KR20240070057A - Foamable phenolic resin composition, phenolic foam and method of manufacturing phenolic foam - Google Patents

Abstract

Provided is a phenolic foam containing a phenol-based resin and a polyphenol-based compound.

Description

Foamable phenolic resin composition, phenolic foam and phenolic foam manufacturing method {FOAMABLE PHENOLIC RESIN COMPOSITION, PHENOLIC FOAM AND METHOD OF MANUFACTURING PHENOLIC FOAM}

The present invention relates to a foamable phenol-based resin composition, phenolic foam, and a method for producing phenolic foam.

Due to a series of recent large-scale fire incidents, there is a movement to strengthen safety regulations for building materials, especially insulation materials. Among building insulation materials, phenol foam, which is based on phenolic resin foam, has recently been attracting attention due to its excellent semi-incombustibility and thermal insulation properties, and the size of the related market is showing an increasing trend.

The purpose of the present invention is to provide phenolic foam with excellent dimensional stability.

The purpose of the present invention is to provide a phenolic foam that simultaneously satisfies excellent dimensional stability and quasi-non-combustible performance.

The purpose of the present invention is to provide a phenolic foam that satisfies excellent dimensional stability, predetermined semi-non-combustible performance, and other KS properties.

The purpose of the present invention is to provide a foamable phenol-based resin composition that can produce phenolic foam with excellent dimensional stability.

The purpose of the present invention is to provide a foamable phenol-based resin composition that simultaneously satisfies excellent dimensional stability and predetermined quasi-incombustibility performance.

The purpose of the present invention is to provide a foamable phenol-based resin composition that satisfies excellent dimensional stability, predetermined quasi-incombustibility performance, and other KS physical properties.

The purpose of the present invention is to provide a method for producing the above-described phenol foam.

The objects of the present invention are not limited to the objects mentioned above, and other objects and advantages of the present invention that are not mentioned can be understood by the following description and will be more clearly understood by the examples of the present invention. Additionally, it will be readily apparent that the objects and advantages of the present invention can be realized by the means and combinations thereof indicated in the patent claims.

In one embodiment of the present invention, a phenol foam containing a phenol-based resin and a polyphenol-based compound is provided.

In another embodiment of the present invention, a foamable phenol-based resin composition comprising a phenol-based resin and a polyphenol-based compound is provided.

In another embodiment of the present invention, phenolic foam is prepared by foaming and curing a foamable phenolic resin composition containing a phenolic resin, a polyphenol-based compound, a residual formaldehyde trapping agent, a foaming agent, a plasticizer, a curing agent, a flame retardant, and a surfactant. Provides a phenol foam manufacturing method.

The foamable phenol-based resin composition according to one embodiment of the present invention can produce phenol foam with excellent dimensional stability.

The foamable phenol-based resin composition according to one embodiment of the present invention exhibits excellent dimensional stability and can simultaneously produce phenol foam that realizes quasi-non-combustible performance.

The expandable phenol-based resin composition according to one embodiment of the present invention can produce phenolic foam that not only has excellent dimensional stability but also satisfies predetermined quasi-non-flammable performance and other KS properties.

In addition to the above-described effects, specific effects of the present invention are described below while explaining specific details for carrying out the invention.

The above-described objects, features, and advantages will be described in detail later, so that those skilled in the art will be able to easily implement the technical idea of the present invention. In describing the present invention, if it is determined that a detailed description of known technologies related to the present invention may unnecessarily obscure the gist of the present invention, the detailed description will be omitted. Hereinafter, preferred embodiments according to the present invention will be described in detail.

Unless otherwise defined, all technical and scientific terms used in this specification have the same meaning as commonly understood by a person skilled in the art to which the present invention pertains. In general, the nomenclature used herein is well known and commonly used in the art.

In addition, throughout this specification, when a part "includes" a certain component, this does not mean excluding other components unless specifically stated to the contrary, but may further include other components.

In one embodiment of the present invention, a phenolic resin; And it provides a phenol foam containing a polyphenol-based compound.

