Polyol composition, expandable polyurethane composition and polyurethane foam

Abstract

To provide a polyol composition capable of preventing contamination by suppressing oozing-out of a foam controlling agent, and obtaining polyurethane foam having a small density difference between an upper part and a central part, to provide an expandable polyurethane composition containing the polyol composition, and to provide polyurethane foam comprising the expandable polyurethane composition.SOLUTION: There provided are: a polyol composition containing polyol, a foaming agent, a catalyst and an additive agent with an SP value of 11 or less, and substantially containing no foam controlling agent; an expandable polyurethane composition containing the polyol composition and polyisocyanate; and polyurethane foam comprising the expandable polyurethane composition.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a polyol composition, a foamable polyurethane composition, and a polyurethane foam. [Background technology]

[0002] Due to its excellent heat insulating properties and adhesive properties, polyurethane foam is used as a heat insulating material for buildings such as apartment complexes, detached houses, various school facilities, commercial buildings, etc. Polyurethane foam is obtained by foaming a foamable polyurethane composition containing a polyol composition and a polyisocyanate.

[0003] The polyol composition generally contains a polyol, a blowing agent, a catalyst, and a foam stabilizer. The use of the foam stabilizer improves the mixability of the composition and allows for the production of a foam having uniform, fine cells. Such a foam has a small density difference between the top and center, uniform flexibility and mechanical strength, and excellent physical properties. On the other hand, when a polyurethane foam is formed using a polyol composition containing a foam stabilizer, the foam stabilizer is likely to bleed out from the surface of the foam, which can result in problems such as contamination of the object to which the foam is to be used or a decrease in adhesion between the foam and the object to which the foam is to be used.

[0004] Patent Document 1 proposes a hydrophilic polyurethane foam obtained from a polyurethane foam composition that does not contain a silicone-based foam stabilizer, and describes that the exudation of silicone-based substances can be prevented. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 2018-172482 Summary of the Invention [Problem to be solved by the invention]

[0006] However, although the invention described in Patent Document 1 reduces the seepage of substances derived from the foam stabilizer, the density difference between the upper and central parts of the resulting polyurethane foam is large, resulting in variations in physical properties depending on the part, leaving room for improvement.

[0007] Therefore, an object of the present invention is to provide a polyol composition that can produce a polyurethane foam in which the bleeding of a foam stabilizer is suppressed and the difference in density between the upper and central portions is small; a foamable polyurethane composition containing the polyol composition; and a polyurethane foam made from the foamable polyurethane composition. [Means for solving the problem]

[0008] The present inventors have conducted extensive research to solve the above-mentioned problems, and as a result have found that the above-mentioned problems can be solved by incorporating an additive having an SP value within a specific range into a polyol composition without substantially incorporating a foam stabilizer, and have thus completed the present invention as described below.

[0009] The present invention is summarized as follows [1] to [7]. [1] A polyol composition comprising a polyol, a blowing agent, a catalyst, and an additive having an SP value of 11 or less, and substantially no foam stabilizer. [2] The polyol composition according to the above [1], wherein the additive is a phosphate ester compound. [3] The polyol composition according to [1] or [2] above, wherein the blowing agent comprises a hydrofluoroolefin. [4] The polyol composition according to any one of the above [1] to [3], wherein the catalyst comprises a urethanization catalyst. [5] The polyol composition according to any one of the above [1] to [4], wherein the catalyst comprises a trimerization catalyst. [6] A foamable polyurethane composition containing the polyol composition according to any one of the above [1] to [5] and a polyisocyanate. [7] A polyurethane foam comprising the foamable polyurethane composition according to [6] above. [Effects of the Invention]

[0010] According to the present invention, it is possible to provide a polyol composition that can suppress the seepage of a foam stabilizer, thereby preventing contamination, and that can produce a polyurethane foam having a small difference in density between the upper and central portions; a foamable polyurethane composition containing the polyol composition; and a polyurethane foam made from the foamable polyurethane composition. DETAILED DESCRIPTION OF THE INVENTION

[0011] The present invention will be described in detail below. [Polyol composition] The polyol composition of the present invention is a polyol composition containing no foam stabilizer, a polyol, a blowing agent, a catalyst, and an additive having an SP value of 11 or less. As will be described later, the polyol composition is mixed with a polyisocyanate to form a foamable polyurethane composition, which can be foamed to form a polyurethane foam. Each component contained in the polyol composition will be described below.

[0012] <Additives> The polyol composition of the present invention contains an additive (hereinafter also referred to as the additive in the present invention) having an SP value (solubility parameter) of not more than 11. If the additive is not contained, the density difference between the upper and central parts of the resulting polyurethane foam will be large, making it impossible to obtain a polyurethane foam with stable physical properties. The SP value of the additive in the present invention is preferably 10.7 or less, more preferably 10.4 or less, from the viewpoint of reducing the density difference between the upper and central portions of the resulting polyurethane foam. Also, the SP value of the additive in the present invention is preferably 7 or more, more preferably 8 or more, and even more preferably 9.5 or more, from the viewpoint of reducing the internal voids of the resulting polyurethane foam.

