Foaming composition for polyurethane foam

Abstract

To provide a foamable composition capable of forming a polyurethane foam excellent in handleability, and compression strength while securing excellent thermal insulation performance.SOLUTION: A composition A includes 1-chloro-3,3,3-trifluoropropene, and 1-chloro-2,3,3,3-tetrafluoropropene together in a foamable composition for forming a polyurethane foam by reaction to foam and cure of the composition A comprising a polyol as a principal constituent, a catalyst, and a foaming agent and a composition B comprising polyisocyanate as a principal constituent.SELECTED DRAWING: None

Description

【Technical Field】 【0001】 The present invention relates to a foaming composition for polyurethane foam, and particularly relates to a foaming composition capable of advantageously producing a polyurethane foam having excellent foam (foam) properties. 【Background Art】 【0002】 Conventionally, polyurethane foam has been mainly used as a heat insulating member by utilizing its excellent heat insulating properties and adhesiveness. It has been put into practical use for heat insulation of building interior and exterior wall materials and panels, heat insulation of metal siding and electric refrigerators, heat insulation and dew condensation prevention of building, condominium, and cold storage wall surfaces, ceilings, roofs, etc., and heat insulation of infusion pipes. Such polyurethane foam generally consists of a polyol composition (premix liquid) mainly composed of a polyol compound, to which various auxiliaries such as a catalyst, a foaming agent, and if necessary, a foam stabilizer, a flame retardant, etc. are blended, and a composition mainly composed of a polyisocyanate. They are continuously or intermittently mixed by a mixing device, applied to the foam forming location, reacted, and foamed and cured to be manufactured. 【0003】 By the way, as the foaming agent currently used for the production of such polyurethane foam, hydrofluorocarbon (HFC) - based foaming agents such as HFC - 134a, HFC - 245fa, and HFC - 365mfc, which are relatively advantageous in terms of the global warming potential, are known. Although this hydrofluorocarbon - based foaming agent is recognized as an alternative refrigerant with less or no ozone layer depletion, it is speculated that in the near future, due to strong demands for environmental destruction problems, the use of such alternative refrigerants will also be restricted. Instead, halogenated hydroolefin - based foaming agents called hydrofluoroolefin (HFO) and hydrochlorofluoroolefin (HCFO), which have a low global warming potential because they are chemically unstable, have been developed. 【0004】 For example, in Japanese Patent Publication No. 2013-500386 (Patent Document 1), a technique is proposed in which polyurethane foam is formed by using HCFO-1233zd, one of the halogenated hydroolefin-based blowing agents, and constructing a composition containing it along with at least one polyester polyol and at least one polyether polyol, and then reacting this composition with polyisocyanate, foaming, and curing it. The halogenated hydroolefin-based blowing agent used therein has good compatibility with polyols and is less likely to detach from the system compared to the HFC-based blowing agents mentioned above. However, simply using the polyester polyol and polyether polyol proposed therein as polyol components does not result in a foam with low flame retardancy, and it is difficult to obtain a rigid polyurethane foam that exhibits good properties in terms of workability and dimensional stability. In addition, the resulting foam has inherent problems in terms of thermal insulation performance and compressive strength. 【0005】 Furthermore, regarding hydrochlorofluoroolefins (HFCOs) used as foaming agents for foaming polyurethane, Japanese Patent Publication No. 2021-116317 and others have revealed, in addition to the above-mentioned HCFO-1233zd, 1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd), 1,1,1,4,4,4-hexafluoro-2-butene (HCFO-1336mzz), etc. However, among these, for example, when HCFO-1224yd is used, its low boiling point makes it difficult to use in hot summer weather, and it inherently has problems such as the chemical solution containing it boiling over or degradation due to boiling. In addition, there are also problems with the physical properties of the foam, such as insufficient compressive strength of the resulting polyurethane foam. [Prior art documents] [Patent Documents] 【0006】 [Patent Document 1] Special Publication No. 2013-500386 [Patent Document 2] Japanese Patent Publication No. 2021-116317 [Overview of the Initiative] [Problems that the invention aims to solve] 【0007】 In this context, the present invention has been made against the aforementioned circumstances, and its objective is to provide a foamable composition capable of forming a polyurethane foam with excellent foam properties, and another objective is to provide a foamable composition that is easy to handle and capable of forming a polyurethane foam with excellent compressive strength while ensuring excellent thermal insulation performance. [Means for solving the problem] 【0008】 Furthermore, in order to solve the above-mentioned problems, the present invention can be suitably implemented in various embodiments as listed below, and any combination of the embodiments described below is possible. It should be understood that the embodiments or technical features of the present invention are not limited in any way to those described below, and can be recognized based on the description of the entire specification and the inventive concept disclosed therein. 