JP5586180B2 - Foamable composition for polyurethane foam and polyurethane foam - Google Patents

Description

  TECHNICAL FIELD The present invention relates to a foamable composition for polyurethane foam and polyurethane foam, and in particular, has excellent characteristics regarding heat insulation performance and dimensional stability of polyurethane foam produced using a non-fluorocarbon foaming agent such as carbon dioxide. The present invention relates to a technique for improving the flame retardancy more advantageously while securing the same.

  Conventionally, polyurethane foam has been used mainly as a thermal insulation member for insulation, such as building interior and exterior wall materials and panels, insulation for metal siding and electric refrigerators, buildings and condominiums. -Practical use for heat insulation and dew condensation prevention for enclosures, walls, ceilings, roofs, etc. for freezers, and for infusion pipes. In addition, such a polyurethane foam generally includes a polyol compound liquid (premix liquid) in which various additives such as a foaming agent and, if necessary, a catalyst, a foam stabilizer, a flame retardant, and the like, are added to the polyol component, and an isocyanate component. Are mixed with a mixing device continuously or intermittently to obtain a foamable composition for polyurethane foam, which is foamed and cured by a method such as a slab foaming method, an injection foaming method, a spray foaming method or a laminate continuous foaming method. It is manufactured by letting.

  In addition, the foamable composition for polyurethane foams used therein has a hydrofluorocarbon-based foaming agent (for example, HFC) which is an alternative fluorocarbon with little or no destruction of the ozone layer as a foaming agent due to the environmental problem of destruction of the stratospheric ozone layer. -245fa, HFC-365mfc, etc.) are used. However, based on the assumption that the use of alternative chlorofluorocarbons will be limited in the near future, in recent years, carbon dioxide (carbon dioxide) has been used as a substitute for some or all of existing blowing agents such as alternative chlorofluorocarbon blowing agents. Polyurethane foams that are manufactured using are being investigated. For example, Patent Documents 1 and 2 disclose a polyurethane foam produced by a so-called “water foaming method” using carbon dioxide generated by a chemical reaction between a polyisocyanate component and water as a foaming agent. . Patent Document 3 discloses a polyurethane produced by using, as a foaming agent, carbon dioxide generated by a reaction between water and a polyisocyanate component, and carbon dioxide in a supercritical state, a subcritical state, or a liquid state. The form is revealed. Furthermore, Patent Document 4 discloses that a polyurethane foam is produced using a low-boiling hydrocarbon or the like as a blowing agent in addition to carbon dioxide (water).

  However, polyurethane foams produced using non-fluorocarbon foaming agents such as carbon dioxide and hydrocarbons are basically inferior in flame retardancy to polyurethane foams produced by other foaming methods. Moreover, the problem of lacking heat insulation performance or dimensional stability was inherent.

  On the other hand, Patent Document 5 discloses that in an isocyanate-free foamable mixture having improved flame behavior, a halogen-containing polyol is introduced into the prepolymer when the prepolymer is produced. Even in a foam formed from such a foamable mixture, it has been difficult to say that the required properties are still sufficiently satisfied in terms of flame retardancy.

JP-A-4-227645 JP 2004-59641 A JP 2004-107376 A JP-A-11-217431 JP 2006-515033 A

  Therefore, the present invention has been made in the background of such circumstances, and the problem to be solved is a polyurethane foam produced using a non-fluorocarbon foaming agent as a foaming agent. The object is to provide a foamable composition for polyurethane foam which can effectively improve the flame retardancy while advantageously ensuring heat insulation performance and dimensional stability, and also uses such a foamable composition for polyurethane foam. Accordingly, an object of the present invention is to provide a polyurethane foam having excellent heat resistance and dimensional stability and excellent flame retardancy.

  And, as a result of intensive studies to solve the above problems, the present inventor used a halogenated polyol as a polyol component or at least one of them, and further added a brominated epoxy compound as a flame retardant imparting component. As a result of the blending, it was found that the excellent heat-insulating performance and dimensional stability of the resulting polyurethane foam can be advantageously maintained, and excellent flame retardancy can be effectively imparted, and the present invention has been completed. is there.

That is, the present invention is a foamable composition used for producing a polyurethane foam obtained by reacting and foaming a polyol component and a polyisocyanate component, and using a non-fluorocarbon foaming agent as a foaming agent, The polyol component contains at least a halogenated polyol and a phenol resin polyol obtained by adding an alkylene oxide to a novolak resin , and the halogenated polyol is contained in an amount of 5 to 80 parts by mass in 100 parts by mass of the polyol component. The foaming composition for polyurethane foam is characterized by containing a brominated epoxy compound as a flame retardancy-imparting component.

  In addition, according to one of the preferable embodiments of the foamable composition for polyurethane foam according to the present invention, the foaming agent is carbon dioxide generated by a reaction between water and a polyisocyanate component.