[0013] The SP value in the present invention means a solubility parameter, and more specifically, refers to the Hansen solubility parameter. The SP value in the present invention can be calculated by the following formula (1). The unit of the SP value in the present invention is "(cal / cm 3 ) 1 / 2 " SP value = ((δD 2 +δP 2 +δH 2 ) / 4.184) 1 / 2 (1) Here, δD((J / cm 3 ) 1 / 2 ) is the dispersion energy, δP((J / cm 3 ) 1 / 2 ) is the polarization energy, δH ((J / cm 3 ) 1 / 2 ) represents the hydrogen bond energy. These values ​​can be calculated based on the estimation method using the neutral network method called Y-MB in the Hansen Solubility Parameter software (HSPiP 5th Edition (ver.5.0.09)). The additive may be used as a single component or as a combination of two or more components. When a plurality of components are used as additives, the SP value can be calculated as a weighted average of the components, and can be calculated using the following formula (2). m = δ1φ1 + δ2φ2(2) Here, m is the SP value when multiple additives are used, δ1 and δ2 are the SP values ​​of each component of the additive, and φ1 and φ2 are the volume fractions of each component of the additive.

[0014] The properties of the additives used in the present invention are not particularly limited, but are preferably liquid at room temperature (23° C.). The additives used in the present invention preferably have a boiling point of not lower than 100° C., and more preferably not lower than 150° C. Use of such additives can reduce the number of voids and gaps in the resulting polyurethane foam.

[0015] The molecular weight of the additive in the present invention is not particularly limited, but is preferably 500 or less, more preferably 400 or less.

[0016] The type of additive in the present invention is not particularly limited as long as it satisfies the above-mentioned SP value, and examples thereof include aliphatic hydrocarbon compounds, ether compounds, carboxylic acid ester compounds, halogen compounds, ketone compounds, phosphate ester compounds, etc. Among these, from the viewpoints of reducing the density difference between the upper and central portions of the resulting polyurethane foam, suppressing the occurrence of cavities, voids, etc., and improving flame retardancy, the additive in the present invention is preferably a phosphate ester compound.

[0017] Examples of the aliphatic hydrocarbon compound include n-hexane, n-heptane, and n-octane. Examples of the ether compound include chain ethers such as diethyl ether, and cyclic ethers such as tetrahydrofuran and dioxane. Examples of the carboxylic acid ester compound include ethyl acetate and butyl acetate. Examples of halogen compounds include dichlorobenzene, trichloroethane, tetrachloroethane, chloroform, and carbon tetrachloride. Examples of the ketone compound include methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.

[0018] Examples of the phosphate ester compound include monophosphate esters and condensed phosphate esters. Monophosphate esters are phosphate esters having one phosphorus atom in the molecule. Examples of the monophosphate ester include trialkyl phosphates such as trimethyl phosphate, triethyl phosphate, tributyl phosphate, and tri(2-ethylhexyl)phosphate; halogen-containing phosphate esters such as tris(β-chloropropyl)phosphate; trialkoxy phosphates such as tributoxyethyl phosphate; aromatic ring-containing phosphate esters such as tricresyl phosphate, trixylenyl phosphate, tris(isopropylphenyl)phosphate, cresyl diphenyl phosphate, and diphenyl(2-ethylhexyl)phosphate; and acidic phosphate esters such as monoisodecyl phosphate and diisodecyl phosphate.

[0019] Examples of the condensed phosphate ester include aromatic condensed phosphate esters such as trialkyl polyphosphate, resorcinol polyphenyl phosphate, bisphenol A polycresyl phosphate, and bisphenol A polyphenyl phosphate.

[0020] Among the above-mentioned phosphate ester compounds, monophosphate esters are preferred from the viewpoint of reducing the density difference between the upper and central portions of the resulting polyurethane foam while suppressing the occurrence of cavities, voids, etc. Among the monophosphate esters, trimethyl phosphate, triethyl phosphate, and tris(β-chloropropyl) phosphate are preferred from the same viewpoint, with tris(β-chloropropyl) phosphate being more preferred.

[0021] The content of the additive in the present invention is not particularly limited, but is preferably 1 part by mass or more, more preferably 5 parts by mass or more, and even more preferably 8 parts by mass or more, per 100 parts by mass of polyol, and is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, and even more preferably 15 parts by mass or less. When the content of the additive is at least these lower limits, the density difference between the upper and central parts of the obtained polyurethane foam can be reduced, and when it is at most these upper limits, the occurrence of voids and other gaps in the polyurethane foam can be easily suppressed.

[0022] <Polyol> The polyol composition of the present invention contains a polyol as a raw material for polyurethane foam. The polyol used in the present invention is not particularly limited, but examples thereof include polylactone polyols, polycarbonate polyols, polyester polyols, polyether polyols, and polymer polyols.

[0023] Examples of polylactone polyols include polypropiolactone glycol, polycaprolactone glycol, and polyvalerolactone glycol. Examples of polycarbonate polyols include polyols obtained by dealcoholization reaction of hydroxyl group-containing compounds such as ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, octanediol, and nonanediol with ethylene carbonate, propylene carbonate, and the like.

