MXPA00005691A - Phenol foam - Google Patents

Abstract

To provide a type of phenol foam characterized by the fact that the phenol foam is formed by using a hydrocarbon as the foaming agent. The phenol foam has excellent heat-insulating performance, high compressive strength and other mechanical strengths, improved brittleness and is friendly to the environment of the earth.

Description

FOAM. OF FENOL TECHNICAL FIELD This invention pertains to a type of phenol foam which can be preferably used for thermal insulation as various building materials.

PREVIOUS TECHNIQUE Among the different types of organic resin foams, phenol foam has excellent flame retardant properties, high thermal resistance, low smoking properties, high dimensional stability, high resistance to solvents and good processability. Consequently, it is widely used in various types of building materials. Usually, the phenol foam is manufactured by mixing the resole resin, which is prepared by condensation of phenol and formalin in the presence of an alkaline catalyst, with foaming agent, surfactant, curing catalyst and other additives homogeneously, followed by foaming. For conventional phenol foam, foaming agents that can be used include trichlorotrifluoroethane (CFC-113), trichloromonofluoromethane (CFC-11), dichlorotrifluoroethane (HCFC-123), dichlorofluoroethane (HCHC-141b), and other halogenated hydrocarbons and their derivatives. For those types of halogenated hydrocarbons and their derivatives to be used as a foaming agent, safety in manufacturing is high, and the heat conductivity of the gas itself is low, so that the thermal conductivity of the foam obtained is also low. This is an advantage. However, at present, it has become clear that CFC-113, CFC-11, and other substances that have chlorine atoms can decompose ozone in the stratosphere and damage ozone in the ozonesphere, the damage of those substances on the environment of the earth have become a global problem. Consequently, they are manufactured and used under control in the world. Also still fluorohydrocarbons 1, 1, 1,2-tetrafluoroethane (HFC-134a), 1,1-difluoroethane (HFC-152a), etc., free of chlor-O and having a zero ozone damage coefficient, also they have relatively high greenhouse effect coefficients on land, it seems that their use can be restricted in Europe. Consequently, pentane and other hydrocarbons have been under observation (as a substitute). In the past, it was known that n-pentane and cyclopentane can be used as a foaming agent for phenol foam. However, although these hydrocarbons do not pose a hazard to the ozonosphere and have relatively small greenhouse effect coefficients over land compared to halogenated hydrocarbons, the average pore size of the foam formed becomes greater, the thermal conductivity of the gas in itself it is high, so that a good thermal insulating performance can not be obtained, and the porous walls are weak and the resistance to compression and other mechanical resistances are also insufficient. These are problems that impede their practical applications. In this regard, Japanese Tokuhyo Patent No. Hei 4 [1992] -503829 describes a method for manufacturing phenol foam with even lower thermal conductivity using a mixture of a prescribed type of fluoroalkane (hereinafter referred to as PFA) and alkane or cycloalkane as the foaming agent. However, fluoroalkane also has a relatively large greenhouse effect coefficient on the earth such as the aforementioned fluorohydrocarbon, so its use can also be restricted. Also, Japanese Patent Application Kokai No. Hei 3 [1991] -231940 which describes a method for manufacturing a phenol foam using polyfluorotrialkylamine as the foaming agent. However, although perfluorotrialkylamine has a low thermal conductivity of the gas itself and a relatively small greenhouse effect coefficient on the earth, it has been found by the present inventors that when phenol foam is tested using perfluorotyralkylamine having methyl or ethyl as the luorocarbon in the molecules, the cell size of the formed phenol foam becomes larger, so that the performance of the thermal insulation is not good, the rigidity of the phenol foam becomes lower, and the compressive strength and other mechanical resistance of the foam are smaller. On the other hand, when the phenol foam is made using perfluorotrialkylamine having butyl and another fluorocarbon having an even higher boiling point as the foaming agent at the foaming temperature of 100 ° C or lower, good foaming can not be achieved. , and a satisfactory phenol foam can not be formed.

DESCRIPTION OF THE INVENTION The purpose of this invention is to solve the above problems of conventional technology. That is, the purpose of this invention is to provide a type of phenol foam that is manufactured using a hydrocarbon as the foaming agent, and which has excellent thermal insulation performance, high compressive strength and other mechanical strengths, better brittleness , and is kind to the earthly environment.

