WO2020080149A1 - Composition de résine phénolique ignifuge et matériau ignifuge obtenu à partir de celle-ci - Google Patents

Composition de résine phénolique ignifuge et matériau ignifuge obtenu à partir de celle-ci Download PDF

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WO2020080149A1
WO2020080149A1 PCT/JP2019/039326 JP2019039326W WO2020080149A1 WO 2020080149 A1 WO2020080149 A1 WO 2020080149A1 JP 2019039326 W JP2019039326 W JP 2019039326W WO 2020080149 A1 WO2020080149 A1 WO 2020080149A1
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flame
retardant
resin composition
phenolic resin
foam
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PCT/JP2019/039326
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English (en)
Japanese (ja)
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山田　修司
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旭有機材株式会社
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Priority to KR1020217007487A priority Critical patent/KR102438544B1/ko
Priority to CN201980061016.4A priority patent/CN112739769A/zh
Priority to JP2020553069A priority patent/JP7473476B2/ja
Publication of WO2020080149A1 publication Critical patent/WO2020080149A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/08—Ingredients agglomerated by treatment with a binding agent
    • 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
    • C08J9/009—Use of pretreated compounding ingredients
    • 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
    • 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
    • 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
    • C08J9/143—Halogen containing compounds
    • C08J9/144—Halogen containing compounds containing carbon, halogen and hydrogen only
    • C08J9/145—Halogen containing compounds containing carbon, halogen and hydrogen only only chlorine as halogen atoms
    • 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
    • C08J9/149—Mixtures of blowing agents covered by more than one of the groups C08J9/141 - C08J9/143
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/01—Hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/02—Halogenated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • C08L61/12—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols with polyhydric phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08L61/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
    • C08L61/28—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with melamine
    • 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
    • C08J2361/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08J2361/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • C08J2361/12—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols with polyhydric phenols

Definitions

  • the present invention relates to a flame-retardant phenolic resin composition and a flame-retardant material obtained from the flame-retardant phenolic resin composition.
  • a flame-retardant material comprising a cured phenolic resin such as a flame-retardant phenolic resin foam (phenol foam) is advantageous.
  • a flame-retardant material obtained from such a phenol resin composition is advantageous.
  • a phenol resin material obtained by curing a phenol resin has been recognized by those skilled in the art as a material having relatively high flame retardance, but as it is, it can be used for construction, civil engineering, and electricity. It does not fully meet the safety standards required in the fields of products, electric and electronic parts, automobile parts, etc., and is difficult to be stipulated by the Japanese Building Standards Act, which is evaluated by a heat generation test with a cone calorimeter. Flame-retardant materials with flammability properties could not be advantageously provided.
  • a predetermined flame retardant is blended with the phenol resin composition, and curing thereof improves the flame retardancy of the intended phenol resin material. It has been planned.
  • a useful flame-retardant phenol foam is obtained by using a phosphorus compound, a sulfur compound or a boron compound as a flame retardant and blending them with a resin composition for phenol foam production. It has been demonstrated that can be manufactured.
  • JP-A-2007-161810, JP-A-2007-70511 and the like aluminum hydroxide and magnesium hydroxide are used as inorganic fillers that are usually added to a resin composition for producing phenol foam.
  • Phenol foam obtained by foaming by using metal hydroxides such as; oxides of metals such as calcium oxide and aluminum oxide; metal powders such as zinc dust; carbonates of metals such as calcium carbonate and magnesium carbonate It has been clarified that the flame retardancy or fire resistance of the can be improved.
  • JP-A-8-176343 discloses a resin composition containing ammonium polyphosphate as a non-halogen flame retardant capable of imparting a high degree of flame retardancy to a resin.
  • a resol type phenolic resin which is one of the phenolic resins, and combining it with an acid curing agent, a foaming agent, etc., and foam-curing it, a phenol consisting of a cured product of a phenolic resin such as phenol foam.
  • a flame retardant composed of ammonium polyphosphate as proposed in the above-mentioned JP-A-8-176343, such polyphosphoric acid is used.
  • a flame retardant composed of ammonium polyphosphate as proposed in the above-mentioned JP-A-8-176343
  • the total calorific value for 5 minutes after starting heating is 8.0 MJ.
