JP2019199489A - Polyurethane foam - Google Patents

Abstract

To provide a polyurethane foam that is foamed in a good state and has an excellent heat insulation property.SOLUTION: The polyurethane foam according to the present invention is a polyurethane foam having a plurality of cells, and in which the cells contain isopropyl chloride and an unsaturated organic halogen compound.SELECTED DRAWING: None

Description

  The present invention relates to a polyurethane foam having a plurality of bubbles.

  Polyurethane foam is used as a heat insulating material or the like. When the thermal conductivity of the polyurethane foam is low, it becomes difficult for heat to be transmitted in the polyurethane foam. Heat insulation can be improved by using a polyurethane foam having a low thermal conductivity as a heat insulating material.

  The thermal conductivity of the polyurethane foam includes (1) the thermal conductivity of the polyurethane constituting the polyurethane foam, (2) the thermal conductivity of the blowing agent gas component present in the polyurethane foam, and (3) the thermal conductivity due to radiation. It depends on the rate. Among these, in particular, it is known that (2) the thermal conductivity of the foaming agent gas component present in the polyurethane foam contributes to the thermal conductivity of the polyurethane foam.

  Conventionally, studies have been widely made to lower the thermal conductivity of polyurethane constituting the polyurethane foam or to lower the thermal conductivity of the blowing agent gas component present in the polyurethane foam.

  Conventionally, hydrofluorocarbon (HFC) used as a foaming agent has a high global warming potential (GWP), and therefore reduction in use is required.

  Patent Document 1 below discloses a rigid polyurethane foam obtained by mixing and reacting raw materials including a polyol, a polyisocyanate, a blowing agent and a catalyst. The polyol includes a polyester polyol having an aromatic concentration of 17 to 35 wt% and a non-amine polyether polyol and / or an aromatic amine polyether polyol. The polyisocyanate is a mixture mixed so that MDI (diphenylmethane diisocyanate) / TDI (tolylene diisocyanate) = 4/6 to 9/1 by weight ratio. The foaming agent contains a halogenated olefin.

  Patent Document 2 below discloses a rigid polyurethane foam obtained by reacting a catalyst, a non-silicon-type cell stabilizer, chloropropane, isocyanate, and an active hydrogen-containing compound.

WO2016 / 136769A1 JP-A-2-283737

  In Patent Document 1, a halogenated olefin is used as a foaming agent. Patent Document 1 does not describe any use of isopropyl chloride and an unsaturated organic halogen compound in combination as a foaming agent. When a halogenated olefin is simply used as a foaming agent, the bubbles of the resulting polyurethane foam may become coarse, and the heat insulating property may be lowered.

  On page 3 of the specification of Patent Document 2, it is described that when chloropropane is used as a foaming agent, the polyurethane foam may shrink. When the polyurethane foam shrinks, the foaming agent gas component is released from the polyurethane foam, and the thermal conductivity may increase. In patent document 2, in order to suppress shrinkage | contraction of a polyurethane foam, the non-silicon type cell stabilizer (foam stabilizer) which has a specific structure is used, or water is further used as a foaming agent. However, the non-silicon type foam stabilizer having the specific structure is difficult to obtain or expensive. Further, when water is further used as the foaming agent, carbon dioxide is generated as the foaming agent gas. Since the thermal conductivity of carbon dioxide is relatively high, the thermal conductivity of the resulting polyurethane foam is also high, and as a result, the heat insulating property may be lowered.

  An object of the present invention is to provide a polyurethane foam having a good foamed state and excellent heat insulation.

  According to a wide aspect of the present invention, there is provided a polyurethane foam having a plurality of bubbles, the polyurethane foam containing isopropyl chloride and an unsaturated organic halogen compound in the bubbles.

  In a specific aspect of the polyurethane foam according to the present invention, the unsaturated organic halogen compound is hydrochlorofluoroolefin or hydrofluoroolefin.

  In a specific aspect of the polyurethane foam according to the present invention, the unsaturated organic halogen compound is 1-chloro-3,3,3-trifluoropropene or 1,1,1,4,4,4-hexa. Fluoro-2-butene.

  On the specific situation with the polyurethane foam concerning this invention, content of the said isopropyl chloride is 0.5 to 5 weight% in 100 weight% of polyurethane foams.

  In a specific aspect of the polyurethane foam according to the present invention, the unsaturated organic halogen compound is an unsaturated organic fluorine compound, and the content of the unsaturated organic fluorine compound is 1 in 100% by weight of the polyurethane foam. % By weight or more and 8% by weight or less.

  In a specific aspect of the polyurethane foam according to the present invention, the closed cell ratio is 85% or more.

  In a specific aspect of the polyurethane foam according to the present invention, the thermal conductivity at 25 ° C. is 0.0190 W / m · K or less.

  The polyurethane foam according to the present invention is a polyurethane foam having a plurality of bubbles, and since the bubbles contain isopropyl chloride and an unsaturated organic halogen compound, the foamed state is good and the heat insulating property is high. Excellent.

  Hereinafter, the present invention will be described in detail.

  The polyurethane foam according to the present invention is a polyurethane foam having a plurality of bubbles. The polyurethane foam according to the present invention contains isopropyl chloride and an unsaturated organic halogen compound in the bubbles.

  Since the polyurethane foam according to the present invention has the above-described configuration, the foamed state is good and the heat insulating property is excellent. In the polyurethane foam according to the present invention, the closed cell ratio can be increased. In the polyurethane foam according to the present invention, the thermal conductivity can be lowered.

  The said bubble means the internal space enclosed by the wall surface in a polyurethane foam. The polyurethane foam according to the present invention contains isopropyl chloride and an unsaturated organic halogen compound in the bubbles, that is, in the internal space. Further, the bubbles may contain a component different from the isopropyl chloride and the unsaturated organic halogen compound. Moreover, the said isopropyl chloride and the said unsaturated organic halogen compound may be contained in the part except the said bubble in the said polyurethane foam, and may be contained in the resin part.

