Polyol composition, reactive liquid set for producing polyurethane foam, polyurethane foam, and method for producing polyurethane foam

Abstract

To provide a technique that at least partially solves problems in improving the appearance of a polyurethane foam panel obtained when used for polyurethane foam panel production, and problems in improving the appearance of a polyurethane foam obtained when used for polyurethane foam injection foaming.SOLUTION: This polyol composition is a polyol composition for polyurethane foam panel production and / or a polyol composition for polyurethane foam injection foaming production, comprising a polyol and a physical blowing agent having a boiling point of 10°C or lower under atmospheric pressure.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present disclosure relates to a polyol composition, a reaction liquid set for producing a polyurethane foam, a polyurethane foam, and a method for producing a polyurethane foam. [Background technology]

[0002] Patent Document 1 discloses a technique in which HFO-1234ze, polyol, and isocyanate are mixed and free-foamed. Patent Documents 2 and 3 disclose polyisocyanurate foam-forming compositions containing a blowing agent. Examples of the blowing agents used in these documents include HCFO-1233zd, HFO-1224yd, and HFO-1336mzz(Z), which have boiling points of more than 10°C under atmospheric pressure. Patent Documents 4 and 5 disclose methods for manufacturing sandwich panels. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2015-091999 [Patent Document 2] Japanese Patent Publication No. 2022-064051 [Patent Document 3] Japanese Patent Publication No. 2023-094361 [Patent Document 4] Japanese Patent Application Laid-Open No. 2008-254305 [Patent Document 5] Japanese Patent Application Publication No. 10-000633 Summary of the Invention [Problem to be solved by the invention]

[0004] There is a need for a polyol composition that, when used in the production of polyurethane foam panels, can improve the appearance of the resulting polyurethane foam panels. There is also a need for a polyol composition that, when used in polyurethane foam injection foaming, can improve the appearance of the resulting polyurethane foams. The present disclosure is intended to solve at least part of the above problems, and can be realized in the following forms. [Means for solving the problem]

[0005] A polyol composition for producing a polyurethane foam panel and / or a polyol composition for producing an injection foamed polyurethane foam, comprising: A polyol composition comprising a polyol and a physical blowing agent having a boiling point of 10°C or less under atmospheric pressure. [Effects of the Invention]

[0006] The present disclosure solves at least part of the above problems. For example, when used in the production of polyurethane foam panels, the resulting polyurethane foam panels have a good appearance. For example, when used in polyurethane foam injection foaming, the resulting polyurethane foam has a good appearance. [Brief explanation of the drawings]

[0007] [Figure 1] 1 is a perspective view schematically showing a polyurethane foam panel according to an embodiment, with part of the frame material omitted. [Figure 2] FIG. 1 is a diagram illustrating injection foaming of a polyurethane foam panel. [Figure 3] FIG. 3 is a diagram showing the press machine of FIG. 2 in a closed state. [Figure 4] FIG. 10 is a diagram showing the state in which foam raw material is injected, foamed, and hardened. DETAILED DESCRIPTION OF THE INVENTION

[0008] The present disclosure will be described in detail below. In this specification, when a numerical range is indicated using "-", it is intended to include both the lower limit and the upper limit unless otherwise specified. For example, the expression "10-20" includes both the lower limit "10" and the upper limit "20". In other words, "10-20" has the same meaning as "10 or more and 20 or less". In addition, in this specification, the upper limit and lower limit of each numerical range can be combined in any way.

[0009] 1. Polyol composition The polyol composition is a polyol composition for producing polyurethane foam panels and / or a polyol composition for producing polyurethane foam injection foam, and contains a polyol and a physical blowing agent having a boiling point of 10°C or less under atmospheric pressure.

[0010] (1) Polyol The polyol is not particularly limited, and various polyols may be used alone or in combination of two or more kinds.

[0011] The polyol is preferably at least one selected from the group consisting of polyether polyol, polyester polyol, polyether ester polyol, polycarbonate diol, and polyol having a carbon-carbon bond main chain. Examples of polyester polyols include aliphatic or aromatic polycondensation polyester polyols and polycaprolactone polyols. Examples of polyether polyols include polyoxypropylene-polyoxyethylene polyols, polymer polyols, and polyoxytetramethylene glycols. Examples of polyols having a carbon-carbon bond-based main chain include polyolefin polyols such as polybutadiene polyol and isoprene polyol, plant-derived polyols, and acrylic polyols.