[0024] Examples of polyester polyols include polymers obtained by dehydration condensation of polybasic acids and polyhydric alcohols, polymers obtained by ring-opening polymerization of lactones such as ε-caprolactone and α-methyl-ε-caprolactone, and condensates of hydroxycarboxylic acids and the above-mentioned polyhydric alcohols. Examples of polybasic acids include adipic acid, azelaic acid, sebacic acid, isophthalic acid (m-phthalic acid), terephthalic acid (p-phthalic acid), and succinic acid. Examples of polyhydric alcohols include bisphenol A, ethylene glycol, 1,2-propylene glycol, 1,4-butanediol, diethylene glycol, 1,6-hexane glycol, and neopentyl glycol. Examples of hydroxycarboxylic acids include castor oil and reaction products of castor oil and ethylene glycol.

[0025] Examples of polyether polyols include polymers obtained by ring-opening polymerization of at least one alkylene oxide, such as ethylene oxide, propylene oxide, or tetrahydrofuran, in the presence of at least one low-molecular-weight active hydrogen compound having two or more active hydrogens. Examples of low-molecular-weight active hydrogen compounds having two or more active hydrogens include diols such as bisphenol A, ethylene glycol, propylene glycol, butylene glycol, and 1,6-hexanediol, triols such as glycerin and trimethylolpropane, and amines such as ethylenediamine and butylenediamine.

[0026] Examples of polymer polyols include polymers obtained by graft polymerizing an ethylenically unsaturated compound such as acrylonitrile, styrene, methyl acrylate, or methacrylate with an aromatic polyol, an alicyclic polyol, an aliphatic polyol, or a polyester polyol; polybutadiene polyol; and modified polyols of polyhydric alcohols or hydrogenated products thereof. Examples of aromatic polyols used in the production of polymer polyols include bisphenol A, bisphenol F, phenol novolac, and cresol novolac. Examples of alicyclic polyols used in the production of polymer polyols include cyclohexanediol, methylcyclohexanediol, isophoronediol, dicyclohexylmethanediol, and dimethyldicyclohexylmethanediol. Examples of aliphatic polyols used in the production of polymer polyols include ethylene glycol, propylene glycol, butanediol, pentanediol, and hexanediol.

[0027] Examples of modified polyols of polyhydric alcohols include those obtained by modifying raw material polyhydric alcohols by reacting them with alkylene oxides. Examples of polyhydric alcohols include trihydric alcohols such as glycerin and trimethylolpropane; tetrahydric to octahydric alcohols such as pentaerythritol, sorbitol, mannitol, sorbitan, diglycerin, and dipentaerythritol; sucrose, glucose, mannose, fructose, methyl glucoside, and derivatives thereof; polyols such as phloroglucinol, cresol, pyrogallol, catechol, hydroquinone, bisphenol A, bisphenol F, bisphenol S, 1,3,6,8-tetrahydroxynaphthalene, and 1,4,5,8-tetrahydroxyanthracene; polyfunctional polyols (e.g., having 2 to 100 functional groups) such as castor oil polyol, (co)polymers of hydroxyalkyl (meth)acrylate, and polyvinyl alcohol; and condensates of phenol and formaldehyde (novolak).

[0028] Although the method for modifying the polyhydric alcohol is not particularly limited, a method of adding alkylene oxide (hereinafter also referred to as "AO") is preferably used. Examples of AO include AOs having 2 to 6 carbon atoms, such as ethylene oxide (hereinafter also referred to as "EO"), 1,2-propylene oxide (hereinafter also referred to as "PO"), 1,3-propylene oxide, 1,2-butylene oxide, and 1,4-butylene oxide. Among these, PO, EO, and 1,2-butylene oxide are preferred from the viewpoints of properties and reactivity, and PO and EO are more preferred. When two or more AOs are used (for example, PO and EO), the addition method may be block addition, random addition, or a combination of these.

[0029] The polyol used in the present invention is preferably at least one selected from the group consisting of polyester polyols and polyether polyols. Furthermore, polyols having two hydroxyl groups are preferred. Among these, aromatic polyester polyols, which are polyester polyols having an aromatic ring, are preferred from the viewpoint of enhancing flame retardancy. More preferred aromatic polyester polyols are those obtained by dehydration condensation of polybasic acids having an aromatic ring, such as isophthalic acid (m-phthalic acid) and terephthalic acid (p-phthalic acid), with dihydric alcohols, such as bisphenol A, ethylene glycol, and 1,2-propylene glycol.

[0030] The weight-average molecular weight of the polyol is preferably more than 300, more preferably 400 or more, even more preferably 430 or more, and preferably 20000 or less, more preferably 10000 or less. When the weight-average molecular weight of the polyol is within this range, the composition has good handleability, and the difference in density between the upper and central portions of the obtained polyurethane foam tends to be small. The weight average molecular weight is a weight average molecular weight measured by gel permeation chromatography (GPC) and converted into polystyrene.

[0031] The hydroxyl value of the polyol is preferably 20 to 300 mgKOH / g, more preferably 40 to 280 mgKOH / g, and even more preferably 100 to 250 mgKOH / g. When the hydroxyl value of the polyol is equal to or less than the upper limit, the viscosity of the polyol composition tends to decrease, which is preferable from the viewpoint of handleability, etc. On the other hand, when the hydroxyl value of the polyol is equal to or more than the lower limit, the crosslink density of the polyurethane foam increases, thereby increasing its strength. The hydroxyl value of the polyol can be measured in accordance with JIS K 1557-1:2007.