  • the curing reaction of the phenol resin composition is less likely to proceed as the compounding amount of ammonium polyphosphate with respect to the phenol resin composition is increased in order to obtain the characteristic of less than 1 / m 2 and the desired phenol resin material such as phenol foam.
  • the (cured product) cannot be obtained at all.
  • the flame-retardant material satisfies the above total calorific value, and the maximum heat generation rate does not exceed 200 kW / m 2 continuously for more than 10 seconds. It is said that there are no cracks and holes that penetrate to the back surface, which is harmful for flame prevention, but the phenol resin materials up to this point have been able to meet such requirements while ensuring useful properties as a phenol resin. It wasn't enough.
  • the problem to be solved is a phenol resin composition containing a resol type phenol resin as an essential component, Flame-retardant phenolic resin which can solve the problems in the case of blending ammonium polyphosphate that can impart the flame-retardant property, and can advantageously form the flame-retardant material specified by the Building Standards Law of Japan. It is to provide a composition, and to provide a flame-retardant material defined by such a building standard method by using such a flame-retardant phenol resin composition.
  • At least an ammonium polyphosphate powder having a surface coating layer as a flame retardant is contained together with a resol-type phenol resin and an acid curing agent.
  • the flame-retardant phenolic resin composition is
  • the surface coating layer is formed of a sparingly soluble thermosetting resin.
  • a melamine resin will be preferably adopted.
  • the flame retardant is used in a proportion of 0.5 to 30 parts by mass with respect to 100 parts by mass of the resol type phenolic resin. It is included.
  • the resol-type phenol resin is adjusted to have a viscosity of 2000 mPa ⁇ s or more at 25 ° C.
  • a foaming agent is further contained, whereby a phenol foam (phenolic resin) having exceptional flame retardant properties is contained. Foams) can be advantageously formed.
  • halogenated alkenes, or chlorinated aliphatic hydrocarbons and / or aliphatic hydrocarbons are preferably used, and among them, a mixture of isopentane and isopropyl chloride is advantageously used. Will be done.
  • the flame-retardant phenolic resin composition as described above a flame-retardant material characterized by comprising a cured product obtained by curing, is also the gist thereof, Furthermore, a flame-retardant material comprising a foam obtained by foam-curing a flame-retardant phenolic resin composition containing a foaming agent as described above is also the subject matter.
  • the foam is 5 after the start of heating when heated at a radiant heat intensity of 50 kW / m 2 in accordance with the exothermic test method specified in ISO-5660. It has the characteristic that the total calorific value per minute is 8.0 MJ / m 2 or less.
  • the ammonium polyphosphate powder formed by forming the surface coating layer is blended as the flame retardant, not the ammonium polyphosphate itself. Therefore, the inhibitory effect of ammonium polyphosphate on the curing reaction of the phenol resin composition containing the resol-type phenol resin and the acid curing agent can be advantageously suppressed or prevented, whereby the phenol resin composition is obtained.
  • the flame retardancy of the target phenolic resin material composed of the cured product of 1) can be effectively improved.
  • a predetermined foaming agent is contained, and by being foam-cured, a phenol foam excellent in flame-retardant properties can be advantageously formed. Therefore, one of the great features of the present invention can be found there.
  • a flame-retardant phenolic resin material such as a flame-retardant phenolic foam can be easily obtained as a flame-retardant material specified by the Building Standards Law of Japan. Moreover, it can be advantageously formed.
  • the resol-type phenol resin used in the present invention as described above is in a liquid form, and it is advantageous that 1.0 mol to 3 mol. It is used in a proportion of about 0 mol, preferably in a proportion of about 1.5 to 2.5 mol, and these are used in the presence of an alkaline reaction catalyst in the same manner as in the conventional manner, for example, in the range of 50 ° C. to the reflux temperature.
  • a neutralization treatment is carried out, and then a predetermined characteristic value, for example, a viscosity at 25 ° C. of 2000 mPa ⁇ s or more, and a water content of 3 to 20 mass% under reduced pressure.
  • dehydration concentration is carried out so that the amount is preferably 5 to 18% by mass, and thereafter, if necessary, predetermined additives are added in the same manner as in the conventional case, and the product is produced.