Means for solving the problems In order to achieve the aforementioned purpose, the inventors of the present have carried out an extensive investigation. As a result of this invention, a type of phenol foam meeting the aforementioned requirements was discovered, and this invention was achieved. That is, this invention provides the following type d phenol resin foam thermal insulating material: 1. A type of phenol resin foam thermal insulator, characterized by the following facts: the phenol foam has a porosity of at least 80%, a pore size - average in the range of 10-400 mm, and a thermal conductivity of 0.025 kcal / mhr ° C or less, the phenol foam is composed of pores filled with a gas containing saturated hydrocarbon C4-e and a resin portion made of a phenol resin containing 0.01-55 by weight of at least one type of fluoroamine represented by the following formula (1): (CaFb) 3N (1) In the formula (1), a is a natural number of 4 or greater and b is 2a + l. 2. The phenol resin foam thermal insulation material described in Claim 1, characterized in that the weight of the gas filled in the pore portion is in the range of 2-35% by weight of the phenol foam . 3. The phenol foam described in Claim 1 or 2, characterized in that the phenol foam has a density in the range of 10-70 kg / m3, a brittleness of 30% or less, and a resistance to the compression satisfying the ratio shown in formula (2) with respect to density: compressive strength (kg / cm2) > density (kg / m3) x 0.1164 - 2.-5 (2) In the following, this invention will be explained in more detail. The phenol foam of this invention is composed of a portion of pores filled with a gas and a portion of resin made of pore walls and the base material. For the phenol foam of this invention, the independent porosity must be at least 80%, or preferably at least 85%, or more preferably 90%. If the independent porosity is less than 80%, the foaming agent of the phenol foam can be replaced with air, so that the performance of the thermal insulation deteriorates significantly with time. Also, the fragility of the foam surface becomes more serious, so that the mechanical properties of the foam may not be able to meet the demands for practical applications.