[0032] The polyol content in the polyol composition of the present invention is preferably 20 to 90% by mass, more preferably 35 to 85% by mass, and even more preferably 50 to 80% by mass. A polyol content of at least the lower limit is preferred because it facilitates the reaction between the polyol and the polyisocyanate. On the other hand, a polyol content of at most the upper limit is preferred from the viewpoint of ease of handling because the viscosity of the polyol composition does not become too high.

[0033] <Catalyst> The catalyst contained in the polyol composition of the present invention includes a trimerization catalyst, a urethanization catalyst, etc., and more preferably contains both a trimerization catalyst and a urethanization catalyst.

[0034] (trimerization catalyst) The catalyst contained in the polyol composition of the present invention preferably contains a trimerization catalyst. The trimerization catalyst promotes the trimerization of isocyanate groups contained in the polyisocyanate (described below) by reacting them with each other, thereby promoting the formation of isocyanurate rings. Examples of trimerization catalysts that can be used include nitrogen-containing aromatic compounds such as tris(dimethylaminomethyl)phenol, 2,4-bis(dimethylaminomethyl)phenol, and 2,4,6-tris(dialkylaminoalkyl)hexahydro-S-triazine; alkali metal carboxylic acid salts such as potassium acetate, potassium 2-ethylhexanoate, and potassium octoate; tertiary ammonium salts such as trimethylammonium salt, triethylammonium salt, and triphenylammonium salt; and quaternary ammonium salts such as tetramethylammonium salt, tetraethylammonium salt, tetraphenylammonium salt, and triethylmonomethylammonium salt. Examples of ammonium salts include ammonium salts of carboxylic acids such as 2,2-dimethylpropanoic acid, and more specifically, quaternary ammonium carboxylic acid salts. These may be used alone or in combination of two or more. Among these, alkali metal carboxylates and quaternary ammonium carboxylates are selected. One or more of these are preferably used, and an embodiment in which both of these are used is also preferred.

[0035] The amount of the trimerization catalyst is preferably 0.1 to 25 parts by mass, more preferably 0.3 to 20 parts by mass, and even more preferably 0.5 to 15 parts by mass, per 100 parts by mass of the polyol. When the amount of the trimerization catalyst is equal to or greater than these lower limits, trimerization of the polyisocyanate occurs more easily, improving the flame retardancy of the resulting polyurethane foam. On the other hand, when the amount of the trimerization catalyst is equal to or less than the upper limit, the reaction can be more easily controlled.

[0036] (Urethanization catalyst) The urethanization catalyst is a catalyst that promotes the reaction between polyol and polyisocyanate. Examples of the urethanization catalyst include amine-based catalysts such as imidazole compounds and piperazine compounds, and metal-based catalysts. Examples of imidazole compounds include tertiary amines in which the secondary amine at the 1-position of the imidazole ring is substituted with an alkyl group, an alkenyl group, or the like. Specific examples include N-methylimidazole, 1,2-dimethylimidazole, 1-ethyl-2-methylimidazole, 1-methyl-2-ethylimidazole, 1,2-diethylimidazole, and 1-isobutyl-2-methylimidazole. Also suitable are imidazole compounds in which the secondary amine in the imidazole ring is substituted with a cyanoethyl group. Furthermore, examples of the piperazine compound include tertiary amines such as N-methyl-N'N'-dimethylaminoethylpiperazine and trimethylaminoethylpiperazine. Furthermore, examples of the amine catalyst include, in addition to imidazole compounds and piperazine compounds, various tertiary amines such as pentamethyldiethylenetriamine, triethylamine, N-methylmorpholinebis(2-dimethylaminoethyl)ether, N,N,N',N",N"-pentamethyldiethylenetriamine, N,N,N'-trimethylaminoethyl-ethanolamine, bis(2-dimethylaminoethyl)ether, N,N-dimethylcyclohexylamine, diazabicycloundecene, triethylenediamine, tetramethylhexamethylenediamine, and tripropylamine.

[0037] Examples of metal catalysts include metal salts of lead, tin, bismuth, copper, zinc, cobalt, nickel, etc., and preferably organic acid metal salts of lead, tin, bismuth, copper, zinc, cobalt, nickel, etc. More preferred are dibutyltin dilaurate, dioctyltin dilaurate, dioctyltin versatate, bismuth trioctate, bismuth tris(2-ethylhexanoate), tin dioctylate, lead dioctylate, etc., and among these, organic acid bismuth salts are even more preferred. The urethanization catalyst may be used alone or in combination of two or more. Among the above, it is preferable to use one or more selected from imidazole compounds and organic acid bismuth salts, and an embodiment in which both of these are used is also preferable.

[0038] The amount of the urethanization catalyst is preferably 0.1 to 20 parts by mass, more preferably 0.3 to 15 parts by mass, and even more preferably 0.5 to 10 parts by mass, per 100 parts by mass of the polyol. When the amount of the resinification catalyst is equal to or greater than these lower limits, urethane bonds are easily formed and the reaction proceeds quickly. On the other hand, when the amount is equal to or less than these upper limits, the reaction rate is easily controlled.

[0039] The total amount of catalyst in the polyol composition is not particularly limited, but is preferably 0.2 to 30 parts by mass, more preferably 0.6 to 20 parts by mass, and even more preferably 1 to 10 parts by mass. When the amount is equal to or greater than these lower limits, the formation of urethane bonds and trimerization proceed appropriately, and flame retardancy tends to be good. When the amount is equal to or less than these upper limits, control of the urethane formation and trimerization reactions becomes easier.