【0009】 Therefore, the present invention aims to solve the above-mentioned problems by first providing a foaming composition for polyurethane foam, which forms a polyurethane foam by reaction, foaming, and curing of a composition A mainly composed of a polyol and containing a catalyst and a blowing agent, and a composition B mainly composed of a polyisocyanate, wherein composition A contains both 1-chloro-3,3,3-trifluoropropene and 1-chloro-2,3,3,3-tetrafluoropropene as the blowing agent. 【0010】 Furthermore, according to one preferred embodiment of the foaming composition for polyurethane foam according to the present invention, (E)-1-chloro-3,3,3-trifluoropropene is used as the 1-chloro-3,3,3-trifluoropropene. 【0011】 Furthermore, according to another preferred embodiment of the foaming composition for polyurethane foam according to the present invention, (Z)-1-chloro-2,3,3,3-tetrafluoropropene is used as the 1-chloro-2,3,3,3-tetrafluoropropene. 【0012】 Furthermore, according to another preferred embodiment of the foaming composition for polyurethane foam according to the present invention, the ratio of 1-chloro-3,3,3-trifluoropropene to 1-chloro-2,3,3,3-tetrafluoropropene is 20:80 to 60:40 by mass. 【0013】 In addition, the present invention is preferably characterized in that composition A contains an aromatic polyester polyol in proportion to 50% by mass or more of the polyol. 【0014】 Furthermore, in the present invention, preferably, composition A contains an ethylenediamine-based polyether polyol as the polyol. 【0015】 Furthermore, the foaming composition for polyurethane foam according to the present invention is preferably characterized by being prepared as a water-free composition. [Effects of the Invention] 【0016】 Thus, in the foaming composition for polyurethane foam according to the present invention, the foaming agent is a combination of hydrochlorofluoroolefins (HCFOs), namely 1-chloro-3,3,3-trifluoropropene and 1-chloro-2,3,3,3-tetrafluoropropene. Therefore, by reacting such a foaming composition and allowing it to foam and harden, the thermal conductivity of the polyurethane foam obtained can be effectively reduced, providing excellent heat insulation performance, and advantageously offering a foam with superior compressive strength. 【0017】 Furthermore, by using two specific types of hydrochlorofluoroolefins (HCFOs) in combination as foaming agents, their respective advantages as foaming agents can be complemented, contributing favorably to the reduction of thermal conductivity. In addition, the boiling point of the chemical solution is raised, which effectively suppresses deterioration and bumping due to boiling of the chemical solution in summer. As a result, a foaming composition with excellent handling and foaming properties can be provided. 【0018】 Furthermore, according to a preferred embodiment of the present invention, by using a large proportion of aromatic polyester polyols or ethylenediamine-based polyether polyols as the polyol, the features of the present invention can be exhibited even more advantageously. Moreover, by substantially eliminating the presence of water in composition A and eliminating the presence of water as a blowing agent in the reaction system, the thermal conductivity of the polyurethane foam can be reduced even more effectively, thereby further improving its heat insulation properties. [Modes for carrying out the invention] 【0019】 The composition of the foamable composition for polyurethane foam according to the present invention will be described in detail below. 【0020】 First, the foamable composition for polyurethane foam according to the present invention is composed of composition A containing a polyol and composition B containing a polyisocyanate. The target polyurethane foam is formed by the reaction of the polyol and polyisocyanate in these compositions, along with foaming by a blowing agent. The polyol, which is the main component of composition A used therein, is a known polyol compound that reacts with polyisocyanate to produce polyurethane, and is used alone or in appropriate combinations. For example, polyester polyols, polyether polyols, polyolefin polyols, acrylic polyols, polymer polyols, etc., are appropriately selected and used as such polyol compounds. 