  The polyurethane foam according to the present invention can be obtained by foaming a curable composition containing a polyol compound, an isocyanate compound, and a foaming agent. In the curable composition, the foaming agent contains isopropyl chloride and an unsaturated organic halogen compound. That is, the said curable composition contains a polyol compound, an isocyanate compound, and a foaming agent, and the said foaming agent contains isopropyl chloride and an unsaturated organic halogen compound. The polyurethane foam obtained by foaming the curable composition has a plurality of bubbles.

  In addition, a urethane resin (polyurethane) can be obtained by reacting the polyol compound and the isocyanate compound in the presence of a urethanization catalyst.

  The said curable composition can be made to foam favorably, and can obtain the polyurethane foam excellent in heat insulation. The said curable composition can be made to foam favorably so that a closed cell rate may become high. In the said curable composition, the heat conductivity of the polyurethane foam formed with the curable composition can be made low.

  Hereinafter, details of components contained in the polyurethane foam and the curable composition will be described.

[Polyol compound]
Examples of the polyol compound contained in the curable composition include polylactone polyol, polycarbonate polyol, aromatic polyol, alicyclic polyol, aliphatic polyol, polyester polyol, and polyether polyol. The polyol compound may be a polymer polyol. As for the said polyol compound, only 1 type may be used and 2 or more types may be used together.

  Examples of the polylactone polyol include polypropiolactone glycol, polycaprolactone glycol, and polyvalerolactone glycol.

  Examples of the polycarbonate polyol include a dealcoholization reaction product of a hydroxyl group-containing compound and a carbonate compound. Examples of the hydroxyl group-containing compound include ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, octanediol, and nonanediol. Examples of the carbonate compound include diethylene carbonate and dipropylene carbonate.

  Examples of the aromatic polyol include bisphenol A, bisphenol F, phenol novolac, and cresol novolac.

  Examples of the alicyclic polyol include cyclohexanediol, methylcyclohexanediol, isophoronediol, dicyclohexylmethanediol, and dimethyldicyclohexylmethanediol.

  Examples of the aliphatic polyol include ethylene glycol, propylene glycol, butanediol, pentanediol, and hexanediol.

  Examples of the polyester polyol include a dehydration condensation product of a polybasic acid and a polyhydric alcohol, a ring-opening polymerization product of a lactone, a condensation product of a hydroxycarboxylic acid and a polyhydric alcohol, and the like. Examples of the polybasic acid include adipic acid, azelaic acid, sebacic acid, terephthalic acid, isophthalic acid, and succinic acid. Examples of the polyhydric alcohol include bisphenol A, ethylene glycol, propylene glycol, butanediol, diethylene glycol, hexane glycol, and neopentyl glycol. Examples of the lactone include ε-caprolactone and α-methyl-ε-caprolactone. Examples of the hydroxycarboxylic acid include castor oil and a reaction product of castor oil and ethylene glycol.

  Examples of the polyether polyol include a ring-opening polymer of an active hydrogen compound having 2 or more active hydrogen atoms and an alkylene oxide. Examples of the alkylene oxide include ethylene oxide, propylene oxide, and tetrahydrofuran. The molecular weight of the active hydrogen compound is preferably small. Examples of the active hydrogen compounds include diol compounds such as bisphenol A, ethylene glycol, propylene glycol, butylene glycol, and 1,6-hexanediol; triol compounds such as glycerin and trimethylolpropane; amines such as ethylenediamine and butylenediamine. Compounds and the like.

  Examples of the polymer polyol include graft polymers obtained by graft polymerization of unsaturated organic compounds to polyol compounds, polybutadiene polyols, modified polyols of polyhydric alcohols, and hydrogenated products thereof.

  In the graft polymer, examples of the polyol compound include aromatic polyols, alicyclic polyols, aliphatic polyols, polyester polyols, and polyether polyols. Examples of the unsaturated organic compound include acrylonitrile, styrene, and methyl (meth) acrylate.

  Examples of the modified polyol of the polyhydric alcohol include a reaction modified product of a polyhydric alcohol and an alkylene oxide. Examples of the polyhydric alcohol include trihydric alcohols such as glycerin and trimethylolpropane; pentaerythritol, sorbitol, mannitol, sorbitan, diglycerin, dipentaerythritol, sucrose, glucose, mannose, fructose, methyl glucoside, and derivatives thereof. 4 to 9 alcohols: phenol, phloroglucin, cresol, pyrogallol, catechol, hydroquinone, bisphenol A, bisphenol F, bisphenol S, 1-hydroxynaphthalene, 1,3,6,8-tetrahydroxynaphthalene, anthrol Phenol compounds such as 1,4,5,8-tetrahydroxyanthracene and 1-hydroxypyrene; polybutadiene polyol; castor oil polyol; Kill (meth) acrylate (co) polymers; polyfunctional (e.g. two functional groups to 100) polyol such as polyvinyl alcohol; condensates of phenol and formaldehyde (novolac), and the like. Examples of the alkylene oxide include alkylene oxides having 2 to 6 carbon atoms. Specific examples of the alkylene oxide include ethylene oxide, 1,2-propylene oxide, 1,3-propyloxide, 1,2-butylene oxide, 1,4-butylene oxide, and the like. From the viewpoint of improving properties and reactivity, the alkylene oxide is preferably 1,2-propylene oxide, ethylene oxide or 1,2-butylene oxide, and is 1,2-propylene oxide or ethylene oxide. It is more preferable. As for the said alkylene oxide, only 1 type may be used and 2 or more types may be used together.

  When two or more alkylene oxides are used, the form of addition may be block addition, random addition, or both block addition and random addition.

  From the viewpoint of increasing the effect of reducing the total calorific value during combustion, the polyol compound is preferably a polyester polyol or a polyether polyol, more preferably a polyester polyol, and a molecular weight of 300 to 500. More preferably, it is a certain polyester polyol.

