WO1999011697A1 - Resine phenolique expansee - Google Patents

Resine phenolique expansee Download PDF

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Publication number
WO1999011697A1
WO1999011697A1 PCT/JP1998/003895 JP9803895W WO9911697A1 WO 1999011697 A1 WO1999011697 A1 WO 1999011697A1 JP 9803895 W JP9803895 W JP 9803895W WO 9911697 A1 WO9911697 A1 WO 9911697A1
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WIPO (PCT)
Prior art keywords
resin foam
resin
weight
phenolic resin
phenol
Prior art date
Application number
PCT/JP1998/003895
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English (en)
Japanese (ja)
Inventor
Yuuichi Arito
Kenzi Takasa
Original Assignee
Asahi Kasei Kogyo Kabushiki Kaisha
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Application filed by Asahi Kasei Kogyo Kabushiki Kaisha filed Critical Asahi Kasei Kogyo Kabushiki Kaisha
Priority to AU88886/98A priority Critical patent/AU8888698A/en
Priority to JP51660399A priority patent/JP4711469B2/ja
Publication of WO1999011697A1 publication Critical patent/WO1999011697A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/141—Hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2205/00—Foams characterised by their properties
    • C08J2205/04—Foams characterised by their properties characterised by the foam pores
    • C08J2205/052—Closed cells, i.e. more than 50% of the pores are closed
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2205/00—Foams characterised by their properties
    • C08J2205/10—Rigid foams
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers

Definitions

  • the present invention relates to a heat-insulating phenol resin foam suitable as various building materials.
  • Fuunol resin foam is widely used as a building material among organic resin foams because of its excellent flame retardancy, heat resistance, low smoke emission, dimensional stability, solvent resistance, and processability. ing.
  • a phenolic resin foam is produced by uniformly mixing and foaming a resole resin obtained by condensing phenol and formalin with an alkaline catalyst, a blowing agent, a surfactant, a curing catalyst, and other additives.
  • Conventional phenolic resin foams are used as blowing agents such as trichloro-mouth trifluoroethane (CFC-113), trichloro-mouth monofluoromethane (CFC-111) and dichloro-mouth trifluoroene (HCFC-1).
  • Halogenated hydrocarbons and their derivatives such as 2 3
  • dichlorofluoroethane HCF C-141b
  • These halogenated hydrocarbons and their derivatives as foaming agents are excellent in safety during production, and furthermore, since the gas itself has low thermal conductivity, it is possible to reduce the thermal conductivity of the obtained foam. Had the advantage to say.
  • an object of the present invention is to provide a phenolic resin foam having a foaming agent of hydrocarbon, having excellent heat insulating performance, excellent mechanical strength such as compressive strength, and improved brittleness. .
  • the present inventors have set forth conditions for producing a phenolic resin foam, for example, the molar ratio of the charged formaldehyde and phenol during the polymerization of the resin, the molecular weight of the resole resin, and the like.
  • the foaming conditions such as the amount of the catalyst and the foaming temperature
  • a phenolic resin foam having a specific foam form and a specific resin crosslinked structure can achieve the above-mentioned object of the present invention.
  • the invention has been completed. Disclosure of the invention
  • the present invention is the following phenol resin foam.
  • the hydrocarbon in the closed cell is composed of one or more kinds of hydrocarbons, and at least one of the hydrocarbons is a saturated hydrocarbon having 4 to 6 carbon atoms.
  • FIG. 1 is an example of a pyrogram of pyrolysis gas chromatography of a phenol resin foam sample according to the present invention.
  • FIG. 2 shows an example of a mass spectrum of a structural component derived from one urea bridge (the component of peak 7 in FIG. 1) of a pie mouth gram of pyrolysis gas chromatography of a phenol resin foam sample according to the present invention. is there.
  • FIG. 3 is an example of a mass spectrum of a structural component derived from one urea bridge (the component of peak 8 in FIG. 1) in a pie mouth gram of pyrolysis gas chromatography of a phenol resin foam sample according to the present invention. is there.
  • FIG. 4 is an example of a mass spectrum of a structural component derived from one urea bridge (the component at peak 9 in FIG. 1) in a pyrogram of a pyrolysis gas chromatograph of a phenol resin foam sample according to the present invention. .
  • FIG. 5 shows an example of a mass spectrum of a structural component derived from one urea bridge (the component at peak 10 in FIG. 1) in a pie mouthgram of pyrolysis gas chromatography of a phenol resin foam sample according to the present invention. It is.
  • FIG. 6 shows an example of a mass spectrum of one urea crosslink-derived structural component (the component of peak 11 in FIG. 1) of a pie mouth gram of pyrolysis gas chromatography of a phenol resin foam sample according to the present invention. It is. BEST MODE FOR CARRYING OUT THE INVENTION
  • the structure of the fu ⁇ ol resin foam be a specific structure.
  • the closed cell ratio is 70% or more, preferably 80% or more, and more preferably 90% or more. If the closed cell ratio is less than 70%, the blowing agent of the phenolic resin foam may be replaced with air, which may significantly reduce the heat insulation performance with time, and increase the surface brittleness of the foam. There is a concern that mechanical practical performance will not be satisfied.