[0012] Polyester polyols are more advantageous than polyether polyols in terms of flame retardancy. From the viewpoint of flame retardancy, the polyol of the present disclosure preferably contains a polyester polyol. The content of the polyester polyol is preferably more than 85 parts by mass, more preferably 90 parts by mass or more, and even more preferably 95 parts by mass or more, based on 100 parts by mass of the total polyol. The upper limit of the content of the polyester polyol is not particularly limited and may be 100 parts by mass.

[0013] The polyester polyol is, for example, a polyester polyol obtained by condensing one or more compounds having at least two hydroxyl groups with one or more compounds having at least two carboxyl groups, or a ring-opening polymer of a cyclic ester such as caprolactone or methylvalerolactone.

[0014] The compound having at least two hydroxy groups may be, for example, one or more selected from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, 1,3-butanediol, 1,4-butanediol, tetramethylene glycol, neopentyl glycol, methylpentanediol, butylethylpropanediol, hexamethylene glycol, decamethylene glycol, glycerin, trimethylolpropane, pentaerythritol, and sorbitol. Among these, one or more selected from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, and propylene glycol are preferred, and a mixture of ethylene glycol, diethylene glycol, and triethylene glycol is more preferred.

[0015] The compound having at least two carboxyl groups may be an aromatic carboxylic acid or an aliphatic carboxylic acid. The compound having at least two carboxyl groups is preferably at least one selected from the group consisting of phthalic acid, isophthalic acid, terephthalic acid, malonic acid, maleic acid, succinic acid, adipic acid, tartaric acid, pimelic acid, azelaic acid, sebacic acid, oxalic acid, trimellitic acid, and hemellitic acid, and more preferably phthalic acid, isophthalic acid, or terephthalic acid. The compound having at least two carboxyl groups may be an anhydride of the above carboxylic acid.

[0016] Among the polyester polyols mentioned above, the polyol preferably contains an aromatic polyester polyol, and more preferably contains a phthalate polyester polyol, which is a condensate of phthalic acid and a polyhydric alcohol.

[0017] The number average molecular weight, the number of functional groups, and the hydroxyl value of the polyol are not particularly limited. The number average molecular weight of the polyol is preferably 100 to 3000, more preferably 150 to 2000, and even more preferably 200 to 1500. The number average molecular weight of the polyol can be calculated based on polystyrene standards by gel permeation chromatography (GPC) measurement. The number of functional groups of the polyol is preferably 2 to 7, more preferably 2 to 6, even more preferably 2 to 5, still more preferably 2 to 4, still more preferably 2 to 3, and particularly preferably 2. The hydroxyl value (OHV) of the polyol is preferably 100 mgKOH / g to 600 mgKOH / g, more preferably 120 mgKOH / g to 500 mgKOH / g, and even more preferably 150 mgKOH / g to 450 mgKOH / g.

[0018] (2) Foaming agent The polyol composition contains a physical blowing agent (hereinafter also referred to as physical blowing agent A) having a boiling point of 10°C or lower under atmospheric pressure (1 atmosphere). The lower limit of the boiling point of physical blowing agent A is not particularly limited. The lower limit of the boiling point of physical blowing agent A is usually −50°C or higher. Only one type of physical blowing agent A may be used, or two or more types may be used in combination.

[0019] The physical blowing agent A is preferably at least one selected from the group consisting of partially halogenated hydrocarbons, hydrocarbons, and ethers. From the viewpoint of reducing the environmental load, the partially halogenated hydrocarbon is preferably a hydrohaloolefin, more preferably a hydrofluoroolefin (HFO) or a hydrochlorofluoroolefin (HCFO). The number of carbon atoms in the hydrohaloolefin is not particularly limited, and may be, for example, 3 or more and 6 or less. The hydrohaloolefin may be, for example, one or more selected from the group consisting of trans-1,1,1,4,4,4-hexafluoro-2-butene, 3,3,3-trifluoropropene, trans-1,3,3,3-tetrafluoropropene, cis-1,3,3,3-tetrafluoropropene, 2,3,3,3-tetrafluoropropene, 1,1,3,3-tetrafluoropropene, trans-1,2,3,3,3-pentafluoropropene, cis-1,2,3,3,3-pentafluoropropene, 1,1,3,3,3-pentafluoropropene, and 1,1,2,3,3-pentafluoropropene. Among these, trans-1,1,1,4,4,4-hexafluoro-2-butene is preferred.

