a binder composition. It was confirmed that the produced binder had a solid content of about 9%.

Example 3
350 kg of urea-formaldehyde resin composition obtained in Production Example 2, 274 kg of glucose (D-glucose 91%), 30 kg of citric acid (98%), 3800 kg of distilled water, 2 kg of silicon water repellent (SI1420Z-KCC) and dustproof 3 kg of oil (Dust Oil-Govi Garo 217S) was added and stirred for 30 minutes with a stirrer to produce a binder composition. It was confirmed that the produced binder had a solid content of about 9%.

Example 4
161 kg of dihydroxymethyl-4,5-dihydroxyethylene (DMDHEU), 214 kg of maltodextrin (99%), 30 kg of diammonium sulfate (99%), 3800 kg of distilled water, 2 kg of silicone water repellent (SI1420Z-KCC) and dustproof oil ( (Dust Oil-Garo 217S) (3 kg) was added and stirred for 30 minutes with a stirrer to prepare a binder composition. It was confirmed that the produced binder had a solid content of about 9%.

Example 5
Add 88 kg of hexamethylolmelamine (Cymel 303), 266 kg of dextrin, 50 kg of citric acid (98%), 3800 kg of distilled water, 2 kg of silicone water repellent (SI1420Z-KCC) and 3 kg of dustproof oil (Dust Oil-Garo 217S), stirrer The mixture was stirred for 30 minutes to prepare a binder composition. It was confirmed that the produced binder had a solid content of about 9%.

Example 6
151 kg of urea-formaldehyde composition obtained in Production Example 2, 292 kg of glucose (D-glucose 91%), 211 kg of acrylic resin (KCC HW7002A, solid content 40%), 3800 kg of distilled water, silicon water repellent (SI1420Z- 2 kg of KCC) and 3 kg of dustproof oil (Dust Oil-Garo 217S) were added and stirred with a stirrer for 30 minutes to prepare a binder composition. It was confirmed that the produced binder had a solid content of about 9%.

Comparative Example 1
404 kg of phenol / formaldehyde resin (manufactured by KCC, CAC00112, solid content 42%, formaldehyde / phenol molar ratio = 4), 1,500 kg of distilled water, 2 kg of silicone water repellent (SI1420Z-KCC) and dustproof oil (Dust Oil- 3 kg of Garo 217S) was added and stirred for 30 minutes with a stirrer to produce a binder composition. It was confirmed that the produced binder had a solid content of about 9%.

Comparative Example 2
A binder composition was prepared from the material disclosed in Example 1 of Korean Patent Publication No. 2008-0049012.

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

Experimental Example With respect to the binder compositions produced in Examples 1 to 6 and Comparative Examples 1 and 2, water resistance, formaldehyde emission, dust rate, tensile strength, restoration rate, and mold resistance were measured. The measurement results are shown in Table 1 below.

The experimental conditions are as follows.
1) Preparation of test piece The above-mentioned Examples 1 to 6 and comparison were made to glass fibers descending into a cotton collection chamber while passing a high-temperature glass through a spinner and fiberizing at a rate of 2100 kg / hr per hour. After injecting the binder produced in Examples 1 and 2 in an amount of 47 L / min, a glass cotton heat insulating material was obtained through a drying process. The produced glass cotton was sampled to 100 mm (width) × 100 mm (length) × 50 mm (thickness).

2) Measurement conditions of water resistance Water resistance was basically tested for 48 hours, and after floating in a beaker containing fresh water, the time taken to completely sink was measured. The closer the water resistance rating is to 0, the better, and the closer to 5, the better.

3) Measurement conditions for formaldehyde release amount The formaldehyde release amount is determined by collecting the air in the chamber on the 7th day after leaving the test piece in the small chamber by the small chamber method, and then using the HPLC (liquid chromatography). ). The specific test method was a test set by the Air Clean Association (Korea), and the result was judged on the seventh day.

4) Measurement conditions of dust rate For measurement of the dust rate, four measurement samples each having a width of 1.5 cm and a width of 10 cm were prepared. After weighing before measurement, the above sample was placed in a dust rate measuring device, and the measurement sample was shaken back and forth and left and right at a speed of 1 m / min. The total measurement time was 10 minutes per sample, and the weight was weighed after the testing machine stopped automatically. The dust rate was determined by a calculation formula of [(measured weight before measurement / measured weight after measurement) −1] × 100 and expressed in%.