  From the viewpoint of increasing the mechanical strength of the polyurethane foam, the polyol compound preferably includes both a polyester polyol and a polyether polyol, and includes both the polyester polyol and a polyether polyol having four or more hydroxyl groups. More preferably.

  When the polyol compound contains both a polyester polyol and a polyether polyol, the weight ratio of the polyester polyol content to the polyether polyol content (polyester polyol content / polyether polyol content) is: , Preferably 1 or more, preferably 20 or less, more preferably 10 or less.

[Isocyanate compound]
As an isocyanate compound contained in the said curable composition, aromatic polyisocyanate, alicyclic polyisocyanate, aliphatic polyisocyanate, etc. are mentioned. From the viewpoint of efficiently proceeding the curing reaction, the isocyanate compound is preferably a polyisocyanate compound. As for the said isocyanate compound, only 1 type may be used and 2 or more types may be used together.

  Examples of the aromatic polyisocyanate include phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, dimethyldiphenylmethane diisocyanate, triphenylmethane triisocyanate, naphthalene diisocyanate, and polymethylene polyphenyl polyisocyanate.

  Examples of the alicyclic polyisocyanate include cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and dimethyldicyclohexylmethane diisocyanate.

  Examples of the aliphatic polyisocyanate include methylene diisocyanate, ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, and hexamethylene diisocyanate.

  The isocyanate compound is preferably polymethylene polyphenyl polyisocyanate because it is easily available and is convenient.

  The polyol compound and the isocyanate compound can be used in an appropriate amount so as to efficiently form a urethane bond. From the viewpoint of increasing the reaction efficiency, the content of the isocyanate compound is preferably 100 parts by weight or more, more preferably 120 parts by weight or more, preferably 450 parts by weight or less, more preferably 100 parts by weight of the polyol compound. Is 400 parts by weight or less.

[Foaming agent]
A foaming agent is a substance that generates a gas upon decomposition or a substance that itself becomes a gas.

  The curable composition contains isopropyl chloride and an unsaturated organic halogen compound as a foaming agent. By using isopropyl chloride and an unsaturated organic halogen compound as a foaming agent, isopropyl chloride and an unsaturated organic halogen compound can be contained in the bubbles of the resulting polyurethane foam.

  By using both isopropyl chloride and an unsaturated organic halogen compound as a foaming agent, the curable composition can be foamed well, and a polyurethane foam having a high closed cell ratio and a small cell diameter can be obtained. Can do.

  The thermal conductivity of the isopropyl chloride at 25 ° C. is 0.012 W / m · K. The thermal conductivity of the isopropyl chloride is smaller than that of other blowing agents. For this reason, the polyurethane foam excellent in heat insulation can be obtained by using both isopropyl chloride and an unsaturated organic halogen compound as a foaming agent.

  In the unsaturated organic halogen compound, all of the hydrogen atoms may be substituted with halogen atoms, or some of the hydrogen atoms may be substituted with halogen atoms.

  Examples of the unsaturated organic halogen compounds include unsaturated organic chlorine compounds, unsaturated organic fluorine compounds, unsaturated organic bromine compounds, and unsaturated organic iodine compounds. As for the said unsaturated organic halogen compound, only 1 type may be used and 2 or more types may be used together.

  Examples of the unsaturated organic fluorine compound include hydrofluoroolefin. Examples of the hydrofluoroolefin include 2,3,3,3-tetrafluoropropene (HFO-1234yf), 1,3,3,3-tetrafluoropropene (HFO-1234ze) (E and Z isomers), and 1 1,1,4,4,4-hexafluoro-2-butene (HFO1336mzz) (E and Z isomers) and the like.

  Further, examples of the unsaturated organic fluorine compound include compounds having a chlorine atom, a fluorine atom and a double bond. Examples of the compound having a chlorine atom, a fluorine atom and a double bond include 1,2-dichloro-1,2-difluoroethene (E and Z isomers), hydrochlorofluoroolefin and the like. Examples of the hydrochlorofluoroolefin include 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd) (E and Z isomers), 1-chloro-2,3,3-trifluoropropene (HCFO-). 1233yd) (E and Z isomers), 1- (4) chloro-1,3,3-trifluoropropene (HCFO-1233zb) (E and Z isomers), 2-chloro-1,3,3-tri Fluoropropene (HCFO-1233xe) (E and Z isomers), 2-chloro-2,2,3-trifluoropropene (HCFO-1233xc), 2-chloro-3,3,3-trifluoropropene (HCFO- 1233xf), 3-chloro-1,2,3-trifluoropropene (HCFO-1233ye) (E and Z isomers), 3-chloro-1,1, -Trifluoropropene (HCFO-1233yc), 3,3-dichloro-3-fluoropropene, 1,2-dichloro-3,3,3-trifluoropropene (HCFO-1223xd) (E and Z isomers), 2 -Chloro-1,1,1,4,4,4-hexafluoro-2-butene (E and Z isomers) and 2-chloro-1,1,1,3,4,4,4-heptafluoro -2-butene (E and Z isomers) and the like.

  From the viewpoint of further improving the foamability at the time of forming the polyurethane foam and further improving the heat insulation of the polyurethane foam, the unsaturated organic halogen compound is preferably an unsaturated organic fluorine compound. More preferred is a fluoroolefin or a hydrofluoroolefin.

  From the viewpoint of further improving the foamability at the time of forming the polyurethane foam and further improving the heat insulating property of the polyurethane foam, the unsaturated organic halogen compound is 1-chloro-3,3,3-trimethyl. Preferred is fluoropropene or 1,1,1,4,4,4-hexafluoro-2-butene.