[0020] The content of physical foaming agent A is not particularly limited. From the viewpoint of improving the appearance, the content of physical foaming agent A is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and even more preferably 2 parts by mass or more, relative to 100 parts by mass of polyol. From the viewpoint of storage stability, the content of physical foaming agent A is preferably 10 parts by mass or less, more preferably 8 parts by mass or less, and even more preferably 5 parts by mass or less. From these viewpoints, the content of physical foaming agent A is preferably 0.5 parts by mass or more and 10 parts by mass or less, more preferably 1 part by mass or more and 8 parts by mass or less, and even more preferably 2 parts by mass or more and 5 parts by mass or less.

[0021] From the viewpoint of storage stability, the polyol composition preferably further contains a physical blowing agent (hereinafter also referred to as physical blowing agent B) having a boiling point at atmospheric pressure of higher than 10°C. The upper limit of the boiling point of physical blowing agent B is not particularly limited. The upper limit of the boiling point of physical blowing agent B is usually 100°C or lower, and preferably 50°C or lower. Only one type of physical blowing agent B may be used, or two or more types may be used in combination.

[0022] The physical blowing agent B is preferably at least one selected from the group consisting of partially halogenated hydrocarbons, hydrocarbons, and ethers. From the viewpoint of reducing the environmental load, the partially halogenated hydrocarbon is preferably a hydrohaloolefin, more preferably a hydrofluoroolefin (HFO) or a hydrochlorofluoroolefin (HCFO). The number of carbon atoms in the hydrohaloolefin is not particularly limited, and may be, for example, 3 or more and 6 or less. The hydrohaloolefin may be, for example, one or more selected from the group consisting of trans-1-chloro-3,3,3-trifluoropropene, cis-1,3,3,3-tetrafluoropropene, cis-1,1,1,4,4,4-hexafluoro-2-butene, and cis-1-chloro-2,3,3,3-tetrafluoropropene. Among these, trans-1-chloro-3,3,3-trifluoropropene is preferred.

[0023] The content of physical blowing agent B is not particularly limited. From the viewpoint of foamability, the content of physical blowing agent B is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and even more preferably 20 parts by mass or more, per 100 parts by mass of polyol. From the viewpoint of cost and suppressing catalyst deactivation, the content of physical blowing agent B is preferably 60 parts by mass or less, more preferably 50 parts by mass or less, even more preferably 45 parts by mass or less, and particularly preferably 40 parts by mass or less. From these viewpoints, the content of physical blowing agent B is preferably 5 parts by mass or more and 60 parts by mass or less, more preferably 10 parts by mass or more and 50 parts by mass or less, even more preferably 20 parts by mass or more and 45 parts by mass or less, and particularly preferably 20 parts by mass or more and 40 parts by mass or less.

[0024] The polyol composition may further contain a chemical foaming agent. The chemical foaming agent is, for example, a compound that reacts with isocyanate to generate carbon dioxide gas and form a foam. Water is a suitable chemical foaming agent. From the viewpoint of reducing density, the water content is 0 parts by mass or more, preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and even more preferably 0.8 parts by mass or more, per 100 parts by mass of polyol. From the viewpoint of improving appearance, the water content is preferably 6 parts by mass or less, more preferably 4 parts by mass or less, and even more preferably 3 parts by mass or less. From these viewpoints, the water content is preferably 0.1 parts by mass or more and 6 parts by mass or less, more preferably 0.5 parts by mass or more and 4 parts by mass or less, and even more preferably 0.8 parts by mass or more and 3 parts by mass or less.

[0025] (3) Catalyst (optional component) The polyol composition may contain a catalyst. The catalyst may be used alone or in combination of two or more.

[0026] The catalyst may contain a trimerization catalyst from the viewpoint of improving flame retardancy. The trimerization catalyst is a catalyst that reacts isocyanate groups contained in isocyanate to trimerize them and promote the formation of isocyanurate rings. Only one trimerization catalyst may be used, or two or more trimerization catalysts may be used in combination.