  • the liquid resol-type phenol resin thus obtained is generally 2000 mPa ⁇ s or more, preferably 2000 to 100000 mPa ⁇ s, more preferably 3000 to 80000 mPa ⁇ s, further preferably 4000 to 30000 mPas at 25 ° C. -By having a viscosity of s, it is possible to more effectively realize the preparation work of the intended phenol resin composition, in particular, the dispersion and the containing operation of the ammonium polyphosphate powder having the surface coating layer. Since the stability of the dispersed state can be advantageously increased, the advantage that flame retardancy and thermal conductivity can be further improved can be enjoyed.
  • the phenols as one raw material of the resol type phenol resin used in the present invention include phenol, o-cresol, m-cresol, p-cresol, p-tert-butylphenol, m-xylenol, bisphenol F, Bisphenol A and the like can be mentioned, and as the other raw material aldehyde used in combination with this phenol, formaldehyde, paraformaldehyde, trioxane, polyoxymethylene, glyoxal and the like can be mentioned.
  • examples of the reaction catalyst include potassium hydroxide, sodium hydroxide, barium hydroxide, calcium hydroxide, potassium carbonate, ammonia and the like.
  • any of these phenols, aldehydes and reaction catalysts is by no means limited to the above examples, and various known ones can be appropriately used, and they are respectively They can be used alone or in combination of two or more.
  • a phenol foam as a flame-retardant phenol resin material, together with the resole type phenol resin as described above, as the foaming agent
  • various known foaming agents are used.
  • a chlorinated aliphatic hydrocarbon and / or an aliphatic hydrocarbon having a low global warming potential and a halogenated alkene are advantageously used, and a phenol resin such as phenol foam is used.
  • a foam will be formed.
  • chlorinated aliphatic hydrocarbon as a foaming agent, generally, a chlorinated product of a linear or branched aliphatic hydrocarbon having about 2 to 5 carbon atoms is preferably used.
  • the number of bonded atoms is generally about 1 to 4.
  • Specific examples of such chlorinated aliphatic hydrocarbons include dichloroethane, propyl chloride, isopropyl chloride, butyl chloride, isobutyl chloride, pentyl chloride, isopentyl chloride and the like. These may be used alone or in combination of two or more. Among them, chloropropanes such as propyl chloride and isopropyl chloride are preferable, and isopropyl chloride is particularly preferably used. .
  • aliphatic hydrocarbon as the foaming agent, a conventionally known hydrocarbon-based foaming agent having about 3 to 7 carbon atoms can be appropriately selected and used.
  • a conventionally known hydrocarbon-based foaming agent having about 3 to 7 carbon atoms can be appropriately selected and used.
  • Propane, butane, pentane, isopentane, hexane, isohexane, neohexane, heptane, isoheptane, cyclopentane and the like can be mentioned, and from these, one kind or a combination of two or more kinds is used.
  • a mixed foaming agent obtained by combining the above-mentioned chlorinated aliphatic hydrocarbon and aliphatic hydrocarbon is also suitably used, and the mixing ratio thereof is, in terms of mass ratio, aliphatic hydrocarbon.
  • Chlorinated aliphatic hydrocarbon 25: 75 to 5:95, which is advantageously adopted.
  • a combination of such two kinds of foaming agents a combination of isopentane and isopropyl chloride is recommended, whereby the object of the present invention can be achieved even more advantageously.
  • a halogenated alkene is also advantageously used as a blowing agent, which can contribute to further improvement of the properties of the obtained phenol foam, particularly flame retardancy and heat insulating properties.
  • Halogenated alkenes having such characteristics include those called halogenated olefins and halogenated hydroolefins, and in general, chlorine or fluorine is bonded and contained as a halogen and has 2 to 4 carbon atoms.
  • Tetrafluoro which is an unsaturated hydrocarbon derivative of about 6, for example, propene, butene, pentene and hexene having 3 to 6 fluorine substituents, substituted with halogen such as fluorine or chlorine.
  • Examples thereof include propene, fluorochloropropene, trifluoromonochloropropene, pentafluoropropene, fluorochlorobutene, hexafluorobutene, and a mixture of two or more thereof.
  • hydrofluoroolefin which is one of such halogenated alkenes (halogenated olefins)
  • halogenated olefins for example, pentafluoro such as 1,2,3,3,3-pentafluoropropene (HFO1225ye) is used.