  Weight ratio of content of unsaturated organic halogen compound in foaming agent to content of isopropyl chloride in foaming agent (content of unsaturated organic halogen compound in foaming agent / isopropyl chloride in foaming agent) Is preferably 1 or more, more preferably 1.3 or more, preferably 50 or less, more preferably 20 or less. When the weight ratio (content of unsaturated organic halogen compound in foaming agent / content of isopropyl chloride in foaming agent) is not less than the above lower limit and not more than the above upper limit, the foamability at the time of forming the polyurethane foam is further improved. It is possible to further improve the heat insulating property of the polyurethane foam.

  The content of the isopropyl chloride is preferably 0.1 parts by weight or more, more preferably 0.5 parts by weight or more, and further preferably 1 part by weight with respect to a total of 100 parts by weight of the polyol compound and the isocyanate compound. That's it. The content of the isopropyl chloride is preferably 30 parts by weight or less, more preferably 20 parts by weight or less, and still more preferably 15 parts by weight or less with respect to 100 parts by weight of the total of the polyol compound and the isocyanate compound. When the content of the isopropyl chloride is not less than the above lower limit and not more than the above upper limit, the foamability at the time of forming the polyurethane foam can be further improved, and the heat insulation of the polyurethane foam can be further enhanced.

  The content of the unsaturated organic halogen compound is preferably 0.1 parts by weight or more, more preferably 0.5 parts by weight or more, and still more preferably 100 parts by weight in total of the polyol compound and the isocyanate compound. 0.7 parts by weight or more, particularly preferably 1 part by weight or more. The content of the unsaturated organic halogen compound is preferably 50 parts by weight or less, more preferably 40 parts by weight or less, still more preferably 30 parts by weight or less with respect to 100 parts by weight of the total of the polyol compound and the isocyanate compound. The amount is particularly preferably 25 parts by weight or less. When the content of the unsaturated organic halogen compound is not less than the above lower limit and not more than the above upper limit, the foamability at the time of forming the polyurethane foam can be further improved, and the heat insulation of the polyurethane foam can be further enhanced.

  The total of the content of the isopropyl chloride and the content of the unsaturated organic halogen compound is preferably 0.1 parts by weight or more, more preferably, with respect to 100 parts by weight of the total of the polyol compound and the isocyanate compound. 0.5 parts by weight or more, more preferably 0.7 parts by weight or more, particularly preferably 1 part by weight or more. The total of the content of the isopropyl chloride and the content of the unsaturated organic halogen compound is preferably 50 parts by weight or less, more preferably 40 parts by weight with respect to 100 parts by weight of the total of the polyol compound and the isocyanate compound. Parts or less, more preferably 30 parts by weight or less, particularly preferably 25 parts by weight or less. When the total of the content of the isopropyl chloride and the content of the unsaturated organic halogen compound is equal to or more than the lower limit, foaming is promoted and a polyurethane foam having a low density is favorably formed. When the total of the content of the isopropyl chloride and the content of the unsaturated organic halogen compound is not more than the above upper limit, the inhibition of foaming can be suppressed. When the total of the content of the isopropyl chloride and the content of the unsaturated organic halogen compound is not less than the above lower limit and not more than the above upper limit, the heat insulating property of the polyurethane foam can be further enhanced.

  Unless the effect of this invention is inhibited, the said foaming agent may contain foaming agents other than the said isopropyl chloride and the said unsaturated organic halogen compound. Examples of the blowing agent other than the isopropyl chloride and the unsaturated organic halogen compound include water and saturated organic halogen compounds other than isopropyl chloride. As for saturated organic halogen compounds other than the said isopropyl chloride, only 1 type may be used and 2 or more types may be used together. Saturated organic halogen compounds other than the water and the isopropyl chloride may not be used.

  In the saturated organic halogen compound, all of the hydrogen atoms may be substituted with halogen atoms, or some of the hydrogen atoms may be substituted with halogen atoms.

  Examples of the saturated organic halogen compound include saturated organic chlorine compounds other than isopropyl chloride, saturated organic fluorine compounds, saturated organic bromine compounds, and saturated organic iodine compounds. From the viewpoint of improving the foamability at the time of forming the polyurethane foam and improving the heat insulation of the polyurethane foam, the saturated organic halogen compound may be a saturated organic chlorine compound other than isopropyl chloride, or a saturated organic fluorine compound. preferable.

  Examples of saturated organic chlorine compounds other than the isopropyl chloride include dichloroethane, isopropyl chloride, butyl chloride, isobutyl chloride, pentyl chloride, and isopentyl chloride.

  Examples of the saturated organic fluorine compound include hydrofluorocarbon. Examples of the hydrofluorocarbon include difluoromethane (HFC32), 1,1,1,2,2-pentafluoroethane (HFC125), 1,1,1-trifluoroethane (HFC143a), 1,1,2,2- Tetrafluoroethane (HFC134), 1,1,1,2-tetrafluoroethane (HFC134a), 1,1-difluoroethane (HFC152a), 1,1,1,2,3,3,3-heptafluoropropane (HFC227ea) ), 1,1,1,3,3-pentafluoropropane (HFC245fa), 1,1,1,3,3-pentafluofane (HFC365mfc) and 1,1,1,2,2,3,4 , 5,5,5-decafluoropentane (HFC4310mee) and the like.

  From the viewpoint of effectively demonstrating the effects of the present invention, the water content is preferably 1 part by weight or less, more preferably 0.001 part by weight with respect to a total of 100 parts by weight of the polyol compound and the isocyanate compound. 5 parts by weight or less. From the viewpoint of more effectively exerting the effects of the present invention, it is most preferable that the curable composition does not contain the water.

  From the viewpoint of effectively exhibiting the effects of the present invention, the content of the saturated organic halogen compound other than isopropyl chloride is preferably 1 part by weight with respect to 100 parts by weight of the total of the polyol compound and the isocyanate compound. Below, more preferably 0.5 parts by weight or less. From the viewpoint of more effectively exerting the effects of the present invention, it is most preferable that the curable composition does not contain the saturated organic halogen compound other than isopropyl chloride.