[0027] The trimerization catalyst may be, for example, one or more selected from the group consisting of alkali metal carboxylates, nitrogen-containing aromatic compounds, tertiary ammonium salts, and quaternary ammonium salts. Examples of alkali metal carboxylates include potassium octoate and potassium acetate. Examples of nitrogen-containing aromatic compounds include tris(dimethylaminomethyl)phenol, 2,4-bis(dimethylaminomethyl)phenol, and 2,4,6-tris(dialkylaminoalkyl)hexahydro-S-triazine. Examples of tertiary ammonium salts include trimethylammonium salts, triethylammonium salts, and triphenylammonium salts. Examples of quaternary ammonium salts include tetramethylammonium salts, tetraethylammonium salts, and tetraphenylammonium salts. Among these, alkali metal carboxylates are preferred, and potassium carboxylate is more preferred.

[0028] The content of the trimerization catalyst is not particularly limited. The content of the trimerization catalyst is 0 parts by mass or more relative to 100 parts by mass of the polyol. When a trimerization catalyst is contained, from the viewpoint of improving flame retardancy, it is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and even more preferably 1 part by mass or more. From the viewpoint of improving appearance, the content of the trimerization catalyst is preferably 5 parts by mass or less, more preferably 4 parts by mass or less, and even more preferably 3 parts by mass or less. From these viewpoints, the content of the trimerization catalyst is preferably 0.1 parts by mass or more and 5 parts by mass or less, more preferably 0.5 parts by mass or more and 4 parts by mass or less, and even more preferably 1 part by mass or more and 3 parts by mass or less.

[0029] The catalyst may include a foaming catalyst, which may be, for example, one or more compounds selected from the group consisting of morpholine compounds, amine compounds, and piperazine compounds. An example of the morpholine compound is 2,2-dimorpholine diethyl ether. Examples of the amine compound include N,N-dimethyl-N-(1-methylethyl)-N-[2-methyl(1-methylethyl)amino]ethyl-1,2-ethylenediamine, bis(2-dimethylaminoethyl) ether, N,N-dimethylaminoethoxyethanol, and N,N,N',N',N''-pentamethyldiethylenetriamine. The catalyst may include a resinification catalyst, a catalyst that can promote both foaming and resinification (a balanced catalyst). The catalyst content is preferably 0.1 to 15 parts by mass, more preferably 0.5 to 10 parts by mass, in total, relative to 100 parts by mass of polyol.

[0030] (4) Other ingredients The polyol composition may contain other components in addition to the above components, such as known additives such as a foam stabilizer, a flame retardant, a plasticizer, a colorant, an antioxidant, an ultraviolet absorber, an antibacterial agent, a tackifier, and a compatibilizer.

[0031] The foam stabilizer may be, for example, one or more selected from the group consisting of silicone-based foam stabilizers and fluorine-containing compound-based foam stabilizers. Only one type of foam stabilizer may be used, or two or more types may be used in combination. From the viewpoint of flame retardancy, it is preferable that the polyol composition does not contain any foam stabilizer other than a silicone-based foam stabilizer. Examples of foam stabilizers other than silicone-based foam stabilizers, i.e., undesirable foam stabilizers, include ethoxylates of fatty alcohols and / or fatty acids, block copolymers of propylene oxide and / or butylene oxide and ethylene oxide, including diblock and triblock copolymers, and ethoxylates of polyethylene oligomers. Examples of silicone-based foam stabilizers include polyether-modified siloxanes and block copolymers of polydimethylsiloxane and polyethylene-polypropylene glycol. The amount of the foam stabilizer is preferably 1 part by mass or more and 20 parts by mass or less, and more preferably 4 parts by mass or more and 15 parts by mass or less, relative to 100 parts by mass of the polyol.

[0032] The flame retardant may be, for example, one or more selected from the group consisting of phosphate ester compounds, phosphorus compounds, melamine compounds, metal hydrates, and antimony compounds. Only one flame retardant may be used, or two or more flame retardants may be used in combination. Examples of the phosphate ester compounds include tris(chloropropyl) phosphate, triethyl phosphate, and tricresyl phosphate. Examples of phosphorus compounds include red phosphorus and ammonium polyphosphate. The amount of the flame retardant is preferably 5 parts by mass or more and 30 parts by mass or less, and more preferably 10 parts by mass or more and 30 parts by mass or less, relative to 100 parts by mass of the polyol.

