KR100311437B1 - Phenolic resin foam - Google Patents

Abstract

The present invention has a phenolic resin structure having an independent bubble ratio of 70 or more, an average bubble diameter of 10 µm or more and 400 µm or less, a density of 10 kg / m 3 or more and 70 kg / m 3, containing fluorohydrocarbons in an independent bubble and having a urea crosslinking structure. It is characterized in that the phenol resin foam having a specific crosslinking density and forming urea-derived crosslinking has excellent heat insulating performance even when HFC is used as a blowing agent, and has improved mechanical strength and surface brittleness. .

Description

Phenolic resin foam {PHENOLIC RESIN FOAM}

Phenolic resin foams are particularly useful as various building materials because of their excellent flame retardancy, heat resistance, low smoke resistance, dimensional stability, solvent resistance and processability among organic resin foams.

In general, the conventional phenolic resin foam has a big drawback that the foam is weak, which causes the surface surface embrittlement of the foam deteriorates or cracks, or pin holes in the foam wall to replace the blowing agent with air, resulting in poor thermal insulation performance. There was a problem such as being.

In order to remedy this drawback, Japanese Laid-Open Patent Publication No. 53-13669 limits the amount of water in the resol resin extremely, and Japanese Laid-Open Patent No. 63-20460 uses a high molecular weight resol resin, respectively, to provide high viscosity of the foamable mixture. A technique for obtaining an independent foamed foam by improving the strength of the bubble wall by improving the foam wall has been proposed, but due to its high viscosity, it is difficult to handle the resin, and due to the inherent fragility of the phenolic resin, the surface brittleness is poor, resulting in differentiation or peeling of the surface material. There was a flaw of ease.

In addition, in order to improve the brittleness of the resin, Japanese Patent Laid-Open Publication No. 61-238833 has added an saccharide, Japanese Patent Laid-Open Publication No. 62-48978 uses modified phenols or various additives to improve the resin. However, all of them were inadequate and high independence was not obtained.

Therefore, in these prior arts, the thermal conductivity is only 0.020 (kcal / mhr ° C.) or more, so that the fire resistance is particularly required to be used as a heat insulating material.

Moreover, in these prior arts, halogenated hydrocarbons having a relatively high boiling point such as 1,1,2-trichloro-1,2,2-trifluoroethane or dichlorofluoromethane are used as blowing agents. Contained chlorofluorocarbons (hereinafter referred to as "CFC") or hydrogenated chlorofluorocarbons (hereinafter referred to as "HCFC") in which a small amount of CFC chlorine is replaced with hydrogen are limited in that they destroy the ozone layer. It became.

Accordingly, fluorohydrocarbons (hereinafter referred to as "HFC") in which chlorine atoms do not exist as a gas having a low thermal conductivity that does not destroy the ozone layer are attracting attention as blowing agents. Examples of HFCs that can be used industrially for economic reasons include HFC-134a (1,1,1,2-tetrafluoroethane), HFC-152a (1,1-difluoroethane), HFC-125 (1 (1,1,2,2-pentafluoroethane) and the like, all of which have a low boiling point, and thus, the pressure at the time of foaming increases, so that the bubble wall is broken or the bubble diameter is large. In the technology of manufacturing the HFC as a blowing agent it was more difficult to manufacture a product with high thermal insulation performance.

A general method for producing these phenol resin foams is to uniformly mix and foam a resol resin obtained by condensing phenol and formalin with an alkaline catalyst, a blowing agent, a surfactant, a curing catalyst, and other additives.

An object of the present invention is to use a HFC as a foaming agent, to provide a thermally insulating phenolic resin foam having excellent thermal insulation performance, excellent mechanical strength such as compressive strength, and improved surface brittleness.

The present invention relates to a phenolic resin foam for thermal insulation having excellent thermal insulation performance, excellent mechanical strength such as compressive strength, and improved surface brittleness.

1 is a pyrogram of pyrolysis gas chromatography of a phenolic resin foam sample. The vertical axis represents relative intensity.

Figure 2 is a mass spectrum of the phenolic component of the pyrogram of pyrolysis gas chromatography of a phenolic resin foam sample.

Fig. 3 is a mass spectrum of the trimethylphenol component of the pyrogram of pyrolysis gas chromatography of a phenol resin foam sample.

4 is a mass spectrum of the o-methylphenol component of the pyrogram of pyrolysis gas chromatography of a phenolic resin foam sample.

