KR102282011B1 - Phenol resin for aqueous binder and preparing method thereof - Google Patents

Abstract

The present invention relates to a phenolic resin, a composition thereof and a method for preparing it. Specifically, the present invention relates to a phenol resin for an aqueous binder and a method for preparing the same. The phenolic resin composition of the present invention contains phenol and formaldehyde in a molar ratio of 1:1 to 1:2, and 0.1 to 20 parts by weight of the first formaldehyde scavenger and 0.1 to 20 parts by weight of the second formaldehyde scavenger based on 100 parts by weight of the phenol. 15 to 40 parts by weight of the cabin.

Description

A phenolic resin for an aqueous binder and a manufacturing method thereof {Phenol resin for aqueous binder and preparing method thereof}

The present invention relates to a phenolic resin and a method for preparing the same. Specifically, the present invention relates to a phenol resin for an aqueous binder and a method for preparing the same.

Resol resins, which are generally formed by the condensation of phenols with aldehydes in the presence of alkali catalysts, have a number of commercially important uses. Since these resol resins have properties of being cured by heat, they are mainly used as binders that are cured by applying heat under pressure after being applied to a substrate.

In particular, phenolic resins prepared using formaldehyde as the above aldehyde are an important class of the above resol resins, and are mainly used in binders for artificial boards, laminated wood products, textile products, laminated products, and the like. For example, a binder resin for a laminated product should exhibit properties such as good substrate penetration that other resins did not need to exhibit, have good dimensional stability, less panel distortion, less moisture absorption, and thermal blister (blister). ) to be able to manufacture high-resistance laminates.

However, known phenolic resins prepared using formaldehyde have formaldehyde concentrations that release formaldehyde into the environment upon processing, storage and curing of the treated substrate. At this time, the release of formaldehyde is known to cause disease as well as odor when workers inhale and come into contact with eyes, mouth and other parts of the body. Release into the environment is undesirable.

Accordingly, in order to reduce the amount of formaldehyde emitted from the phenol resin, based on the general basicity of the phenol resin prepared from phenol and formaldehyde, the pH of the phenol resin is adjusted to 5.5 or less using an acid catalyst to process the phenol resin , a method of reducing the amount of formaldehyde emitted during curing has been devised, but this still has limitations in controlling the amount of release of formaldehyde, and when the phenol resin solution is acidified, the stability of the binder composition using the same decreases, resulting in poor storage properties. The problem is reported.

In addition, a method of minimizing the emission of formaldehyde by spraying a scavenger of formaldehyde when manufacturing a phenol resin from phenol and formaldehyde has also been devised, but this is because formaldehyde emitted by the condensation reaction in the curing process of the resin is It has been found to be of little use in adsorption of formaldehyde released from the final product as it reacts with the formaldehyde scavenger.

An object of the present invention is to provide a phenol resin that can be used in an aqueous binder for binding fibers and an aqueous binder composition comprising the same.

Specifically, an object of the present invention is to provide a phenol resin having excellent mechanical properties while reducing the amount of formaldehyde emitted, and a method for preparing the same.

In order to achieve the above object, the present invention contains phenol and formaldehyde in a molar ratio of 1:1 to 1:2, and 0.1 to 20 parts by weight of the first formaldehyde scavenger and 0.1 to 20 parts by weight of the first formaldehyde scavenger based on 100 parts by weight of the phenol. 2 To provide a phenolic resin composition comprising 15 to 40 parts by weight of a formaldehyde scavenger.

In addition, the present invention provides a step of addition reaction of phenol and formaldehyde in a molar ratio of 1:1 to 1:2 in the presence of a catalyst to form a phenol resin intermediate, and based on 100 parts by weight of the phenol, the first formaldehyde It provides a method for producing a phenol resin, comprising mixing 0.1 to 20 parts by weight of a caver and 15 to 40 parts by weight of a second formaldehyde scavenger, and reacting the phenol resin intermediate to form a phenol resin.