[0033] 2. Polyurethane foam manufacturing reaction liquid set The polyol composition may be used to form a two-component reaction liquid set for producing a polyurethane foam, which includes, for example, the polyol composition as component A and an isocyanate component as component B.

[0034] (2.1) Isocyanate component The isocyanate component is not particularly limited. The isocyanate component may be at least one selected from the group consisting of aromatic isocyanates, alicyclic isocyanates, and aliphatic isocyanates. One or more aliphatic isocyanates and one or more aromatic isocyanates may be used in combination. The isocyanate component may be either a bifunctional isocyanate having two isocyanate groups in one molecule, or a trifunctional or higher isocyanate having three or more isocyanate groups in one molecule, and may be used alone or in combination. For example, bifunctional isocyanates include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, xylylene diisocyanate, 3,3'-dimethyl-4,4'-biphenylene diisocyanate, and 3,3'-dimethoxy-4,4'-biphenylene diisocyanate. Examples of the isocyanate include aromatic isocyanates such as phenylene diisocyanate, alicyclic isocyanates such as cyclohexane-1,4-diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, and methylcyclohexane diisocyanate, and aliphatic isocyanates such as butane-1,4-diisocyanate, hexamethylene diisocyanate, isopropylene diisocyanate, methylene diisocyanate, and lysine isocyanate. Examples of tri- or higher functional isocyanates include 1-methylbenzene-2,4,6-triisocyanate, 1,3,5-trimethylbenzene-2,4,6-triisocyanate, biphenyl-2,4,4'-triisocyanate, diphenylmethane-2,4,4'-triisocyanate, methyldiphenylmethane-4,6,4'-triisocyanate, 4,4'-dimethyldiphenylmethane-2,2',5,5'tetraisocyanate, triphenylmethane-4,4',4"-triisocyanate, and polymeric MDI. Additionally, urethane prepolymers, carbodiimide-modified isocyanates, isocyanurate-modified isocyanates, and biuret-modified isocyanates can also be used.

[0035] The reaction liquid set for producing polyurethane foam can be used by mixing a polyol composition (liquid A) and an isocyanate component (liquid B) in a predetermined mixing ratio. The mixing ratio of the polyol composition and the isocyanate component is not particularly limited. The mixing ratio of the polyol composition and the isocyanate component can be determined according to the isocyanate index. The isocyanate index is preferably 80 or more and 350 or less, and more preferably 100 or more and 350 or less. In the case of an isocyanurate foam, the isocyanate index may be, for example, 200 or more and 350 or less, or 250 or more and 350 or less. By increasing the isocyanate index, the nurate formation reaction can be suitably promoted. The isocyanate index (INDEX) is the value obtained by multiplying the number of moles of isocyanate components per mole of active hydrogen groups contained in the polyol composition by 100, and is calculated as [(isocyanate equivalent of isocyanate component / active hydrogen equivalent in polyol composition) × 100].

[0036] 3. Polyurethane foam manufacturing method The method for producing the polyurethane foam is not particularly limited. For example, the method for producing the polyurethane foam includes mixing the polyol composition (liquid A) and the isocyanate component (liquid B). When producing polyurethane foam, there is no particular limitation on the method for mixing liquid A and liquid B. For example, liquid A and liquid B can be mixed using a small mixer or a foaming machine for injection foaming that is used in the production of general polyurethane foam. When foam molding polyurethane foam, a mixture of liquid A and liquid B can be injected into a molding cavity in a predetermined amount at a predetermined liquid temperature. Hereinafter, the mixture of liquid A and liquid B will also be simply referred to as foam raw material.

[0037] As an example of a method for manufacturing polyurethane foam, a method for manufacturing a polyurethane foam panel 10 shown in FIG. 1 will be described. The polyurethane foam panel 10 includes a pair of face plates 11 and 13 and a polyurethane foam 20 formed between the pair of face plates 11 and 13. The face plates 11 and 13 are preferably metal face plates, such as color steel plates. The polyurethane foam panel 10 is a so-called sandwich panel (a panel with steel plates) in which the face plates 11 and 13 form the design surface. A frame member 15 is provided around the periphery of the polyurethane foam panel 10. The frame member 15 has an injection port 15A formed therein for injecting foam raw materials. The space surrounded by the face plates 11 and 13 and the frame member 15 forms a molding space for molding the polyurethane foam 20. Note that the technology disclosed herein is not limited to sandwich panels and is also useful for polyurethane foam panels in which polyurethane foam forms the design surface.

