JPWO2020025544A5

JPWO2020025544A5 -

Info

Publication number: JPWO2020025544A5
Application number: JP2021505391A
Authority: JP
Publication date: 2023-11-13
Anticipated expiration: 2039-07-29

Description

前記フェノール樹脂発泡性組成物は、更に可塑剤、無機充填剤、難燃剤、靱性化剤及びその組合せの少なくとも１つからなり得る。 The phenolic resin foamable composition may further comprise at least one of a plasticizer, an inorganic filler, a flame retardant, a toughening agent , and combinations thereof.

前記靱性化剤は、尿素、ジシアンジアミド及びメラミンからなる群から選択することができる。 The toughening agent can be selected from the group consisting of urea, dicyandiamide and melamine.

前記靱性化剤は、前記フェノール樹脂１００重量部当たり１～１０重量部の量で存在し得る。 The toughening agent may be present in an amount of 1 to 10 parts by weight per 100 parts by weight of the phenolic resin.

好ましくは、前記靱性化剤は尿素であり、前記フェノール樹脂１００重量部当たり約５重量部の量で存在する。 Preferably, the toughening agent is urea and is present in an amount of about 5 parts by weight per 100 parts by weight of the phenolic resin.

Claims

A phenol resin, a surfactant, an acid catalyst, a blowing agent made of a hydrocarbon having 6 or less carbon atoms, and
(a) where n is 0 to 4, R is a C ₁ to C ₆ aliphatic chain, and R ¹ is H or alkyl, the following formula

Alkoxy alcohol represented by , or
(b) propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monopentyl ether, propylene glycol monohexyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, Dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopentyl ether, dipropylene glycol monohexyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monopropyl ether, tripropylene glycol an alkoxy alcohol selected from the group consisting of monobutyl ether and tripropylene glycol monopentyl ether;
A phenol foam formed by foaming and curing a phenolic resin foamable composition comprising:
A phenol foam having a closed cell content of 85% or more and a density of 10 kg/m ³ or more and 100 kg/m ³ or less.

The phenolic foam according to claim 1, wherein the phenolic resin has a water content ranging from 8 wt% to 16 wt%.

1 . The moisture content of the phenolic resin foamable composition is in the range of 7.5 wt % to 14 wt %, such as in the range of 8 wt % to 11 wt %, based on the total weight of the phenolic resin foamable composition. Or the phenol foam according to 2.

The phenolic foam according to any of claims 1 to 3, wherein the n is 0, 1 or 2, preferably the n is 0 or 1.

Said R ¹ is H or C 1 to C ₆ alkyl, such as methyl, ethyl, propyl, butyl, pentyl or hexyl, or an isomer thereof ; for example, said R ¹ _is methyl, ethyl, propyl, butyl. , pentyl or hexyl or an isomer thereof .

Said R is selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl and isomers thereof, for example said R is methyl, ethyl, propyl or butyl, preferably said R is butyl. , the phenol foam according to any one of claims 1 to 5 .

The alkoxy alcohol is present in an amount of 0.5 to 15 parts by weight per 100 parts by weight of the phenolic resin, for example in an amount of 0.5 to 12.5 parts by weight per 100 parts by weight of the phenolic resin; is present in an amount of 1 to 12 parts by weight per 100 parts by weight of said phenolic resin, for example in an amount of 1 to 10 parts by weight per 100 parts by weight of said phenolic resin . body.

The hydrocarbon having 6 or less carbon atoms is one or more compounds selected from the group consisting of butane, pentane, hexane, and isomers thereof; for example, the hydrocarbon having 6 or less carbon atoms is n-butane. 8. A phenolic foam according to any one of claims 1 to 7 , which is one or more compounds selected from the group consisting of , isobutane, cyclobutane, n-pentane, isopentane, cyclopentane and cyclohexane.