5 is a mass spectrum of the p-methylphenol component of the pyrogram of pyrolysis gas chromatography of a phenolic resin foam sample.

Fig. 6 is a mass spectrum of 2,4-dimethylphenol component of the pyrogram of pyrolysis gas chromatography of a phenol resin foam sample.

Fig. 7 is a mass spectrum of 2,6-dimethylphenol component of the pyrogram of pyrolysis gas chromatography of a phenol resin foam sample.

FIG. 8 is a mass spectrum of urea-derived structural components, which is one of the pyrograms of pyrolysis gas chromatography of phenolic resin foam samples.

9 is a mass spectrum of urea crosslinking-derived structural components, which is one of the pyrograms of pyrolysis gas chromatography of phenolic resin foam samples.

FIG. 10 is a mass spectrum of urea cross-linked structural components, which is one of the pyrolysis gas chromatograms of phenolic resin foam samples.

11 is a mass spectrum of urea cross-linked structural components, which is one of the pyrolysis gas chromatography of phenol resin foam samples.

12 is a mass spectrum of urea-derived structural components, which is one of the pyrolysis gas chromatography of phenolic resin foam samples.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

In general, if the independent bubble ratio is low, not only the surface embrittlement of the shape is increased, but also the foaming gas in the bubble is replaced with air, thereby deteriorating the thermal insulation performance over time. In this invention, it is important to raise the ratio of the existence of the independent bubble which can hold | maintain foaming gas for a long time, in order to remove this fall of heat insulation performance. That is, in the present invention, the independent bubble ratio needs to be 70 or more, more preferably 80 or more, and still more preferably 90 or more.

In the present invention, the independent bubble ratio is a volume ratio of the independent bubbles occupied by the voids in the phenolic resin foam, and is measured by the method described below.

In addition, if the average bubble diameter of the foam is too small, the thickness of the bubble wall has a limit, so that the shape density inevitably increases, and as a result, the heat transfer ratio of the resin portion increases, resulting in a decrease in the thermal insulation performance of the phenol resin foam. On the contrary, if the bubble diameter is too large, the thermal conductivity due to radiation is increased to lower the thermal insulation performance. In order to eliminate this fall of heat insulation performance, in this invention, the average bubble diameter needs to be 10 micrometers or more and 400 micrometers or less, More preferably, they are 20 micrometers or more and 300 micrometers or less.

If the density of the phenolic resin foam is too small, the mechanical strength such as compressive strength becomes small, which is easy to break during handling, and the surface brittleness also increases. On the contrary, if the density is too large, the heat transfer of the resin portion increases, which lowers the heat insulating performance. In order to eliminate such a problem, in the present invention, the density of the phenol resin foam needs to be 10 kg / m 3 or more and 70 kg / m 3 or less, and more preferably 20 kg / m 3 or more and 50 kg / m 3 or less.

The phenol resin foam according to the present invention comprises a phenol resin structure having a urea crosslinked structure. The phenol resin structure can be specified by displaying the pattern of the pyrolysis product of the pyrolysis gas chromatography of the phenol resin forming the foam (hereinafter referred to as "pyrogram") (see Fig. 1). In the above pyrogram, the ratio C = A / B to the ratio B of the phenol of the ratio A of the trimethylphenol and the ratio F = D / E of the component D derived from the urea crosslinking to the phenol derivative component E of the phenol resin foam It does not represent the structure directly, but indirectly reflects the structure of the original polymer. In other words, the ratio C of the pyrogram of pyrolysis gas chromatography is an index reflecting the crosslinking density of the phenol resin, and the ratio F is an index reflecting the density of the urea crosslinking structure of the phenol resin. The crosslinking density and the density of the urea crosslinking structure, and also the ratio C and the ratio F, the amount of urea methylol to be blended, the molar ratio of the feed formaldehyde and phenol (hereinafter referred to as the "F / P ratio"), the temperature at the time of foaming, the amount of the catalyst, etc. The phenolic resin foam of the present invention having the above excellent characteristics can be obtained by appropriately selecting these factors.

The component D of urea crosslinking derived from the ratio F is a component which is released during the holding time of 8 to 18 minutes in the pyrogram and contains a phenyl group and an isocyanate (-NCO) group in the molecule. These components are identified by mass spectrum and the like, specifically, for example, peaks 7 to 11 of FIG. 1, and mass spectra corresponding to these are shown in FIGS. 8 to 12, respectively.