The phenolic foam can be used as a building material such as an insulation material.

In general, phenolic foam has excellent semi-incombustibility and thermal insulation properties, but is relatively poor in terms of dimensional stability, so methods to improve this are being attempted. However, phenol foam, whose dimensional stability has been improved by known methods, promotes smoldering during combustion, weakening its semi-non-combustible performance.

On the other hand, the phenolic foam has excellent dimensional stability and suppresses fuming during combustion, thereby simultaneously realizing quasi-non-combustible performance.

The phenolic resin refers to a thermosetting resin produced by reacting phenols and formaldehydes. The phenol-based resin can be produced by inducing addition and condensation reactions of phenol and formaldehyde at an appropriate temperature and time, and then neutralizing them with acids such as hydrochloric acid and formic acid.

The phenolic resin may be a phenolic resin known to be used in foam production. For example, the phenolic resin may be a resol or novolac type, but is not limited thereto.

The resol type phenolic resin is synthesized using alkali metal hydroxide or alkaline earth metal hydroxide, and may include an ammonia resol type phenolic resin synthesized using ammonia. The novolak-type phenol-based resin may be synthesized using an acid catalyst. Such phenol-based resin may be a mixture of resol or novolac type.

The phenolic resin may contain 3% to 15% moisture. By setting the moisture contained in the phenolic resin within the above range, process control can be facilitated, and the thermal conductivity and other physical properties of the phenol foam can be maintained within the desired range.

The phenolic foam may contain 50 to 95% by weight of the phenolic resin. The phenolic foam can maintain thermal conductivity and other physical properties at a predetermined level by including the phenolic resin in the content within the above range.

The polyphenol-based compound is a type of aromatic alcohol compound and refers to a compound having a polyphenol structure containing two or more aromatic rings substituted with a plurality of hydroxy groups in one molecule.

The phenol-based skeleton and the hydroxy group connected to the polyphenol-based compound improve the dimensional stability of the phenol foam by crosslinking reaction with the phenolic resin. Therefore, thereby, the phenolic foam can exhibit dimensional stability.

In addition, the polyphenol-based compound has the function of capturing radicals and preventing the spread of combustion by capturing free radicals during fire or combustion.

The polyphenol-based compounds may be, for example, catechin compounds, quercetin, curcuminoid compounds and derivatives thereof. The polyphenol-based compound may include, but is not limited to, at least one selected from the group consisting of catechin-based compounds, quercetin, curcumin-based compounds, and derivatives thereof.

The catechin-based compound may specifically be catechin, epicatechin, epigallocatechin, epicatechin gallate, epigallocatechin gallate, etc., or derivatives thereof, but is not limited thereto.

The cucumin-based compound is a polyphenol-based compound contained in plants such as turmeric and turmeric. Specifically, it may be curcumin, desmethoxycucumin, bisdesmethoxycucumin, etc., or derivatives thereof, but is not limited thereto. No.

The phenol foam may contain 1 to 15 parts by weight of the polyphenol-based compound based on 100 parts by weight of the phenol-based resin. In one embodiment, the phenol foam may include 5 to 15 parts by weight, specifically, 9 to 15 parts by weight, of the polyphenol-based compound based on 100 parts by weight of the phenol-based resin. The phenolic foam can simultaneously achieve excellent dimensional stability and semi-incombustibility by including the polyphenol-based compound in the content within the above range. In addition, the foamable phenol-based resin composition for producing the phenol foam uses a polyphenol-based compound at the above content ratio, making it easy to control the viscosity of the composition, and thus enabling the foaming operation to be properly performed.

The phenolic foam may be manufactured by foaming and curing a composition for forming phenolic foam, and the composition for forming phenolic foam may include the phenol-based resin; The polyphenol-based compounds; and an additive containing at least one selected from the group consisting of a residual formaldehyde trapping agent, a foaming agent, a plasticizer, a curing agent, a flame retardant, and a surfactant.