The phenol foaming agent according to any one of claims 1 to 8, wherein the blowing agent further comprises a halogenated hydrocarbon having 6 or less carbon atoms, for example, the halogenated hydrocarbon is propyl chloride, dichloroethane, or an isomer thereof. body.

The blowing agent further comprises a hydrofluoroolefin, such as 1-chloro-3,3,3-trifluoropropene, 1,3,3,3-tetrafluoropropene, 2,3,3 , 3-tetrafluoropropene, and 1,1,1,4,4,4-hexafluoro- 2 -butene.

11. The blowing agent is present in an amount of from 1 to 20 parts by weight per 100 parts by weight of the phenolic resin, such as from 5 to 15 parts by weight per 100 parts by weight of the phenolic resin. phenolic foam.

The phenolic resin has a molar ratio of phenol groups to aldehyde groups ranging from 1:1 to 1:3, and optionally, the molar ratio of phenol groups to aldehyde groups ranges from 1.5 to 2.3. There is something and
The phenol resin has a weight average molecular weight of 700 to 2000,
The phenolic resin has a number average molecular weight of 330 to 800, for example 350 to 700;
the acid catalyst is present in an amount of 5 to 25 parts by weight per 100 parts by weight of phenolic resin;
The acid catalyst comprises at least one of benzenesulfonic acid, para-toluenesulfonic acid, xylene sulfonic acid, naphthalenesulfonic acid, ethylbenzenesulfonic acid, and phenolsulfonic acid; optionally, the acid catalyst comprises para-toluenesulfonic acid and consisting of xylene sulfonic acid;
The phenolic resin foamable composition further comprises at least one of a plasticizer, an inorganic filler, a flame retardant, a toughening agent, and a combination thereof;
The surfactant is a castor oil-ethylene oxide adduct, and preferably more than 10 moles and less than 60 moles of ethylene oxide are added per mole of castor oil;
the surfactant is present in an amount of 1 to 6 parts by weight per 100 parts by weight of phenolic resin;
The phenolic resin foamable composition further comprises a plasticizer, the plasticizer being a polyester polyol which is a reaction product of a polybasic carboxylic acid and a polyhydric alcohol, and the polybasic carboxylic acid being a dibasic carboxylic acid, a tribasic carboxylic acid, a tetrabasic carboxylic acid, or a combination thereof; the polyhydric alcohol is a dihydric alcohol, a trihydric alcohol, a tetrahydric alcohol, a pentahydric alcohol, or a combination thereof; optionally, the polyester Polybasic carboxylic acids used to synthesize polyols include phthalic acid, isophthalic acid, terephthalic acid, naphthalene-2,3-dicarboxylic acid, naphthalene-1,4-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, It preferably consists of at least one of adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, cyclohexane-1,2-dicarboxylic acid, cyclohexane-1,3-dicarboxylic acid, and cyclohexane-1,4-dicarboxylic acid. The polybasic carboxylic acid used to synthesize the polyester polyol consists of one or more of phthalic acid, isophthalic acid, or terephthalic acid, and is optionally used to synthesize the polyester polyol. Polyhydric alcohols include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 1,2-cyclohexanedimethanol, Preferably, the polyhydric alcohol used to synthesize the polyester polyol is composed of at least one of 1,3-cyclohexanedimethanol and 1,4-cyclohexanedimethanol, diethylene glycol, propylene glycol, dipropylene glycol, or consisting of one or more of 1,4-butanediol;
The phenolic resin foamable composition further comprises a plasticizer, the plasticizer being present in an amount of 0.1 to 10 parts by weight per 100 parts by weight of phenolic resin, preferably the plasticizer is present in an amount of 0.1 to 10 parts by weight per 100 parts by weight of phenolic resin. present in an amount of 5 parts by weight;
The phenolic resin foamable composition further comprises an inorganic filler, and the inorganic filler is a metal hydroxide or metal carbonate having an ionic equilibrium solubility product of less than 1×10 −8 (Ksp) measured at 25 ° ^C. optionally said metal carbonate is calcium carbonate, optionally said calcium carbonate having an average particle size of 100 to 300 μm, preferably 150 to 250 μm;
The pH of the phenol foam is pH 4 or higher;
The phenolic resin foamable composition further comprises a flame retardant, the flame retardant comprising the group consisting of organic phosphorus compounds and inorganic phosphorus compounds, such as triethyl phosphate, diphenyl phosphite, diethyl ethyl phosphonate, ammonium polyphosphate, and red phosphorus. or aluminum trihydrate, zinc borate, or a halogenated flame retardant;
The phenolic resin foamable composition further comprises a toughening agent selected from the group consisting of urea, dicyandiamide, and melamine, and optionally the toughening agent is 1 to 10 parts by weight per 100 parts by weight of the phenolic resin. optionally, said toughening agent is urea, present in an amount of about 5 parts by weight per 100 parts by weight of said phenolic resin;
The phenolic foam has a facing on at least one side thereof, and optionally the facing is made of glass fiber nonwoven fabric, spunbond nonwoven fabric, aluminum foil, bonded nonwoven fabric, metal sheet, metal foil, plywood, calcium silicate board, gypsum board, kraft. comprising at least one of paper or other paper product and wood board, optionally said at least one facing is perforated, and optionally said facing is coated or impregnated with a formaldehyde scavenger and/or a flame retardant. optionally, the facing is impregnated with urea, sodium sulfite, carbohydrazide, aminoguanidine bicarbonate, arginine, oxalyl dihydrazide, adipic dihydrazide, or a combination thereof;
The density of the phenolic foam is 10 to 60 kg/m ³ , preferably the density of the phenolic foam is 20 to 45 kg/m ³ ,
The phenol foam has a compressive strength of 80 kPa to 220 kPa, for example 90 kPa to 180 kPa;
The phenolic foam according to any one of claims 1 to 11 , comprising any one or more of the following.