The phenol derivative component E of the above ratio F is the sum of phenol, methylphenol, dimethylphenol and trimethylphenol. These components are identified by mass spectrum and the like, specifically, peaks 1 to 6, and the mass spectrum corresponding to these is shown in Figs.

Ratio C by this invention becomes like this. Preferably it is 0.2 or more and 4.0 or less, More preferably, it is 0.2 or more and 2.0 or less, Especially preferably, it is 0.25 or more and 1.5 or less, And ratio F is preferably 0.03 or more and 0.3 or less, More Preferably they are 0.035 or more and 0.2 or less, Especially preferably, they are 0.04 or more and 0.15 or less. Such phenolic resin improves the strength of the phenolic resin itself in the specificity of this crosslinked structure, and the resin with the improved strength is remarkably reflected in the brittleness improvement and strength improvement of the phenolic resin foam.

That is, the phenol resin foam according to the present invention can provide a very excellent phenol resin foam having a brittleness of 30 or less and a thermal conductivity of 0.018 kcal / mhr ° C. or less, as can be seen in the examples described later.

In the present invention, when the resin structure is specified, the pyrolysis of the foam sample is performed at 670 ° C. using a furnace pyrolysis device. In addition, gas chromatography is measured by the method and conditions mentioned later.

The present invention uses HFC having a low ozone depletion coefficient and low thermal conductivity as a blowing agent. As HFC, HFC having 1 to 8 carbon atoms can be used, but HFC having 2 carbon atoms is preferable for thermal conductivity and economic reasons. Specifically, 1,1,1,2-tetrafluoroethane, 1,1-difluoroethane, 1,1,1,2,2-pentafluoroethane, etc. are mentioned. Among these, 1,1,1,2-tetrafluoroethane is more preferable. These HFCs can also be used in mixture of 2 or more types. In addition, perfluorobutane, perfluorocyclobutane, perfluoropentane, perfluorocyclopentane, perfluorohexane, perfluorocyclohexane, perfluoroheptane and perfluoro as foaming aids in these HFCs. It is also possible to use a mixture of fluorocarbons such as cycloheptane, perfluorooctane, and perfluorocyclooctane. And low boiling point substances, such as nitrogen, helium, argon, and air, can also be melt | dissolved in a foaming agent as a foaming nucleus, and can also be used.

Next, the manufacturing method of the phenol resin foam of this invention is demonstrated.

The phenol resin foam according to the present invention is a method for producing a foam, characterized in that a sol resin composition comprising a resol resin and a methylolated urea is foamed and cured with fluorohydrocarbon as a blowing agent to form a phenol resin structure having a urea crosslinked structure. . It demonstrates in detail below.

In general, in order to obtain a phenol resin foam having a high independent foaming rate, the viscosity of the resin composition such that the foam wall is not destroyed by the vapor pressure of the volatile components such as blowing agent, water, formaldehyde, etc. in the resin composition at the time of foaming, and the foaming agent in the foam Reactivity is required to cure the resin before it is released. The factor influencing the viscosity of the resin composition is the temperature and the degree of crosslinking of the resin. Therefore, controlling the crosslinking reactivity of the resin is the most important point in forming an independent fine cell structure.

Resol resins for producing phenolic resin foams are polymerized by heating phenol and formaldehyde as raw materials in an alkali catalyst at a temperature in the range of 40 ° C to 100 ° C. Curing reactivity of resol resin is largely dependent on F / P ratio and molecular weight. Generally, the resol resin having a small F / P ratio has a fast initial reaction, but the increase in viscosity in the second half accompanying the progress of crosslinking is inversely small. Regarding the molecular weight, the initial reaction of the resol resin having a low molecular weight is quick, but the increase in viscosity in the second half accompanying the progress of the crosslinking is inversely small. Therefore, in addition to the production examples shown here, it is thought that the phenol resin foam of the present invention can be obtained by optimizing the F / P ratio and the molecular weight distribution to control the resol resin.

The present inventors synthesized a resol resin having a high initial reactivity and a large increase in viscosity in the second half of the reaction, and then mixing methylolated urea to obtain a resol resin composition, and using this resol resin composition to form a phenol resin foam containing a urea crosslinked structure. Got it.