  • the upper limit of the closed cell rate is preferably 99.3% or less.
  • the average cell diameter of the funor resin foam in the present invention is from 10 to 400 m, preferably from 15 to 300 m. Particularly preferably, it is 20 m or more and 150 am or less. If the average cell diameter is less than 10 zm, there is a limit to the thickness of the cell wall, so the foam density inevitably increases, and as a result, the heat transfer ratio of the resin part in the foam increases, and The thermal insulation performance of the resin foam may be insufficient. On the other hand, when the cell diameter exceeds 400 m, heat conduction by radiation increases, and the heat insulating performance of the foam decreases.
  • the density of the foam in the present invention is not more than 1 0 k gZm 3 or 7 0 k gZm 3, more preferably 5 0 k gZm 3 below 2 0 k gZm 3 or more. If the density is less than 10 kg / m 3 , the mechanical strength such as the compressive strength will be reduced, the material will be easily damaged during handling, and the surface brittleness will also increase. Conversely, if the density exceeds 70 kg / m 3 , there is a concern that heat transfer in the resin section will increase and the heat insulation performance will decrease.
  • the phenol resin foam needs to have a specific resin crosslinked structure.
  • pyrolysis gas chromatography is used as a means for indirectly measuring the crosslinked structure of the resin.
  • the area of each component of trimethylphenol in the pyrolysis gas chromatography pyrogram when a phenolic resin foam is used as a sample directly indicates the structure of the phenolic resin foam.
  • it can be a powerful indicator that indirectly reflects the structure of the polymer that constitutes the original phenolic resin foam.
  • the C value increases when there are many methylene and methyl ether crosslinks in the phenolic resin, and the C value decreases when there are few methylene and methyl ether crosslinks.
  • the C value needs to be not less than 0.05 and not more than 4.0. It is preferably in the range of 0.1 to 2.0, more preferably in the range of 0.1 to 1.0.
  • the present inventors adjusted the molecular weight distribution of the resin, the charge ratio of formaldehyde to phenol during the polymerization, and the foaming conditions so that the C value was within this range. That is, the charge ratio of formaldehyde to phenol during polymerization is preferably from 1.3 to 3.0, more preferably from 1.5 to 2.5, and the molecular weight of the resole resin is 40 ° of the resole resin composition.
  • the viscosity at C is adjusted so as to be in the range of 100 to 500 cps, and the temperature in the mixer during foaming should not exceed 80 ° C.
  • the molecular weight distribution of the resole resin, the charge ratio of formaldehyde to phenol during polymerization, and the foaming conditions are adjusted, the strength and foaming properties of the resin itself of the obtained foam are remarkably improved, and It has been found that even with the use of a foaming agent, a foamed resin foam having excellent heat insulation performance and mechanical strength can be obtained.
  • the foam may be brittle and the practical performance may be insufficient, as is apparent from Comparative Example 2 described later. Furthermore, there is a possibility that the viscosity of the resin is too high during the production of the foam, which may cause disadvantages such as an increase in the expansion ratio. If the C value is less than 0.05, it is apparent from Comparative Example 3 described later. Thus, the compressive strength and the like of the funinol resin foam decrease.
  • the present inventors have found that the formation of a urea crosslinked structure in the phenol resin further improves the strength of the phenol resin foam.
  • the index indicating the urea cross-linked structure can be obtained from the area ratio of the components appearing in the pi-mouth graph of pyrolysis gas chromatography of the foam sample.
  • the component D derived from urea crosslinking is a component released in the pyrogram during a retention time of 8 minutes to 18 minutes under the measurement conditions described later, and a phenyl group and an isocyanate in the molecule. It is a compound containing (-NCO) group. Specifically, peaks 7 to 11 in FIG. 1 are shown, and the corresponding mass spectra are shown in FIGS. 2 to 6, respectively. Let D be the sum of the areas from peaks 7 to 11.
  • the phenol derivative in the present invention is phenol, 2-methylphenol, 4-methylphenol, 2,4-dimethylphenol, 2,6-dimethylphenol, 2,4,6-trimethylphenol, and specifically, Are peaks 1 to 6 in Fig. 1.
  • E is the sum of the areas of these pyrograms.
  • the F value is preferably from 0.01 to 3 and more preferably from 0.02 to 0.2.
  • the phenol resin foam according to the present invention has greatly improved brittleness and compressive strength as compared with the conventional hydrocarbon blowing agent phenol resin foam.
  • optimizing the urea cross-linking structure significantly improves brittleness. As a result, it is expected that the range of use can be expanded to applications where the use of conventional phenolic foam has been restricted due to its brittleness.
  • the phenolic resin foam of the present invention has a brittleness of 30% or less, more preferably 20% or less, as measured by a measurement method described later.
  • the lower limit of brittleness is preferably 1% or more.
  • the compression strength is 0.5 kg / cm 2 or more, and more preferably 1.0 kg / cm 2 or more. If the compressive strength is less than 0.5 kgZcm 2 , not only is it easy to break during construction and the like, but also its use is limited due to its low mechanical strength.
  • the upper limit of the compressive strength is preferably 20 kgZcm2 or less.