  Furthermore, according to another preferred embodiment of the foamable composition for polyurethane foam according to the present invention, the polyol component further includes an aromatic diamine-based polyol obtained by adding an alkylene oxide to an aromatic diamine. .

  In addition, the gist of the present invention is a polyurethane foam obtained by foaming and curing such a foamable composition for polyurethane foam.

Thus, in the foamable composition for polyurethane foam according to the present invention, although a non-fluorocarbon foaming agent such as carbon dioxide is used for forming the foam, a halogenated polyol or a phenol resin-based polyol is used as the polyol component. In addition, since a brominated epoxy compound is blended as a flame retardant imparting component, the flame retardancy of the resulting polyurethane foam can be effectively improved, and thus excellent flame retardant performance. Can be advantageously exerted. Moreover, the polyurethane foam thus obtained has excellent heat insulation performance and remarkably excellent dimensional stability, and can be advantageously applied to various uses.

  Further, in the polyurethane foam according to the present invention, since it is formed using the foamable composition for polyurethane foam as described above, the same effects as described above can be enjoyed, and the heat insulation performance and dimensions can be obtained. The stability and flame retardancy can be further advantageously improved.

  Hereinafter, the foamable composition for polyurethane foam according to the present invention and the polyurethane foam obtained using the same will be described in detail.

  First, in the foamable composition for polyurethane foam according to the present invention, at least a non-fluorocarbon foaming agent is used as the foaming agent, and a halogenated polyol is used as at least one of the polyol components. As an imparting component, brominated epoxy compounds are used and blended and contained.

  Therein, the halogenated polyol preferably contains bromine and / or chlorine, more preferably has an average molar mass of 100 to 4000 g / mol, and particularly preferably has a molar mass of 250 to 1000 g / mol. have. In that case, on average, polyols in which at least 2, particularly preferably at least 4 halogen atoms are present in each halogenated polyol molecule will be used advantageously. Specifically, brominated polyols such as dibromoneopentyl glycol, 2,3-dibromobut-2-ene-1,4-diol, brominated bisphenol A derivatives, and epichlorohydrin to such brominated polyols. And chlorobrominated polyol obtained by adding. Various halogen-containing polyols are commercially available. For example, Ixol B-251, M-125, T-301 (all are products of Solvay Cie), Dow FR-200 (product of Dow Chemical), There are Saytex RB-77, RB-34 diol (product of Saytech Inc.), etc., which are appropriately selected and used.

  The amount of the halogenated polyol to be used is appropriately determined so that it is generally contained in a proportion of 5 to 80 parts by mass, preferably 5 to 50 parts by mass, in 100 parts by mass of the polyol component. It becomes. This is because when the amount of the halogenated polyol used is less than 5 parts by mass, it is difficult to sufficiently improve the flame retardancy of the formed polyurethane foam, and when it exceeds 80 parts by mass, Causes problems of poor compatibility and stability.

  In the present invention, as the polyol component, in addition to the above-described halogenated polyol, various other polyol compounds can be used. Among them, the thermal conductivity and dimensional stability of the obtained polyurethane foam can be further improved. In the improvement, the phenol resin-based polyol and the aromatic diamine-based polyol can be advantageously used alone or in combination, and in particular, these two polyols are advantageously used as a polyol component together with the halogenated polyol. It will be.

  As one of such polyol components, the phenol resin polyol used together with the halogenated polyol is obtained by adding an alkylene oxide such as ethylene oxide or propylene oxide to a novolac resin, in other words, a novolac type phenol resin. , What you get. In addition, as a novolak-type phenol resin (novolak resin) used for the preparation of such a phenol resin-based polyol, advantageously, free phenols are contained in an amount of 1 to 50% by mass, preferably 5 from the viewpoint of reducing the viscosity. What is contained in a proportion of about 35% by mass, more preferably about 10-30% by mass is adopted. This is because if the content ratio of free phenols is less than 1% by mass, it is difficult to effectively reduce the viscosity, and the intended foamable composition for polyurethane foam may not be used. This is because, if it exceeds 50% by mass, the polyurethane foam becomes too soft and tends to deteriorate the moldability.

  Such a novolak-type phenol resin is prepared by blending, for example, phenols and aldehydes at a ratio of 0.3 to 1.0 mol with respect to 1 mol of phenols, and then an acid catalyst. Then, after the reaction is carried out under predetermined reaction conditions (temperature and time), a dehydration treatment under reduced pressure is performed as necessary, so that it is advantageously produced as an initial condensate of a novolac type phenol resin. Here, the initial condensate is a phenol resin having a relatively low molecular weight, and is a condensate having about 2 to 10 phenol skeleton or a mixture of unreacted phenols in one molecule. The method for producing such novolak-type phenolic resin (initial condensate) is not limited to the above-described method, and a predetermined proportion of the above-mentioned free phenols is present in the resulting novolak-type phenolic resin. It can be produced by appropriately setting reaction conditions and reaction environment (for example, normal pressure, reduced pressure, pressurization, presence / absence of coexistence of inert gas, stepwise or sequential reaction, etc.). Furthermore, it is also possible to adjust the content ratio of free phenols as described above by adding phenols separately to the condensate after completion of the reaction, if necessary.