  • Tetrafluoro such as propene, 1,3,3,3-tetrafluoropropene (HFO1234ze), 2,3,3,3-tetrafluoropropene (HFO1234yf), 1,2,3,3-tetrafluoropropene (HFO1234ye)
  • Propene trifluoropropene such as 3,3,3-trifluoropropene (HFO1243zf), tetrafluorobutene isomer (HFO1354), pentafluorobutene isomer (HFO1345), 1,1,1,4,4,4 4-hexafluoro-2-butene (HFO 336mzz) and other hexafluorobutene isomers (HFO1336), heptafluorobutene isomers (HFO1327), heptafluoropentene isomers (HFO1447), octafluoropentene isomers (HFO1438), nonafluoropen
  • hydrochlorofluoroolefin HCFO
  • 1-chloro-3,3,3-trifluoropropene HCFO-1233zd
  • 2-chloro-3,3,3-trifluoropropene HCFO-1233xf
  • Dichlorotrifluoropropene HCFO1223
  • 1-chloro-2,3,3-trifluoropropene HCFO-1233yd
  • 1-chloro-1,3,3-trifluoropropene HCFO-1233zb
  • 2-chloro- 1,3,3-trifluoropropene HCFO-1233xe
  • 2-chloro-2,2,3-trifluoropropene HCFO-1233xc
  • 3-chloro-1,2,3-trifluoropropene HCFO- 1233ye
  • 3-chloro-1,1,2-trifluoropropene HCF
  • the total amount of each of the above-mentioned foaming agents is generally 1 to 30 parts by mass, preferably 5 to 25 parts by mass, relative to 100 parts by mass of the resol-type phenol resin.
  • the blowing agent preferably used in the present invention is characterized by containing a chlorinated aliphatic hydrocarbon and / or an aliphatic hydrocarbon as described above, or a halogenated alkene, but for the purpose of the present invention, As long as they do not cause adverse effects, for example, fluorinated hydrocarbons such as 1,1,1,3,3-pentafluorobutane (alternative CFCs), salt fluorinated hydrocarbons such as trichloromonofluoromethane and trichlorotrifluoroethane, It is also possible to contain water, an ether compound such as isopropyl ether, a gas such as nitrogen, argon, carbon dioxide, air or the like in an appropriate ratio.
  • fluorinated hydrocarbons such as 1,1,1,3,3-pentafluorobutane (alternative CFCs)
  • salt fluorinated hydrocarbons such as trichloromonofluoromethane and trichlorotri
  • the acid curing agent used in the present invention is a component (curing catalyst) for accelerating the curing reaction of the resol type phenolic resin as described above, and a conventionally known acid curing agent is appropriately selected. , Will be used.
  • an acid curing agent include aromatic sulfonic acids such as benzenesulfonic acid, phenolsulfonic acid, cresolsulfonic acid, toluenesulfonic acid, xylenesulfonic acid and naphthalenesulfonic acid; methanesulfonic acid and trifluoromethanesulfonic acid.
  • inorganic acids such as sulfuric acid, phosphoric acid, polyphosphoric acid, borofluoric acid, etc., which may be used alone, or may be used in combination of two or more kinds.
  • acid curing agents for example, phenol sulfonic acid, toluene sulfonic acid, and aromatic sulfonic acid such as naphthalene sulfonic acid can achieve an appropriate curing rate in the production of phenol foam.
  • the balance between the curing of the resol-type phenol resin and the foaming by the foaming agent is further improved, and a desired foamed structure is realized, and therefore, it is particularly preferably used.
  • paratoluenesulfonic acid the combined use of paratoluenesulfonic acid and xylenesulfonic acid is recommended.
  • the usage ratio thereof it is desirable that the amount of paratoluenesulfonic acid used is more than the amount of xylenesulfonic acid used on a mass basis.
  • paratoluenesulfonic acid: xylenesulfonic acid is within the range of 51:49 to 95: 5, it is advantageously adopted.