  • Brittleness and compressive strength are closely related to the closed cell ratio, average cell diameter, density and strength of the resin itself of the phenol resin foam.
  • the strength of the resin can be improved, and the brittleness and compressive strength of the resin foam can be significantly improved. .
  • hydrocarbons can be used, but cyclic or linear alkanes, algens, and alkynes having 3 to 7 carbon atoms can be preferably used. Further, an alkane or cycloalkane having 4 to 6 carbon atoms is more preferable from the viewpoints of chemical stability and thermal conductivity.
  • alkane or cycloalkane having 4 to 6 carbon atoms is more preferable from the viewpoints of chemical stability and thermal conductivity.
  • normal butane, isobutane, cyclobutane, normal pentane, isopentane, cyclopentane, neopentane, normal hexane, isohexane, 2,2-dimethylbutane, 2,3-dimethylbutane, cyclohexane, etc. Can be mentioned.
  • butanes of normal butane, isobutane and cyclobutane and pentanes of normal pentane, isopentane, cyclopentane and neopentane are particularly suitable for the present invention.
  • two or more of these hydrocarbons can be used in combination.
  • pentanes 5 to 95% by weight and butanes 95 to 5% by weight, more preferably pentanes 25 to 75% by weight and butanes 75 to 25% by weight are mixed. Mixtures are particularly preferred because they exhibit good thermal insulation properties over a wide temperature range.
  • the combination of normal pentane and isobutane can be used from a low temperature range (for example, insulation material for freezer at about -80 ° C) to a high temperature range (for example, heat insulation material for heating body at about 200 ° C). It is particularly preferable because excellent heat insulation performance can be secured in a wide range, and these compounds are relatively inexpensive and economically advantageous.
  • Fluorocarbons such as perfluorooctane, perfluorocyclooctane, etc. can be mixed and used at the time of foaming.
  • low-boiling substances such as nitrogen, helium, argon, and air can be used as foam nuclei dissolved in a foaming agent.
  • the amount of the foaming agent used in the present invention may be arbitrarily selected depending on the desired density of the foam, foaming conditions, and the like, but is usually 3 to 40 parts by weight based on 100 parts by weight of the resin. In It is more preferably 5 to 30 parts by weight.
  • the phenolic resin foam according to the present invention has a thermal conductivity of not more than 0.025 kcal Zm hr ° C and excellent heat insulation performance even though the blowing agent is a hydrocarbon.
  • a more preferable thermal conductivity is 0.020 kca 1 / mhr ° C or less.
  • the lower limit of the thermal conductivity is preferably at least 0.012 kcal Zm hr ° C.
  • the present inventors have found that a high-boiling aliphatic hydrocarbon, a high-boiling alicyclic hydrocarbon, or a mixture thereof during foaming forms a better phenolic resin foam when present at the time of foaming.
  • High-boiling aliphatic hydrocarbons or high-boiling alicyclic hydrocarbon or mixtures thereof of the present invention 1 X 1 0 5 normal boiling point at P a is 1 5 0 alkane structure comprising at ° C or more or It is preferably a hydrocarbon mainly having a cycloalkane structure, and specific examples include solid paraffin, liquid paraffin, mineral spirit, low molecular weight polyethylene, and low molecular weight polypropylene.
  • Solid paraffin, also called paraffin wax has a carbon number ranging from 16 to 60 and is mainly composed of normal paraffin, but many contain isoparaffin and naphthene, and usually have a melting point of 35 ° C to 80 ° C. ° C.
  • Fluidized baffles are hydrocarbon oils with a pour point typically above 120 ° C and a relatively light lubricating oil fraction, for example, a spindle oil fraction, highly refined by washing with sulfuric acid. Low, with saturated hydrocarbon as the main component.
  • Mineral spirit is also called petroleum spirit and is specified in Japanese Industrial Standard K2201 (Industrial Gasoline Standard) No.4.
  • the amount of the high-boiling aliphatic hydrocarbon or the high-boiling alicyclic hydrocarbon or a mixture thereof is from 0.01% to 10% by weight based on the phenolic resin foam; More preferably, it is 0.05 to 5% by weight. If the amount of high-boiling aliphatic hydrocarbon or high-boiling alicyclic hydrocarbon or a mixture thereof is less than 0.01% by weight, there is little effect. If the weight exceeds 10% by weight, high-boiling aliphatic hydrocarbons or high-boiling alicyclic hydrocarbons or a mixture thereof are liquefied in air bubbles to lower the heat insulation performance, and the rigidity of the resin is reduced. Is likely to decrease.
  • the fluoroether of the present invention is a fluoroether represented by the following general formula (I) and having both a perfluoropropyl ether structure and a fluoromethylene structure in the molecule.
  • Galden HT-70 and Galden HT-55, which are ropolyethers, can be preferably used.
  • n are each an integer of 1 or more, more preferably 1 or more and 10 or less.
  • the amount of the fluoroether used in the present invention is 0.0 with respect to the phenol resin foam.
  • the fluoroether in the present invention When the fluoroether in the present invention was used alone as a foaming agent, the fluoroether was rapidly separated from the resin phase at the time of foaming, so that a foam was not obtained and the phenol resin was agglomerated.