  The phenols used in the production of the novolak type phenolic resin are not particularly limited, and generally phenol is adopted. For example, cresol, ethylphenol, xylenol, p- One kind of alkylphenols such as t-butylphenol, octylphenol, nonylphenol, dodecylphenol, p-phenylphenol or the like may be used alone, or two or more kinds may be used in combination, or one or more of such alkylphenols may be used. And phenol can be used in combination. Furthermore, halogenated phenols such as m-chlorophenol and o-bromophenol, polyphenols such as resorcinol, catechol, hydroquinone and phloroglicinol, bisphenol A [2,2-bis (4-hydroxyphenyl) propane], Bisphenol F (4,4'-dihydroxydiphenylmethane) and other bisphenols, resorcinol, catechol, bisphenol A, bisphenol F and other refined phenol compounds, α-naphthol, β-naphthol, β-hydroxyanthracene Can be used alone or in admixture of two or more, or one or more of them can be used in combination with phenol or alkylphenol.

  On the other hand, the aldehydes to be reacted with the phenols are not particularly limited, and generally one or both of formalin and paraformaldehyde is used, but other formaldehydes (if necessary) For example, trioxane, tetraoxane, polyoxymethylene, etc.), glyoxal, etc. can be used alone or in combination.

  In addition, oxalic acid is suitable as the acid catalyst used in the production of the novolak type phenol resin, but in addition, organic sulfonic acid (for example, p-toluenesulfonic acid), organic carboxylic acid (for example, acetic acid, etc.) ) Salts of divalent metals (eg, magnesium, zinc, lead, etc.), chlorides of divalent metals, oxides of divalent metals, inorganic acids (eg, hydrochloric acid, sulfuric acid, etc.) may be used alone, Of course, two or more of these may be used in combination.

  Furthermore, the phenol resin-based polyol used as one of the polyol components is obtained by subjecting the novolak type phenol resin produced as described above to an addition reaction with a predetermined alkylene oxide in the presence of a basic catalyst. Thus, advantageously, the above-mentioned predetermined alkylene oxide is added to the phenolic hydroxyl group part of the novolak-type phenol resin containing free phenols, and the phenolic hydroxyl group is converted to an alcoholic hydroxyl group. The resulting phenol resin polyol. As described above, the addition of a predetermined alkylene oxide modifies the phenol resin and further improves the hydrophilicity of the polyol component. As a result, the phenol resin-based polyol particularly uses carbon dioxide as a blowing agent. This is not only suitable as a polyol used in the foaming method, but also has excellent mixing properties with the polyisocyanate component described below.

  The phenol resin polyol is appropriately selected from 150 to 450 mgKOH / g so that its hydroxyl value is advantageously 100 to 600 mgKOH / g by appropriately selecting the blending amount of alkylene oxide and the like. More preferably, it is comprised so that it may become 200-450 mgKOH / g. This is because if the hydroxyl value is too low, the foam obtained by using it becomes too soft, the moldability tends to deteriorate, and the intended polyurethane foam tends not to be obtained. This is because if the viscosity is too high, the viscosity is not sufficiently lowered and the miscibility with the polyisocyanate component tends to deteriorate. In addition, the viscosity of the phenolic resin polyol also varies in accordance with the hydroxyl value, but the viscosity of the phenolic resin polyol used in the present invention is in the range of 500 to 30000 mPa · s / 25 ° C. .

  Here, the alkylene oxide used in the production of the phenol resin-based polyol is generally ethylene oxide, propylene oxide, or the like, and is appropriately selected according to the characteristics of the foam to be obtained. Moreover, generally the compounding quantity of such an alkylene oxide will be suitably selected in the range used as 1-20 times equivalent with respect to the phenolic hydroxyl group of a novolak-type phenol resin.

  And as a basic catalyst used for manufacture of the said phenol resin type polyol, in other words, used for the addition reaction of the said novolak type phenol resin and a predetermined alkylene oxide, for example, sodium hydroxide, potassium hydroxide, Alkaline catalysts such as barium hydroxide and calcium hydroxide can be suitably employed, and at least one of them can be appropriately selected and used, but of course, the present invention is not limited to these. It goes without saying that there is nothing.

  An aromatic diamine-based polyol used as another one of the polyol components together with or in place of the phenol resin-based polyol is an aromatic diamine according to a known technique, such as ethylene oxide and propylene oxide. It can be obtained by adding the alkylene oxide. In other words, the aromatic diamine-based polyol is a polyfunctional polyether polyol compound having a terminal hydroxyl group obtained by ring-opening addition of an alkylene oxide such as ethylene oxide or propylene oxide to an aromatic diamine as an initiator. is there.