  • the amount of such an acid curing agent to be used is appropriately set depending on the type and temperature conditions during mixing with the resol-type phenol resin, but in the present invention, the resol-type phenol is used. It is desirable that the amount is generally 1 to 50 parts by mass, preferably 5 to 30 parts by mass, and particularly preferably 7 to 25 parts by mass, relative to 100 parts by mass of the resin. If the amount used is less than 1 part by mass, the progress of curing is slow, while if it exceeds 50 parts by mass, the curing rate becomes too fast and it becomes difficult to obtain the desired phenol foam advantageously. Cause.
  • At least a ammonium polyphosphate powder having a surface coating layer is contained as a flame retardant in the phenol resin composition constituted by containing the resol-type phenol resin and the acid curing agent as described above.
  • the curing reaction of the phenol resin composition can be effectively progressed, and thus, with excellent flame retardant properties,
  • the ammonium polyphosphate powder having a surface coating layer used therein is obtained by coating or microencapsulating ammonium polyphosphate particles with a thermosetting resin, polyphosphoric acid such as melamine monomer or other nitrogen-containing organic compound.
  • a thermosetting resin such as melamine monomer or other nitrogen-containing organic compound.
  • examples thereof include those obtained by coating the surface of ammonium particles, those treated with a surfactant or silicon, etc., and normally, they are appropriately selected from commercial products and used.
  • Exolit AP462 available from Clariant Chemicals Co., Ltd.
  • FR CROS486, FR CROS487 available from CBC
  • Terrage C30, Terrage C60, Terrage C70, Terrage C80, etc. can be mentioned.
  • the surface coating layer of the ammonium polyphosphate powder is preferably sparingly soluble in the liquid phenol resin composition, that is, sparingly soluble in water.
  • the curable resin a phenol resin, a melamine resin or the like is used, and among them, the melamine resin is preferably used.
  • an easily soluble thermosetting resin can be advantageously used by advancing the curing reaction of the surface coating layer formed thereon to form a hardly soluble surface coating layer.
  • a surface coating layer made of such a sparingly soluble thermosetting resin a cured product such as phenol foam having excellent properties in compressive strength and initial thermal conductivity can be advantageously obtained. You can do it.
  • the amount of the ammonium polyphosphate powder having such a surface coating layer to be used is generally 0.5 to 30 parts by mass, preferably 1 to 25 parts by mass, and further 100 parts by mass of the resol type phenol resin. Preferably, it will be appropriately determined within the range of 2 to 20 parts by mass.
  • the addition amount of the ammonium polyphosphate powder having such a surface coating layer is too small, it is difficult to sufficiently exert the effect of imparting flame retardancy to the phenol resin material composed of the cured product such as phenol foam. Further, if the addition amount becomes too large, it becomes difficult to avoid the inhibitory effect on the curing reaction of the phenol resin composition, and it increases the viscosity of the composition to which it is added, causing problems such as poor stirring. In addition to causing such problems, problems such as deterioration in properties such as compressive strength and thermal conductivity of the phenol resin material will occur.
  • the average particle diameter of the ammonium polyphosphate powder having such a surface coating layer is generally about 1 to 100 ⁇ m, preferably about 5 to 50 ⁇ m. If the particle size of the ammonium polyphosphate powder having this surface coating layer becomes too small, it causes problems such as difficulty in handling and uniform dispersion in the phenol resin composition, and the particle size becomes large. Even if it is too much, it is difficult to obtain a uniform dispersion effect in the phenol resin composition, which causes a problem that the object of the present invention cannot be sufficiently achieved.
  • ammonium polyphosphate powder having a surface coating layer is used as a flame retardant, but if necessary, other publicly known substances that do not impair the object of the present invention. It is also possible to use the above flame retardant together.
  • flame retardant include phenylphosphonic acid, guanidine phosphate derivatives, carbamate phosphate derivatives, phosphorus-based flame retardants such as red phosphorus and ammonium phosphate, sulfamic acid-based flame retardants, and borohydrides.
  • examples thereof include acid flame retardants, halogen flame retardants, inorganic hydroxides such as metal hydroxides, metal oxides and graphite.
  • ammonium polyphosphate powder having a surface coating layer as a flame retardant is added as an essential component together with the resole-type phenolic resin and the acid curing agent as described above.