For the phenol foam of this invention, the average pore size should be in the range of 10-400 nm, or preferably in the range of 20-200 mm. If the average pore size is less than 10 mm, because there is a limit in the thickness of the pore walls, the density of the foam rises naturally. As a result, the portion that transfers heat from the resin portion in the foam increases, and the thermal insulation performance of the phenol foam may become insufficient. On the other hand, if the average pore size becomes larger than 400 mm, the transfer due to radiation increases, and the thermal insulation performance of the foam begins to deteriorate. In the phenol foam of this invention, C4_6 alkane or cycloalkane was used as the foaming agent, that is, the gas to fill the pore portion. Examples include n-bucane, isobutane, n-pentane, isopentane, cyclopentane, neopentane, n-hexane, isohexane, 2,2-dimethylbutane, 2, 3-dimethylbutane, cyclohexane, etc. Among them, n-butane, isobutane, n-pentane, isopentane, cyclopentane, neopentane and other butanes and pentanes are preferred in this invention. According to this invention, it is also possible to make use of a mixture of one or more types of hydrocarbons. Examples of mixtures that can be used include a mixture of n-pentane and n-butane, a mixture of isobutane and isopentane, a mixture of n-butane and isopentane, a mixture of isobutane and n-pentane, a mixture of cyclopentane and n-butane, a mixture of cyclopentane and isobutane, etc. Also, it is possible to make use of nitrogen, argon, air, or other low boiling substances as foaming cores dissolved in the foaming agent to be used. The amount of foaming agents used in this invention can be appropriately selected according to the density of the desired foam, the foaming conditions, etc. Usably, with respect to 100 parts by weight of the resin, the amount of foaming agent should be in the range of 3-40 parts by weight, or preferably in the range of 5-20 parts by weight. According to this invention, the fluoroamine has to be contained in the resinous portion of the phenol foam, usually not present in the form of a gas. More specifically in the method of quantitative determination of the foaming agent to be explained later, the amount of fluoroamine detected is 0.001% by weight or less. In this invention, the types of fluoroamine that may be used include preferably the following Sumitomo 3-M Co products. , Ltd: Fluorinate [transliteration] FC-43 (triperfluorobutylamine), FC-70 (triperfluoroamylamine), FC-71 (triperfluorohexylamine), etc. The amount of fluoramine in this invention with respect to the phenol foam should be in the range of 0.01-5% by weight, or preferably in the range of 0.05-3% by weight. If the proportion of fluoroamine is less than 0.01% by weight, it is possible to obtain a high independent porosity. On the other hand, if the proportion of fluoroamine is greater than 5% by weight, the manufacturing costs rise, and this is undesirable from the economic point of view. Also in this case the fluoroamine is deposited on the surfaces of the pore wall, leading to deterioration of the performance of the thermal insulation, and the rigidity of the resin may also decrease. The fluoroamine of this invention has a high boiling point, and consequently has no foaming function as a foaming agent. Consequently, when fluoroamine is used alone as the foaming agent, foaming does not take place at all. However, in this invention, fluoroamine and a foaming agent coexist in the foaming process to form the phenol foam. Accordingly, the pore portion and the resin portion of the phenol foam can be well formed. That is, in this invention through the use of a hydrocarbon as the foaming agent and the elaboration of the fluoroamine coexist in the foaming operation, it is possible to have a small pore size and, at the same time obtain a high independent porosity for the foam of phenol. Accordingly, for the phenol foam of this invention, the thermal insulation performance can be significantly improved. For the phenol foam of this invention, although a hydrocarbon was used as a foaming agent, the thermal conductivity is still 0.025 kcal / mhr ° C or less. That is, it has an excellent thermal insulation performance. More preferably, the thermal conductivity is 0.020 kcal / mhr ° C or less. In addition, since the fluoramine used in this invention has a high boiling point, even when released to the atmosphere, the greenhouse effect coefficient on the soil is small, so that there is little effect. Consequently, it is kind to the environment of the earth. The density of the phenol foam can be appropriately selected depending on the proportion of the foaming agent, the temperature of the curing oven and the other conditions of foaming. The density of the phenol foam xie this invention should be in the range of 10-70 kg / m3, or preferably in the range of 20-50 kg / m3. If the density is less than 10 kg / m3, the compressive strength and other mechanical resistances of the phenol foam are low, it is prone to damage when the phenol foam is handled, and the surface brittleness is also increased. On the other hand, if the density is greater than 70 kg / m3 the transfer of the resinous portion increases, and the thermal insulation performance of the resinous portion may deteriorate. The phenol foam of this invention has better fragility and compressive strength compared to conventional phenol foam. Although the detailed reason is not yet clear, it is believed that, due to the coexistence of the fluoramine and the foaming agent in the foaming operation the foaming takes place more uniformly and with better synchronization, so that the pore size of the obtained phenol foam becomes better and the structure of the resin to form the pores themselves becomes stronger due to those compounds. Within the aforementioned density range, the phenol foam of this invention has a certain brittleness using the "measurement method" which will be explained below, 30% or less, or preferably 20% or less. is greater than 30%, the amount of resin powder cutting of the resin surface becomes greater, leading to deterioration in the operation capacity in the operation and tendency to damage of the products during handling in transport, operation etc. Due to these problems, the phenol foam is difficult to use in practical operations It is preferred that the compressive strength of the phenol foam of this invention satisfies the relationship with the density i presented by the formula (2) Such formula (2) shows that pure phenol foam of this invention the compressive strength with respect to density is higher than the conventional type of phenol foam. Fragility and compressive strength are closely related to the independent porosity, the average pore size and the density of the phenol foam, as well as the strength of the resin itself. In particular, it depends significantly on the density. In the phenol foam prepared using the hydrocarbon as the foaming agent in this invention, it is believed that the presence of fluoroamine is the reason that it makes the average pore size better than that of the conventional phenol foam, makes the strength of the resin greater, and makes the balance between force to compression with respect to density and better brittleness for phenol foam. In the following, the method of manufacturing the phenol foam of this invention will be explained. Resole resin for use as the resin feed material is prepared by polymerizing the phenol and formalin as the feed materials in the presence of an alkaline catalyst and heating at a temperature in the range of 40-100 ° C. The resole resin can also be mixed with the different types of modifiers, such as urea, amines, amides, epoxy compounds, monosaccharides, starches, poval resin, furan resin, polyvinyl alcohol, lactones, etc., for use. When the modification with urea is to be carried out it is possible to add urea during the polymerization of the resole resin, or to mix the urea that has been methylated by alkaline catalyst beforehand, in the resole resin. For the resole resin composition, the viscosity is adjusted appropriately by adjusting the water content. The proper viscosity of the resin composition depends on the foaming conditions. Usually, the viscosity at 40 ° C is preferably in the range of 1000-50, 000 cps, or preferably in the range of 2000-30,000 cps. The resole resin composition with its viscosity adjusted to an appropriate value, as well as the foaming agent fluoramine, surfactant, and curing agent, are fed to a mixer, and mixed homogeneously to form a foaming composition. In this case, it is possible to premix the surfactant with the resin and then feed the mixture to the mixer, or feed them by separator in the mixer. There are no special limits on the method for feeding fluoramine in this invention. For example, any of the following methods can be adopted to feed fluoramine when it must be mixed with the resin: the method in which fluoroamine is fed together with the ream in the mixer, the method in which fluoroamine is fed together with the curing catalyst in the mixer, the method in which fluoroamine is fed together with the foaming agent, and the method in which fluoroamine is fed separately into the mixer. Among them, the method in which the fluoroamide of this invention is premixed with the foaming agent and the mixture of fluoroamide and the foaming agent is then fed into the mixer is preferred, since it can have the desired effect in a relatively large amount. little. When the fluoroamide is premixed with the foaming agent, the ratio of fluoroamide to the foaming agent should be in the range of 0.2-20% by weight. When the fluoroamine is mixed with the foaming agent, if the amount of fluoroamine with respect to the foaming agent is less than 0.2% by weight, the effect can not be presented. On the other hand, if this amount is greater than 20% by weight, the performance of the thermal insulation and the mechanical resistance of the phenol foam can deteriorate. The amount of fluoroamine with respect to the foaming agent is preferably in the range of 0.5-15% by weight, more preferably in the range of 1-10% by weight. Also, when the curing catalyst is premixed with the resole resin, the reaction takes place prior to foaming, and a good foam can be obtained. Accordingly, it is preferred that the resole resin and the foaming agent be r >;, < , zced by a mixer. The foaming composition prepared by mixing in the mixer is blown into a mold, etc. , and a heat treatment is carried out to effect the curing process by foaming. In this way, the phenol foam of this invention is formed. Examples of curing catalysts which can be used in the foaming and curing of this invention include toluene sulphonic acid, xylene sulfonic acid, benzenesulfonic acid, phenolsulfonic acid, styrenesulfonic acid, naphthalenesulfonic acid, and other aromatic acids, which can be used alone or as a mixture of several lipos. It is also possible to add curing agents, such as resorcinol, cresol, saligenin (o-methylol phenol), p-methylol phenol, etc. Also, those curing catalysts can be diluted with diethylene glycol, ethylene glycol, or other solvents. Conventional types of surfactants can be used in this invention. Among them, the nonionic surfactants are effective, such as the alkylene oxide as a copolymer of ethylene oxide and propylene oxide; condensation products of alkylene oxide and castor oil; condensation products of alkylene oxide and nonylphenol, dodecylphenol, or other alkylphenols; as well as the polyoxyethylene fatty acid ester and other fatty acid esters; pclidimethylsiloxane and other silicone compounds; polyalcohols, etc. These surfactants can be used alone or as a mixture of several types. There is no special limit on the amount used. Usually in this invention, per 100 parts by weight of resole resin, the amount of surfactant should be in the range of 0.3-10 parts by weight. In the following, methods for evaluating the configuration, structure and characteristics of the phenol foam of this invention will be explained. The independent porosity was measured as follows. From the formed phenol foam, a cylindrical specimen with a diameter of 35-36 mm and a height of 30-40 mm was cut by means of a corkscrew. For the specimen, the volume was measured by a specific gravity meter of the Model 1000 air comparison type (product of Tokyo Science Co., Ltd.) according to the standard method of use. The volume of the sample, the volume of the pore walls of the weight of the sample and the density of the resin were calculated were subtracted. The result was divided by the calculated apparent volume of the external dimensions of the specimen to give the independent porosity. The measurement is made according to ASTM D2856. According to this invention, the density of the phenol resin is 1.27 g / cm3.