[0040] <Foaming agent> The polyol composition of the present invention contains a blowing agent. This allows a polyurethane foam to be obtained by foaming the composition. The blowing agent preferably contains a hydrofluoroolefin (HFO). In the present invention, when a hydrofluoroolefin is used as the blowing agent, the stability of the blowing agent is high, the catalytic activity is less likely to decrease, and the environmental load is also reduced. Examples of hydrofluoroolefins include fluoroalkenes having about 3 to 6 carbon atoms. The hydrofluoroolefin may be a hydrochlorofluoroolefin having a chlorine atom, and therefore may be a chlorofluoroalkene having about 3 to 6 carbon atoms. More specific examples include trifluoropropene, tetrafluoropropenes such as HFO-1234, pentafluoropropenes such as HFO-1225, chlorotrifluoropropenes such as HFO-1233, chlorodifluoropropene, chlorotrifluoropropene, and chlorotetrafluoropropene. More specific examples include 1,3,3,3-tetrafluoropropene (HFO-1234ze), 1,1,3,3-tetrafluoropropene, 1,2,3,3,3-pentafluoropropene (HFO-1225ye), 1,1,1-trifluoropropene, 1,1,1,3,3-pentafluoropropene (HFO-1225zc), 1,1,1,3,3,3-hexafluorobut-2-ene, 1,1,2,3,3-pentafluoropropene (HFO-1225yc), 1,1,1,2,3-pentafluoropropene (HFO-1225yez), 1-chloro-3,3,3-trifluoropropene (HFO-1233zd), and 1,1,1,4,4,4-hexafluorobut-2-ene. Of these, HFO-1233zd is preferred. These hydrofluoroolefins may be used alone or in combination of two or more.

[0041] The amount of hydrofluoroolefin blended is preferably 10 to 60 parts by mass, more preferably 15 to 55 parts by mass, even more preferably 17 to 45 parts by mass, and even more preferably 20 to 40 parts by mass, per 100 parts by mass of polyol. When the amount of hydrofluoroolefin blended is equal to or greater than the lower limit, foaming is promoted, resulting in good foamability and enabling the density of the resulting polyurethane foam to be reduced. On the other hand, when the amount of hydrofluoroolefin blended is equal to or less than the upper limit, excessive foaming can be prevented.

[0042] The polyol composition of the present invention may contain a blowing agent other than hydrofluoroolefin. Examples of blowing agents other than hydrofluoroolefin include water, nitrogen gas, oxygen gas, argon gas, and carbon dioxide gas. Among these, water, oxygen gas, and carbon dioxide gas are preferred from the viewpoint of ease of handling, and water is more preferred from the viewpoint of adjusting the isocyanate index and ease of handling.

[0043] The amount of the blowing agent other than the hydrofluoroolefin in the polyol composition is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, and even more preferably 0.5 to 3.5 parts by mass, per 100 parts by mass of the polyol. When the amount of the blowing agent is equal to or greater than the lower limit, foaming is promoted, and the density of the resulting polyurethane foam can be reduced. On the other hand, when the amount of the blowing agent is equal to or less than the upper limit, excessive foaming can be suppressed.

[0044] <Foam stabilizer> The polyol composition of the present invention is substantially free of a foam stabilizer, which prevents the foam stabilizer from bleeding out from the polyurethane foam, thereby suppressing contamination and effectively preventing problems such as a decrease in adhesion between the polyurethane foam and other components. Here, "substantially free" means that the content of the foam stabilizer is 2% by mass or less, preferably 0.5% by mass or less, more preferably 0.1% by mass or less, and even more preferably 0% by mass, based on the total amount of the polyol composition. Here, the foam stabilizer refers to a foam stabilizer generally used in the production of polyurethane foam, and examples thereof include surfactants such as polyoxyalkylene foam stabilizers such as polyoxyalkylene alkyl ethers, and silicone foam stabilizers such as octamethylcyclotetrasiloxane and organopolysiloxanes. Silicone foam stabilizers are compounds having a polysiloxane chain as the skeleton.

[0045] <Flame retardant> The polyol composition of the present invention may contain a flame retardant. By containing a flame retardant, the flame retardancy of the resulting polyurethane foam can be effectively improved. Examples of the flame retardant include solid flame retardants such as red phosphorus-based flame retardants, phosphate-containing flame retardants, bromine-containing flame retardants, chlorine-containing flame retardants, antimony-containing flame retardants, boron-containing flame retardants, and metal hydroxides.

[0046] (Red phosphorus flame retardant) The red phosphorus-based flame retardant may consist of red phosphorus alone, or may be red phosphorus coated with a resin, metal hydroxide, metal oxide, or the like, or may be red phosphorus mixed with a resin, metal hydroxide, metal oxide, or the like. The resin that coats the red phosphorus or is mixed with the red phosphorus is not particularly limited, but examples thereof include thermosetting resins such as phenolic resin, epoxy resin, unsaturated polyester resin, melamine resin, urea resin, aniline resin, and silicone resin. From the viewpoint of flame retardancy, metal hydroxides are preferred as the compound to be coated or mixed. The metal hydroxide to be used may be appropriately selected from those described below.