  • the fluoroether in the present invention is a specific polyfluoroether and a specific fluorinated ester used in JP-A-3-231 941 and JP-A-4-1202242. In contrast to this, it does not have a foaming function as a foaming agent.
  • the cell diameter of the phenolic resin foam is reduced, thereby improving the heat insulating performance.
  • oxygen is present in the molecule.
  • their lifespan in the atmosphere is shorter, their global warming potential is relatively smaller, and they can be expected to be compatible with global environmental protection.
  • c is a natural number of 4 or more, more preferably a natural number of 4 or more and 16 or less.
  • D is 2c + 1.
  • the fluoroamine in the present invention has a high boiling point and does not function as a blowing agent.
  • Florinato FC-43 triplefluoroamylamine
  • FC-70 triplefluoramylamine
  • FC-71 triplefluo mouth
  • Xylamine Xylamine
  • the amount of fluoramine used must be from 0.01% to 5% by weight, more preferably from 0.05% to 3% by weight, based on the phenol resin foam. If the amount of fluoramine is less than 0.01% by weight, no effect can be obtained. When the amount of fluoramine exceeds 5% by weight, not only is the production cost increased, which is not economically disadvantageous, but also the fluoramine is precipitated on the cell wall surface, thereby deteriorating the heat insulation performance and decreasing the rigidity of the resin. Is concerned about
  • the fluoroamine in the present invention does not have a foaming function as a foaming agent because of its high boiling point. Therefore, when the fluoramine in the present invention is used alone as a foaming agent, foaming does not occur at all.
  • the fluoroamine according to the present invention when the fluoroamine according to the present invention is present in the foamable composition at the time of foaming the phenolic resin, the fluoramine suitably functions to form the structure of the cell portion and the resin portion of the phenolic resin foam. That is, in the present invention, by using a hydrocarbon as a foaming agent and allowing fluoramine to coexist at the time of foaming, the cell diameter of the phenolic resin foam is reduced, and therefore, the phenolic resin foam according to the present invention has heat insulation performance. It will be improved.
  • Resin resin for producing a phenolic resin foam is polymerized by heating phenol and formalin in a temperature range of 40 ° C to 100 ° C with an alkali catalyst. Let At that time, substituting a part of the raw material phenol with saligenin is effective for controlling the C value. That is, as the molecular weight of the resole resin increases, the C value tends to increase. However, if the molecular weight is too high, the viscosity of the resole resin sharply increases, making it difficult to handle.
  • a fininol resin foam having a high C value that is, a high crosslink density
  • a fininol resin foam having a high C value that is, a high crosslink density
  • urea may be added during the resole polymerization to adjust the resole resin that has reacted with the urea. It is more preferable to mix the sol resin with a sol resin and carry out a heat reaction while maintaining the basicity.
  • the amount of methylolated urea in the resole resin composition is usually 1 to 40% by weight, preferably 2 to 30% by weight, based on the resole resin.
  • the resin resin composition is used at a desired viscosity by adjusting the amount of water.
  • the preferred viscosity of the resin composition varies depending on the foaming conditions.
  • the viscosity at 40 ° C. is preferably 100 to 500 cps, and more preferably 200 to 300 cps. It is.
  • the surfactant may be previously mixed with the resin and introduced into the mixer, or these may be separately introduced into the mixer.
  • the curing catalyst is mixed with the resin in advance, the curing reaction proceeds before foaming and a good foam cannot be obtained, so it is desirable to mix the resole resin and the curing catalyst with a mixer.
  • high-boiling aliphatic hydrocarbons high-boiling alicyclic hydrocarbons or mixtures thereof, fluoroethers and fluoramines are used, they may be mixed with the resole resin in advance and introduced into the mixer. Although it may be good, or it may be supplied to the mixer alone, it is more effective and preferable to dissolve it in a blowing agent and introduce it into the mixer.
  • the foamable composition obtained by mixing with a mixer is poured into a mold or the like, and the foaming and curing is completed by heat treatment to obtain a phenol resin foam o
  • aromatic sulfonic acids such as toluenesulfonic acid, xylenesulfonic acid, benzenesulfonic acid, phenolsulfonic acid, styrenesulfonic acid, and naphthalenesulfonic acid are used alone or in combination of two or more. It can be used.
  • resorcinol, cresol, saligenin (0-methylol phenol), p-methylol phenol and the like may be added as a curing aid.
  • these curing catalysts may be diluted with a solvent such as diethylene glycol or ethylene glycol.
  • 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, and an alkylene oxide. And condensation products of alkylphenols such as nonylphenol and dodecylphenol, fatty acid esters such as polyoxyethylene fatty acid esters, silicone compounds such as polydimethylsiloxane, and polyalcohols. These surfactants may be used alone or in combination of two or more. The amount of use is not particularly limited, but is preferably used in the range of 0.3 to 10 parts by weight per 100 parts by weight of the resole resin in the present invention.
  • the average cell diameter of the foam according to the present invention is defined as: The four straight lines having a length of 9 cm are drawn on a 50-times enlarged photograph of the inside of the foam, and the number of cells crossed by each straight line is determined by each straight line. The average value (the number of cells measured according to JISK6402) divided by 1800 / zm.