  In addition, as the aromatic diamine as an initiator that gives such an aromatic diamine-based polyol, various known aromatic diamine compounds can be used, specifically, generically called tolylenediamine, In addition to various methyl substituents of phenylenediamine, derivatives in which substituents such as methyl, ethyl, acetyl, benzoyl are introduced to the amino group, 4,4′-diaminodiphenylmethane, p-phenylenediamine, Examples thereof include o-phenylenediamine and naphthalenediamine. Of these, tolylenediamine is preferably used for enhancing the properties of the resulting polyurethane foam.

  By the way, various aromatic diamine-based polyols obtained by adding predetermined alkylene oxides such as ethylene oxide and propylene oxide to such aromatic diamines are commercially available. For example, tolylenediamine-based polyols Examples of such products are Sannix HA-501, HM-550, HM-551 (all of which are products of Sanyo Chemical Industries, Ltd.). From among these, it will be appropriately selected and used. The hydroxyl value of the aromatic diamine-based polyol is preferably 200 to 600 mgKOH / g, and the viscosity is preferably 500 to 30000 mPa · s / 25 ° C.

  In the present invention, such an aromatic diamine-based polyol or a phenol resin-based polyol is advantageously used as a polyol component together with the halogenated polyol. The group diamine-based polyol and the phenol resin-based polyol are each used in a proportion of 20% by mass or more, preferably 30% by mass or more of the entire polyol component, and therefore the total amount thereof is 40% by mass or more of the polyol component. In order to better achieve the object of the present invention, it is desirable to use it in a proportion that preferably accounts for 60 mass% or more. Of these, the phenol resin polyol and the aromatic diamine polyol are preferably used in a mass ratio of 3/7 to 7/3. In addition, in the blending ratio of these phenol resin-based polyol and aromatic diamine-based polyol, if the amount of phenol resin-based polyol increases too much, the effect of improving dimensional stability decreases, and the amount of aromatic diamine-based polyol increases. If it is too high, the effect of improving the thermal conductivity and flame retardancy will decrease, which is not desirable.

  In the present invention, in addition to the above-mentioned halogenated polyol, the above-described phenol resin-based polyol or aromatic diamine-based polyol is advantageously used as the polyol component. Other known polyol compounds can be used at the same time as long as they do not adversely affect the excellent action and effect of the halogenated polyol as the polyol component. For example, such other known polyol compounds include known polyether polyols such as aliphatic polyether polyols, aliphatic amine polyether polyols, aromatic polyether polyols, or polyhydric alcohols. Ring-opening polymerization of polycarboxylic acid-based polyester polyols, lactones, etc. obtained by reacting acids, adipic acid, sepacic acid, maleic acid, phthalic acid, terephthalic acid, trimellitic acid, dimer acid and other polycarboxylic acids Known polyester polyols such as the obtained lactone polyester polyol can be exemplified.

  Further, in the foamable composition for polyurethane foam according to the present invention, a polyol component containing at least a halogenated polyol as described above is used, and further, a brominated epoxy compound is used as a flame retardant imparting component. Thus, the improvement in flame retardancy of the obtained polyurethane foam is realized even more advantageously. Since such a brominated epoxy compound has an epoxy group in the molecule, at least a part of the brominated epoxy compound reacts with the polyisocyanate component in the polyurethane formation reaction, It is considered that they can be combined and contained, and this can further contribute to the improvement of flame retardancy.

  And as a brominated epoxy compound which implement | achieves such a preferable characteristic, well-known various things can be selected and used suitably, for example, phenyl glycidyl ether, a bisphenol A type epoxy compound, a bisphenol F type epoxy compound, Examples thereof include brominated epoxy compounds that are bromine substitutes such as phenol novolac type epoxy compounds, dicyclopentadiene type epoxy compounds, naphthalene type epoxy compounds, and biphenyl type epoxy compounds. Various types of brominated epoxy compounds are commercially available. For example, brominated phenyl glycidyl ether includes products such as BR-250H manufactured by Nippon Kayaku Co., Ltd. Can be appropriately selected from those commercially available products.

  Furthermore, the blending amount of the brominated epoxy compound as the flame retardant imparting component is difficult to determine uniquely depending on the type, the curing mode in the polyurethane reaction, the foam physical properties, the foamed form, etc. Specifically, it is selected in the range of 1 to 30 parts by mass, preferably 3 to 20 parts by mass, per 100 parts by mass of the polyol component. This is because if the blended amount of the halogenated polyol is too small, it will be difficult to achieve the effect of improving the flame retardancy due to its use, and if the blended amount is too large, the formed foam will stretch laterally. And it becomes easy to raise | generate problems, such as adhesiveness with a housing | casing worsening.