[0038] The polyurethane foam panel 10 can be manufactured by injection foaming. This method of manufacturing the polyurethane foam panel 10 is also called a batch production method. To manufacture the polyurethane foam panel 10, for example, as shown in FIG. 2, a press 30 equipped with press platens 31 and 33, a liner 35, and a high-pressure injection machine (not shown) are used. For ease of explanation, FIG. 2 shows the face materials 11 and 13 separated from the frame material 15.

[0039] The press 30 applies a pressing pressure to the face materials 11 and 13 from above and below. Specifically, when the face materials 11 and 13 are pressed by the foaming pressure of the foam concentrate injected into the molding space, pressing pressure is applied from the press platens 31 and 33 against the foaming pressure of the foam concentrate. The press platens 31 and 33 may be heated to a predetermined pressing temperature. The pressing temperature can be set appropriately depending on the type of polyurethane foam, etc. For example, by increasing the pressing temperature, a suitable polyisocyanurate foam can be obtained. The liner 35 is arranged in a frame shape around the frame material 15 and presses the frame material 15 from the outer peripheral surface side. The high-pressure injector injects foam raw material into the molding space through the injection port 15A.

[0040] As shown in Figures 3 and 4, the method for producing a polyurethane foam panel 10 involves forming a molding space using a pair of opposing face plates 11, 13 and a frame member 15, and injecting a mixture (foam raw material) of a polyol composition (liquid A) and an isocyanate component (liquid B) into the molding space through injection port 15A, followed by foaming and curing. In Figure 3, the position corresponding to injection port 15A is indicated as point P1, and the injection of the foam raw material is indicated by a hollow arrow. The foam raw material injected into the molding space from the high-pressure injection machine flows primarily along the upper surface of the lower face plate 13, reaching every corner of the molding space. The polyol composition of the present disclosure is suitable for producing polyurethane foam panel 10 because it is less likely to produce flow marks. After the injected foam raw material has foamed and hardened, it is appropriately cured, and press 30 is opened to recover polyurethane foam panel 10. This completes the production of polyurethane foam panel 10.

[0041] 4. Polyurethane foam Polyurethane foam is obtained from the reaction liquid set for producing polyurethane foam. The polyurethane foam may be any of polyisocyanurate foam, rigid polyurethane foam, flexible polyurethane foam, and semi-rigid polyurethane foam. The polyurethane foam is preferably a rigid polyurethane foam, and more preferably a polyisocyanurate foam. Polyisocyanurate foam is a type of rigid polyurethane foam containing nurate bonds. Nurate bonds have higher thermal stability than urethane bonds. Polyisocyanurate foam exhibits high flame retardancy due to its high content of nurate bonds.

[0042] The physical properties of the resulting polyurethane foam can be appropriately set depending on the application, etc. The polyurethane foam preferably has the following physical properties. The apparent overall density (free density, JIS K7222:2005 compliant) is 20 kg / m 3More than 50kg / m 3 Less than 25 kg / m is preferable. 3 More than 45kg / m 3 Less than 25 kg / m is more preferable. 3 More than 40kg / m 3 The following is even more preferred:

[0043] The uses of polyurethane foam are not particularly limited. Polyurethane foam has an excellent appearance and is therefore suitable for polyurethane foam panels. In addition, polyurethane foam is suitable for use as a heat insulating material, packaging material, filler, and cushioning material.

[0044] 5. Effects of this embodiment The polyol composition of the present disclosure can improve the appearance of the resulting polyurethane foam. The polyol composition of the present disclosure is particularly useful for polyisocyanurate foams. This point will be explained in detail. Polyisocyanurate foams are more prone to voids and flow marks than rigid polyurethane foams, making it difficult to improve their appearance. This is thought to be due to the fact that polyisocyanurate foams react more quickly than rigid polyurethane foams and require a larger amount of blowing agent. Attempts to improve the appearance of polyisocyanurate foams have included adjusting trimerization catalysts, adjusting foam stabilizers, and using polyether polyols. However, these approaches can sometimes result in other problems, such as a deterioration in the flame retardancy of the polyisocyanurate foam, making them difficult to address. The present inventors have developed the technology of the present disclosure, which improves the appearance of polyisocyanurate foams by using a low-boiling point blowing agent, a different approach from previous approaches. It is presumed that the technology of the present disclosure is useful not only for polyisocyanurate foams, but also for rigid polyurethane foams and other polyurethane foams. [Example]

[0045] 1. Preparation of polyol composition (liquid A) Polyol compositions having the proportions shown in Table 1 were prepared.