[catalyst]
The catalyst accelerates the polyurethane reaction. The curable composition preferably contains a catalyst. Examples of the catalyst include a urethanization catalyst and a trimerization catalyst.

  The urethanization catalyst promotes the formation of urethane bonds by promoting the reaction between the hydroxyl group of the polyol compound and the isocyanate group of the isocyanate compound.

  Examples of the urethanization catalyst include amine catalysts. Examples of the amine catalyst include triethylamine, N-methylmorpholine bis (2-dimethylaminoethyl) ether, N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine, N, N, N′-trimethylamino. Examples include ethyl-ethanolamine, bis (2-dimethylaminoethyl) ether, N-methyl, N′-dimethylaminoethylpiperazine, and imidazole compounds in which the secondary amine functional group in the imidazole ring is substituted with a cyanoethyl group. It is done. As for the said urethanization catalyst, only 1 type may be used and 2 or more types may be used together.

  The urethanization catalyst can be used in an appropriate content so that the polyol compound and the isocyanate compound react well. The content of the urethanization catalyst is preferably 0.01 parts by weight or more, more preferably 0.05 parts by weight or more, preferably 10 parts by weight with respect to a total of 100 parts by weight of the polyol compound and the isocyanate compound. The amount is more preferably 8 parts by weight or less, still more preferably 6 parts by weight or less, and particularly preferably 5 parts by weight or less. When the content of the urethanization catalyst is not less than the above lower limit, the urethane bond effectively proceeds. When the content of the urethanization catalyst is not more than the above upper limit, an appropriate foaming rate can be maintained, and the moldability tends to be good.

  The trimerization catalyst promotes the trimerization reaction of the isocyanate group of the isocyanate compound and promotes the formation of an isocyanurate ring. Further, the trimerization catalyst can suppress the expansion of the polyurethane foam during combustion, and can increase the mechanical strength of the polyurethane foam.

  Examples of the trimerization catalyst include aromatic compounds, alkali metal salts of carboxylic acids, quaternary ammonium salts of carboxylic acids, and quaternary ammonium salts / ethylene glycol mixtures. Examples of the aromatic compound include tris (dimethylaminomethyl) phenol, 2,4-bis (dimethylaminomethyl) phenol, and 2,4,6-tris (dialkylaminoalkyl) hexahydro-S-triazine. Examples of the alkali metal salt of the carboxylic acid include potassium acetate and potassium 2-ethylhexanoate. As for the said trimerization catalyst, only 1 type may be used and 2 or more types may be used together.

  The trimerization catalyst can be used in an appropriate content so that the trimerization reaction is favorably promoted. The content of the trimerization catalyst is preferably 0.01 parts by weight or more, more preferably 1 part by weight or more, still more preferably 3 parts by weight or more, with respect to 100 parts by weight of the total of the polyol compound and the isocyanate compound. The amount is preferably 10 parts by weight or less. When the content of the trimerization catalyst is not less than the above lower limit, the expansion of the polyurethane foam is easily suppressed during the formation of the polyurethane foam. When the content of the trimerization catalyst is not more than the above upper limit, the trimerization of isocyanate groups is hardly inhibited.

[Filler]
The curable composition may contain a filler. The filler is well dispersed on the surface of the cell wall in the polyurethane foam. As for the said filler, only 1 type may be used and 2 or more types may be used together.

  From the viewpoint of maintaining the thermal conductivity of the polyurethane foam low over a long period of time and maintaining the heat insulation property high over a long period of time, and from the viewpoint of increasing the mechanical strength of the polyurethane foam, the curable composition preferably contains a filler. .

  The filler contained in the curable composition includes phosphate, sediment, ash, metal oxide, metal hydroxide, carbonate, mineral, sulfate, magnetic powder, silicate, nitride, carbide, boron. And fluorides, fibrous materials and the like. Specifically, phosphates such as inorganic phosphorus compounds; deposits such as diatomaceous earth; ash such as fly ash; metals such as silica, alumina, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, and antimony oxide Oxides: Metal hydroxides such as calcium hydroxide, magnesium hydroxide, aluminum hydroxide; carbonates such as basic magnesium carbonate, calcium carbonate, magnesium carbonate, zinc carbonate, barium carbonate; dosonite, hydrotalcite, silicon carbide Minerals such as calcium mineral, barium sulfate and magnesium sulfate; magnetic powders such as calcium silicate, potassium silicate, zinc borate and ferrite; silicates such as glass beads and silica balloons; Nitride such as aluminum nitride, boron nitride, silicon nitride Carbides such as carbon black, graphite, hollow carbon particles charcoal powder; titanium oxides such as potassium titanate and lead zirconate titanate; borides such as aluminum borate; sulfides such as molybdenum sulfide; carbon fibers and gypsum fibers And fibrous materials such as glass fiber, stainless steel fiber, slag fiber, silica alumina fiber, alumina fiber, silica fiber, and zirconia fiber.

  The filler is preferably an inorganic mineral, more preferably mica or fly ash because it is inexpensive and easily available in large quantities and can form a good polyurethane foam.

  From the viewpoint of keeping the thermal conductivity of the polyurethane foam low over a long period of time, the average diameter of the filler is preferably 0.1 μm or more, preferably 30 μm or less, more preferably 10 μm or less, and even more preferably 5 μm or less. When the average diameter of the filler is not less than the above lower limit, the filler hardly aggregates and the filler is well dispersed. When the average diameter of the filler is less than or equal to the above upper limit, the filler is difficult to break through the cell when the polyurethane foam is formed, and the polyurethane foam is in a more favorable foamed state. When the filler is difficult to break through the cell, the foaming agent gas component is difficult to diffuse, and the thermal conductivity of the polyurethane foam is effectively lowered. When the polyurethane foam is in a well-foamed state, the closed cell ratio of the polyurethane foam tends to be high.