The amount of methylolated urea in the resol resin composition is not particularly limited, but is usually added in an amount of 2 to 40 wt% based on the resol resin. The resol resin composition can be used by optimizing the viscosity by adjusting the moisture content. The viscosity of the resin composition depends on the foaming conditions, the viscosity at 40 ℃ is preferably 1000 to 50000 cps, more preferably in the range of 2000 to 30000 cps.

A foamable composition can be obtained by introducing a mixed resol resin mixture, a blowing agent, a surfactant, a curing catalyst, and a curing catalyst into a mixer. Thereafter, the foamable composition is foamed and cured by heat treatment to obtain a phenol resin foam.

As a curing catalyst at the time of foaming and hardening, toluene sulfonic acid, xylene sulfonic acid, etc. can be used individually or in mixture of 2 or more types. Moreover, you may add resorcinol, a cresol, salginine (o-methylol phenol), p-methylol phenol, etc. as a hardening adjuvant.

As the surfactant used in the present invention, any of those which show effectiveness in producing a phenol resin foam can be used. Generally, nonionic surfactants are effective, for example, alkylene oxide which is a copolymer of ethylene oxide and propylene oxide, a condensate of alkylene oxide and castor oil, or alkylene oxide such as alkylene oxide, nonylphenol, and dodecylphenol. And condensation products, fatty acid esters such as polyoxyethylene fatty acid esters, silicone compounds such as polydimethylsiloxane, and polyalcohols.

Next, in this invention, the evaluation method of the structure, a structure, and the characteristic of a phenol resin foam is demonstrated.

The independent bubble ratio of a phenol resin foam is measured as follows. Cylindrical samples of 35 to 36 mm in diameter, drilled in cork borer from phenolic resin foam, are cut evenly so that the total thickness is 30 to 40 mm, and standard use of air comparative hydrometer 1000 type (manufactured by Tokyo Science Corporation) is made. The sample volume is measured by the method. This sample volume is obtained by subtracting the volume of the bubble wall calculated from the sample weight and the resin density by the apparent volume calculated from the outside dimension of the sample, measured according to ASTM D2856. In the present invention, the density of the phenol resin is 1.27 g / cm 3.

In the present invention, the average bubble diameter of the phenolic resin foam means that four straight lines of 9 cm length (actual length is 1800 μm) are drawn on a 50 times magnified image of the foam cross section, and the average number of bubbles traversed is 1800. It is the value obtained by dividing µm, and is an average value calculated from the number of cells measured according to JIS K6402.

The thermal conductivity is measured according to the flat plate heat flow meter method of JIS A1412 at a 200 mm corner of a phenol resin foam sample, a low temperature plate 5 degreeC, and a high temperature plate 35 degreeC.

The density is a value obtained by taking a phenol resin foam having a corner of 20 cm as a sample, removing the face material and the siding material of the sample, measuring the weight and the apparent volume, and measuring according to JIS K7222.

The test specimens of the brittleness test shall be cut out of 12 cubes of 25 ± 1.5 mm on one side so as to include a molded skin or face material on one surface. However, the thickness of the test piece when the thickness of the foam is not 25 mm is the thickness of the foam. Twenty-four oak cubes made of dry oak at a temperature of 0.65, one side 19 ± 0.8 mm and twelve specimens were placed in a wooden box made of oak, 191 × 197 × 197 mm, with an inner dimension to seal the dust out of the box. Rotate 600 ± 3 at 60 ± 2 revolutions per minute. After the end of rotation, the contents of the box were transferred to a net with a nominal dimension of 9.5 mm, sieved to remove small pieces, and the weight of the remaining test piece was measured to calculate the rate of reduction from the weight of the test piece before the test. Measure

The compressive strength is measured according to JIS K7220 using a sample with a 50 mm edge as 0.05 specified strain.