5) Tensile strength measurement conditions Three samples each having a width of 4 cm were prepared for measuring the tensile strength. The tension rod was installed so as to be shorter than the length of the sample, and the sample was fixed to the tension rod so as to be horizontal, and then the sample was tightened to be vertical using a support rod. The tensile strength tester was set at a speed of 15 mm / min and operated after passing through the zero point of the rod display. After the test machine stopped automatically, the maximum load displayed was measured and the average value was measured.

6) Conditions for measuring the restoration rate After preparing a glass cotton sample of 10 m (horizontal) x 1 m (vertical) x 0.05 m (thickness), winding it in a roll and storing it at room temperature for 8 weeks In the original state, the change in thickness was confirmed.

7) Measurement conditions for mold resistance Mold resistance was measured by observing the mold growth rate on the test piece for one month according to the ASTM G21-09 test method.

  Referring to Table 1 above, the glass-cotton heat insulating material containing the binder composition according to the present invention has a formaldehyde emission level almost close to 0 as compared with the phenol / formaldehyde binder (Comparative Example 1), the dust rate, Mechanical properties such as water resistance, tensile strength and recovery rate were also comparable to the phenol binder level. In particular, compared to the binder containing no formaldehyde (Comparative Example 2), the water resistance and mechanical properties were generally excellent, and it was confirmed that the dust rate was particularly low.

  The binder composition according to the present invention can be used as a fibrous material.

Claims (10)

One or more amino compounds;
Carbohydrates (but not including acidified starch hydrolysates); and acid catalysts (but not including phenolic resins) ; and
The amino compound is represented by the following formulas (1) to (4).







(Where
R ₁ to R ₄ are each independently hydrogen, a methylol group, an alkoxy group having 1 to 4 carbon atoms, Rutotomoni selected from the group consisting of alkyl groups and amino groups having 1 to 4 carbon atoms, R ₁ to R _At least two of ₄ are methylol groups,
R _{5 to} R ₈ 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, and R _{5 to} R _At least two of ₈ are methylol groups,
R ₉ and R ₁₀ are methylol groups;
R ₁₁ and R ₁₂ are methylol groups;
n is an integer of 1-5. )
The binder composition containing 1 or more types of compounds shown by any one of these.   The binder composition according to claim 1, wherein the thermosetting temperature is 150C to 250C. Based on 100 parts by weight of the entire binder composition,
10 to 90 parts by weight of one or more amino compounds;
5 to 80 parts by weight carbohydrate; and 0.1 to 10 parts by weight acid catalyst;
The binder composition according to claim 1, comprising: Wherein one or more amino compounds, bound urea having a methylotrophic Lumpur groups attached to the nitrogen atom of two or more, the methylotrophic Lumpur groups attached to the nitrogen atom of two or more with ethylene urea, and the nitrogen atom the binder composition of claim 1 comprising one or more of the methylotrophic Lumpur based compound selected from the group consisting of hydroxide ethyleneurea with two or more. The one or more amino compounds,
1,1-bis (hydroxymethyl) urea,
1,3-bis (hydroxymethyl) urea,
1,1,3-tri (hydroxymethyl) urea ,
1,3-bis (hydroxymethyl) ethylene urea ,
The binder composition according to claim 1, comprising one or more compounds selected from the group consisting of dihydroxymethyl-4-hydroxyethyleneurea and dihydroxymethyl-4,5-dihydroxyethyleneurea.   The binder composition according to claim 1, wherein the carbohydrate includes one or more of monosaccharides, disaccharides, oligosaccharides, and polysaccharides.   The binder composition 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.   Furthermore, the binder composition of Claim 1 containing 1 or more types of a water repellent, a rust preventive agent, dustproof oil, a buffering agent, and a coupling agent. Amino compounds, carbohydrates and step spraying a solution containing an acid catalyst; the and sprayed solution step of heat curing; wherein, and,
The amino compound is represented by the following formulas (1) to (4).








(Where
R ₁ to R ₄ are each independently hydrogen, a methylol group, an alkoxy group having 1 to 4 carbon atoms, Rutotomoni selected from the group consisting of alkyl groups and amino groups having 1 to 4 carbon atoms, R ₁ to R _At least two of ₄ are methylol groups,
R _{5 to} R ₈ 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, and R _{5 to} R _At least two of ₈ are methylol groups,
R ₉ and R ₁₀ are methylol groups;
R ₁₁ and R ₁₂ are methylol groups;
n is an integer of 1-5. )
A binding method of a fibrous material using a binder composition containing one or more compounds represented by any one of the above.   A fibrous material that is bound using the binder composition according to claim 1.