The residual formaldehyde trapping agent may include a urea substituent including at least one cyclic substituent. For example, the residual formaldehyde trapping agent may be a urea substituent containing at least one cyclic substituent having a structure such as methylene, ethylene, propylene, etc., but is not limited thereto.

The composition for forming the phenol foam may include 1 to 8 parts by weight of the residual formaldehyde trapping agent based on 100 parts by weight of the phenolic resin. The composition for forming phenolic foam includes the residual formaldehyde trapping agent in the content within the above range, so that it can obtain the effect of removing residual formaldehyde to an appropriate level without deteriorating the heat resistance and physical properties of the phenolic foam obtained therefrom.

The foaming agent is hydrocarbons such as cyclopentane, isopentane, n-pentane, and n-hexane, chlorinated hydrocarbons such as isopropyl chloride, dichloroethane, and pentyl chloride, chlorinated hydrofluoroolefins, and non-chlorinated hydrofluoroolefins. Examples include halogenated hydrocarbons such as fluorinated hydrocarbons, brominated hydrocarbons, and iodine-based hydrocarbons, and one or more of these may be included in combination, but are not limited thereto.

The composition for forming the phenolic foam may include 2 to 20 parts by weight of the foaming agent based on 100 parts by weight of the phenolic resin. The composition for forming phenol foam can prevent deterioration of physical properties by appropriately maintaining the thermal conductivity and density of the phenolic foam manufactured by including the foaming agent in the content within the above range.

The plasticizer may include, but is not limited to, at least one selected from the group consisting of ester, ester polyol, ether polyol, phosphorus-based compound, epoxy resin, fluorine-based compound, and combinations thereof.

The composition for forming the phenol foam may include 2 to 30 parts by weight of the plasticizer based on 100 parts by weight of the phenolic resin. The composition for forming phenol foam can appropriately maintain the flexibility, mechanical properties, and flame retardancy of the phenolic foam manufactured by including the plasticizer in the content within the above range.

The curing agent may include at least one selected from the group consisting of sulfonic acid-based organic acids, inorganic acids, and combinations thereof. Examples of the sulfonic acid series organic acids include phenol sulfonic acid, toluene sulfonic acid, xylene sulfonic acid, ethylbenzene sulfonic acid, and naphthalene sulfonic acid, and the inorganic acids include, but are not limited to, hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid.

The composition for forming the phenol foam may include 2 to 20 parts by weight of the curing agent based on 100 parts by weight of the phenolic resin. The composition for forming phenolic foam includes the curing agent in the content within the above range to ensure that the curing process is properly performed, thereby preventing the physical properties of the phenol foam produced therefrom from being reduced, the thermal conductivity to increase, and the corrosiveness to be strengthened due to pH reduction (enhanced acidity). can do.

The phenolic foam may further include a flame retardant to further improve flame retardancy.

The flame retardant may include flame retardants known to be able to be used in phenol foam, singly or in combination, for example, phosphorus-based flame retardants, halogen-phosphorus-based flame retardants, boron-based flame retardants, metal hydroxides, expanded graphite, It may include at least one selected from the group consisting of water glass and combinations thereof, but is not limited thereto.

The flame retardants include, for example, TCPP (Tris(1-Chloro-2-Propyl)Phosphate), TEP (Triethyl Phosphate), TEPP (Tetraethyl piperazine-1,4-diyldiphosphoramidate), halogen-substituted aromatic polyol (ISOEXTER-3644, etc.) ), TCP (Tricresyl Phosphate), RDP (Resorcinol bis(diphenyl phosphate)), APP (Ammonium Poly Phosphate), DOPO-HQ (10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-xa-10 -phosphaphenanthrene-10-oxide), phosphazene-based, expanded graphite, red phosphorus, boric acid (H ₃ BO ₃ ), borax (Na ₂ B ₄ O ₇ ), aluminum hydroxide, water glass, etc., and these may be used alone or in combination. It can be included.