In addition, the present invention provides a phenol resin prepared according to the above method and an aqueous binder composition comprising the same.

Using the method for producing a phenol resin of the present invention, it is possible to prepare a phenol resin exhibiting a very low level of formaldehyde emission.

In addition, when a fibrous material (in particular, an inorganic fibrous material) is bound using an aqueous binder composition containing such a phenol resin, for example, when ^{a high-density material of 40 to 200 kg/m 3} is bound, excellent mechanical properties can be implemented. .

Hereinafter, the present invention will be described in detail.

The present invention provides a phenolic resin composition.

The phenolic resin composition includes phenol and formaldehyde in a molar ratio of 1:1 to 1:2, and 0.1 to 20 parts by weight of the first formaldehyde scavenger and 0.1 to 20 parts by weight of the second formaldehyde scavenger based on 100 parts by weight of the phenol. 15 to 40 parts by weight.

The phenol resin composition may further include a catalyst for the addition reaction of the phenol and formaldehyde.

The catalyst is not limited thereto, but may be included in an amount of, for example, 1 to 15 parts by weight of the catalyst, for example 2 to 12 parts by weight, based on 100 parts by weight of phenol.

In the phenol resin composition, the reaction of phenol and formaldehyde, the first formaldehyde scavenger, the second formaldehyde scavenger and the configuration of the catalyst and the like will be described later with respect to the method for producing the phenol resin.

The present invention provides a method for producing a phenolic resin.

The method for preparing the phenol resin includes the steps of adding phenol and formaldehyde in a molar ratio of 1:1 to 1:2 in the presence of a catalyst to form a phenol resin intermediate, and based on 100 parts by weight of the phenol, the first and mixing 0.1 to 20 parts by weight of a formaldehyde scavenger and 15 to 40 parts by weight of a second formaldehyde scavenger, and reacting the phenolic resin intermediate to form a phenolic resin.

The catalyst is for creating alkaline conditions for the addition reaction of phenol and formaldehyde, and it is preferable to use a basic catalyst, and the type of the basic catalyst is not particularly limited, but for example, hydroxides and amines of alkaline earth metals. At least one or more of the group-containing compounds may be used. As the hydroxide of the alkaline earth metal, for example, sodium hydroxide, potassium hydroxide, magnesium hydroxide or a mixture thereof can be used, and as the amine group-containing compound, ammonia, triethylamine or a mixture thereof can be used.

The amount of the catalyst used is enough to be involved in the addition reaction of the phenol and formaldehyde, and is not particularly limited thereto, but when the amount of the catalyst is too small, the reaction rate of the addition reaction decreases. It may cause the release of formaldehyde in the reactant, so it may be preferable to use, for example, in an amount of 1 to 15 parts by weight of the catalyst, such as 3 to 13 parts by weight, based on 100 parts by weight of phenol. In the present invention, In the presence of the catalyst as described above, the addition reaction of phenol and formaldehyde includes forming a phenol resin intermediate.

Specifically, in consideration of the content of residual formaldehyde after the addition reaction and the amount of formaldehyde released from the resin to be prepared, the formaldehyde is added in an amount such that the molar ratio with the phenol is 1:2 (phenol: formaldehyde) or less. It may be desirable to react. For example, the phenol and formaldehyde may be reacted using a molar ratio of 1:1 to 1:2 (phenol:formaldehyde), or may be used in a molar ratio of 1:1.3 to 1:1.8.

In the addition reaction, the order or temperature of the reaction is not limited thereto, but for example, after dissolving phenol in an aqueous solution in which the formaldehyde is dissolved, the catalyst is added and the solution is stable at 40 to 95° C., for example, 40 It can be carried out at a temperature of ˜80° C.

By the addition reaction, formaldehyde is added to at least one of two ortho and one para (-para) positions based on a hydroxyl group (-OH) to phenol to form methylol (-CH ₂ OH) A phenolic resin intermediate in this substituted form can be formed.