[0047] (phosphate-containing flame retardants) Examples of phosphate-containing flame retardants include phosphates formed from salts of various phosphoric acids with at least one metal or compound selected from metals of Groups IA to IVB of the periodic table, ammonia, aliphatic amines, aromatic amines, and heterocyclic compounds containing nitrogen in the ring. The phosphoric acid is not particularly limited, but examples thereof include monophosphoric acid, pyrophosphoric acid, and polyphosphoric acid. Examples of metals in Groups IA to IVB of the periodic table include lithium, sodium, calcium, barium, iron (II), iron (III), and aluminum. Examples of the aliphatic amine include methylamine, ethylamine, diethylamine, triethylamine, ethylenediamine, piperazine, etc. Examples of the aromatic amine include aniline, o-toliidine, 2,4,6-trimethylaniline, anisidine, 3-(trifluoromethyl)aniline, etc. Examples of the heterocyclic compound containing nitrogen in the ring include pyridine, triazine, melamine, etc.

[0048] (Bromine-containing flame retardants) The bromine-containing flame retardant is not particularly limited as long as it contains bromine in its molecular structure and is a compound that is solid at room temperature and normal pressure, and examples thereof include brominated aromatic ring-containing aromatic compounds. Examples of the brominated aromatic ring-containing aromatic compound include monomeric organic bromine compounds such as hexabromobenzene, pentabromotoluene, hexabromobiphenyl, decabromobiphenyl, decabromodiphenyl ether, octabromodiphenyl ether, hexabromodiphenyl ether, bis(pentabromophenoxy)ethane, ethylenebis(pentabromophenyl), ethylenebis(tetrabromophthalimide), and tetrabromobisphenol A.

[0049] The brominated aromatic ring-containing aromatic compound may also be a bromine compound polymer. Specific examples include brominated polycarbonates such as polycarbonate oligomers produced using brominated bisphenol A as a raw material, copolymers of the polycarbonate oligomers with bisphenol A, and diepoxy compounds produced by reacting brominated bisphenol A with epichlorohydrin. Further examples include brominated epoxy compounds such as monoepoxy compounds obtained by reacting brominated phenols with epichlorohydrin, poly(brominated benzyl acrylate), brominated phenol condensates of brominated polyphenylene ether, brominated bisphenol A, and cyanuric chloride, brominated (polystyrene), poly(brominated styrene), brominated polystyrenes such as crosslinked brominated polystyrene, and crosslinked or non-crosslinked brominated poly(methylstyrene). Furthermore, compounds other than brominated aromatic ring-containing aromatic compounds such as hexabromocyclododecane may also be used. These bromine-containing flame retardants may be used alone or in combination of two or more.

[0050] (Chlorine-containing flame retardants) Chlorine-containing flame retardants include those commonly used in flame-retardant resin compositions, such as polychlorinated naphthalene, chlorendic acid, and dodecachlorododecahydrodimethanodibenzocyclooctene, which is sold under the trade name "Dechlorane Plus."

[0051] (Antimony-containing flame retardant) Examples of antimony-containing flame retardants include antimony oxide, antimony salts, and pyroantimony salts. Examples of antimony oxide include antimony trioxide and antimony pentoxide. Examples of antimony salts include sodium antimonate and potassium antimonate. Examples of pyroantimonate salts include sodium pyroantimonate and potassium pyroantimonate. The antimony-containing flame retardants may be used alone or in combination of two or more.

[0052] (Boron-containing flame retardants) Examples of boron-containing flame retardants include borax, boron oxide, boric acid, borate salts, etc. Examples of boron oxide include diboron trioxide, boron trioxide, diboron dioxide, tetraboron trioxide, and tetraboron pentoxide. Examples of borates include borates of alkali metals, alkaline earth metals, elements of Groups 4, 12, and 13 of the periodic table, and ammonium. Specific examples include alkali metal borates such as lithium borate, sodium borate, potassium borate, and cesium borate, alkaline earth metal borates such as magnesium borate, calcium borate, and barium borate, zirconium borate, zinc borate, aluminum borate, and ammonium borate. The boron-containing flame retardants may be used alone or in combination of two or more.

[0053] (metal hydroxide) Examples of metal hydroxides include magnesium hydroxide, calcium hydroxide, aluminum hydroxide, iron hydroxide, nickel hydroxide, zirconium hydroxide, titanium hydroxide, zinc hydroxide, copper hydroxide, vanadium hydroxide, tin hydroxide, etc. The metal hydroxides may be used alone or in combination of two or more.

[0054] When a flame retardant is contained in the polyol composition, the amount of the flame retardant is preferably 1 to 100 parts by mass, more preferably 5 to 80 parts by mass, and even more preferably 10 to 70 parts by mass, per 100 parts by mass of the polyol.

[0055] <Inorganic fillers> The polyol composition of the present invention may contain an inorganic filler other than the above-mentioned solid flame retardant, as long as the effect of the present invention is not impaired. Examples of inorganic fillers include alumina, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, ferrites, basic magnesium carbonate, calcium carbonate, magnesium carbonate, zinc carbonate, barium carbonate, dawsonite, hydrotalcite, calcium sulfate, barium sulfate, gypsum fiber, calcium silicate, talc, clay, mica, montmorillonite, bentonite, activated clay, seviolite, imogolite, sericite, glass fiber, glass beads, silica balloon, aluminum nitride, boron nitride, silicon nitride, graphite, carbon fiber, carbon balloon, charcoal powder, various metal powders, potassium titanate, magnesium sulfate, lead zirconate titanate, molybdenum sulfide, silicon carbide, stainless steel fiber, various magnetic powders, slag fiber, fly ash, silica alumina fiber, alumina fiber, silica fiber, zirconia fiber, etc. Inorganic fillers are solid components that become solid at room temperature and normal pressure. The inorganic filler may be used alone or in combination of two or more kinds.