  The average diameter of the filler is an average diameter measured on a number basis, and is a median diameter (D50) value of 50%. The average diameter can be measured by a laser diffraction / scattering method, an image analysis method, a Coulter method, a centrifugal sedimentation method, or the like. Measurement by laser diffraction / scattering method is preferred.

  From the viewpoint of keeping the thermal conductivity of the polyurethane foam low over a long period of time, the average aspect ratio of the filler is preferably 5 or more, and preferably less than 40. When the average aspect ratio is not less than the above lower limit, the foaming agent gas component is easily held in the cell, and the thermal conductivity of the polyurethane foam can be kept low. When the average aspect ratio is less than the above upper limit, the filler is unlikely to break through the cells when the polyurethane foam is formed, and the polyurethane foam is in a more favorable foamed state.

  The aspect ratio is the ratio of the average diameter of the filler to the average thickness of the filler (average diameter of filler / average thickness of filler). The aspect ratio can be measured by a water surface particle film method or the like. The average aspect ratio is an average of the aspect ratios of a plurality of fillers.

  Examples of the method for obtaining the aspect ratio from the water surface particle film method include the following examples.

  After hydrophobizing a plurality of fillers, the weight is measured, and the filler volume is calculated from the known filler density. Float the filler in water and determine the surface area of the filler. The average thickness is calculated from the volume and the surface area. When the weight of the hydrophobized filler is w, the density is d, the volume is V, the area is S, and the average thickness is l, the average thickness of the filler can be calculated by the following formula.

  l = V / S = w / (d · S)

  The content of the filler is preferably 1 part by weight or more, more preferably 2 parts by weight or more, still more preferably 3 parts by weight or more, preferably 13 parts by weight based on 100 parts by weight of the total of the polyol compound and the isocyanate compound. The amount is not more than parts by weight, more preferably not more than 10 parts by weight, still more preferably not more than 8 parts by weight. When the content of the filler is not less than the above lower limit, the foaming agent gas component is difficult to diffuse, and the thermal conductivity of the polyurethane foam is effectively lowered. When the content of the filler is less than or equal to the above upper limit, the filler is difficult to break through the cells when the polyurethane foam is formed, and the polyurethane foam is in a more favorable foamed state. When the content of the filler is not less than the above lower limit and not more than the above upper limit, the cell average diameter of closed cells can be made relatively small, and the thermal conductivity of the polyurethane foam can be kept low over a long period of time.

[Foam stabilizer]
The curable composition preferably contains a foam stabilizer. As for the said foam stabilizer, only 1 type may be used and 2 or more types may be used together.

  Examples of the foam stabilizer include polyoxyalkylene foam stabilizer and silicone foam stabilizer. Examples of the polyoxyalkylene foam stabilizer include polyoxyalkylene alkyl ethers. Examples of the silicone foam stabilizer include organopolysiloxane. The foam stabilizer is preferably a surfactant.

  The content of the foam stabilizer can be used at an appropriate content so that bubbles are stably and satisfactorily formed. From the viewpoint of forming air bubbles stably and satisfactorily, the content of the foam stabilizer is preferably 0.01 parts by weight or more, preferably 15 parts per 100 parts by weight in total of the polyol compound and the isocyanate compound. It is 8 parts by weight or less, more preferably 8 parts by weight or less.

[Other ingredients]
The said curable composition may contain other components, such as a flame retardant, in addition to the component mentioned above, unless the effect of this invention is inhibited. As for said other component, only 1 type may be used and 2 or more types may be used together.

  Examples of the flame retardant include nitrogen-containing non-halogen flame retardant, red phosphorus, phosphate ester, phosphate-containing flame retardant, bromine-containing flame retardant, boron-containing flame retardant, antimony-containing flame retardant, and metal hydroxide. It is done.

(Other details of curable composition)
The said curable composition mixes the said polyol compound, the said isocyanate compound, the said foaming agent, and other components, such as a catalyst, a filler, a foam stabilizer, and a flame retardant mix | blended as needed. Can be prepared. The mixing method of each component is not specifically limited. A plurality of liquids containing one or a plurality of components may be prepared, and a plurality of liquids may be mixed to obtain a curable composition. The mixing of the plurality of liquids may be performed at the time of forming the polyurethane foam. A curable composition may be obtained during the formation of the polyurethane foam. A curable composition may be obtained by preparing a first liquid containing the isocyanate compound and a second liquid containing the polyol compound and the foaming agent, and mixing these liquids. The filler, the catalyst, the flame retardant, and the foam stabilizer may be added to the first liquid, may be added to the second liquid, the first liquid, and the first liquid, respectively. You may add to both of 2 liquids.

  From the viewpoint of efficiently allowing urethane bonding to proceed at an appropriate time, the urethanization catalyst is preferably added to the second liquid. From the viewpoint of effectively increasing the flame retardancy, the flame retardant is preferably added to the second liquid.

(Polyurethane foam)
The polyurethane foam according to the present invention is a foam obtained by foaming the curable composition. The polyurethane foam according to the present invention has a plurality of bubbles. The polyurethane foam according to the present invention contains isopropyl chloride and an unsaturated organic halogen compound in the bubbles. The bubbles include closed cells and bubbles other than closed cells.

  The polyurethane foam according to the present invention can be formed by a known method using the curable composition.

  For example, a polyurethane foam can be formed by heating and curing and curing the curable composition at 60 to 70 ° C.

  From the viewpoint of further reducing the thermal conductivity of the polyurethane foam and further increasing the heat insulation, it is preferable that the polyurethane foam has a high closed cell ratio. The closed cell ratio is a ratio of the independent bubbles in the cells (bubbles) of the polyurethane foam. The closed cell ratio can be measured by JIS K7138 (pressure change method).

  From the viewpoint of further lowering the thermal conductivity of the polyurethane foam and further improving the heat insulating property, the closed cell ratio of the polyurethane foam is preferably 80% or more, more preferably 85% or more, still more preferably. Is 90% or more.