  • Density is a value obtained by measuring the weight and apparent volume of a 20 cm square phenolic resin foam as a sample, removing the face material and siding material of this sample, and measuring according to JISK7222. did.
  • the closed cell ratio was measured as follows. A 35 to 36 mm diameter cylindrical sample cut through a phenolic resin foam with a cork boiler is cut to a height of 30 to 40 mm. Measure the sample volume according to the standard method of using an air-comparison hydrometer 100000 (manufactured by Tokyo Science). The value obtained by subtracting the cell wall volume calculated from the sample weight and the resin density from the sample volume was divided by the apparent volume calculated from the outer dimensions of the sample, and measured in accordance with ASTM D2856. However, the density of the phenol resin was 1.27 gZcm 3 .
  • the thermal conductivity was measured according to the plate heat flow meter method of JISA1412 at a sample of 200 mm square, a low temperature plate at 5 ° C, and a high temperature plate at 35 ° C.
  • a test piece for the brittle test was cut out of 12 cubes of 2.5 mm each side and 1.5 mm in length so as to include a molded skin or face material on one side. However, when the thickness of the foam was less than 25 mm, the thickness of the test piece was the thickness of the foam. Inner dimensions 1 9 1 X 1 9 7 X 1 that can be sealed with room temperature-dried 1 9 ⁇ 0.8 mm oak cubes 24 and 2 test pieces so that dust does not come out of the box Place in a wooden box of 97 mm oak and make 600 ⁇ 3 revolutions at 60 ⁇ 2 revolutions per minute.
  • the contents of the box are transferred to a mesh with a nominal size of 9.5 mm, sieved to remove small pieces, the weight of the remaining test piece is measured, and the reduction rate from the weight of the test piece before the test is calculated. Is brittle and was measured according to JISA 9511.
  • the compressive strength was measured in accordance with JISK 7220 with a specified strain of 0.05.
  • the pyrogram of pyrolysis gas chromatography was measured as follows. For the phenolic resin foam sample used for measurement, the powder obtained by shaving the foam core from which the face material and siding material have been removed with a cutter knife, etc., is further carefully ground in a mortar, and 0.3 to 0 per measurement. 4 mg was used as the sample amount.
  • the thermal decomposition apparatus PY210D manufactured by Frontier Lab Co., Ltd., which is a heating furnace type thermal decomposition apparatus, was used. The thermal decomposition temperature was 670 ° C.
  • FIG. 1 shows an example of a gas chromatogram of a phenol resin foam sample according to the present invention.
  • the structure of each component was confirmed by a mass spectrum obtained by introducing the component separated by gas chromatography into a mass spectrometer.
  • the mass spectrum was measured with an electron impact ionization method (EI method) at an ionization voltage of 70 eV and an ionization current of 30 OmA using JEOL JMSAX-505H.
  • EI method electron impact ionization method
  • the foaming agent and high-boiling aliphatic hydrocarbons, high-boiling alicyclic hydrocarbons or mixtures thereof, fluoroethers, and fluoroamines remaining in the bubbles can be confirmed as follows.
  • the phenolic resin foam sample is ground in a suitable solvent selected from pyridine, toluene, tetrahydrofuran (THF), dimethylformamide (DMF), etc., placed in a closed container, and the foaming agent and high boiling point fat
  • Aromatic hydrocarbons, high-boiling alicyclic hydrocarbons or mixtures thereof, fluoroethers, and fluoroamines can be extracted and identified by gas chromatography or liquid chromatography.
  • the ratio of the structure derived from urea crosslinking in the phenolic resin foam can be calculated from the area of each component by measuring pyrolysis gas chromatography in the same manner as the ratio of phenol to trimethylphenol.
  • the resin used in the following examples and comparative examples was prepared as follows.
  • Reactor was charged with 37% formalin (Wako Pure Chemical Industries, special grade reagent) 550 g and 99% phenol (Wako Pure Chemical Co., special grade reagent) 300 g, and the propeller rotating type Stir with a stirrer and adjust the temperature inside the reactor to 40 ° C with a temperature controller.
  • 60 g of a 50% aqueous solution of sodium hydroxide (NaOH) was added, and the reaction solution was heated from 40 ° C to 85 ° C and held for 115 minutes. Then, cool the reaction solution to 5 ° C. This is referred to as Resin Resin A-1.
  • resole resin B was performed in the same manner as resole resin A, except that the weight of added methylol urea U was changed to 300 g.
  • Resin resin C was synthesized in the same manner as resole resin A, except that the weight of added methylol urea U was changed to 250 g.
  • Reactor was charged with 37% formalin (380 g) and 99% ethanol (300 g) Stir with a propeller rotary stirrer and adjust the temperature inside the reactor with a temperature controller.
  • Resin Resin D-1 a 50% aqueous sodium hydroxide (NaOH) solution was added, and the reaction solution was kept at 50 ° C to 55 ° C for 20 minutes. The temperature was then raised to 85 and held for 125 minutes after the temperature reached 85 ° C. Thereafter, the reaction solution was cooled to 5 ° C. This is referred to as Resin Resin D-1.
  • resole resin D was performed in the same manner as resole resin A except that resole resin A-1 was changed to D-1 and the weight of added methylol urea U was changed to 100 g.