[0056] <Other ingredients> The polyol composition may contain one or more selected from phenol-based, amine-based, sulfur-based, and other antioxidants, heat stabilizers, metal inhibitors, antistatic agents, stabilizers, crosslinking agents, lubricants, softeners, pigments, and the like, as needed, within the scope of the object of the present invention.

[0057] <Method of producing polyol composition> There are no particular limitations on the method for producing the polyol composition of the present invention, and it can be produced, for example, by stirring each component at about 20 to 40° C. for about 30 seconds to 20 minutes using a homodisper or the like.

[0058] [Foamable polyurethane composition and polyurethane foam] The foamable polyurethane composition of the present invention contains the polyol composition of the present invention and a polyisocyanate, and is obtained by mixing them. The polyurethane foam of the present invention is made of the foamable polyurethane composition, and specifically, is a reaction product obtained by reacting and foaming the foamable polyurethane composition.

[0059] <Polyisocyanate> Examples of polyisocyanates include aromatic polyisocyanates, alicyclic polyisocyanates, and aliphatic polyisocyanates. Examples of aromatic polyisocyanates include phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, dimethyldiphenylmethane diisocyanate, triphenylmethane triisocyanate, naphthalene diisocyanate, and polymethylene polyphenyl polyisocyanate.

[0060] Examples of alicyclic polyisocyanates include cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and dimethyldicyclohexylmethane diisocyanate.

[0061] Examples of the aliphatic polyisocyanate include methylene diisocyanate, ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, and hexamethylene diisocyanate.

[0062] Among these, from the viewpoints of ease of use and availability, aromatic polyisocyanates are preferred, and diphenylmethane diisocyanate is more preferred. One type of polyisocyanate may be used alone, or two or more types may be used in combination. Furthermore, known additives that are typically added to polyisocyanates may be appropriately added to the polyisocyanate before it is mixed with the polyol composition.

[0063] <Isocyanate Index> The isocyanate index of the foamable polyurethane composition of the present invention is not particularly limited, but is preferably 150 or higher. If the isocyanate index is equal to or higher than the lower limit, the amount of polyisocyanate relative to the polyol becomes excessive, facilitating the formation of isocyanurate bonds due to the trimerization of the polyisocyanate, resulting in improved flame retardancy of the polyurethane foam. Furthermore, if the isocyanate index is equal to or higher than the lower limit, combined with the use of the various catalysts described above, it becomes easier to produce a polyurethane foam having sufficient isocyanurate bonds, i.e., a polyurethane foam that combines high levels of flame retardancy and thermal insulation. From these perspectives, the isocyanate index is more preferably 150 or higher, even more preferably 200 or higher, and even more preferably 250 or higher. The isocyanate index is preferably not more than 800, more preferably not more than 600, and even more preferably not more than 400. When the isocyanate index is not more than the upper limit, the resulting polyurethane foam will have a good balance between flame retardancy and production costs.

[0064] The isocyanate index can be calculated by the following method. Isocyanate Index = number of equivalents of polyisocyanate ÷ (number of equivalents of polyol + number of equivalents of water) × 100 Here, each equivalent number can be calculated as follows: Polyisocyanate equivalent number = Amount of polyisocyanate used (g) × NCO content (mass%) / Molecular weight of NCO (mol) × 100 Equivalent weight of polyol = OHV × amount of polyol used (g) ÷ molecular weight of KOH (mmol) OHV is the hydroxyl value of the polyol (mg KOH / g). Equivalents of water = Amount of water used (g) / Molecular weight of water (moles) × Number of OH groups in water In the above formulas, the molecular weight of NCO is 42 (mol), the molecular weight of KOH is 56,100 (mmol), the molecular weight of water is 18 (mol), and the number of OH groups in water is 2.

[0065] <Method of manufacturing polyurethane foam> Although there are no particular limitations on the method for producing the polyurethane foam, it is preferable to foam and react a foamable polyurethane composition obtained by mixing a polyisocyanate and a polyol composition. Specifically, it is preferable to mix the polyisocyanate and the polyol composition by collision mixing using a spray gun or the like, and then spray the mixture. In the present invention, the polyurethane foam may be obtained by mixing the polyisocyanate and the polyol composition, pouring the mixture into a container such as a mold or a frame, and curing the mixture.