The phenolic foam has a thermal conductivity over time of 0 as measured at an average temperature of 10°C after heat aging at 70+/-2°C for 175+/-5 days according to the procedure specified in European Standard BS EN 13166:2012. .025W/m・K or less, for example, 0.022W/m・K or less, or 0.020W/m・K or less, or 0.018W/m・K or less, or 0.016W/m・K or less . , for example, the phenol foam has a thermal conductivity over time in the range of 0.025 W/m·K to 0.016 W/m·K, for example, in the range of 0.025 W/m·K to 0.017 W/m·K. The phenolic foam according to any one of claims 1 to 12 .

The viscosity of the phenolic foam containing the alkoxy alcohol and surfactant was measured using a Brookfield viscometer (model DV-II+Pro) equipped with a temperature-controlled water bath with spindle number S29 rotating at 20 rpm. 14. A temperature of 2500 to 7000 mPa·s at 25°C, for example 4000 to 6000 mPa·s at 25°C, as measured by maintaining the temperature at 25°C. Phenolic foam.

A method for producing a phenolic foam according to any one of claims 1 to 14 , comprising:
A phenol resin, a surfactant, an acid catalyst, a blowing agent made of a hydrocarbon having 6 or less carbon atoms, and
(a) where n is 0 to 4, R is a C ₁ to C ₆ aliphatic chain, and R ¹ is H or alkyl, the following formula

Alkoxy alcohol represented by, or
(b) propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monopentyl ether, propylene glycol monohexyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, Dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopentyl ether, dipropylene glycol monohexyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monopropyl ether, tripropylene glycol comprising the steps of foaming and curing a phenolic resin foamable composition comprising monobutyl ether and an alkoxy alcohol selected from the group consisting of tripropylene glycol monopentyl ether ;
The phenol foam has a closed cell content of 85% or more and a density of 10 kg/m ³ or more and 100 kg/m ³ or less.