The composition for forming the phenol foam may include 1 to 20 parts by weight of the flame retardant based on 100 parts by weight of the phenolic resin. The composition for forming phenolic foam includes the flame retardant in the content within the above range to facilitate process control with an appropriate viscosity, and can prevent deterioration of other physical properties while realizing excellent flame retardant performance of the phenolic foam.

The surfactant makes the cells of the phenol foam uniform and increases hydrophobicity. Examples of the surfactant may include, but are not limited to, at least one selected from the group consisting of siloxane-based compounds, castor oil-ethylene oxide, ester compounds, ether compounds, silicone-based compounds, fluorine-based compounds, and combinations thereof. .

The composition for forming the phenolic foam may include 2 to 20 parts by weight of the surfactant based on 100 parts by weight of the phenolic resin. The composition for forming phenolic foam includes the surfactant in the content within the above range and can prevent an increase in moisture permeability, a decrease in physical properties, and an increase in thermal conductivity while regularly controlling the cell size of the phenol foam.

In one embodiment of the present invention, a phenolic resin; It provides a foamable phenol-based resin composition comprising; and a polyphenol-based compound.

The phenolic foam described above can be manufactured from the foamable phenol-based resin composition.

In one embodiment, the foamable phenol-based resin composition includes 100 parts by weight of a phenolic resin, 1 to 15 parts by weight of a polyphenol-based compound, 1 to 8 parts by weight of a residual formaldehyde trapping agent, 2 to 20 parts by weight of a blowing agent, and 2 to 2 parts by weight of a plasticizer. It may include 30 parts by weight, 2 to 20 parts by weight of hardener, 1 to 20 parts by weight of flame retardant, and 2 to 20 parts by weight of surfactant.

In addition to the above-described additives, the foamable phenol-based resin composition may further include other additives that can be used in the production of phenol foam depending on the purpose or for practice.

In one embodiment, the expandable phenol-based resin composition is such that the phenol foam manufactured therefrom has excellent dimensional stability as described above, can satisfy a predetermined quasi-non-flammable performance, and satisfies other desired KS properties including appropriate additives. It can be appropriately designed to do so.

In one embodiment of the present invention, phenolic foam is manufactured by foaming and curing a foamable phenolic resin composition containing a phenolic resin, a polyphenol-based compound, a residual formaldehyde trapping agent, a foaming agent, a plasticizer, a curing agent, a flame retardant, and a surfactant. Provides a phenolic foam manufacturing method.

Specifically, the foamable phenol-based resin composition may be mixed by stirring at a constant speed and then cured in a mold. The curing can be carried out under known suitable conditions and methods. Specifically, the curing may be performed at a temperature of 70°C or less, 10 to 70°C, 20 to 70°C, 30 to 70°C, or 40 to 70°C. Any mold that can release moisture generated during the curing reaction of the foamable phenol-based resin composition to the outside can be used. The size of the mold can be designed to an appropriate size by a person skilled in the art as needed.

In addition, the method for producing phenolic foam may further include an additional reaction step in an oven for effects such as yield and moisture discharge. The further reaction can be carried out at an appropriate temperature and time by a person skilled in the art.

As described above, the phenol foam, the phenol foam obtained from the expandable phenolic resin composition, or the phenol foam manufactured by the phenol foam manufacturing method can simultaneously realize excellent dimensional stability and semi-incombustibility performance.

In one embodiment, the phenolic foam, the phenolic foam obtained from the expandable phenolic resin composition, or the phenolic foam manufactured by the phenolic foam manufacturing method has a rate of change in horizontal, vertical, or thickness dimensions measured by the KS M ISO 2796 method. It is within 2.0%.

In one embodiment, the phenolic foam, the phenolic foam obtained from the expandable phenolic resin composition, or the phenolic foam manufactured by the phenolic foam manufacturing method is tested in a cone calorimeter test by the method of KS F ISO 5660-1 for 10 minutes. During this period, the total heat release is less than 8 MJ/㎡, and no cracks penetrate the test specimen.