  • a predetermined blowing agent in particular, a chlorinated aliphatic hydrocarbon and / or an aliphatic hydrocarbon, or a halogenated alkene is mixed, and further, If necessary, conventionally known foam stabilizers, inorganic fillers, plasticizers, urea, etc. may be added.
  • the foam stabilizer among the additives to be added and contained as necessary, is used for assisting the mixing and emulsification of the mixed components in the phenol resin composition, dispersing the generated gas, stabilizing the foam cell membrane, and the like. It is mixed for the purpose.
  • various foam stabilizers conventionally used in the technical field will be selected and used, among them, poly Nonionic surfactants such as siloxane compounds, polyoxyethylene sorbitan fatty acid esters, alkylphenol ethylene oxide adducts, and castor oil ethylene oxide adducts are particularly preferably used. These foam stabilizers may be used alone or in combination of two or more.
  • the amount used is also not particularly limited, but it is generally used within a range of 0.5 to 10 parts by mass with respect to 100 parts by mass of the resol-type phenol resin.
  • inorganic filler for example, aluminum hydroxide, magnesium hydroxide, metal hydroxide such as calcium hydroxide, magnesium oxide, aluminum oxide, metal oxide such as zinc oxide, metal powder such as zinc, Mention may be made of metal carbonates such as calcium carbonate, magnesium carbonate, barium carbonate and zinc carbonate.
  • inorganic fillers may be used alone or in combination of two or more.
  • flame retardancy and fire resistance can be improved, but the amount thereof is appropriately determined within the range of the amount not hindering the object of the present invention. It goes without saying that it is done.
  • the plasticizer can be advantageously used as a cured phenolic resin material in the case of producing a phenol foam, and by its use, it imparts flexibility to the cell wall of the phenol foam, thereby improving the heat insulation performance. It exhibits characteristics such as suppressing deterioration with time.
  • the plasticizer is not particularly limited, and known plasticizers conventionally used in the production of phenol foams, such as triphenyl phosphate, dimethyl terephthalate, and dimethyl isophthalate, can be used, and further polyesters can be used. The use of polyols is also effective.
  • the polyester polyol since the polyester polyol has a structure containing an ester bond and a hydroxyl group, which are hydrophilic and have excellent surface activity, it has good compatibility with the hydrophilic phenol resin solution and should be mixed uniformly with the phenol resin. Can be done. Further, by using this polyester polyol, uneven distribution of air bubbles is avoided, the air bubbles are uniformly distributed throughout the foam, and a phenol resin foam (phenol foam) which is homogeneous in terms of quality is easily produced, which is preferable plasticization. It can be called an agent.
  • phenol resin foam phenol foam
  • the amount of such a plasticizer is usually 0.1 to 20 parts by mass, preferably 0.5 to 15 parts by mass, and more preferably 1 to 12 parts by mass with respect to 100 parts by mass of the resol-type phenol resin. It is used in the range, whereby the effect of imparting flexibility to the cell wall can be satisfactorily exerted without impairing the other properties of the resulting phenol foam, and the object of the present invention can be achieved even better.
  • urea will be suitably added and contained in the flame-retardant phenolic resin composition constructed according to the present invention.
  • urea By containing such urea, it is possible to effectively reduce the initial thermal conductivity of the obtained phenol resin material such as phenol foam, and further to obtain a phenol resin material such as phenol foam having strength, particularly low brittleness.
  • it also contributes to maintaining the thermal conductivity low over a medium to long term, which makes it easy to obtain a phenolic resin material such as phenol foam having excellent thermal insulation performance for a long period of time. It will be.
  • the flame-retardant phenolic resin composition according to the present invention which contains the above-described compounding ingredients, is, for example, the above-mentioned resole-type phenolic resin, to which, as a flame retardant, ammonium polyphosphate powder having the above-mentioned surface coating layer is added. Then, the mixture is mixed, and if necessary, the above-mentioned other flame retardant, inorganic filler, foam stabilizer, further plasticizer, urea, etc. are added and mixed, and the resulting mixture is mixed as necessary.
  • a phenol resin composition thus prepared is used and cured to form a desired phenol resin material such as a solid material or a foam
  • various conventionally known various resins are used.