  By the way, the foamable composition for polyurethane foam according to the present invention contains at least a halogenated polyol as described above as a polyol component, and a brominated epoxy compound as described above as a flame retardant component. Further, as the blowing agent, carbon dioxide and / or a source of formation thereof, and known non-fluorocarbon blowing agents such as low-boiling hydrocarbons represented by pentane, hexane and the like can be introduced. In particular, in the present invention, carbon dioxide and / or a forming source thereof is advantageously used as the foaming agent.

  Here, such carbon dioxide or its formation source can be obtained by (1) adding water as a blowing agent source, or (2) adding subcritical or supercritical carbon dioxide. Although it is introduced into the foamable composition for polyurethane foam, either one of (1) and (2) may be used, or both of them may be combined. The subcritical carbon dioxide is liquid carbon dioxide in which the pressure is higher than the critical pressure and the temperature is lower than the critical temperature, carbon dioxide in the liquid state in which the pressure is lower than the critical pressure and the temperature is higher than the critical temperature, Or, the temperature and pressure are below the critical point, but it is near carbon dioxide, and supercritical carbon dioxide is above the critical point of critical pressure and critical temperature. It refers to carbon dioxide in a fluid state.

  In particular, in the case of water foaming of the above (1), water as a foaming agent source plays a role of generating carbon dioxide gas used for foam formation by reaction with a polyisocyanate component described later. It contributes a little to the viscosity reduction of the polyol component. The blending amount of water for water foaming can be appropriately set so as to obtain a desired foam density, but is usually 0.5 to 12 parts by mass, preferably 1 with respect to 100 parts by mass of the polyol component. -10 mass parts, More preferably, it may be set suitably in the range of 2-8 mass parts. When the amount of water is less than 0.5 parts by mass with respect to 100 parts by mass of the polyol component, the amount of carbon dioxide gas generated is not sufficient. There is a risk that weakening of the foam will be caused by a serious decline.

  On the other hand, when carbon dioxide in a subcritical state or a supercritical state is mixed, the addition amount can be appropriately set so as to obtain a desired foam density, and usually a polyol containing at least a halogenated polyol. The amount can be appropriately set in the range of 0.3 to 10 parts by mass, preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the components.

  Moreover, the polyisocyanate component which reacts with the polyol component containing a halogenated polyol and produces | generates a polyurethane is used for the foamable composition for polyurethane foams according to this invention. This polyisocyanate component is an organic isocyanate compound having two or more isocyanate groups (NCO groups) in the molecule, such as diphenylmethane diisocyanate, polymethylene polyphenylene polyisocyanate, tolylene diisocyanate, polytolylene polyisocyanate, xylylene. Aromatic polyisocyanates such as diisocyanate and naphthalene diisocyanate, aliphatic polyisocyanates such as hexamethylene diisocyanate, alicyclic polyisocyanates such as isophorone diisocyanate, urethane prepolymer having an isocyanate group at the molecular terminal, isocyanurate of polyisocyanate A modified body, a carbodiimide modified body, etc. can be mentioned. These polyisocyanate components may be used alone or in combination of two or more. In general, polymethylene polyphenylene polyisocyanate (crude MDI) is preferably used from the viewpoints of reactivity, economy, and handling properties.

  The blending ratio of the polyisocyanate component and the polyol component containing the halogenated polyol is changed depending on the type of foam (for example, polyurethane, polyisocyanurate). Generally, the isocyanate group ( NCO / OH index (equivalent ratio) indicating the ratio between the NCO) and the hydroxyl component (OH) of the polyol component (total of each polyol) is appropriately set so as to be in the range of about 0.9 to 2.5. The

  The foamable composition for polyurethane foam according to the present invention generally includes a polyol component containing a halogenated polyol and a brominated epoxy compound, carbon dioxide (water that is a foaming agent source in the case of the water foaming method), and the like. In addition to the non-fluorocarbon foaming agent and the polyisocyanate component, catalysts and foam stabilizers conventionally used in the production of polyurethane foams can be blended.

  Specifically, for example, when water is used as a foaming agent source, when it is required to generate carbon dioxide gas generated by the reaction between the polyisocyanate component and water at an early stage, these polyisocyanate component and water are used. An amine-based foaming catalyst having the effect of promoting the reaction with is advantageously used. Examples of such amine-based foaming catalysts include pentamethyldiethylenetriamine, bis (dimethylaminoethyl) ether, N, N, N′-trimethylaminoethylethanolamine, and the like. Or two or more of them may be used in combination. Moreover, as the compounding quantity, about 1-30 mass parts is suitable with respect to 100 mass parts of the polyol component containing a halogenated polyol normally.