【0021】 Among these polyol compounds, known examples of polyester polyols include polyols of the polyhydric alcohol-polyhydric carboxylic acid condensation system and polyols of the cyclic ester ring-opening polymer system. Examples of polyhydric alcohols include ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, glycerin, trimethylolpropane, and pentaerythritol, with dihydric alcohols being preferred. Examples of polyhydric carboxylic acids include succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid, terephthalic acid, isophthalic acid, and their anhydrides. Examples of cyclic esters include ε-caprolactone. 【0022】 In the present invention, as the polyester polyol, it is preferable to use an aromatic polyester polyol so as to account for 50% by mass or more of the polyol. Specifically, it is preferable to use a phthalic acid-based polyester polyol, and it is also effective to combine two or more such polyester polyols. The phthalic acid-based polyester polyol preferably comprises a condensate of phthalic acid, terephthalic acid, isophthalic acid, and their anhydrides, etc. with a dihydric alcohol such as ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, etc. Using such a phthalic acid-based polyester polyol has the advantage that a rigid polyurethane foam excellent in heat insulation performance and compressive strength can be advantageously obtained. Also, when combining and containing two specific hydrochlorofluorocarbons (HCFOs) according to the present invention, it has the characteristic of providing a composition with excellent storage stability as a foaming composition. 【0023】 Furthermore, as polyether polyols, which are one of the polyol compounds mentioned above, various types of polyether polyols can be cited, such as ethylenediamine-based, Mannich-based, glycerin-based, aromatic-based, sucrose-based, sorbitol-based, toluenediamine-based, and tolylenediamine-based polyether polyols. However, in the present invention, ethylenediamine-based polyether polyols are preferably used to advantageously achieve the objective. In this case, the ethylenediamine-based polyether polyol is preferably a polyol obtained by adding an alkylene oxide to ethylenediamine, which is used as the main reaction initiator, and is adjusted so that its hydroxyl value is 400 to 1000 mg KOH / g, preferably 500 to 900 mg KOH / g. Therefore, as the ethylenediamine, the ordinary type produced by the reaction of ethylene dichloride and ammonia can be used, and as the alkylene oxide, ethylene oxide, propylene oxide, butylene oxide, etc. can be used individually or in combination of two or more, but propylene oxide is advantageous in terms of raw material cost and the physical properties of rigid foam. 【0024】 In the present invention, a polyol as described above is used as the main component (generally contained at a ratio of 50% by mass or more), and a catalyst for reacting and curing polyurethane and polyisocyanate, and a foaming agent for forming a foam are contained therein. Furthermore, a composition A containing various additives conventionally used in the production of polyurethane foams, such as flame retardants and foam stabilizers, is prepared. In particular, in the present invention, as the foaming agent, 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd) and 1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd) are combined so that both are contained therein, whereby a foaming composition capable of forming a foam having excellent heat insulation performance (low thermal conductivity) and excellent compressive strength can be advantageously provided. Also, by using such a combination of two specific types of HCFOs, the advantages of each foaming agent can be complemented, the heat conduction characteristics can be advantageously reduced, and the boiling point of the chemical solution can be effectively increased. Therefore, a foam having high heat insulation performance can be advantageously obtained, and the characteristics of suppressing or preventing deterioration and bumping due to boiling of the chemical solution in summer can be exhibited. 【0025】 In addition, each of these two specific types of hydrochlorofluorocarbons (HCFOs) has geometric isomers. In the present invention, (E)-1-chloro-3,3,3-trifluoropropene, which is the E-isomer, in other words, 1-chloro-3,3,3-trifluoropropene, is preferably used. Also, (Z)-1-chloro-2,3,3,3-tetrafluoropropene, which is the Z-isomer, in other words, 1-chloro-2,3,3,3-tetrafluoropropene, will be advantageously used. 【0026】 Furthermore, while 1-chloro-3,3,3-trifluoropropene and 1-chloro-2,3,3,3-tetrafluoropropene can be used in appropriate proportions as described above, in the present invention, they are used in combination in a ratio of 20:80 to 60:40 by mass, more preferably 30:70 to 55:45. Furthermore, if the proportion of 1-chloro-3,3,3-trifluoropropene used exceeds 80%, the proportion of 1-chloro-2,3,3,3-tetrafluoropropene used will become too low, leading to problems such as difficulty in fully achieving the compressive strength improvement effect of using them together. On the other hand, if the proportion of 1-chloro-3,3,3-trifluoropropene used falls below 20% (the proportion of 1-chloro-2,3,3,3-tetrafluoropropene used exceeds 80%), the boiling point of the chemical solution will become too low, potentially causing the solution to boil in the summer, leading to degradation or bumping, which could negatively affect its handling and, consequently, its foaming properties. 