The measurement of the pyrogram of pyrolysis gas chromatography is performed as follows. The phenolic resin foam sample used in the measurement is used to finely grind the powder squeezed by the cutter knife from the shape core portion from which the face material and the siding material are removed again in a mortar, and to adjust the sample amount in the range of 0.3 to 0.4 mg in one measurement. . The pyrolysis device uses PY2010D manufactured by Frontier Laboratories, a furnace type pyrolysis device. Pyrolysis temperature is carried out at 670 ℃. Gas chromatographic measurement was performed using Hewlett-Packard Co., Ltd. HP5890A type Durabond DB-1 (0.25 mm inner diameter, 0.25 탆 thickness, 30 m length), which is a nonpolar liquid capillary column. The carrier gas is helium (He), the total flow rate is 100 kW / min, the head pressure is 100 kPa, the oven temperature starts at 50 ° C and the temperature is raised to 340 ° C at a speed of 20 ° C for 15.5 minutes. The detection of each component is carried out by a hydrogen ionization detector (FID), and the area value of each peak is normalized to all the detection components to be the ratio of each component. However, when the lower part of the peak overlaps, the waterline is lowered to the baseline between the valleys of the overlapping peaks, and the area surrounded by the baseline and the waterline is made into the peak area. An example of the gas chromatogram of the phenol resin foam sample which concerns on this invention is shown in FIG. The structure of each component is confirmed by mass spectra obtained by introducing a component separated by gas chromatography into a mass spectrometer. The mass spectrum is measured by ionization voltage 70 eV and ionization current 300 mA by Nippon Denshi JMS AX-505H by electron impact ionization method (EI method). 2 and 3 show mass spectra of phenol and trimethyl phenol.

Confirmation of a blowing agent can be performed as follows. Phenol resin foam samples can be identified by immersing and pulverizing in a solvent selected from pyridine, toluene, tetrahydrofuran (THF), dimethylformamide (DMF) and the like, extracting the blowing agent, and performing gas chromatography. If necessary, the molecular structure can be confirmed by introducing a component separated by gas chromatography into a mass spectrometer.

The present inventors have diligently studied phenolic resin foams, and as a result, phenolic resin foams having specific crosslinking densities and forming urea-derived crosslinking have excellent heat insulating properties even when HFC is used as a blowing agent, and have improved mechanical strength and surface brittleness. It was found that can be obtained to complete the present invention.

That is, the present invention

1. A phenolic resin structure having an independent bubble ratio of 70 or more, an average bubble diameter of 10 µm or more and 400 µm or less, a density of 10 kg / m 3 or more and 70 kg / m 3 or less, containing fluorohydrocarbons in an independent bubble and having a urea crosslinking structure. Phenolic resin foam, characterized in that

2. Phenol resin structure is pyrolysis pattern of pyrolysis gas chromatography of phenol resin, wherein ratio of C = A / B to ratio B of phenol of pyrolysis product of ratio A of trimethylphenol of pyrolysis product is 0.2 or more and 4.0 or less; The phenol resin foam according to the above 1, wherein the ratio F = D / E of the component D derived from urea crosslinking of the pyrolysis product is 0.03 or more and 0.3 or less,

3. The phenol resin foam according to the above 1 or 2, wherein the thermal conductivity is 0.018 kcal / mhr ° C or less and brittleness is 30 or less,

4. The fluorohydrocarbon is at least one of 1,1,1,2-tetrafluoroethane, 1,1-difluoroethane or 1,1,1,2,2-pentafluoroethane. The phenol resin foam of any one of said 1-3,

5. The resol resin composition composed of resol resin and methylolated urea is formed by foaming and curing fluorohydrocarbon as a blowing agent and forming a urea crosslinking structure, having an independent bubble ratio of 80 or more, an average bubble diameter of 20 µm or more and 300 µm or less, A phenol resin foam having a density of 20 kg / m 3 or more and 50 kg / m 3 or less, a thermal conductivity of 0.018 kcal / mhr ° C. or less and brittleness of 30 or less.

Next, an Example and a comparative example demonstrate this invention further in detail.

[Synthesis of Resol Resins (A)]

Into the reactor, 5380 g of 37 formaldehyde (made by Wako Pure Chemical, reagent express) and 3000 g of 99 phenol (made by Wako Pure Chemical, reagent express) were added and stirred with a propeller rotary stirrer. Adjust Then, 39 g of 50 aqueous sodium hydroxide solution is added, and the reaction solution is raised from 40 ° C to 85 ° C and held at 85 ° C for 2 hours. Thereafter, the reaction solution is cooled to 5 ° C. This is called Resol resin A-1.

Separately, 540 g of 37 formaldehyde, 500 g of water, and 50 g of 50% sodium hydroxide solution were added to the reactor, and 800 g of urea (made by Wako Pure Chemical Industries, Ltd.) was added and stirred with a propeller rotary stirrer. Is adjusted to 40 ° C. Subsequently, the reaction solution is raised from 40 ° C. to 70 ° C. and held for 60 minutes. This is called methylol element A-2.