  • a method for producing a phenol foam (1) a molding method in which a phenol resin composition is allowed to flow out on an endless conveyor belt to foam and cure, and (2) spot filling is performed. Partially foaming and curing, (3) foaming and curing under pressure in a mold, and (4) foaming and curing by filling into a predetermined large space. Examples include a method of forming a body block and (5) a method of filling and foaming while press-fitting into a cavity.
  • the above-mentioned phenol resin composition is discharged onto a carrier that moves continuously, and this discharged material passes through a heating zone.
  • a method is employed in which the desired phenolic foam is made by foaming and molding. Specifically, the phenolic resin composition is discharged onto a face material on a conveyor belt, then the face material is placed on the upper surface of the resin material on the conveyor belt, and moved to a curing furnace, and a curing furnace. In the above, press the other conveyor belt from above to adjust the resin material to a predetermined thickness, and foam and cure it under the conditions of about 60 to 100 ° C for about 2 to 15 minutes, and then cure furnace. By cutting the foam taken out from the product into a predetermined length, a phenol foam having a desired shape is produced.
  • the face material used here is not particularly limited, and generally, natural fibers, synthetic fibers such as polyester fibers and polyethylene fibers, non-woven fabrics such as inorganic fibers such as glass fibers, papers, aluminum Foil-clad non-woven fabrics, metal plates, metal foils and the like are used, but usually glass fiber non-woven fabrics, spunbonded non-woven fabrics, aluminum foil-clad non-woven fabrics, metal plates, metal foils, plywood, structural panels, particle boards, hard boards.
  • Wood cement board flexible board, perlite board, calcium silicate board, magnesium carbonate board, pulp cement board, seeding board, medium density fiberboard, gypsum board, lath sheet, volcanic vitreous composite board, natural stone, brick, tile , Glass molding, lightweight cellular concrete molding, cement mortar Body, molded bodies of water-curable cement hydrate glass fiber-reinforced cement moldings such as a binder component, and thus preferably used.
  • This face material may be provided on one side of the phenol foam, or on both sides, without any problem. Further, when provided on both sides, the face materials may be the same or different. Further, it does not matter even if it is formed by laminating the face materials by using an adhesive later.
  • the phenol resin material (cured product) such as the phenol foam thus obtained contains the predetermined ammonium polyphosphate powder dispersed and contained therein.
  • the property can be effectively enhanced, and in a heat generation test by a corn calorimeter, the property as a flame retardant material stipulated by the Building Standards Law of Japan is advantageously provided.
  • the exothermic test method specified in ISO-5660 when heated at a radiant heat intensity of 50 kW / m 2 , the total calorific value from the start of heating until 5 minutes has elapsed is The material having the characteristic of 8.0 MJ / m 2 or less is advantageously provided, and thus, it can be advantageously used in various applications as a flame retardant material.
  • a phenolic resin material such as such a phenolic foam is advantageously generally 0.0230 W / m ⁇ K (20 ° C.) or less, preferably 0.0200 W / m ⁇ K (20 ° C.) or less, more preferably It can be easily produced as having an initial thermal conductivity of 0.0195 W / m ⁇ K (20 ° C.) or less, and in the case of phenol foam, its closed cell ratio is Generally, it is constituted to be 80% or more, preferably 85% or more, more preferably 90% or more, whereby it is produced as one that advantageously exhibits excellent flame retardancy and excellent low thermal conductivity characteristics. It will be.
  • the phenolic resin material such as phenol foam obtained according to the present invention
  • its density is generally 10 to 150 kg / m 3 , preferably 15 to 100 kg / m 3 , and more preferably 15 to 70 kg / m 3 . Yes, more preferably 20 to 50 kg / m 3 , and most preferably 20 to 40 kg / m 3 .
  • a phenol foam having a density lower than 10 kg / m 3 the strength is low and the foam (foam) may be damaged during transportation or construction. If the density is low, the bubble film tends to be thin.
  • Example 1 In a three-neck reaction flask equipped with a reflux condenser, a thermometer and a stirrer, 1600 parts of phenol, 2282 parts of 47% formalin and 41.6 parts of 50% sodium hydroxide aqueous solution were charged, and the temperature was 80 ° C. for 70 minutes. It was made to react. Then, after cooling to 40 ° C., it was neutralized with a 50% paratoluenesulfonic acid aqueous solution, and then dehydrated and concentrated to a water content of 10% under reduced pressure and heating to obtain a liquid resol-type phenol resin. .