The product of the addition reaction may include unreacted phenol, formaldehyde, water, etc. as well as the phenol resin intermediate, but it may be preferable to proceed with the addition reaction so that there is no residual phenol.

At this time, in order to remove the unreacted formaldehyde, it includes the step of mixing a formaldehyde scavenger to the product of the addition reaction.

Specifically, the formaldehyde scavenger may include 0.1 to 20 parts by weight of the first formaldehyde scavenger and 15 to 40 parts by weight of the second formaldehyde scavenger based on 100 parts by weight of the phenol, and a mixture thereof may be using

The inventors of the present invention, when preparing a phenol resin from phenol and formaldehyde, remove the residual formaldehyde by adding a formaldehyde scavenger after forming the phenol resin intermediate, and finally remove the formaldehyde from the phenol resin produced. It was confirmed that the emission amount can be drastically reduced. In addition, as the formaldehyde scavenger, it was confirmed that when a guanidine-based compound and urea are used together, the emission amount of formaldehyde is reduced and the amount of reactants remaining other than formaldehyde, such as phenol, is also dramatically reduced, and at this time, the amount of phenol produced It was confirmed that the mechanical properties of the resin were also excellent.

When only urea is used as the formaldehyde scavenger, a binder composition including a phenol resin prepared therefrom may have a problem in that physical properties such as strength and water resistance of the thermosetting product are poor. Accordingly, the first formaldehyde scavenger preferably includes a guanidine-based compound or a salt thereof, and the guanidine-based compound is 2-cyanoguanidine, guanylurea, 1-methylguanidine, 1-ethylguanidine, 1 -Cyclohexylguanidine, 1-phenylguanidine, dimethylguanidine, diphenylguanidine and trimethylguanidine, may include at least one selected from the group consisting of cyanoguanidine. More specifically, the first formaldehyde scavenger may include cyanoguanidine.

The first formaldehyde scavenger may be used in an amount of 0.1 to 20 parts by weight, such as 3 to 10 parts by weight, based on 100 parts by weight of the phenol.

Preferably, the second formaldehyde scavenger includes urea, and the urea together with the first formaldehyde scavenger, for example, removes unreacted formaldehyde remaining during an addition reaction between phenol and formaldehyde to release formaldehyde. It is possible to significantly reduce the mechanical strength of the product and to improve the mechanical strength of the product. In addition, the cost competitiveness of the final phenolic resin binder can be strengthened when urea is applied at a low raw material cost.

The second formaldehyde scavenger may be used in an amount of 15 to 40 parts by weight, for example, 15 to 35 parts by weight, and 20 to 35 parts by weight based on 100 parts by weight of the phenol.

and mixing the first and second formaldehyde scavengers with the product of the addition reaction including the phenolic resin intermediate, and then condensing the phenolic resin intermediate to form a phenolic resin.

The condensation reaction of the phenol resin intermediate is preferably carried out at a temperature lower than the curing temperature of the phenol resin to be prepared, for example, it may be preferably carried out at 40 to 95 ℃, specifically 40 to 80 ℃. If the reaction temperature is too low outside the above temperature range, there is a problem in that the reaction rate is too slow, and if the temperature is too high, the condensation reaction rate is too fast and the molecular weight of the phenol resin is too large, resulting in poor compatibility with the solvent or gelation there may be a problem with Accordingly, in the method for producing a phenol resin of the present invention, it is easy to remove unreacted residues, for example, unreacted reactants such as phenol and formaldehyde, and a step of separately removing or recovering a catalyst or a solvent is performed. Energy saving effect can also be exhibited by shortening the time for producing the phenol resin.

Completion of the condensation reaction is not limited thereto, but may be confirmed, for example, by measuring the content of unreacted formaldehyde in the final phenol resin. Specifically, when the unreacted formaldehyde content in the final phenolic resin is, for example, less than 1%, preferably less than 0.5%, it can be confirmed that the reaction is complete.

It may further include a pH adjusting agent for adjusting the pH when the phenolic resin of the present invention is prepared, for example, the pH adjusting agent may be boric acid or the like.