The average pore size of the phenol foam of this invention was measured as follows. On a 50X photograph of the cross section of the foam, straight lines of 9 cm in length were drawn, and the average value of the number of pores traversing each straight line was divided by 1800 mm to give the average pore size. This is the average value of the cell index measured according to JIS K 6402. The thermal conductivity was measured using a 200 mm square sample of the phenol foam according to the "Flat plate thermal flow measurement method" JIS A 1412 with the plate at a lower temperature at 5 ° C and with the plate at a higher temperature at 35 ° C. The density was measured with a specimen of 20 square cm of phenol foam. This was derived by measuring the weight and apparent volume, excluding the surface material and separating the material from the specimen, and was measured according to the JIS K 7222. In the brittleness test, 12 cubes were cut with an edge length of 25 ± 15 mm so that the molding skin or surface material was included on a surface. If the thickness of the foam is less than 25 mm, the thickness of the specimen is taken as the thickness of the foam. In a box made of oak with internal dimensions of 191 x 197 x 197 mm that allows to seal without leaking remains, 24 cubes of dried oak wood were made at room temperature with a specific gravity of 0.65 and with an edge length of 19 ± 0.8 mm and 12 specimens were loaded, followed by the rotation of the oak box at a speed of 0 ± 12 rpm for 600 + 3 cycles. After rotation, the contents of the box were poured into a mesh with a nominal dimension of 9.5 mm to sift the remains. The rest of the residual specimens were measured. The reduction in the weight of the specimens was measured before the test and was taken as the fragility. The measurement was made according to JIS A 9511. The compressive strength was measured with a tension of 0.05 according to JIS K 7220. Verification of the content of foaming agent and fluoramine in the phenol foam was made as follows7: After of measuring a specimen of 200 x 200 x (thickness) mm this was maintained at a standard temperature level 3 (temperature of 23 ± 5 ° C) and at a level of 3 standard humidity (40-70% RH) for 16 hours or more, the surface agent [sic; surface layer] was removed and cut into pieces measuring 20 x 20 x (thickness) mm, and the weight was determined exactly. The specimen was then crushed in a gas-tight container. After grinding, nitrogen or air was fed at a rate of 100 cc / min and in a volume five times that of the sealed container from a door of the gas-tight container. From the other container door, the gas was fed to a trap containing pyridine, toluene, DMF, or other solvent to extract the foaming agent. Next, the foaming agent absorbed in the solvent is analyzed quantitatively by gas chromatography. If necessary, the components separated by gas chromatography are fed to a mass spectroscope to determine the molecular structure. Next, the powder or sample weight is measured precisely after the gas is flowed. From the difference between this and the weight before grinding, the weight of the gas is obtained. The determination of the perfluorotrialkylamine was carried out as follows: The cured sample was immersed in a solvent selected from pyridine, toluene, DMF, etc., to extract the fluoroamine, followed by gas chromatography or lysis chromatography. If necessary, the components selected by gas chromatography can be fed to a mass spectroscope to determine the molecular structure [sic]. Or, the extracted components can be continuously identified by means of LC-IR (liquid chromatography-IR absorption spectrometer).