[0046] The details of each raw material are as follows: Polyol 1: Aromatic polyester polyol (phthalic polyester polyol), hydroxyl value 250 mg KOH / g, Maximol RFK505, manufactured by Air Water Performance Chemicals Polyol 2: Aromatic polyester polyol, hydroxyl value 210 mg KOH / g, Lupraphen 3907 / 2, manufactured by BASF Polyol 3: Aromatic polyester polyol (phthalic polyester polyol), hydroxyl value 200 mg KOH / g, Maximol RLK087, manufactured by Air Water Performance Chemicals Polyol 4: Aromatic polyester polyol (phthalic polyester polyol), hydroxyl value 250 mg KOH / g, Maximol RFK556, manufactured by Air Water Performance Chemicals Polyol 5: Aromatic polyester polyol (phthalic polyester polyol), hydroxyl value 200 mg KOH / g, Maximol RFK509, manufactured by Air Water Performance Chemicals Polyol 6: Polyester polyol, hydroxyl value 360 ​​mg KOH / g, Maximol RAK253, manufactured by Air Water Performance Chemicals Flame retardant: Tris(1-chloro-2-propyl)phosphate (TCPP) Foam stabilizer 1: Silicone foam stabilizer, polyether-modified siloxane, SZ1711, manufactured by Dow Toray Foam stabilizer 2: Silicone foam stabilizer, block copolymer of polydimethylsiloxane and polyethylene polypropylene glycol, L5340, manufactured by Dow Toray Trimerization catalyst: Potassium octylate Foaming catalyst 1: 2,2-dimorpholine diethyl ether Foaming catalyst 2: N,N-dimethyl-N-(1-methylethyl)-N-[2-methyl(1-methylethyl)amino]ethyl-1,2-ethylenediamine Physical blowing agent A: trans-1,1,1,4,4,4-hexafluoro-2-butene (boiling point 7.5°C), Opteon 1150, manufactured by Chemours Physical blowing agent B: trans-1-chloro-3,3,3-trifluoropropene (boiling point 19°C), Solstice LBA, manufactured by Honeywell Chemical foaming agent: Water

[0047] [Table 1]

[0048] The following raw materials were used as the isocyanate component (liquid B). Isocyanate: Polymeric MDI, MR200, manufactured by Tosoh Corporation

[0049] The polyol composition (liquid A) and the isocyanate component (liquid B) were mixed in the blending ratio (mass ratio) shown in Table 1 to obtain a foam raw material.

[0050] Free foaming was carried out according to the following procedure. The polyol composition (liquid A) and the isocyanate (liquid B) were adjusted to a liquid temperature of 20° C. A plastic bag measuring 150 mm×150 mm×200 mm was used as a mold for free foaming. The polyurethane foam composition was allowed to free foam in the mold to obtain a polyurethane foam.

[0051] The reactivity (cream time, gel time, rise time) of the reaction liquid set for producing polyurethane foam was measured by the following methods. Cream time: The time it took for the mixture to become cloudy and creamy and for the foam to start rising was measured as the cream time (seconds). Gel time: The time from when the mixture thickened to when it started to gel was measured as the gel time (seconds). Rise time: The time until the rise of the foam caused by foaming in the above mixed liquid stopped was measured as the rise time (seconds). In the above measurement, the time when the composition (liquid A) and the isocyanate (liquid B) started to be mixed was set as zero seconds.

[0052] The apparent density (free density) of the polyurethane foam obtained by free foaming was measured in accordance with JIS K7222:2005 after cutting the foam into a size of 100 mm x 100 mm x 100 mm.