  • Resin resin E was synthesized in the same manner as resole resin D, except that the weight of added methylol urea U was changed to 500 g.
  • Resin Resin F was synthesized in the same manner as Resin Resin D, except that the weight of added methylol urea U was changed to 1500 g.
  • a reactor was charged with 37% formalin (520 g) and 99% ethanol (300 g), stirred with a propeller rotating stirrer, and the temperature inside the reactor was adjusted to 50 ° C with a temperature controller. Adjust to C.
  • 60 g of a 50% aqueous sodium hydroxide (NaOH) solution was added, and the reaction solution was kept at 40 ° C for 10 minutes. Thereafter, the temperature was increased to 85 ° C, and was maintained for 120 minutes after the temperature reached 85 ° C. Thereafter, the reaction solution was cooled to 20 ° C. This is referred to as Resin Resin G-1.
  • Resol Resin G The resole resin G-1 was neutralized with a 50% aqueous solution of paratoluenesulfonic acid monohydrate until the pH reached 5, and the reaction solution was dehydrated at 60 ° C. This is referred to as Resol Resin G.
  • a reactor was charged with 37% formalin (304 g) and saligenin (Tokyo Kasei Kogyo Co., Ltd.) (330 g) and 99% ethanol (500 g), and stirred with a propeller rotary stirrer. Adjust the temperature inside the reactor to 50 ° C with a temperature controller. Then 60 g of a 50% aqueous sodium hydroxide (NaOH) solution was added, and the reaction solution was kept at 50 ° C to 55 ° C for 20 minutes. Thereafter, the temperature was raised to 85 ° C, and was maintained for 110 minutes after the temperature reached 85 ° C. Thereafter, the reaction solution was cooled to 5 ° C. This is designated as Resin Resin H-1.
  • Resin resin H-1 was neutralized with a 50% aqueous solution of paratoluenesulfonic acid monohydrate until the pH reached 5, and the reaction solution was dehydrated at 60 ° C. This is called Resole Resin H.
  • resole resin I The synthesis of resole resin I was performed in the same manner as resole resin D, except that the weight of methylol urea U to be added was changed to 400 g.
  • resole resin J The synthesis of resole resin J was performed in the same manner as resole resin A, except that resole resin A-1 was changed to J-1.
  • Paintase 32 (a surfactant made by Dow Corning Asia Co., Ltd.) was dissolved in Resin Resin A at a ratio of 3.5 g to 100 g of Resin Resin.
  • This resin resin mixture as a foaming agent, normal pentane (Wako Pure Chemical, purity of more than 99%) in which 0.3% by weight of nitrogen was dissolved, and isobutane (purity of 99 %)
  • paratoluenesulfonic acid monohydrate as a curing catalyst (Wako Pure Chemical, purity 95% or more) 60% by weight and diethylene glycol (Wako Pure Chemical, purity 98% or more) 4 0% by weight of the mixture was supplied to a pin mixer with a temperature-controlled jacket at a ratio of 100 parts of the resin mixture, 7 parts of the foaming agent, and 15 parts of the curing catalyst.
  • the mixer was cooled with a temperature control jacket so that the temperature in the mixer did not exceed 80 ° C.
  • the mixture coming out of the mixer is poured into a formwork laid with Spunbond E104 (made by Asahi Kasei Kogyo Co., Ltd.), placed in an oven at 80 ° C for 5 hours, and the phenolic resin foam of this example is placed in the oven. Obtained.
  • Example 1 A mixture of 40% by weight of para-toluenesulfonic acid monohydrate, 30% by weight of diethylene glycol, and 30% by weight of resorcinol was used as a curing catalyst, except that the ratio was changed to 14 parts to 100 parts of resin. A phenol resin foam was produced in exactly the same manner as in 1.
  • phenolic resin foams were produced using the resins shown in Table 1 as resole resins, while adjusting the number of catalysts, and otherwise in exactly the same manner as in Example 1. .
  • a phenol resin foam was produced in exactly the same manner as in Example 1 except that isobutane in which 0.3% by weight of nitrogen was dissolved was used as a foaming agent.
  • the phenol was prepared in the same manner as in Example 1 except that a one-to-one mixture of normal pentane in which 0.3% by weight of nitrogen was dissolved and normal butane (purity: 9.9% or more) was used as a blowing agent. A resin foam was manufactured.
  • Foam resin foaming was carried out in exactly the same manner as in Example 1, except that a 1: 1 mixture of isopentane (0.3% by weight of nitrogen) and isobutane containing 0.3% by weight of nitrogen was used as the blowing agent. Body manufactured.
  • a phenolic resin foam was produced in exactly the same manner as in Example 1 except that a one-to-one mixture of isopentane in which 0.3% by weight of nitrogen was dissolved as a blowing agent and normal butane was used.
  • Example 2 The same procedure as in Example 1 was repeated except that a mixture of normal hexane (Wako Pure Chemical, a primary reagent) in which 0.3% by weight of nitrogen was dissolved and isobutane as a foaming agent was used. was manufactured.