[0066] <Applications of polyurethane foam> The polyurethane foam of the present invention is not particularly limited in its application, but can be suitably used in buildings such as walls, ceilings, roofs, and floors of buildings. It can also be suitably used as a member for filling any openings that occur in buildings, including joints and holes that occur between structural members of buildings. [Example]

[0067] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0068] 1. Polyurethane foam manufacturing To obtain polyurethane foams according to the examples and comparative examples, two components, a polyol composition and a polyisocyanate, were prepared according to the formulations shown in Table 1. The details of each component in the table are as follows:

[0069] (1) Polyol composition [Polyol] p-Phthalic acid polyester polyol (Kawasaki Chemical Industries, Ltd., product name: Maximol RFK-505, hydroxyl value = 250 mg KOH / g)

[0070] 〔catalyst〕 Urethane catalyst, bismuth tris(2-ethylhexanoate) (Shepherd Chemical Company, product name: BiCAT8210) concentration 28% by mass Urethane catalyst, imidazole derivative (Kao Corporation, product name: Kaolizer No. 390) concentration 68% by mass Trimerization catalyst, organic ammonium salt (manufactured by Air Products, product name: DABCO TMR7) concentration 85% by mass

[0071] [Blowing Agent] HFO-1233zd (hydrofluoroolefin), (Honeywell, product name: Soltis LBA) ·water

[0072] [Additives] n-Hexane SP value 7.30 Boiling point 69℃ Triethyl phosphate (TEP) SP value 9.83 Boiling point 216°C Trimethyl phosphate (TMP) SP value 9.09 Boiling point 180-195°C Tris(β-chloropropyl)phosphate (TMCPP) SP value 10.11 No boiling point (decomposes at 200°C) Resorcinol bis(diphenyl phosphate) (manufactured by Daihachi Chemical Industry, product name: CR733S) SP value 11.56, no boiling point N,N-dimethylformamide (DMF) SP value 12.05 Boiling point 153°C Ethanol SP value 12.23 Boiling point 78℃ Dimethyl sulfoxide SP value 12.16 Boiling point 189°C Diethylene glycol SP value 14.23 Boiling point 244℃

[0073] [Foam stabilizer] Silicone foam stabilizer (Toray Dow Corning, product name SH-193)

[0074] (2) Polyisocyanate Polymethylene polyphenyl polyisocyanate (polymeric-MDI) (manufactured by Sumika Covestro Urethane Co., Ltd., product name: Sumidur 44V20L)

[0075] The polyurethane foams in Examples 1 to 5 and Comparative Examples 1 to 8 were formed according to the following procedure. To a kneaded mixture of the components of the polyol composition shown in the formulation in Table 1, polyisocyanate was added in the blending ratio shown in Table 1. The mixture was then stirred for 5 seconds at 8,000 rpm using a hand mixer (PRIMIX Corporation's high-speed disperser, Homodisper 2.5 model) at an ambient temperature of 20°C and a liquid temperature of 15±1°C, and poured into a mold (200 mm x 200 mm x 200 mm) to produce a foamable polyurethane composition. The resulting foamable polyurethane resin composition lost fluidity over time, and a foamed polyurethane resin composition (polyurethane foam) was obtained.

[0076] 2. Evaluation The evaluation was based on the following criteria. [External contamination] A line was drawn on the surface of the obtained polyurethane foam with a marker (ZEBRA's "Maki Extra Fine" oil-based black), and those that did not repel the marker ink were rated as "A", and those that did repel the marker ink were rated as "D". Note that if the marker ink is repelled, this means that the foam stabilizer or the like has bled out onto the surface of the polyurethane foam, indicating that it is likely to contaminate the object of use.

[0077] [Density ratio] The densities of the upper and central parts of the polyurethane foam were measured, and the density ratio was calculated based on the following formula. The density at the top refers to the density at a distance of 1 to 3 cm from the surface (skin) of the polyurethane foam, and the density at the center refers to the density at a distance of 7 to 9 cm from the surface (skin) of the polyurethane foam. The closer the density ratio is to 1, the smaller the density difference. Density ratio = Top density / Middle density (Evaluation criteria) A: Density ratio is 0.90 or more and less than 1.08 B: Density ratio is 1.08 or more and less than 1.10 C: Density ratio is 1.10 or more and less than 1.20 D: Density ratio is less than 0.90 or more than 1.20

[0078] [Foam properties] The properties of the polyurethane foam (foam) were evaluated based on the following criteria by visually observing the formation of abnormalities (cavities, voids, etc.). A: No cavities or voids were found in the foam. B: Very few cavities or voids were observed in the foam. C: Slight cavities or voids were observed in the foam. D: Many cavities or voids were found in the foam.

[0079] [Table 1]

[0080] As is clear from the results of the above examples, the polyurethane foams formed from the polyol compositions of the present invention were able to prevent contamination of the objects to which they were used, and also had good physical properties with small density differences. In contrast, it was found that polyurethane foams formed from the polyol compositions shown in the comparative examples tend to stain the objects to which they are used or have large density differences and poor physical properties.

Claims

1. A polyol composition comprising a polyol, a blowing agent, a catalyst, and an additive having an SP value of 11 or less, and substantially no foam stabilizer.

2. The polyol composition of claim 1 , wherein the additive is a phosphate ester compound.

3. The polyol composition of claim 1 or 2, wherein the blowing agent comprises a hydrofluoroolefin.

4. The polyol composition according to any one of claims 1 to 3, wherein the catalyst comprises a urethanization catalyst.

5. The polyol composition according to any one of claims 1 to 4, wherein the catalyst comprises a trimerization catalyst.

6. A foamable polyurethane composition comprising the polyol composition according to any one of claims 1 to 5 and a polyisocyanate.

7. A polyurethane foam comprising the foamable polyurethane composition according to claim 6.

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