【0027】 Thus, the present invention is characterized by using a combination of 1-chloro-3,3,3-trifluoropropene and 1-chloro-2,3,3,3-tetrafluoropropene, which are specific compounds of hydrochlorofluoroolefins (HCFOs), as blowing agents. However, other known blowing agents can also be used auxiliaryly, as long as they do not impair the objective of the present invention. Examples of such known blowing agents include hydrochlorofluoroolefins (HCFOs) other than the specific compounds mentioned above, as well as hydrofluoroolefins (HFOs), hydrocarbons (HCs), hydrofluorocarbons (HFCs), and water. Among these auxiliary blowing agents, water has been commonly used in the manufacture of polyurethane foam. In particular, in the present invention, it is recommended to use composition A, which substantially does not contain water as a blowing agent. This makes it possible to further reduce the thermal conductivity of the formed polyurethane foam, thereby contributing even more to the improvement of its thermal insulation performance. Here, the statement that water as a foaming agent is substantially absent means that no water is added to composition A, excluding the water contained in the additives. Even including the water in the additives, the amount of water in composition A is less than 1% by mass, preferably 0.8% by mass or less, more preferably 0.6% by mass or less, and even more preferably 0.5% by mass or less. 【0028】 The total amount of the two hydrochlorofluoroolefins mentioned above is preferably 15 to 50 parts by mass, and more preferably 25 to 40 parts by mass, per 100 parts by mass of the total polyol in composition A containing the polyol. If the total amount of hydrochlorofluoroolefins used exceeds 50 parts by mass, the core density of the foam will decrease, which may lead to a decrease in the strength of the foam and, consequently, a deterioration in dimensional stability. There are also disadvantages in terms of cost. On the other hand, if the total amount of hydrochlorofluoroolefins used is less than 15 parts by mass, they may not be able to fully exhibit their properties as a foaming agent, resulting in a high density of the resulting foam, and the viscosity of polyol composition A may increase, leading to problems such as poor miscibility with isocyanate and the inability to obtain a good spray pattern. 【0029】 In this invention, a rigid polyurethane foam is formed by mixing composition A, which mainly consists of a polyol, with composition B, which mainly consists of a polyisocyanate, reacting them in the presence of a catalyst, foaming them with a blowing agent, and then curing them. As one of the catalysts used, a resin-forming catalyst is advantageously used to promote the reaction between the polyol and the polyisocyanate. This resin-forming catalyst is appropriately selected and used depending on the type of foam, and for example, a urethane-forming catalyst or an isocyanurate-forming catalyst may be used alone or in combination. Examples of urethane-forming catalysts include dibutyltin dilaurate, bismuth octoate (bismuth 2-ethylhexylate), bismuth neodecanoate, bismuth neododecanoate, bismuth naphthenate, and other fatty acid bismuth salts, as well as lead naphthenate. On the other hand, examples of isocyanurate catalysts include quaternary ammonium salts, fatty acid alkali metal salts such as potassium octylate and sodium acetate, and tris(dimethylaminopropyl)hexahydrotriazine. Of these, the use of quaternary ammonium salts is particularly preferred. 【0030】 Examples of quaternary ammonium salts that can be advantageously used here include aliphatic ammonium compounds such as tetramethylammonium, methyltriethylammonium, ethyltrimethylammonium, propyltrimethylammonium, butyltrimethylammonium, pentyltrimethylammonium, hexyltrimethylammonium, heptyltrimethylammonium, octyltrimethylammonium, nonyltrimethylammonium, decyltrimethylammonium, undecyltrimethylammonium, dodecyltrimethylammonium, tridecyltrimethylammonium, tetradecyltrimethylammonium, heptadecyltrimethylammonium, hexadecyltrimethylammonium, heptadecyltrimethylammonium, and octadecyltrimethylammonium; hydroxyammonium compounds such as (2-hydroxypropyl)trimethylammonium, hydroxyethyltrimethylammonium, and trimethylaminoethoxyethanol; and alicyclic ammonium compounds such as 1-methyl-1-azania-4-azabicyclo[2,2,2]octanium, 1,1-dimethyl-4-methylpiperidinium, 1-methylmorpholinium, and 1-methylpiperidinium. Among these, tetramethylammonium, methyltriethylammonium, ethyltrimethylammonium, butyltrimethylammonium, hexyltrimethylammonium, octyltrimethylammonium, decyltrimethylammonium, dodecyltrimethylammonium, tetradecyltrimethylammonium, hexadecyltrimethylammonium, octadecyltrimethylammonium, (2-hydroxypropyl)trimethylammonium, hydroxyethyltrimethylammonium, 1-methyl-1-azania-4-azabicyclo[2,2,2]octanium, and 1,1-dimethyl-4-methylpiperidinium are preferred due to their excellent catalytic activity and industrial availability. 