MODES FOR CARRYING OUT THE INVENTION In the following, the invention will be explained in more detail with reference to the application examples and comparative examples.

(A) Preparation of the phenol resin 5000 g of 37% formalin (guaranteed grade, product of Wako Puré Chemical Co., Ltd.) and 3000 g of 99% phenol (guaranteed grade, product of Wako Puré Chemical Co. , Ltd.) were loaded into a reactor and agitated by means of a propeller agitator, with the temperature of the solution inside the reactor adjusted to 40 ° C by a temperature adjuster. Next, 60 g of 50% aqueous solution of sodium hydroxide was added, and the reaction solution was heated from 40 ° C to 85 ° C and maintained [at 85 ° C] for 110 minutes. Subsequently, the reaction solution was cooled to 5 ° C, and was taken as the resin of resol A-1. On the other hand, in another reactor, 1080 g of 35% formalin, 1000 g of water, and 78 g of 50% aqueous solution of sodium hydroxide were charged, followed by the addition of 1600 g of urea (guaranteed grade, product of Wako Puré Chemical Co., Ltd.). The content was stirred by means of a propeller agitator, with the temperature of the solution inside the reactor adjusted to 40 ° C by a temperature adjuster. Then, the reaction solution was heated from 40 ° C to 75 ° C and maintained [at 70 ° C] for 60 minutes. This was taken as methylolurea U. Subsequently, 1350 g of methylolurea U were mixed with resole resin A-1, the solution of the mixture was heated to 60 ° C, at which the solution was kept for 1 h. Then, the reaction solution was cooled to 30 ° C and neutralized to a pH of 6 with 50% aqueous solution of p-toluenesulfonic acid monohydride. The reaction solution was subjected to a dehydration process at 60 ° C, and the viscosity was measured. It was found that the viscosity at 40 ° C was 6700 cps. This was taken as the resin of resol A.