  • normal hexane Waako Pure Chemical, a primary reagent
  • Paraffin manufactured by Wako Pure Chemical, melting point: 44 to 46 ° C, primary reagent
  • a phenolic resin foam was produced in exactly the same manner as in Example 1 except that this was performed.
  • a 1: 1 mixture of normal pentane in which 5% by weight of liquid paraffin (a first-class reagent manufactured by Wako Pure Chemical Industries, Ltd.) and 0.3% by weight of nitrogen are dissolved and isobutane is used.
  • a phenol resin foam was produced in exactly the same manner as in Example 1 except for the above.
  • Example 1 Except for using a 1: 1 mixture of normal pentane and isobutane in which 3% by weight of nitrogen and 0.3% by weight of nitrogen were dissolved as a blowing agent, Galden (HT1) HT-55 (Audimond Co., Ltd.) A phenol resin foam was produced in exactly the same manner as in 1.
  • Example 1 except that a 1: 1 mixture of normal pentane in which 3% by weight and 0.3% by weight of nitrogen were dissolved and normal pentane and isobutane were used as a foaming agent was used.
  • a phenol resin foam was produced in exactly the same manner as in 1.
  • Example 2 Exactly the same as in Example 1 except that a 1: 1 mixture of normal pentane and isobutane in which 3% by weight of Florinato FC-71 (manufactured by SLEEM) and 0.3% by weight of nitrogen were dissolved was used as a foaming agent. To produce a fininol resin foam.
  • Example 1 was repeated except that a 1: 1 mixture of normal pentane in which 3% by weight of Fluorinert FC-70 (manufactured by Sliem) and 0.3% by weight of nitrogen were dissolved and isobutane was used as a blowing agent.
  • a phenolic resin foam was produced in exactly the same manner.
  • Table 1 shows the ratio of the area D of all urea cross-linked components to the area E of all phenol derivatives, the closed cell ratio of foams, the average cell diameter, density, thermal conductivity, brittleness, and compressive strength. Are shown together.
  • Table 1 (Part 1) Resin F value German u-air, rate average ⁇ 2 diameter ⁇ jj * .1
  • Difficult 6 D 0.1 4 0.041 89.7 1 08 28 0.01 88 1 9 1.6 Difficult 7 E 0.22 0.021 92.4 98 29 0.01 90 1 6 1.7 Difficult 8 F 0.13 0.062 91.5 1 1 3 28 0.01 87 1 7 1.6 Difficult 9 G 0.38 0.000 82.4 1 1 5 29 0.0201 24 1.5 Difficult 1 0 H 0.64 0.00 87.3 1 1 2 29 0.01 97 21 1.6 Difficult 1 1 A 0.38 0.093 93.1 90 29 0.01 98 1 1 1. 7 Difficult 1 2 A 0.40 0.092 91.2 1 1 8 27 0.01 9 1 1 0 1.6 Out of order 13 A 0.39 0.091 92.3 83 28 0.01 83 9 1.6
  • a phenol resin foam having a C value in the range of 0.05 to 0, a closed cell ratio of 70% or more, and an average cell diameter of 10 to 400 m was used.
  • the brittleness is also improved to less than 30%.
  • the thermal conductivity of the example was 0.025 kca 1 / mhr r ° C or less, indicating excellent heat insulation performance.
  • the F value was in the range of 0.01 to 3, the brittleness was less than 20%, and the thermal conductivity was 0.020 kca 1 / mh. r ° C or less, indicating better performance.
  • Comparative Example 2 where the C value was too large as 4.13
  • Comparative Example 3 where it was too small as 0.04
  • the thermal conductivity was 0.025 kca 1 no mh r ° C in both cases.
  • the brittleness is a large value of 30% or more, and the heat insulation and the mechanical strength are inferior.
  • Comparative Example 1 although the C value was 0.11, which was within the range of the present invention, the closed cell rate was 61.8%, which was outside the range of the present invention, and the thermal conductivity was 0.1. 0 2 7 3 kca 1 / mh r ° C, poor heat insulation, brittleness 43%, poor mechanical strength.
  • the fu ⁇ ol resin foam according to the present invention has excellent heat insulating performance, excellent mechanical strength such as compressive strength, and significantly improved surface brittleness. Since the resin foam according to the present invention uses a foaming agent having a low global warming coefficient without fear of destruction of the ozone layer, it is suitable as a building insulation material more suitable for the global environment.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

L'invention porte sur une résine phénolique expansée utilisant comme agent moussant un hydrocarbure ne contribuant pas à l'appauvrissement en ozone, et faiblement au réchauffement du globe, excellent isolant thermique et d'une excellente résistance mécanique notamment à la compression et peu fragile. Ladite résine comporte 70 % ou plus de cellules fermées d'un diamètre moyen de 10 à 400 νm, sa densité est comprise entre 10 et 70 kg/m3 et elle produit par chromatographie gazeuse pyrolytique un diagramme de pyrolyse dans lequel le rapport C de l'aire A de tous les triméthylphénols produits de la pyrolyse à l'aire B des phénols autres produits de la pyrolyse (C=A/B) est défini par l'inégalité 0,05 ≤ C ≤ 4,0.