  On the other hand, in order to accelerate the reaction between the polyisocyanate component and the polyol component, a resinification catalyst is advantageously used. The resinification catalyst is appropriately selected and used according to the type of foam. For example, a urethanization catalyst and an isocyanurate catalyst are used alone, or these are used in combination. Examples of the urethanization catalyst include tertiary amine, dibutyltin dilaurate, ethylmorpholine, triethylenediamine, tetramethylhexamethylenediamine, bismuth octylate (bismuth 2-ethylhexylate), bismuth neodecanoate, bismuth neodecanoate, and naphthenic acid. Fatty acid bismuth salts such as bismuth, lead naphthenate and the like can be mentioned. Examples of the isocyanuration catalyst include fatty acid alkali metal salts such as hydroxyalkyl quaternary ammonium salts, potassium octylate and sodium acetate, tris ( And (dimethylaminopropyl) hexahydrotriazine. These resinification catalysts may be used independently and may use 2 or more types together. In general, the blending amount of the resinification catalyst is desirably about 0.1 to 15 parts by mass with respect to 100 parts by mass of the polyol component.

  Moreover, the said foam stabilizer is used in order to arrange | equalize the cell structure of a polyurethane foam uniformly, Comprising: Silicone and a nonionic surfactant are employ | adopted suitably here. Specific examples include polyoxyalkylene-modified dimethylpolysiloxane, polysiloxaneoxyalkylene copolymer, polyoxyethylene sorbitan fatty acid ester, castor oil ethylene oxide adduct, lauryl fatty acid ethylene oxide adduct, etc. Species are used alone or in combination of two or more. The blending amount of the foam stabilizer can be appropriately determined according to the desired foam characteristics, the type of foam stabilizer to be used, and the like. Preferably, the blend amount of the foam stabilizer is 0.1 with respect to 100 parts by mass of the polyol component. The ratio is about 10 to 10 parts by mass.

  In addition, in the foamable composition for polyurethane foam according to the present invention, if necessary, in addition to known flame retardants and foaming agents, for example, formaldehyde scavengers such as urea and melamine, bubble refining agents, Various conventionally known auxiliaries such as a plasticizer and a reinforcing base material can be appropriately selected and blended.

  As the flame retardant, phosphate esters such as trischloroethyl phosphate, trischloropropyl phosphate, and triethyl phosphate, which have a low environmental impact and function as a viscosity reducer for the foamable composition, are advantageously used. It is done. When this phosphoric acid ester is blended, the blending amount can be appropriately determined according to the desired foam characteristics, the type of flame retardant, and the like, but preferably 10 to 60 mass per 100 mass parts of the polyol component. In the range, about 10 to 40 parts by mass is particularly preferable. Moreover, aluminum hydroxide etc. can be used suitably as a flame retardant other than the said phosphate ester.

  In addition, when the foaming agent uses water as a foaming agent source, the foaming due to the soap function of the foaming agent (high foaming property) It is used to make up for the foam stability), and is particularly useful when the foamable composition for polyurethane foam according to the present invention is foamed and cured by the blowing method (spray foaming method). Such foaming agents include fatty acid alkali metal salts known as soap components, particularly lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid and the like having 12 to 18 carbon atoms. Examples thereof include sodium salts and potassium salts of fatty acids. Among these, in the water foaming method, a fatty acid potassium salt is particularly preferably used.

  Furthermore, in the foamable composition for polyurethane foam according to the present invention, as described above, a non-fluorocarbon foaming agent such as carbon dioxide is employed as the foaming agent from the viewpoint of maintaining the ozone layer. As non-fluorocarbon foaming agents, when carbon dioxide is used as the main blowing agent, hydrogen peroxide, pentafluoropropane (HFC-245fa), pentafluorobutane (HFC-365mfc), Add hydrofluorocarbons typified by tetrafluoroethane (HFC-134a) and halogenated hydrocarbons typified by dichloromethane and isopropyl chloride as foaming aids to assist the foaming action of carbon dioxide Is also possible.

  Then, when producing a foamable composition for polyurethane foam according to the present invention using a polyol component containing a halogenated polyol as described above, a brominated epoxy compound, a non-fluorocarbon foaming agent, a polyisocyanate component, etc., A manufacturing method similar to the foamable composition for polyurethane foam may be employed.

  For example, when the water foaming method is adopted, that is, when carbon dioxide generated by the reaction of water and polyisocyanate is used as a foaming agent, first, flame retardancy with respect to the polyol component containing the halogenated polyol. Along with the brominated epoxy compound as an imparting component, water as a foaming agent source, if necessary, a foaming catalyst, a resinification catalyst, a foam stabilizer, a flame retardant, a foaming agent, and other various auxiliary agents are blended, A polyol compounding liquid (premix liquid) is prepared. Subsequently, the prepared polyol compounded liquid and the polyisocyanate component are mixed at high speed using a low-pressure high-speed stirring mixer, or high pressure using a high-pressure impingement mixer (for example, an on-site spray foaming machine). A liquid foamable composition for polyurethane foam can be produced by impact mixing. In the present invention, a phenol resin polyol or aromatic diamine polyol having a low viscosity suitable for the water foaming method is used as a polyol component together with the halogenated polyol according to the present invention. Is advantageous in that a homogeneous foamable composition can be produced.