  The thermal conductivity of the polyurethane foam at 25 ° C. is preferably 0.0200 W / m · K or less, more preferably 0.0190 W / m · K or less, and still more preferably 0.0185 W / m · K or less. When the thermal conductivity is less than or equal to the above upper limit, the heat insulation is considerably excellent.

  The thermal conductivity can be measured according to JIS A9521: 2014.

  In 100% by weight of the polyurethane foam, the content of the isopropyl chloride is preferably 0.1% by weight or more, more preferably 0.5% by weight or more, still more preferably 1% by weight or more, particularly preferably 2% by weight or more, Preferably it is 15 weight% or less, More preferably, it is 5 weight% or less. When the content of the isopropyl chloride is not less than the above lower limit and not more than the above upper limit, the thermal conductivity of the polyurethane foam can be further lowered and the heat insulation can be further enhanced.

  In the case where the unsaturated organic halogen compound is the unsaturated organic fluorine compound, the content of the unsaturated organic fluorine compound is preferably 0.5% by weight or more, more preferably 1% in 100% by weight of the polyurethane foam. % By weight or more, preferably 15% by weight or less, more preferably 8% by weight or less, and further preferably 5% by weight or less. When the content of the unsaturated organic fluorine compound is not less than the above lower limit and not more than the above upper limit, the thermal conductivity of the polyurethane foam can be further lowered and the heat insulation can be further enhanced.

  The content of the isopropyl chloride and the content of the unsaturated organic fluorine compound in 100% by weight of the polyurethane foam can be measured, for example, as follows.

  The polyurethane foam is cut out to obtain a polyurethane foam sample. The obtained polyurethane foam sample is immersed in tetrahydrofuran (THF) and pulverized using a homogenizer to extract gas components contained in the polyurethane foam to obtain an extract.

  The standard gas for the blowing agent and the resulting extract are analyzed using a gas chromatograph mass spectrometer (GC / MS). The retention time and mass spectrum obtained by measuring the standard gas of the foaming agent are compared with the retention time and mass spectrum obtained by measuring the above extract, and the gas components contained in the polyurethane foam are identified. .

  From the obtained detection area area and detection sensitivity, and the weight of the polyurethane foam sample, the content of the isopropyl chloride and the content of the unsaturated organic fluorine compound contained in the polyurethane foam are quantified. In addition, the said extract may be filtered.

  The GC / MS measurement conditions can be set as follows, for example.

Column used: DB-1 (manufactured by Agilent Technologies), length 30 m, inner diameter 0.25 mm, film thickness 1 μm
Column temperature: Hold at 40 ° C. for 10 minutes, then hold at 100 ° C. for 20 minutes, and then hold at 250 ° C. for 3 minutes Inlet temperature: 200 ° C.
Carrier gas: He, flow rate 1.0 mL / min Split ratio: 20: 1

(Example)
Hereinafter, the present invention will be specifically described by giving examples and comparative examples. The present invention is not limited to the following examples.

  The following materials were prepared.

(Polyol compound)
Terephthalic acid polyester polyol ("Maximol RDK142" manufactured by Kawasaki Kasei Kogyo Co., Ltd.)
Polyether polyol 1 (“SBU polyol J610” manufactured by Sumika Covestro Urethane Co., Ltd.)
Polyether polyol 2 (“Sanix HS-209” manufactured by Sanyo Chemical Industries)
Polyether polyol 3 ("Accor GR-84T" manufactured by Mitsui Chemicals SKC Polyurethanes)

(Isocyanate compound)
Diphenylmethane diisocyanate (“Sumijour 44V” manufactured by Sumika Covestro Urethane Co., Ltd.)

(Foaming agent)
Isopropyl chloride trans-1-chloro-3,3,3-trifluoropropene ("Solstick LBA" manufactured by Honeywell): Unsaturated organic halogen compound 1,1,1,4,4,4-hexafluoro-2-butene ("HFO1336mzz" manufactured by DuPont): Unsaturated organic halogen compound

(catalyst)
Tertiary amine mixture (urethane catalyst, "TOYOCAT-CX40" manufactured by Tosoh Corporation)
Quaternary ammonium salt / ethylene glycol mixture (trimerization catalyst, “TOYOCAT-TRX” manufactured by Tosoh Corporation)

(Foam stabilizer)
Silicone foam stabilizer 1 ("SH193" manufactured by Toray Dow Corning)
Silicone foam stabilizer 2 ("Niax Silicone L-6900" manufactured by Momentive)
Silicone foam stabilizer 3 (“TEGOSTAB B8558” manufactured by Evonik)

(Filler)
Mica (“L-XF” manufactured by Repco, average diameter 4 μm, average aspect ratio 15)
Fly ash ("Fly ash type I" manufactured by Shikoku Electric Power Co., Inc., average diameter 3.5μm)

  The average diameter of the filler was measured by a laser diffraction / scattering method.

  The average thickness for obtaining the average aspect ratio of the filler was measured by a water surface particle film method.

Example 1
(Preparation of curable composition)
Each component other than the isocyanate compound was mixed to obtain a polyol premix. The curable composition was prepared by mix | blending and mixing an isocyanate compound with the obtained polyol premix. Each component was used in the amount (parts by weight) shown in Table 1 below.

(Production of polyurethane foam)
Vertical 300mm × horizontal 300mm to cut the face material (Marusan Paper Co., a surface material having a polyethylene sheet / thickness 7μm three-layer structure of an aluminum sheet of kraft paper / thickness 20μm basis weight 75 g / ^{m 2,} the kraft paper And a face material in which the polyethylene sheet and the aluminum sheet are heat-sealed. A metal mold (length 300 mm × width 300 mm × thickness 50 mm) was prepared. The face material was placed on the bottom surface of the mold so that the aluminum sheet was positioned on the side in contact with the curable composition, and preheated at 70 ° C.