  • the obtained phenol resin had the following properties: viscosity: 10000 mPa ⁇ s / 25 ° C., number average molecular weight: 380, free phenol content: 4.0%.
  • the foamable phenolic resin molding material thus prepared, it is poured into a mold having a length of 300 mm, a width of 300 mm, and a thickness of 50 mm, which has been heated to 70 to 75 ° C. in advance.
  • the mold was housed in a dryer at 70 to 75 ° C., foamed and cured for 10 minutes, and further heated at a temperature of 70 ° C. for 12 hours in a heating furnace to be post-cured, A phenol foam (phenol resin foam) was produced.
  • Example 2 In Example 1, FR CROS486 (sold by CBC Co., Ltd .; an average particle size: 18 ⁇ m) of polyphosphorus which is an ammonium polyphosphate powder in which a silane coating layer is formed as a surface coating layer in place of the TELLAGE C80 used as the flame retardant. A phenol foam was produced in the same manner as in Example 1 except that ammonium acid powder having a surface treated with silane) was used.
  • Example 3 In Example 1, the blowing agent was changed to hydrofluoroolefin (1,1,1,4,4,4-hexafluoro-2-butene: HFO-1336mzz, a product of Chemours), and the addition amount was 17. A phenol foam was produced in the same manner as in Example 1 except that the amount was 5 parts.
  • Example 1 A phenolic foam was produced in the same manner as in Example 1 except that ammonium polyphosphate powder having a surface coating layer as a flame retardant was not added.
  • Example 2 In Example 1, except that ammonium polyphosphate powder (FR CROS484 sold by CBC Co., average particle size: 18 ⁇ m) having no surface coating layer was used as the flame retardant, Similarly, an attempt was made to produce a phenol foam, but the curing reaction of the phenol resin composition did not proceed sufficiently, and a foam whose physical properties could be measured could not be obtained.
  • ammonium polyphosphate powder FR CROS484 sold by CBC Co., average particle size: 18 ⁇ m
  • the phenol foams formed in Examples 1 to 3 all had a total calorific value of 8 MJ / m 2 or less in the combustion test, and the maximum heat generation rate was also the specified value. From the following points, we have found that it is useful as a flame-retardant material specified by the Building Standards Law of Japan. Among them, the phenol foams obtained in Examples 1 and 3 all have an initial thermal conductivity of 0.0193 W / mK or less, a closed cell rate of 91% or more, and a compression strength. It was about 16 N / cm 2 or more, and it was confirmed that the mechanical properties as well as the heat insulating properties were excellent.
  • Comparative Example 1 since the phenol foam obtained in Comparative Example 1 does not contain any flame retardant, it cannot impart effective flame retardancy and is easily burned. Further, in Comparative Example 2 in which the powder of ammonium polyphosphate as it is having no surface coating layer was used, the curing reaction of the phenol resin composition did not proceed smoothly, and therefore a foam capable of measuring physical properties was prepared. I could't get it.

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Abstract

L'invention concerne une composition de résine phénolique ignifuge qui résout les problèmes provoqués par l'incorporation de polyphosphate d'ammonium, qui peut conférer un degré élevé d'ininflammabilité, dans des compositions de résine phénolique contenant une résine phénolique de type résol utilisée comme constituant essentiel et qui peut donner avantageusement des matériaux ignifuges conformément à la loi sur les normes de construction du Japon. La composition de résine phénolique ignifuge est une composition de résine phénolique qui comprend une résine phénolique de type résol et un durcisseur acide et qui contient en outre un agent ignifuge comprenant au moins une poudre de polyphosphate d'ammonium comportant une couche de revêtement de surface.
PCT/JP2019/039326 2018-10-16 2019-10-04 Composition de résine phénolique ignifuge et matériau ignifuge obtenu à partir de celle-ci WO2020080149A1 (fr)

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CN201980061016.4A CN112739769A (zh) 2018-10-16 2019-10-04 阻燃性酚醛树脂组合物及由其得到的阻燃材料
JP2020553069A JP7473476B2 (ja) 2018-10-16 2019-10-04 難燃性フェノール樹脂組成物及びそれから得られた難燃材料

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