In one embodiment, the phenol foam, the phenol foam obtained from the expandable phenolic resin composition, or the phenol foam manufactured by the phenol foam manufacturing method has a formaldehyde emission of less than 50 mg/m2·h as a result of a test using a small chamber method. You can get results.

In one embodiment, the phenolic foam, the phenolic foam obtained from the expandable phenolic resin composition, or the phenolic foam manufactured by the phenolic foam manufacturing method has a thermal conductivity of 0.015 W/m·K to 0.030 W/m at 20°C. ·K, specifically, may be 0.015W/m·K to 0.030W/m·K.

In one embodiment, the phenolic foam, the phenolic foam obtained from the expandable phenolic resin composition, or the phenolic foam manufactured by the phenolic foam manufacturing method may have a compressive strength of 40 kpa to 250 kpa according to KS M ISO 845.

In one embodiment, the phenolic foam, the phenolic foam obtained from the expandable phenolic resin composition, or the phenolic foam manufactured by the phenolic foam manufacturing method may have a bending failure load of 10N to 40N.

In one embodiment, the phenol foam, the phenol foam obtained from the expandable phenolic resin composition, or the phenol foam manufactured by the phenol foam manufacturing method may have a moisture absorption rate of 1.0% to 10.0%.

In one embodiment, the phenol foam, the phenol foam obtained from the expandable phenol-based resin composition, or the phenol foam manufactured by the phenol foam manufacturing method may have a water vapor permeability of 3.0 to 20.0 ng/m·s·Pa.

In one embodiment, the phenolic foam, the phenol foam obtained from the expandable phenol-based resin composition, or the phenolic foam manufactured by the phenolic foam manufacturing method may have a density of 30 kg/㎥ to 60 kg/㎥.

In one embodiment, the phenolic foam, the phenolic foam obtained from the expandable phenolic resin composition, or the phenolic foam manufactured by the phenolic foam manufacturing method may have a closed cell ratio of 60% to 99%.

The phenolic foam can be manufactured by additionally attaching a face material. The face material may be aluminum, glass fiber, cloth, glass paper, fabric, or a mixed face material, but is not limited thereto.

Hereinafter, examples and comparative examples of the present invention will be described. The following example is only an example of the present invention, and the present invention is not limited to the following example.

(Example)

Example 1

100 parts by weight of phenol resin with a viscosity of 13,500 cps at 25°C, 6 parts by weight of cucumin, 10 parts by weight of cyclopentane as a blowing agent, 7 parts by weight of ester polyol as a plasticizer, xylene sulfonic acid and ethylene glycol (90 wt%: 10 wt%) as a hardener ) 15 parts by weight of a mixture, 3 parts by weight of silicone surfactant, 7 parts by weight of TCPP (Tris(1-Chloro-2- Propyl)Phosphate) as a flame retardant, 6 parts by weight of APP (Ammonium Poly Phosphate), and 2 parts by weight as a residual formaldehyde trapping agent. -6 parts by weight of imidazolidone (2-imidazolidone) was mixed with stirring to prepare a foamable phenol-based resin composition.

The foamable phenol-based resin composition was placed in a mold measuring 400 mm

Example 2

A foamable phenolic resin composition was prepared by replacing 6 parts by weight of cucumin with 11 parts by weight of catechin in the foamable phenolic resin composition of Example 1, and the foaming and curing process was performed in the same manner as in Example 1. This was performed to prepare phenol foam.

Comparative Example 1

A foamable phenolic resin composition was prepared except for 6 parts by weight of cucumin in the foamable phenolic resin composition of Example 1, and the foamable phenolic resin composition was subjected to the same foaming and curing processes as in Example 1 to produce phenol foam. Manufactured.

(Evaluation example)

The phenolic foams prepared in Example 1-2 and Comparative Example 1 were evaluated by the following physical property evaluation method. The evaluation results are shown in Tables 1 and 2 below.