Subsequently, the entire amount of the obtained resol resin A-1 and methylol urea A-2 are mixed, and the liquid temperature is raised to 60 ° C. and maintained for 1 hour. Subsequently, the reaction solution is cooled to 30 ° C and neutralized with 50 aqueous solution of paratoluenesulfonic acid monohydrate until the pH becomes 5. When the reaction solution was dehydrated at 60 ° C. to measure the viscosity, the viscosity at 40 ° C. was 5800 cps. This is called Resol Resin A.

[Synthesis of Resol Resins (B)]

Synthesis of the resol resin B is carried out in the same manner as the resol resin A except for changing the weight ratio of A-2 to A-1 to 0.05 in the resol resin A.

[Synthesis of Resol Resins (C)]

Synthesis of the resol resin C is carried out in the same manner as the resol resin A except for changing the weight ratio of A-2 to A-1 to 0.49 in the resol resin A.

[Synthesis of Resol Resins (D)]

4350 g of 37 formaldehyde and 3000 g of 99 phenol were added to the reactor and stirred with a propeller rotary stirrer, and the reactor internal liquid temperature was adjusted to 50 ° C using a temperature controller. Subsequently, 60 g of 50 aqueous sodium hydroxide solution is added, and the reaction solution is kept at 50 ° C to 55 ° C for 20 minutes. Thereafter, the temperature is increased to 85 ° C. and maintained for 130 minutes after the temperature reaches 85 ° C. Thereafter, the reaction solution is cooled to 5 ° C. This is called Resol resin D-1.

Synthesis of the resol resin D is carried out in the same manner as the resol resin A except that the resol resin A-1 is changed to D-1 in the synthesis of the resol resin A.

[Synthesis of Resol Resins (E)]

2613 g of 37 formaldehyde and 1836 g of 99 phenol were added to the reactor, followed by stirring with a propeller rotary stirrer. The temperature inside the reactor was adjusted to 50 ° C. using a temperature controller. Subsequently, 36.3 g of 50 aqueous sodium hydroxide solution are added, and the reaction solution is maintained at a temperature in the range of 50 ° C to 55 ° C for 20 minutes. Thereafter, the temperature is increased to 85 ° C. and maintained for 130 minutes after the temperature reaches 85 ° C. Thereafter, the reaction solution is cooled to 30 ° C and neutralized with 50 aqueous solution of paratoluenesulfonic acid monohydrate until the pH becomes 5. When the reaction liquid was dehydrated at 60 ° C. to measure the viscosity, the viscosity was 2700 cps at 40 ° C. This is called Resol resin E.

[Synthesis of Resol Resins (F)]

3174 g of 37 formaldehyde and 1600 g of 99 phenol were added to the reactor and stirred with a propeller rotary stirrer, and the temperature inside the reactor was adjusted to 50 ° C. using a temperature controller. Subsequently, 34.1 g of 50 aqueous sodium hydroxide solution are added, and the reaction solution is maintained at a temperature in the range of 50 ° C to 55 ° C for 20 minutes. Thereafter, the temperature is increased to 85 ° C. and maintained for 105 minutes after the temperature reaches 85 ° C. Thereafter, the reaction solution is cooled to 30 deg. C and neutralized with 50 aqueous solution of paratoluenesulfonic acid monohydrate until the pH becomes 5. When the reaction solution was dehydrated at 60 ° C. to measure the viscosity, the viscosity at 40 ° C. was 1300 cps. This is called Resol resin F.

[Synthesis of Resol Resins (G)]

Synthesis of the resol resin G is carried out in the same manner as the resol resin A except that the weight ratio of A-2 to A-1 in Resol resin A is changed to 0.01.

[Synthesis of Resol Resin (H)]

3330 g of 37 formaldehyde and 3000 g of 99 phenol were added to the reactor, followed by stirring with a propeller rotary stirrer, and the temperature of the reactor liquid was adjusted to 40 ° C. with a temperature controller. Subsequently, 57 g of 50 aqueous sodium hydroxide solution is added, and the reaction solution is raised from 40 ° C to 85 ° C and held for 2 hours 30 minutes. Thereafter, the reaction solution is cooled to 5 ° C. This is called Resol resin H-1.