The present invention provides a phenol resin prepared according to the above production method.

The phenol resin may be prepared by condensation polymerization of a phenol resin intermediate produced by an addition reaction of a mixture in which phenol and formaldehyde are mixed in a molar ratio of 1:1 to 1:2 (phenol:formaldehyde). Specifically, it may be prepared by mixing in a molar ratio of 1:1.3 to 1:1.8. When the formaldehyde is mixed in excess of the molar ratio, there may be a problem in that the amount of formaldehyde emitted from the phenol resin increases.

The phenolic resin exhibits excellent properties such as heat resistance, flame retardancy, electrical insulation, and mechanical strength. Although not limited thereto, for example, the viscosity of the phenolic resin may represent 10 to 200 cps, specifically 10 to 100 cps, when measured with a Brookfield viscometer at 25°C.

The present invention provides an aqueous binder composition comprising the phenol resin prepared as described above.

The phenolic resin may be included as the main resin of the aqueous binder composition, and its content is not limited thereto, but for example, based on the total weight of the aqueous binder composition, the phenolic resin solids content is 5 to 40% by weight, specifically 5 to 20% by weight or 5 to 15% by weight.

The aqueous binder composition may exhibit the effect of increasing the binding force with the fibrous material by including the silicon-containing compound as a binder together.

The silicon-containing compound may be a silane-based compound, a siloxane compound, or a mixture thereof.

The silane-based compound is not limited thereto, but for example, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3- Glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-(2-aminoethyl)aminopropyltrimethoxysilane, 3-Aminopropyltrimethoxysilane, 3-phenylaminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptotriethoxysilane, 3-ureidopropyltriethoxysilane, trimethoxy Silylbenzoic acid, 3-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane or a mixture thereof may be used, more preferably 3-glycidoxypropyltrimethoxysilane, 3 -Glycidoxypropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane or mixtures thereof can be used.

The siloxane compound is a generic term for organic silicon compounds in the form of circular or chain oligomers or polymers including siloxane bonds. The siloxane compound is, but is not limited thereto, for example, hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, dimethyltetramethoxydisiloxane, trimethyltrimethoxydisiloxane, tetramethyltetramethoxytrisiloxane, hexamethyl Tetramethoxytetrasiloxane or mixtures thereof may be used.

As the silicon-containing compound, most preferably 3-aminopropyltriethoxysilane (A-1100) may be included.

The silicon-containing compound may be included in an amount of 0.001 to 10% by weight based on the solid weight of the phenolic resin in the aqueous binder composition, for example, 0.01 to 5% by weight, 0.01 to 2% by weight, or 0.01 to 0.5% by weight. may be included in the amount of When included within the above range, it is possible to excellently improve the bonding strength with the fibrous material.

In addition, the aqueous binder composition may further include a curing accelerator as an additive.

The curing accelerator is, but is not limited thereto, for example, ammonium sulfate (milk), ammonium tetraoxosulfate (VI) (Cas No. 7783-20-2), ammonium paratoluene sulfate, citric acid salt ) and may include at least one selected from the group consisting of acrylic resins containing carboxylic acids.

The curing accelerator may be included in an amount of 0.01 to 20% by weight based on the solids weight of the phenolic resin in the aqueous binder composition, for example, 1 to 20% by weight, 1 to 17% by weight, or 3 to 15% by weight. can be included as When included within the above range, it is possible to exhibit the effect of shortening the working time by increasing the binding speed of the aqueous binder composition with the fibrous material, and it is possible to improve the problem of mixing impurities.

In addition, the aqueous binder composition may optionally further include one or more additives as needed within a range capable of achieving the object of the present invention in addition to the above components. Such additives include, but are not limited to, a water repellent agent for increasing the water resistance of the fibrous material, a rust preventive agent for preventing corrosion of equipment, a dustproof oil for lowering the dust generation rate of the product, a buffering agent for adjusting pH, and the like, It may include additives commonly used in the art. There is no particular limitation on the amount of the additive used, for example, it may be used in the range of 0.1 to 10% by weight based on the total weight of the aqueous binder resin, but is not limited thereto.