<Method for evaluating physical properties>

(1) Measurement of dimensional change rate (%): Measured using the KS M ISO 2796 method. The manufactured sample was cut into 100 mm × 100 mm × 50 mm, and then the width (W0), length (L0), and thickness (T0) of the sample were measured using the method described in KS M ISO 1923. The sample for which the dimensional measurements were completed was left at 70°C and 25% humidity for 48 hours, and then the width (W1), length (L1), and thickness (T1) were measured. The dimensional change rate was measured as follows.

Width (%) = 100 × (W0-W1)/W0, Vertical (%) = 100 × (L0-L1)/L0, Thickness (%) = 100 × (T0-T1)/T0,

(2) Measurement of total heat release (MJ/㎡): The manufactured sample was cut into 100mm × 100mm × 50mm and measured using the KS F ISO 5660-1 method using a cone calorimeter. The heater temperature was set to 713°C, and radiant heat was applied for 10 minutes at a blower speed of 24 L/min and an oxygen concentration of 20.950% to measure the total amount of heat released.

(3) Check whether the test specimen is perforated: The manufactured sample was cut into 100mm After applying radiant heat for 10 minutes at an oxygen concentration of 20.950%, it was checked whether the test specimen was perforated.

(4) Limiting oxygen index (LOI) measurement: The minimum concentration (%) of oxygen required to burn the specimen under the test conditions specified in KS M ISO 4589-2 was measured. The results were measured as percent oxygen volume in the oxygen and nitrogen mixture.

(5) Viscosity Test: Viscosity was measured at 25°C using a Brookfield viscometer.

(6) Residual formaldehyde measurement: Measured according to the small chamber method. The phenolic foam was cut to 50 mm thick and 165 mm × 165 mm in size and then installed in the release test chamber. Air was flowed at a rate of 10 L per hour for 7 days (168 hours) at a temperature of 25 ± 1°C and relative humidity of 50 ± 5%. A DNPH (2,4-dinitrophenylhydrazine) cartridge equipped with an ozone scrubber was connected to the chamber air outlet, and the air flow rate was adjusted to 0.5 to 1.2 L/min for reaction for 30 minutes (proceeded twice). After passing 5ml of acetonitrile through the DNPH cartridge, the cartridge filtrate was collected in a volumetric flask, and then acetonitrile was added to adjust the solution to 5ml. The solution was analyzed for DNPH-formaldehyde derivative concentration using HPLC. The above process was repeated for the chamber where the specimen was not installed, and the concentration of DNPH-formaldehyde derivative in the blank sample was analyzed.

The formaldehyde concentration (C) in indoor air is calculated as follows:

C(㎍/㎥) = (AsVs-AbVb/V) × 1,000

As: Analyzed concentration of DPH-formaldehyde derivative in sample (㎍/㎖)

Vs: Total volume of solution extracted from the sample cartridge (ml)

Ab: Analyzed concentration of DPH-formaldehyde derivative in blank sample (㎍/㎖)

Vb: Total volume of solution extracted from blank sample cartridge (ml)

V: Converted total indoor air sampling volume (L)

Formaldehyde emission (SER) is calculated using the following formula:

SER (mg/㎡·h) = C × Q / A × 1,000

Q: Emission test chamber flow rate (㎥/h)

A: Surface area of test piece (㎡)

(7) Measurement of thermal conductivity: Phenolic foam was cut into 50mm thick and 300mm × 300mm sizes and pretreated. The thermal conductivity of the specimen was measured using a thermal conductivity device at a temperature of 20°C according to the KS L 9016 method.

(8) Compressive strength measurement: Phenolic foam was cut into 50mm × 50mm × 50mm sizes and the specimen was measured using the KS M ISO 844 method. The universal testing machine (UTM) was placed between wide plates, the specimen thickness was set at a speed of 5 mm/min in the UTM device, and the first compressive yield point strength that appeared while the thickness was decreasing at the start of the compressive strength test was recorded.