Synthesis of the resol resin H is carried out in the same manner as the resol resin A except that the resol resin A-1 is changed to the resol resin H-1 in the resol resin A.

[Synthesis of Resol Resins (I)]

Synthesis of resol resin I is obtained in the same manner as resol resin D except that the weight ratio of methylol urea A-2 to resol resin D-1 in resol resin D is changed to 0.012.

[Synthesis of Resol Resins (J)]

3174 g of 37 formaldehyde and 1600 g of 99 phenol were added to the reactor and stirred with a propeller rotary stirrer, and the temperature inside the reactor was adjusted to 50 ° C. using a temperature controller. Subsequently, 34.1 g of 50 aqueous sodium hydroxide solution is added, and the reaction solution is maintained at 50 ° C to 55 ° C for 20 minutes. Thereafter, the temperature is raised to 85 ° C. and maintained for 155 minutes after the temperature reaches 85 ° C. Thereafter, the reaction solution is cooled to 5 ° C. This is called Resol resin J-1.

Synthesis of the resol resin J was performed in the same manner as the resol resin A, except that in the resol resin A, the resol resin A-1 was changed to J-1 and the weight ratio of methylol urea A-2 was changed to 0.96. Get J

(Example 1)

A polysiloxane nonionic surfactant SH-193 (manufactured by Tores Silicone Co., Ltd.) is dissolved in resol resin A at a rate of 3.5 g relative to 100 g of resol resin. This resol resin mixture, a mixture of 99.5 weight of HFC-134a (manufactured by Daikin Kogyo Co., Ltd.) and 0.5 weight of nitrogen as a blowing agent, paratoluenesulfonic acid monohydrate 50 (wako Pure Yaku 95+) and diethylene glycol 50 as a curing catalyst The mixture of (Wakkoyayaku 98+) is supplied to a pin mixer with a temperature control jacket at a ratio of 100 parts of a resin mixture, 17 parts of a blowing agent, and 15 parts of a curing catalyst, respectively. At this time, the mixer jacket was adjusted to 40 degreeC, and the mixer internal pressure was 15 kg / cm <2>. The mixture from the mixer was poured into a mold covered with Spanbond E1040 (manufactured by Asahi Kasei Kogyo Co., Ltd.), placed in an oven at 85 ° C, and held for 5 hours to obtain a phenolic resin foam.

The ratio C of the ratio A of the trimethylphenol of the pyrogram of the pyrolysis gas chromatography of the obtained phenol resin foam and the ratio B of the phenol of the decomposition product, the ratio F of the component D derived from urea crosslinking, and the phenol derivative component E and the independent bubble ratio Table 1 shows the measurement results such as average bubble diameter, density, thermal conductivity, brittleness and compressive strength.

(Example 2)

A phenol resin foam was prepared in the same manner as in Example 1, except that a mixture of paratoluenesulfonic acid monohydrate 20, diethylene glycol 50, and resorcinol 30 was changed at a ratio of 12 parts relative to 100 parts of the resin as a curing catalyst. Table 1 shows the measurement results of the obtained phenol resin foam.

(Example 3)

A phenol resin foam was prepared in the same manner as in Example 1 except that HFC-134a was added with 3 weights of PF-5050 (perfluoropentane manufactured by 3M) as a blowing agent.

Table 1 shows the measurement results of the obtained phenol resin foam.

(Comparative Example 1)

A phenol resin foam was prepared in the same manner as in Example 1 except that the resol resin A was changed to the resol resin E.

Table 1 shows the measurement results of the obtained phenol resin foam.

(Comparative Example 2)

A phenol resin foam was prepared in the same manner as in Example 1 except that Resol resin A was changed to Resol resin E and 5 parts by weight of urea was added to 100 parts by weight of resin. In this case, the foaming agent almost disappeared at the time of curing and did not form a foam.

Table 1 shows the measurement results of the obtained phenol resin foam.

(Comparative Example 3)

A phenol resin foam was prepared in the same manner as in Example 1 except that the resol resin A was changed to the resol resin F.

Table 1 shows the measurement results of the obtained phenol resin foam.

(Comparative Example 4)

A phenol resin foam was prepared in the same manner as in Example 1, except that 10 parts by weight of urea was added to 100 parts by weight of resin, and the curing agent was changed to 25 parts by weight with respect to 100 parts by weight of resin. do.

Table 1 shows the measurement results of the obtained phenol resin foam.