(B) Preparation of the resole resin 4350 g of 37% formalin and 3000 g of 99% phenol were charged to a reactor and agitated by means of a propeller stirrer, with the temperature of the solution inside the reactor adjusted at 50 ° C by a temperature adjuster. Next, 60 g of 50% aqueous solution of sodium hydride was added, and the reaction solution was heated from 50 ° C to 5.5 ° C and kept [at 55 ° C] for 20 minutes. Subsequently, the reaction solution was heated to 85 ° C and maintained at 85 ° C for 115 minutes. Then, the reaction solution was cooled to 30 ° C, and the pH was adjusted to 6 by means of a 50% aqueous solution of p-toluenesulfonic acid monohydride. The reaction solution was subjected to a dehydration process at 60 ° C, and the viscosity was measured. It was found that the viscosity at 40 ° C was 5800 cps. This was taken as the resole resin B.

Application Example 1 Paintad [transliteration] 32 (a surfactant manufactured by Dow Corning Asia Co., Ltd.) in an amount of 3.5 g of each 100 g of resole resin A was dissolved [in resole resin A]. The resole resin mixture was mixed with a foaming agent made of a mixture of 96.7% by weight of isopentane (product of Wako Puré Chemical Co., Ltd., with a purity of 99% or more), 3% by weight of FC-71 Fluorinated (product of 3M Co.), And 0.3% by weight of nitrogen, as well as a curing catalyst made of a mixture of 60% by weight of p-toluenesulfonic acid monohydride (purity of 95% or greater, product of Wako Puré Chemical Co., Ltd.) and 40% by weight of diethylene glycol (purity 98% or greater, product of Wako Puré Chemical Co., Ltd.), with a composition of 100: 7: 13 parts by weight of the resin mixture, foaming agent, and curing catalyst, respectively, and the The mixture was stirred into a bolt mixer equipped with a thermoset jacket. The mixer exit mixture was blown in a mold coated with Spandbond [transliteration] E1040 (non-woven fabric manufactured by Asahi Chemical Industries, Ltd.), followed by maintenance in an oven at 80 ° C for 5 h to manufacture a phenol foam .

Application Example 2 A phenol foam was manufactured in the same manner as in Application Example 1, except that the foaming agent was changed to a mixture of 79.7% by weight of isopentane, 20.0% by weight of FC-71 Fluorinated, and 0.3% by weight of nitrogen, and that the amount of foaming agent was changed to 8.5 parts by weight.

Application Example 3 A phenol foam was manufactured in the same manner as in Application Example 1, except that 5% by weight of FC-71 was dissolved in the resin mixture and the foaming agent was changed to a mixture of 99.6% by weight of isopentane and 0.3% by weight of nitrogen.

Application Example 4 A phenol foam was manufactured in the same manner as in Application Example 1, except that the foaming agent was changed to a mixture of 99.5% by weight of isopentane, 0.2% by weight of FC-71 Fluorinated, and 0.3% by weight of nitrogen.

Application Example 5 A phenol foam was manufactured in the same manner as in Application Example 1, except that resole resin B was used instead of resole resin A, and the foaming agent was changed to a mixture of 93.7% by weight of isopentane, 7 by weight of FC-71 Fluorinated, and 0.3% by weight of nitrogen.

Application Example 6 A phenol foam was manufactured in the same manner as in Application Example 1, except that the foaming agent was changed to a mixture of 89.7% by weight of n-pentane (guaranteed grade, product of Wako Pure Chemical Co., Ltd.), 10% by weight of FC-71 Fluorinated, and 0.3% by weight of nitrogen, and that the amount of foaming agent was changed to 7.7 parts by weight.