[0053] 2. Polyurethane foam panel manufacturing A panel with a steel plate having a thickness of 100 mm x 2700 mm x 900 mm was produced using the method described in the embodiment. Specifically, a 0.4 mm thick, 2700 mm x 900 mm color steel plate and a resin frame were prepared. The frame had an injection port at the center of one long side of the color steel plate. The pair of color steel plates and the frame were assembled and placed in a press. At this time, the thickness direction of the polyurethane foam panel was aligned with the vertical direction. A liner was placed around the frame, and the press was closed. The foam raw material was injected into the molding space through the injection port using a high-pressure injection machine (MEG-HK650, manufactured by Maruka Kakoki Co., Ltd.). The press temperature was set to 55°C to 60°C. After the injected foam raw material foamed and cured, it was appropriately cured, and the press was opened to recover the polyurethane foam panel.

[0054] 3. Evaluation Method (1) Void evaluation The lower surface of the polyurethane foam panel was visually observed for voids and evaluated according to the following criteria: The lower surface of the polyurethane foam panel was the outer surface of the color steel plate located below in the press. "A": The total area of ​​voids is less than 1 / 3 of the panel area. "B": The total area of ​​voids is 1 / 3 or more and less than 1 / 2 of the panel area. "C": The total area of ​​voids is 1 / 2 or more of the panel area. (2) Flow mark evaluation Flow marks were visually observed on the lower surface of the polyurethane foam panel and evaluated according to the following criteria: The lower surface of the polyurethane foam panel was the outer surface of the color steel plate located below in the press. "A": Flow marks are short and shallow. "B": Either the flow marks are short and deep, or the flow marks are long and shallow. "C": Flow marks are long and deep.

[0055] 4.Results The results are shown in Table 1. Comparative Example 1 is an example in which the foaming agent does not contain a physical foaming agent A having a boiling point of 10°C or less under atmospheric pressure. In Comparative Example 1, the void evaluation was "C" and the flow mark evaluation was "C". Comparative Example 2 is an example in which the polyol used in Comparative Example 1 was changed. In Comparative Example 2, the void evaluation was "B", which was an improvement over Comparative Example 1, but the flow mark evaluation was "C", and the effect of improving the appearance was not sufficient. In contrast, Example 1 has the same composition as Comparative Example 1 except for the blowing agent, and contains a physical blowing agent A having a boiling point of 10°C or less under atmospheric pressure as the blowing agent. Example 1 was evaluated as "A" for voids and "A" for flow marks. Compared to Comparative Example 1, Example 1 showed significant improvements in both voids and flow marks.

[0056] Comparative Example 3 is an example in which the foaming agent does not contain a physical foaming agent A having a boiling point of 10° C. or less under atmospheric pressure. Comparative Example 3 was evaluated as "C" for voids and "C" for flow marks. In contrast, Example 2 has the same composition as Comparative Example 3 except for the blowing agent, and contains a physical blowing agent A having a boiling point of 10°C or less under atmospheric pressure as the blowing agent. Example 2 was evaluated as "A" for voids and also as "A" for flow marks. Compared to Comparative Example 3, Example 2 showed significant improvements in both voids and flow marks.

[0057] According to the above examples, when used in the production of polyurethane foam panels, the resulting polyurethane foam panels had good appearance. According to the above examples, when used in the injection foaming of polyurethane foam, the resulting polyurethane foams had good appearance.

[0058] The present disclosure is not limited to the above-described embodiments, and various modifications and variations are possible within the scope of the present disclosure. [Explanation of symbols]

[0059] 10...Polyurethane foam panel 11...Surface material 13...Surface material 15…Frame material 15A…Inlet 20...Polyurethane foam 30... Press machine 31... Press plate 33... Press plate 35...liner

Claims

1. A polyol composition for producing a polyurethane foam panel and / or a polyol composition for producing an injection foamed polyurethane foam, comprising: A polyol composition comprising a polyol and a physical blowing agent having a boiling point of 10°C or less under atmospheric pressure.

2. 2. The polyol composition of claim 1, further comprising a physical blowing agent having a boiling point at atmospheric pressure higher than 10°C.

3. A reaction liquid set for producing a polyurethane foam, comprising the polyol composition according to claim 1 or 2 and an isocyanate component.

4. A polyurethane foam obtained from the reaction solution set for producing a polyurethane foam according to claim 3.

5. A method for producing a polyurethane foam, comprising mixing the polyol composition according to claim 1 or 2 with an isocyanate component.

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