  On the other hand, when subcritical or supercritical carbon dioxide is used as the foaming agent, first, if necessary, a foaming catalyst, a resination catalyst, a foam regulating agent is used for the polyol component containing the halogenated polyol. An agent, a flame retardant, a foaming agent, and other various auxiliary agents are blended to prepare a polyol blend liquid (premix liquid). And, immediately before the prepared polyol blending liquid is mixed with the polyisocyanate component, preferably, the polyol blending liquid is added with carbon dioxide in a subcritical or supercritical state under a predetermined pressure and temperature. After mixing, a polyisocyanate component is further added and mixed, whereby a liquid foamable composition for polyurethane foam can be produced.

  And the foamable composition for polyurethane foam produced in this way requires, for example, a laminate continuous foaming method in which it is applied onto a face material and foamed and cured in a plate shape, and heat insulation performance such as an electric refrigerator. Foaming is achieved by the injection foaming method for foaming and curing by injecting and filling into the honeycomb structure of the space and lightweight / high-strength board, and the spray foaming method for blowing and curing to the adherend from the spray gun head of the on-site foaming machine. It will be cured to form the desired polyurethane foam.

  Thus, in the polyurethane foam obtained by using the foamable composition for polyurethane foam described above, at least a halogenated polyol is used as the polyol component, and further, as a flame retardant imparting component, a brominated epoxy compound is used. In spite of the fact that non-fluorocarbon foaming agents such as carbon dioxide are used as foaming agents, excellent flame retardant performance can be realized, and its thermal conductivity In addition, excellent characteristics are imparted in terms of dimensional stability.

  Some examples of the present invention will be shown below to clarify the present invention more specifically. However, the present invention is not limited by the description of such examples. Needless to say. In addition to the following examples, the present invention includes various changes and modifications based on the knowledge of those skilled in the art without departing from the spirit of the present invention, in addition to the specific description described above. It should be understood that improvements can be made. The “%” and “part” shown below are based on mass.

  First, a novolac-type phenol resin was prepared, and a predetermined alkylene oxide was added to the obtained novolac-type phenol resin to prepare a target phenol resin-based polyol. In addition, the viscosity and hydroxyl value of the obtained phenol resin polyol were measured by the following measuring methods.

(1) The viscosity (mPa · s) was measured according to JIS K 7117-1 using a B-type viscometer.
(2) The hydroxyl value (mgKOH / g) was measured according to JIS K1557-1.

<Preparation of novolac type phenolic resin>
In a reaction vessel equipped with a stirrer, 9400 parts of phenol, 1630 parts of 92% paraformaldehyde, and 19 parts of oxalic acid as an acid catalyst were charged and then reacted at a temperature of 100 ° C. for 5 hours while mixing with stirring. . Then, the target novolak-type phenol resin was obtained by distilling water off under reduced pressure. The content of free phenol was 30% by mass.

<Preparation of phenol resin polyol>
In pressure-resistant reaction vessel equipped with a stirrer, 4000 parts of the upper Symbol phenolic novolak resin, with 200 parts of potassium hydroxide as the alkaline catalyst, were charged, with stirring mixture, under pressure, 0.99 ° C. At a temperature of 3,400 parts of ethylene oxide was added and added to the novolac phenolic resin. Thereafter, potassium hydroxide (catalyst) was neutralized with acetic acid to obtain a target phenol resin polyol. When the hydroxyl value and the viscosity at 25 ° C. of the obtained phenol resin-based polyol were measured, they were 300 mgKOH / g and 2500 mPa · s / 25 ° C., respectively.

Experimental Example 1-7
First, the phenol resin-based polyol prepared above is used as the polyol component, and further, a halogenated polyol (trade name: Ixol B-251, manufactured by Solvey Fluor Gmbh), a tolylenediamine-based polyol (trade name: Sanniks HM-). 551, manufactured by Sanyo Chemical Industries, Ltd., hydroxyl value: 400 mg KOH / g), glycerin-based polyol (trade name: EXCENOL-430, manufactured by Asahi Glass Co., Ltd.), ethylenediamine-based polyol (product name: EXCENOL-450ED, manufactured by Asahi Glass Co., Ltd.) In addition, a silicone foam stabilizer (trade name: SH-193, manufactured by Toray Dow Corning), brominated epoxy compound (brominated phenyl glycidyl ether, trade name: BR-250H, manufactured by Nippon Kayaku Co., Ltd.) , Flame retardant (Trischloropropyl phosphate), Catalyst A (Product name: TOYOCAT-TT, manufactured by Tosoh Corporation), catalyst B (trade name: Kaulizer No. 31, manufactured by Kao Corporation) and a foaming agent (potassium ricinoleate), the combinations shown in Table 1 below. In proportion, each component was mixed to prepare various polyol blending solutions.