  The obtained curable composition was poured into a mold provided with a face material. After the pouring, the face material was placed on the upper surface of the mold so that the aluminum sheet was located on the side in contact with the curable composition, and heated in a 70 ° C. oven for 10 minutes to foam and harden. In this way, a polyurethane foam containing isopropyl chloride and an unsaturated organic halogen compound in the bubbles was produced.

(Examples 2 to 11)
Except having changed the kind and compounding quantity (weight part) of the compounding component which were used as shown in the following Tables 1 and 2, it was the same as that of Example 1, and the curable composition and the isopropyl chloride in the bubble were not. A polyurethane foam containing a saturated organic halogen compound was obtained.

(Comparative Example 1)
A curable composition and a polyurethane foam were obtained in the same manner as in Example 1 except that the type and the amount (parts by weight) of the components used were changed as shown in Table 2 below. In Comparative Example 1, since an unsaturated organic halogen compound is not used as a foaming agent, the unsaturated organic halogen compound is not contained in the bubbles of the obtained polyurethane foam.

(Evaluation)
(1) Closed cell ratio The closed cell ratio of the obtained polyurethane foam was measured according to JIS K7138 (pressure change method). The higher the closed cell ratio, the better the foamed state.

[Criteria for closed cell ratio]
○: Closed cell ratio is 85% or more Δ: Closed cell ratio is 80% or more and less than 85% ×: Closed cell ratio is less than 80% (foam failure)

(2) Thermal conductivity (25 ° C)
The thermal conductivity at 25 ° C. of the obtained polyurethane foam was measured according to JIS A 9521: 2014. The lower the thermal conductivity, the better the heat insulation.

[Criteria for thermal conductivity (25 ° C)]
○: Thermal conductivity of 0.0190 W / m · K or less Δ: Thermal conductivity of over 0.0190 W / m · K, 0.0200 W / m · K or less ×: Thermal conductivity of 0.0200 W / m · K Over K

(3) Content of isopropyl chloride in 100% by weight of polyurethane foam, and content of unsaturated organic fluorine compound After cutting out the obtained polyurethane foam to obtain 0.4 g of a polyurethane foam sample, the sample Was collected in a glass container for grinding, and 40 mL of tetrahydrofuran (THF) was added. After crushing the sample to such an extent that it was immersed in tetrahydrofuran, the sample was pulverized for 90 seconds using a homogenizer (“SX08” manufactured by Mitsui Denki Seiki Co., Ltd.) to extract the gas component contained in the polyurethane foam to obtain an extract. The obtained extract was filtered through a 0.45 μm membrane filter.

  The standard gas of the blowing agent and the extract after the filtrate were analyzed using a gas chromatograph mass spectrometer (GC / MS) (“GCMS-QP2020” manufactured by Shimadzu Corporation). The retention time and mass spectrum obtained by measuring the standard gas of the foaming agent are compared with the retention time and mass spectrum obtained by measuring the above extract, and the gas components contained in the polyurethane foam are identified. It was.

  The detection sensitivity of each gas component contained in the polyurethane foam was measured with a standard gas. From the detection area area and detection sensitivity of each gas component obtained by the above GC / MS, and the weight of the polyurethane foam sample, the isopropyl chloride was measured. The content and the content of the unsaturated organic fluorine compound were calculated. The GC / MS measurement conditions were set as follows.

Column used: DB-1 (manufactured by Agilent Technologies), length 30 m, inner diameter 0.25 mm, film thickness 1 μm
Column temperature: Hold at 40 ° C. for 10 minutes, then hold at 100 ° C. for 20 minutes, and then hold at 250 ° C. for 3 minutes Inlet temperature: 200 ° C.
Carrier gas: He, flow rate 1.0 mL / min Split ratio: 20: 1

[Criteria for content of isopropyl chloride]
○: In 100% by weight of polyurethane foam, the content of isopropyl chloride is 0.5% by weight or more and 5% by weight or less. Δ: In 100% by weight of polyurethane foam, the content of isopropyl chloride is 0.1% by weight or more. Less than 5% by weight, or more than 5% by weight and not more than 15% by weight X: In 100% by weight of polyurethane foam, the content of isopropyl chloride is less than 0.1% by weight or more than 15% by weight

[Criteria for content of unsaturated organic fluorine compounds]
○: In 100% by weight of polyurethane foam, the content of unsaturated organic fluorine compound is from 1% by weight to 8% by weight. Δ: In 100% by weight of polyurethane foam, the content of unsaturated organic fluorine compound is 0.5% by weight. % To less than 1% by weight, or more than 8% by weight and 15% by weight or less X: In 100% by weight of polyurethane foam, the content of unsaturated organic fluorine compound is less than 0.5% by weight or 15% by weight Exceed

  The compositions and results are shown in Tables 1 and 2 below.

Claims (7)

A polyurethane foam having a plurality of bubbles,
A polyurethane foam comprising isopropyl chloride and an unsaturated organic halogen compound in the bubbles.   The polyurethane foam according to claim 1, wherein the unsaturated organic halogen compound is hydrochlorofluoroolefin or hydrofluoroolefin.   The unsaturated organic halogen compound is 1-chloro-3,3,3-trifluoropropene or 1,1,1,4,4,4-hexafluoro-2-butene. The polyurethane foam described.   The polyurethane foam according to any one of claims 1 to 3, wherein a content of the isopropyl chloride is 0.5 wt% or more and 5 wt% or less in 100 wt% of the polyurethane foam. The unsaturated organic halogen compound is an unsaturated organic fluorine compound;
The polyurethane foam according to any one of claims 1 to 4, wherein a content of the unsaturated organic fluorine compound is 1% by weight or more and 8% by weight or less in 100% by weight of the polyurethane foam.   The polyurethane foam according to any one of claims 1 to 5, wherein the closed cell ratio is 85% or more.   The polyurethane foam according to any one of claims 1 to 6, wherein the thermal conductivity at 25 ° C is 0.0190 W / m · K or less.