Application Example 7 A phenol foam was manufactured in the same manner as in Application Example 1, except that the foaming agent was changed to a mixture of 97.7% by weight of n-butane, 2% by weight of FC- 71 Fluorinated, and 0.3% by weight of nitrogen, and the amount of foaming agent was changed to 5 parts by weight.

Application Example 8 A phenol foam was manufactured in the same manner as in Application Example 1, except that the foaming agent was changed to a mixture of 98.7% by weight of isoprene, 1% by weight of FC-71 Fluorinated, and 0.3% by weight of nitrogen, and the amount of foaming agent was changed to 5 parts by weight.

Application Example 9 A phenol foam was manufactured in the same manner as in Application Example 1, except that the foaming agent was changed to a mixture of 96.7% by weight of isopentane, 3% by weight of FC-71 Fluorinated, and 0.3% by weight of nitrogen.

Application Example 10 A phenol foam was manufactured in the same manner as in Application Example 1, except that the amount of foaming agent was changed to 13 parts by weight.

Comparative Example 1 A phenol foam was manufactured in the same manner as in Application Example 1, except that 15% by weight (based on the resin mixture) of FC-71 was dissolved in the resin mixture. , and the foaming agent was changed to a mixture of 99.7% by weight of isopentane and 0.3% by weight of nitrogen.

Comparative Example 2 A phenol foam was manufactured in the same manner as in Application Example 1, except that the foaming agent was changed to a mixture of 99.7% by weight of isopentane and 0.3% by weight of nitrogen.

Comparative Example 3 A phenol foam was manufactured "in the same manner as in Application Example 1, except that the foaming agent was changed to a mixture of 99.6% by weight of isopentane, 0.1% of FC-171 Fluorinated, and 0.3 % by weight of nitrogen.

Comparative Example 4 • A phenol foam was manufactured in the same manner as in Application Example 1, except that the foaming agent was changed to a mixture of 99.7% by weight of isopentane, and 0.3% by weight of nitrogen, and the amount of foaming agent was changed to 13 part by weight.

Comparative Example 5 A phenol foam was manufactured in the same manner as in Application Example 1, except that resole resin B was used instead of resole resin A, and that the foaming agent was changed to a mixture of 99.7. % by weight of isopentane, and 0.3% by weight of nitrogen. In the phenol foam samples prepared in the aforementioned comparative examples, the fed resin, the independent porosity, the average pore size, and the thermal conductivity, as well as the fluoroamine content, the density, brittleness, and resistance to foam compression are listed in Table I.

Table I Table I (continued) Table I (continued) Table I (continued) Effects of the Invention The phenol foam of this invention has excellent thermal insulation performance, high compressive strength and other mechanical strengths, and significantly improved surface brittleness. The foaming agent used in this invention does not endanger the ozonosphere, and has a coefficient of glue for the greenhouse effect on the earth. Accordingly, "phenol foam" of this invention is a type of thermally insulating construction material that is kind to the environment of the earth.It is noted that in relation to this date, the best method known to the applicant to carry out the practice said invention is the conventional one for the manufacture of the objects to which it refers.

Claims (3)

CLAIMS Having described the invention as above, the content of the following claims is claimed as property:

1. A type of phenol resin foam thermal insulation material, characterized by the following facts: the phenol foam has an independent porosity of at least 80%, an average pore size in the range of 10-4000 mm, and a thermal conductivity of 0.025 kcal / mhr ° C or less; the phenol foam is composed of a portion of pores filled with a gas containing saturated C4_6 hydrocarbon and a resin portion made of a phenol resin containing 0.01-5% by weight of at least one type of fluoroamine represented by the following formula (I): (CaFb) 3N (1) In formula (I), a is a natural number of 4 or greater, and b is 2a + 1.

2. The thermal insulation material of phenol resin foam in accordance with claim 1, characterized in that the weight of the gas filled in the pore portion is in the range of 2-35% by weight of the phenol foam.

3. The phenol foam according to claim 1 or 2, characterized in that the phenol foam has a density in the range of 10-70 kg / m3, a brittleness of 30% or less, and a resistance to compression satisfying the ratio shown in formula (2) with respect to density: compressive strength (kg / cm3) > density (kg / m3) x 0.1164 - 2.5 (2).