PCT/JP1998/003895 1997-09-03 1998-09-01 Resine phenolique expansee WO1999011697A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
AU88886/98A AU8888698A (en) 1997-09-03 1998-09-01 Phenolic resin foam
JP51660399A JP4711469B2 (ja) 1997-09-03 1998-09-01 フェノール樹脂発泡体

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JP9/238656 1997-09-03
JP23865697 1997-09-03

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WO1999011697A1 true WO1999011697A1 (fr) 1999-03-11

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007131803A (ja) * 2005-11-14 2007-05-31 Asahi Kasei Construction Materials Co Ltd フェノール樹脂発泡体の製造方法
WO2012053493A1 (fr) * 2010-10-18 2012-04-26 旭化成建材株式会社 Plaque expansée de résine phénolique
JP2014055305A (ja) * 2013-12-25 2014-03-27 Sekisui Chem Co Ltd 発泡性レゾール型フェノール樹脂成形材料およびフェノール樹脂発泡体
WO2015194174A1 (fr) * 2014-06-18 2015-12-23 旭化成建材株式会社 Mousse de résine phénolique et procédé pour la fabriquer
JPWO2014092086A1 (ja) * 2012-12-11 2017-01-12 旭化成建材株式会社 フェノール樹脂発泡体とその製造方法
JP2017114993A (ja) * 2015-12-22 2017-06-29 旭化成建材株式会社 フェノール樹脂発泡体及びその製造方法
WO2017110946A1 (fr) * 2015-12-22 2017-06-29 旭化成建材株式会社 Mousse de résine phénolique et procédé pour sa production

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE69924253T2 (de) * 1998-07-03 2005-12-22 Asahi Kasei Kabushiki Kaisha Phenolhaltiger schaum
JP6791643B2 (ja) * 2015-03-24 2020-11-25 積水化学工業株式会社 フェノール樹脂発泡体

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61185535A (ja) * 1984-11-29 1986-08-19 オウエンズ―コーニング　カナダ　インコーポレイテッド フエノ−ル樹脂フオ−ム材とその製造方法
JPH07196838A (ja) * 1993-12-29 1995-08-01 Asahi Organic Chem Ind Co Ltd 発泡硬化型フェノール樹脂系組成物

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11512131A (ja) * 1995-08-28 1999-10-19 オウェンス コーニング フェノール樹脂フォームの製造方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61185535A (ja) * 1984-11-29 1986-08-19 オウエンズ―コーニング　カナダ　インコーポレイテッド フエノ−ル樹脂フオ−ム材とその製造方法
JPH07196838A (ja) * 1993-12-29 1995-08-01 Asahi Organic Chem Ind Co Ltd 発泡硬化型フェノール樹脂系組成物

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007131803A (ja) * 2005-11-14 2007-05-31 Asahi Kasei Construction Materials Co Ltd フェノール樹脂発泡体の製造方法
WO2012053493A1 (fr) * 2010-10-18 2012-04-26 旭化成建材株式会社 Plaque expansée de résine phénolique
CN103154106A (zh) * 2010-10-18 2013-06-12 旭化成建材株式会社 酚醛树脂发泡板
JP5894926B2 (ja) * 2010-10-18 2016-03-30 旭化成建材株式会社 フェノール樹脂発泡板
US9976026B2 (en) 2010-10-18 2018-05-22 Asahi Kasei Construction Materials Corporation Phenol resin foamed plate
JP2017206714A (ja) * 2012-12-11 2017-11-24 旭化成建材株式会社 フェノール樹脂発泡体とその製造方法
JPWO2014092086A1 (ja) * 2012-12-11 2017-01-12 旭化成建材株式会社 フェノール樹脂発泡体とその製造方法
JP2014055305A (ja) * 2013-12-25 2014-03-27 Sekisui Chem Co Ltd 発泡性レゾール型フェノール樹脂成形材料およびフェノール樹脂発泡体
WO2015194174A1 (fr) * 2014-06-18 2015-12-23 旭化成建材株式会社 Mousse de résine phénolique et procédé pour la fabriquer
JPWO2015194174A1 (ja) * 2014-06-18 2017-04-20 旭化成建材株式会社 フェノール樹脂発泡体及びその製造方法
KR20170007396A (ko) 2014-06-18 2017-01-18 아사히 가세이 겐자이 가부시키가이샤 페놀 수지 발포체 및 그 제조 방법
JP2017114993A (ja) * 2015-12-22 2017-06-29 旭化成建材株式会社 フェノール樹脂発泡体及びその製造方法
WO2017110946A1 (fr) * 2015-12-22 2017-06-29 旭化成建材株式会社 Mousse de résine phénolique et procédé pour sa production
JPWO2017110946A1 (ja) * 2015-12-22 2018-07-12 旭化成建材株式会社 フェノール樹脂発泡体及びその製造方法
KR20180081093A (ko) 2015-12-22 2018-07-13 아사히 가세이 겐자이 가부시키가이샤 페놀 수지 발포체 및 그 제조 방법
RU2703133C1 (ru) * 2015-12-22 2019-10-15 Асахи Касеи Констракшн Матириалс Корпорейшн Пенопласт на основе фенольной смолы и способ его изготовления

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JP4711469B2 (ja) 2011-06-29

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