In addition, the aqueous binder composition may use water such as industrial water, groundwater, process water, and purified water as a diluent (or solvent) for uniformly applying the above components to the fibrous material, and the content of the diluent is in the aqueous binder composition. It may be the remaining amount other than the above-mentioned components in. In addition, the content of the solid content in the composition may be adjusted by adjusting the content of the diluent as necessary. For example, a diluent may be included such that the total amount of solids in the composition is 5 to 40% by weight, specifically 5 to 30% by weight, preferably 5 to 20% by weight, more preferably 5 to 15% by weight. .

In addition, the present invention provides a method for binding a fibrous material using the aqueous binder composition.

In this case, the fibrous material to be bound may include, but is not limited to, inorganic fibers (eg, rock wool, glass wool, ceramic fibers, etc.) or organic fibers such as fibers obtained from natural and synthetic resins. In the present invention, the 'fibrous material' may preferably be glass fiber, rock wool, or the like.

The method for binding the fibrous material of the present invention may include a step of spraying the aqueous binder composition according to the present invention onto the fibrous material, followed by thermal curing.

The aqueous binder composition is preferably sprayed onto the fibrous material in the form of an uncured aqueous solution or aqueous dispersion.

The heat treatment for the thermosetting is preferably performed at a temperature of 140 °C or higher, for example, 140 to 300 °C, preferably at a temperature of 150 to 250 °C. If the heat treatment temperature is less than the above range, a problem of non-curing may occur, and if the heat treatment temperature exceeds the above range, overcuring may occur, which may cause dust and decomposition of the binder.

The content of the aqueous binder contained in the fibrous material bound according to the binding method of the fibrous material of the present invention may be 1.5 to 15 wt%, more preferably 1.5 to 10 wt%, based on the total weight of the bound fibrous material. .

The fibrous material may have a release amount of formaldehyde of 0.008 mg/m ³ ·hr or less, or 0.006 mg/m ³ ·hr or less. When the fibers are bound using the aqueous binder according to the present invention, the binding result may exhibit excellent physical properties in formaldehyde emission, tensile strength, dust rate, recovery rate, mold excellence, color change during outdoor storage, non-combustibility, and the like.

Hereinafter, the present invention will be described in more detail through examples.

<Preparation of Examples and Comparative Examples. Preparation of Aqueous Binder Composition>

A phenol resin was prepared using the compositions of Tables 1 and 2 below. Specifically, after formaldehyde (purity 37%) was added to phenol (solid content 100%), sodium hydroxide solution (33 wt%) was added dropwise at 40°C for 2 hours. Thereafter, the mixture was stirred at 60° C. for 4 hours to obtain a mixture containing a phenol resin intermediate. Cyanoguanidine (Cas No. 461-58-5), urea and boric acid were added to the obtained mixture, followed by stirring at 35° C. for 2 hours to obtain a phenol resin.

(weight%) preparation example One 2 3 4 5 6 Phenol (100%) 296 278 262 240 296 296 Formaldehyde (37%) 358 384 409 405 358 358 Sodium Hydroxide (33%) 100 100 100 120 80 100 Cyanoguanidine 15 20 15 21 6 55 Urea (50%) 170 164 160 160 220 115 boric acid 61 54 54 54 40 76 total 1000 1000 1000 1000 1000 1000 Phenol:formaldehyde molar ratio 1.4 1.6 1.8 1.95 1.4 1.4

(weight%) Comparative preparation example One 2 3 4 5 6 7 Phenol (100%) 418 195 296 335 286 296 296 Formaldehyde (37%) 180 505 408 462 348 358 358 Sodium Hydroxide (33%) 127 90 90 101 70 90 110 Cyanoguanidine 15 15 0 50 10 90 100 Urea (50%) 170 150 160 0 250 110 80 boric acid 90 45 46 52 36 56 56 total 1000 1000 1000 1000 1000 1000 1000 Phenol:formaldehyde molar ratio 0.5 3 1.6 1.6 1.4 1.4 1.4