(9) Measurement of bending failure load: Phenolic foam was cut into 250 mm × 100 mm × 20 mm, and the specimen was measured using the KS M ISO 1209-1 method. The specimen using the universal testing machine (UTM) was placed symmetrically on the support bar so that a load could be applied perpendicularly to the specimen, the pressure bar was lowered, and this position was set as the no-strain point. Afterwards, a load was applied to the specimen while moving the pressure bar at a speed of 10 ± 2 mm/min, and the load (N) corresponding to the specimen bending deformation of 20 ± 0.2 mm was recorded. If the specimen failed before the bending strain reached 20 mm, the failure load and bending were recorded.

(10) Measurement of moisture absorption rate: Phenolic foam was cut into 150mm × 150mm × 75mm, and the specimen was measured using the KS M ISO 2896 method. After measuring the initial specimen mass (m1), the specimen was assembled/immersed in a mesh net and hung on a scale to measure the mass (m2). After 96 hours, the mass of the net in water (m3) was measured, and then the dimensions of the specimen before and after subsidence were measured to calculate the volume. The moisture absorption rate (WAv(%)) was calculated as follows.

WAv(%) = (m3+V ₁ ×ρ-(m1+m2))/(V ₀ ×ρ) × 100

m3 is the mass of the specimen after 96 hours,

V ₀ is the specimen volume before immersion,

V ₁ is the volume of the specimen after immersion,

ρ is the density of water (1 g/cm3).

(11) Measurement of water vapor permeability: Phenolic foam was cut into 150mm × 150mm × 25mm and measured using the KS M ISO 1663 method. At 23°C and 50% humidity, a 20 mm thick desiccant was placed on the bottom of the assembly container, and then the desiccant was spaced 15 mm apart from the specimen. Mass measurements (m1, m2) were performed at regular intervals for 24 hours. The mass change per unit time was measured until the average of five consecutive measurements was within 2.0%. Water vapor permeability (W _P (ng/m·s·Pa)) was calculated using the formula below.

W _P (ng/m·s·Pa) = G/(A×P)×100000/36×s/1000

G is the average of 5 G ₁₂ ,

G ₁₂ = (m2-m1)/(t2-t1),

A is the surface area (㎠) of the specimen exposed to humidity,

P is the vapor pressure difference (Pa), which is 1,400 Pa under the above test conditions,

s is the thickness of the specimen (mm),

G ₁₂ is the mass change per unit time (㎍/h) when the mass of the specimen was measured twice in succession,

(m2-m1) is the difference (㎍) in the mass (m2, m1) of the specimen measured twice in succession,

(t2-t1) is the difference (h) between the times (t2, t2) when the mass of the specimen was measured twice.

(12) Density measurement: Density was calculated after aging at 70°C for 10 to 20 hours.

(13) Measurement of closed cell rate: The phenolic foam was cut into 25 mm × 25 mm × 25 mm and measured using a closed cell rate measuring device (Pycnometer) using the KS M ISO 4590 measurement method.

phenolic foam Horizontal dimension change rate (%) Vertical dimension change rate (%) Thickness dimension change rate (%) Total heat release (MJ/㎡) test body
Perforated or not compressive strength
(kpa) thermal conductivity
(W/m·K) bending destruction
Load (N) Example 1 0.8 1.0 1.5 4.9 X 90 0.021 35 Example 2 1.1 0.9 1.3 6.5 X 105 0.019 33 Comparative Example 1 2.2 2.1 2.7 14.6 O 78 0.025 21

phenolic foam moisture
Absorption rate (%) Water vapor permeability (ng/ms·Pa) density
(kg/㎥) Closed cell rate
(%) Formaldehyde emission (mg/㎡·h) Example 1 3.1 8.5 37 92 38 Example 2 2.8 9.1 36 95 12 Comparative Example 1 4.3 11.3 38 83 56

Although the present invention has been described as above, it is obvious that the present invention is not limited to the embodiments disclosed in this specification, and that various modifications can be made by those skilled in the art within the scope of the technical idea of the present invention. In addition, although the operational effects according to the configuration of the present invention were not explicitly described and explained in the above description of the embodiments of the present invention, it is natural that the predictable effects due to the configuration should also be recognized.