(Examples 4-6, Comparative Examples 5-8)

Examples 4-6 and Comparative Examples 5-8 use the resin shown in Table 1 as resol resin similarly to Example 1 thru | or Comparative Example 4, and produce a phenol resin foam according to Example 1, adjusting the number of catalysts. .

The ratio A and ratio C of the trimethylphenol of pyrogram of the pyrolysis gas chromatography of the phenol resin foam samples obtained by each Example and the comparative example, the component B and the phenol derivative derived from urea crosslinking. Table 1 shows the component E and ratio F values, and the independent bubble ratio, average bubble diameter, density, thermal conductivity, brittleness, and compressive strength of the foam.

Suzy C F Independent Bubble Rate () Average bubble diameter (㎛) Density (㎏ / ㎥) Thermal Conductivity (㎉ / mhr ℃) Brittleness () Compressive strength (㎏ / ㎠) Example 1 A 0.70 0.11 92.1 192 39 0.0161 14 2.8 Example 2 A 0.72 0.12 91.3 220 29 0.0162 20 1.6 Example 3 A 0.68 0.13 91.1 190 30 0.0160 17 1.8 Example 4 B 0.83 0.04 85.3 211 40 0.0171 25 2.9 Example 5 C 0.61 0.26 82.1 250 25 0.0166 28 1.8 Example 6 D 0.34 0.15 87.3 205 35 0.0167 21 2.2 Comparative Example 1 E 0.15 0 58.0 250 30 0.0260 51 1.1 Comparative Example 2 E 0.12 0.01 - - - - - - Comparative Example 3 F 1.52 0 12.3 355 18 0.0282 65 0.2 Comparative Example 4 F 1.12 0.02 65.3 215 43 0.0230 46 2.2 Comparative Example 5 G 0.65 0.02 64.1 220 42 0.0233 48 2.0 Comparative Example 6 H 0.15 0.17 34.1 310 25 0.0251 52 0.6 Comparative Example 7 I 0.27 0.01 54.0 230 40 0.0245 48 2.1 Comparative Example 8 J 4.2 0.39 65.0 380 22 0.0241 55 0.6 However, C value: area ratio of trimethylphenol A to phenol B in the pyrolysis product (C = A / B) F value: area ratio of phenol derivative component E of component D derived from urea crosslinking in the pyrolysis product (F = D / E )

The foam of the present invention has excellent heat insulating performance, excellent mechanical strength such as compressive strength, and improved surface brittleness, so it is suitable as a heat insulating material for construction, and is suitable for the global environment because it uses a foaming agent that does not cause ozone layer destruction.

Claims (6)

It consists of a phenol resin structure having an independent bubble ratio of 70 or more, an average bubble diameter of 10 µm or more and 400 µm or less, a density of 10 kg / m 3 or more and 70 kg / m 3 or less, containing fluorohydrocarbons in an independent bubble and having a urea crosslinking structure. A phenol resin foam characterized by the above-mentioned. The thermal decomposition pattern of the pyrolysis gas chromatography of the phenol resin according to claim 1, wherein the ratio C = A / B to the ratio B of the pyrolysis product of the ratio A of trimethylphenol of the pyrolysis product is 0.2 or more. The phenol resin foam of 4.0 or less and a ratio F = D / E with respect to the phenol derivative component E of the component D derived from urea crosslinking of a pyrolysis product are 0.03 or more and 0.3 or less. The phenol resin foam according to claim 1, wherein the thermal conductivity is 0.018 kcal / mhr ° C or less and brittleness is 30% or less. The phenolic resin foam according to claim 2, wherein the thermal conductivity is 0.018 kcal / mhr ° C or less and brittleness is 30% or less. 7. The fluorohydrocarbon of claim 1, wherein the fluorohydrocarbon is 1,1,1,2-tetrafluoroethane or 1,1-difluoroethane or 1,1,1, Phenol resin foam, characterized in that at least one of 2,2-pentafluoroethane. The resol resin composition composed of resol resin and methylolated urea is formed by foaming and curing fluorohydrocarbon as a blowing agent and forming a urea crosslinking structure, having an independent bubble ratio of 80% or more, an average bubble diameter of 20 μm or more and 300 μm or less 20 kg / m 3 or more, 50 kg / m 3 or less, thermal conductivity 0.018 kcal / mhr ℃ or less, brittle 30% or less, characterized in that the phenol resin foam.