An aqueous binder composition was prepared with the composition of Tables 3 and 4 below using the prepared phenol resin (solid content: 45%). Specifically, a phenol resin, distilled water, silane A-1100, and oil ((NH ₄ ) ₂ SO ₄ ) were mixed and stirred with a stirrer for 30 minutes to prepare an aqueous binder composition.

weight% Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Phenolic Resin (45%) Preparation example 1 25 Preparation Example 2 25 Preparation example 3 25 Preparation example 4 25 Preparation example 5 25 Preparation example 6 25 binder Silane A-1100 0.02 0.02 0.02 0.02 0.02 0.02 hardening accelerator yuan 1.5 1.2 One 0.8 0.6 0.4 menstruum water 73.48 73.78 73.98 74.18 74.38 74.58 total 100 100 100 100 100 100

weight% Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Phenolic Resin (45%) Comparative Preparation Example 1 25 Comparative Preparation Example 2 25 Comparative preparation example 3 25 Comparative Preparation Example 4 25 Comparative preparation example 5 25 Comparative Preparation Example 6 25 Comparative Preparation Example 7 25 binder Silane A-1100 0.02 0.02 0.02 0.02 0.02 0.02 0.02 hardening accelerator yuan 0.5 0.5 0.5 0.5 0.5 0.5 0.5 menstruum water 74.48 74.48 74.48 74.48 74.48 74.48 74.48 total 100 100 100 100 100 100 100

<Experimental example. Binding of Fibrous Materials Using Aqueous Binder>

The adhesive composition of the Examples and Comparative Examples was sprayed at an amount of 16 L/min on the glass fibers coming down to the collecting room while passing the high-temperature glass water through a spinner and fiberizing it at a speed of 2100 kg per hour, and then passing through a drying process to make the glass wool insulation material got The physical properties of the prepared glass surface insulation material were measured in the following manner, and the results are shown in Table 5.

(1) Resin adhesion rate

To measure the binder content in the bound fibrous material, a glass cotton sample of 100 mm (width) x 100 mm (length) x 50 mm (thickness) was prepared, and then heat-treated in an oven at 500 ° C. for 1 hour to measure the weight loss before and after.

(2) Compression rate

Three specimens (250mmX250mmX100mm, width X length X thickness) were taken as samples from each of the glass surface insulation materials prepared as described above. The dimensions of the specimen were taken by cutting in half in the thickness direction and the vertical direction in consideration of the uniform collection surface. After binding the specimen to the jig for measuring the compressibility, it was placed in the center of the universal testing machine. Afterwards, when the load was 40 kgf, the compressed displacement was measured, and the arithmetic mean value was obtained by measuring three times. At this time, the compression ratio was calculated by Equation 1 below. [Equation 1]

Compression rate (%) = [(initial thickness-compression displacement)/initial thickness]x100

(3) absorption rate

Three samples of glass wool insulation were cut to the size of 254mmX254mmX100mm (product thickness) (length X width X thickness), and the weight (W1) was measured accurately up to 0.01 g. After that, the water bath was filled with water at room temperature from the bottom up to 10 Step steps (30 mm per step), the sample was put, and the screen (square mesh wire mesh) was fixed so that it came to 7 Steps from the bottom. (If the sample is not fixed by buoyancy, a weight of 2 kg or more is applied to fix the square mesh.)

The screen was fixed so as not to float on water and water was absorbed for 15 minutes. After 15 minutes, the sample was taken out, and one corner was held with a fingertip and stood upright for 150±5 seconds to allow water droplets to fall. After placing the sample on a silver foil plate (W2) weighed in advance, the weight (W3) was measured accurately up to 0.01 g, and the average value was taken. At this time, the absorption rate was calculated by Equation 2 below.