Claims (17)

phenolic resin; And a polyphenol-based compound; a phenolic foam containing a. According to paragraph 1,
The moisture content of the phenolic resin is 3 to 15% by weight.
Phenol foam. According to paragraph 1,
The polyphenol-based compound includes at least one selected from the group consisting of catechin-based compounds, cucumin-based compounds, and derivatives thereof.
Phenol foam. According to paragraph 1,
The phenolic foam includes the phenolic resin; The polyphenol-based compounds; and an additive containing at least one selected from the group consisting of a residual formaldehyde trapping agent, a foaming agent, a plasticizer, a curing agent, a flame retardant, and a surfactant; prepared by foaming and curing a composition for forming phenolic foam containing a
Phenol foam. According to clause 4,
The residual formaldehyde trapping agent includes a urea substituent containing at least one cyclic substituent.
Phenol foam. According to clause 4,
The foaming agent includes at least one selected from the group consisting of hydrocarbons, halogenated hydrocarbons, and combinations thereof.
Phenol foam. According to clause 4,
The plasticizer includes at least one selected from the group consisting of esters, ester polyols, ether polyols, phosphorus-based compounds, epoxy resins, fluorine-based compounds, and combinations thereof.
Phenol foam. According to clause 4,
The curing agent includes at least one selected from the group consisting of sulfonic acid-based organic acids, inorganic acids, and combinations thereof.
Phenol foam. According to clause 4,
The flame retardant includes at least one selected from the group consisting of phosphorus-based flame retardants, halogen-phosphorus-based flame retardants, boron-based flame retardants, metal hydroxides, expanded graphite, red water glass, and combinations thereof.
Phenol foam. According to clause 4,
The surfactant includes at least one selected from the group consisting of siloxane-based compounds, castor oil-ethylene oxide, ester compounds, ether compounds, silicone-based compounds, fluorine-based compounds, and combinations thereof.
Phenol foam. According to paragraph 1,
Containing 50 to 95% by weight of the phenolic resin
Phenol foam. According to paragraph 1,
Containing 1 to 15 parts by weight of a polyphenol-based compound relative to 100 parts by weight of the phenol-based resin
Phenol foam. According to paragraph 1,
The rate of change in horizontal, vertical, or thickness dimensions as measured by the KS M ISO 2796 method is within 2.0%, and the total heat released for 10 minutes is 8 MJ/㎡ or less as a result of the cone calorimeter test using the KS F ISO 5660-1 method, No cracks penetrating the test specimen
Phenol foam. According to paragraph 1,
The thermal conductivity at 20°C is 0.015W/m·K to 0.030W/m·K,
The compressive strength according to KS M ISO 845 is 40kpa to 250kpa,
The bending failure load is 10N to 40N,
The moisture absorption rate is 1.0% to 10.0%,
The water vapor permeability is 3.0 to 20.0ng/m·s·Pa,
The density is 30kg/㎥ to 60kg/㎥,
The closed cell rate is 60% to 99%,
Formaldehyde emissions less than 50mg/㎡·h
Phenol foam. phenolic resin; And a polyphenol-based compound; a foamable phenol-based resin composition comprising a. According to clause 15,
The foamable phenol-based resin composition includes 100 parts by weight of a phenol-based resin, 1 to 15 parts by weight of a polyphenol-based compound, 1 to 8 parts by weight of a residual formaldehyde trapping agent, 2 to 20 parts by weight of a foaming agent, 2 to 30 parts by weight of a plasticizer, and a curing agent. 2 to 20 parts by weight, 1 to 20 parts by weight of flame retardant and 2 to 20 parts by weight of surfactant.
Foamable phenolic resin composition. A phenolic foam manufacturing method for producing phenolic foam by foaming and curing a foamable phenolic resin composition containing a phenol-based resin, a polyphenol-based compound, a residual formaldehyde capture agent, a foaming agent, a plasticizer, a curing agent, a flame retardant, and a surfactant.