Next, various on-site spray foaming machines using the obtained various polyol blend solutions and crude MDI (trade name: Lupranate M-11S, manufactured by BASF INOAC Polyurethane Co., Ltd.) as a polyisocyanate component at a volume ratio of 1: 1 were used. (Product name: FF-1600, manufactured by Gasmer Co., Ltd.) The mixture is stirred and mixed to obtain a foaming stock solution, which is sprayed onto the surface of the inorganic flexible board as the adherend under the condition of the atmospheric temperature: 15 ° C. , by curing, to prepare a variety of rigid polyurethane foam according to experiment examples 1-7.

  The various polyurethane foams thus obtained were used to measure their density, thermal conductivity, dimensional stability, and flame retardancy, and the results obtained are shown in Table 2 below.

In this characteristic evaluation, “density” was measured in accordance with JIS K 7222. In addition, the measurement of “thermal conductivity (W / m · K)” is performed on the obtained polyurethane foam by using JIS A 1412-2 with a thermal conductivity measuring device (manufactured by MADDERLAKE SCIENTIFIC GROUP COMPANY, Anacon TCA POINT2). A6. Of plate comparison method in Appendix A (normative). The measurement was performed according to the measurement method. Furthermore, “dimensional stability” is obtained by cutting the obtained polyurethane foam into a shape of 150 mm × 150 mm × 30 mm, leaving it at 50 ° C. for 24 hours, and measuring the change in thickness. [= (Size after cutting-size after standing) × 100 / size after cutting] was determined and evaluated. In the evaluation results, a case where the dimensional change rate was less than 1% was evaluated as ◯, a case where the dimensional change rate was 1% to 3%, and a case where the dimensional change rate exceeded 3% was evaluated as ×. Furthermore, in the evaluation of “flame retardant”, first, three foams bonded to the inorganic flexible board were cut out so that the vertical and horizontal sizes were 99 ± 1 mm, and then the thickness of the foam part was In these three cut samples, the skin layer side was cut so as to be 20 mm. Then, about this obtained sample, using a cone calorimeter (made by Toyo Seiki Seisakusho Co., Ltd., CONEIII), the Japan Building Research Institute edition "Fireproofing performance test and evaluation business method manual". In accordance with “12.1 Exothermic test / evaluation method”, measure the total calorific value, the maximum exothermic rate, the time during which the exothermic rate exceeded 200 kW / m ² in 5 minutes after the start of heating, and evaluate the flame retardancy. The result was obtained as an average value of the three specimens. And the result obtained in those characteristic evaluation was combined with following Table 2, and was shown.

As apparent from the results of such Table 2, in the experimental example 2 and the polyurethane foam obtained in 4 according to the present invention, both, while maintaining excellent thermal conductivity and dimensional stability, flame retardant It is recognized that the property is remarkably improved. That is, as compared with Experimental Example 1, as the polyol component, with a halogenated polyol, in the case of a combination of phenolic resin polyol (Experiment Example 2) is improved in dimensional stability and thermal conductivity it is recognized, further, a combination of them phenolic resin polyol and the aromatic diamine-based polyol, with a halogenated polyol, in the case of using as the polyol component (experiment example 4), the improvement effect further significant It is recognized that

On the other hand, when halogenated polyol or brominated epoxy compound is used alone ( Experimental Example 5 and Experimental Example 6 ) and they are not used in combination, they are not sufficient in flame retardancy, In the case of Experimental Example 7 in which neither of them is used, it is recognized that although there is an effect of improving the flame retardancy due to the use of the phenol resin-based polyol, there is a major problem in dimensional stability. .

Claims (5)

A foamable composition used for producing a polyurethane foam obtained by reacting and foaming a polyol component and a polyisocyanate component,
A non-fluorocarbon foaming agent is used as the foaming agent, and the polyol component contains at least a halogenated polyol and a phenol resin polyol obtained by adding an alkylene oxide to a novolak resin , and the halogenated polyol is a polyol. A foamable composition for polyurethane foam , comprising 5 to 80 parts by mass in 100 parts by mass of the component , and further containing a brominated epoxy compound as a flame retardant component.   The foamable composition for polyurethane foam according to claim 1, wherein the foaming agent is carbon dioxide generated by a reaction between water and a polyisocyanate component. The foamable composition for polyurethane foam according to claim 1 or 2, wherein a phosphoric ester is further contained as a flame retardant .   The foamable composition for polyurethane foam according to any one of claims 1 to 3, further comprising an aromatic diamine-based polyol obtained by adding an alkylene oxide to an aromatic diamine as the polyol component.   A polyurethane foam obtained by foaming and curing the foamable composition for polyurethane foam according to any one of claims 1 to 4.