[Equation 2]

Absorption (%) = [(W3 - W2)/W1] X 100

(4) Formaldehyde emission

According to the small chamber method specified in KS M ISO 16000 and KS M 1998, the glass wool insulation material was left in the small chamber, 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, and the results were judged on the 7th day.

(5) dust rate

The glass surface insulation material was cut to produce 4 samples each having a width of 1.5 cm and a width of 10 cm. After weighing before measurement, the sample was placed on a dust rate meter and shaken back and forth at a speed of 1 m/min. The total measurement time was carried out for 10 minutes per sample, and after the tester stopped automatically, the weight of the sample was measured. At this time, the dust rate was calculated by Equation 3 below.

[Equation 3]

Dust rate = [(Weighing weight after measurement / Weighing weight before measurement)-1]×100

Resin adhesion rate (%) Compression rate (%) Absorption rate (%) Formaldehyde emission (mg/m3·hr) Dust rate (%) target properties 5±1 below 10 - 0.008 or less 1 or less Example 1 4.8 9.3 378 0.003 0.8 Example 2 4.9 9.4 365 0.004 0.9 Example 3 5 9.4 324 0.006 0.9 Example 4 4.8 9.0 352 0.007 0.9 Example 5 4.9 9.6 450 0.007 0.9 Example 6 5.1 9.0 432 0.007 0.9 Comparative Example 1 3.8 11.2 542 0.003 1.9 Comparative Example 2 5.3 8.6 291 0.02 1.1 Comparative Example 3 4.8 10.2 284 0.01 1.5 Comparative Example 4 5.1 10.5 212 0.01 1.2 Comparative Example 5 5.1 10.2 720 0.007 1.5 Comparative Example 6 5.0 10.2 700 0.007 1.4 Comparative Example 7 4.9 10.3 695 0.005 1.4

As can be seen in Table 5 above, in Comparative Example 1 using a phenol resin prepared in a phenol:formaldehyde molar ratio of less than 1:1, the formaldehyde emission amount was 0.008 or less, but the resin adhesion rate, compression rate, and dust rate were It was confirmed that the physical properties were poor. In addition, Comparative Example 2 using a phenol resin prepared in a phenol:formaldehyde molar ratio of more than 1:2 or Comparative Examples 3 and 4 in which the first formaldehyde scavenger or the second formaldehyde scavenger was not prepared when the phenol resin was prepared In the case of , it was confirmed that the amount of formaldehyde emission was excessive.

In addition, in Comparative Examples 5 to 7, in which the content of the first formaldehyde scavenger and/or the second formaldehyde scavenger was prepared outside the present invention, the dust rate, compressibility (strength) and absorption rate ( It was confirmed that the effect was poor in terms of water resistance).

Claims (6)

phenol and formaldehyde in a molar ratio of 1:1 to 1:2,
3 to 10 parts by weight of the first formaldehyde scavenger and 20 to 40 parts by weight of the second formaldehyde scavenger based on 100 parts by weight of the phenol;
The first formaldehyde scavenger includes a guanidine-based compound or a salt thereof,
The second formaldehyde scavenger is a phenolic resin composition comprising urea.
delete delete The method according to claim 1,
The phenol resin composition further comprising a catalyst in an amount of 1 to 15 parts by weight based on 100 parts by weight of the phenol.
An aqueous binder composition comprising a phenol resin formed using the phenol resin composition according to any one of claims 1 and 4.
addition reaction of phenol and formaldehyde in a molar ratio of 1:1 to 1:2 in the presence of a catalyst to form a phenolic resin intermediate; and
Based on 100 parts by weight of the phenol, 3 to 10 parts by weight of the first formaldehyde scavenger and 20 to 40 parts by weight of the second formaldehyde scavenger are mixed, and the phenol resin intermediate is reacted to form a phenol resin. includes,
The first formaldehyde scavenger includes a guanidine-based compound or a salt thereof,
The second formaldehyde scavenger comprises urea (Urea).