【0031】 Furthermore, examples of organic or inorganic acid groups constituting such quaternary ammonium salts include formic acid, acetate, octic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, benzoic acid, toluic acid, ethylbenzoic acid, methyl carbonate, phenol, alkylbenzene sulfonic acid, toluene sulfonic acid, benzene sulfonic acid, and phosphate ester groups, as well as inorganic acid groups such as halogen, hydroxyl, bicarbonate, and carbonate groups. Among these, formic acid, acetate, octic acid, methyl carbonate, halogen, hydroxyl, bicarbonate, and carbonate groups are preferred because they exhibit excellent catalytic activity and are industrially available. 【0032】 Furthermore, various catalysts consisting of such quaternary ammonium salts are commercially available, for example, U-CAT 18X, U-CAT 2313 (manufactured by Sunapro Co., Ltd.), Kaolizer No. 410, and Kaolizer No. 420 (manufactured by Kao Corporation). 【0033】 The amount of resinification catalyst used as one of these catalysts is selected within the range of 0.1 to 5 parts by mass, preferably 0.5 to 3 parts by mass, per 100 parts by mass of the total polyol in polyol-containing composition A, while effectively exhibiting its catalytic function. If the amount of resinification catalyst used is less than 0.1 parts by mass, the resulting foam will become sticky, attracting dirt and other debris, resulting in a poor appearance. In the spray foaming operation, the spray will become sticky on the floor, resulting in poor workability. On the other hand, if the amount is more than 5 parts by mass, the heat generated during the resinification reaction will be high, causing abnormalities in the appearance of the foam, such as yellowing. Furthermore, the quaternary ammonium salt catalyst contained in the spray generated during foaming may worsen the working environment at the spraying site. 【0034】 In addition to the resinification catalyst described above, known catalysts conventionally used in the manufacture of polyurethane foam may be appropriately selected and included in composition A containing polyol, as needed. For example, amine-based catalysts can advantageously improve the initial foaming properties of polyurethane, reduce the overall density of the foam without changing the density difference between the skin layer and the core layer, improve the stickiness of the foam, advantageously prevent deterioration of appearance due to the adhesion of dirt, etc., and in spray foaming methods, they exhibit the characteristic of improving the deterioration of workability due to the stickiness of sprays adhering to the floor, etc. As such amine-based catalysts, it is recommended to use reactive amine compounds having OH groups or NH groups in their chemical structure, or cyclic amine compounds having a cyclic structure, and in particular, using reactive amine compounds as catalysts can further reduce odor. 【0035】 The reactive amine compounds and cyclic amine compounds used as such amine catalysts can be appropriately selected from known urethane catalysts. For example, reactive amine compounds include 2,4,6-tri(dimethylaminomethyl)phenol, tetramethylguanidine, N,N-dimethylaminoethanol, N,N-dimethylaminoethoxyethanol, ethoxylated hydroxylamine, N,N,N',N'-tetramethyl-1,3-diamino-2-propanol, N,N,N'-trimethylaminoethylethanolamine, 1,4-bis(2-hydroxypropyl), 2-methylpiperazine, 1-methylimidazole, 1,2-dimethylimidazole, 1-ethyl-2-methylimidazole, 1-methyl-2-ethylimidazole, 1-isobutyl-2-methylimidazole, 1-(2-hydroxypropyl)imidazole, 3,3-diamino-N-methyldipropylamine, and N-methyl-N'-hydroxyethylpiperazine. Furthermore, examples of cyclic amine compounds include triethylenediamine, N,N'-dimethylcyclohexylamine, N,N-dicyclohexylmethylamine, methylenebis(dimethylcyclohexyl)amine, N,N-dimethylbenzylamine, morpholine, N-methylmorpholine, N-ethylmorpholine, N-(2-dimethylaminoethyl)morpholine, 4,4'-oxydiethylenedimorpholine, N,N'-diethylpiperazine, N,N'-dimethylpiperazine, N-methyl-N'-dimethylaminoethylpiperazine, and 1,8-diazobicyclo(5,4,0)-undecene-7. 【0036】 The amount of amine-based catalyst used as one of these catalysts is selected within the range of 0.1 to 7 parts by mass, preferably 0.2 to 3 parts by mass, and more preferably 0.3 to 1 part by mass, per 100 parts by mass of the total polyol in composition A, in order to obtain effective foam properties while effectively exhibiting its catalytic function and reducing problems such as odor and deterioration of the working environment. If the amount of amine-based catalyst used is less than 0.1 parts by mass, it becomes difficult to fully exhibit its catalytic function, and problems such as the resulting foam becoming sticky, attracting dirt and other debris, and having a poor appearance occur. In spray foaming operations, the spray that adheres to the floor and other surfaces becomes sticky, causing problems such as poor workability. If the amount of amine-based catalyst used is more than 7 parts by mass, the resulting polyurethane foam will have a noticeable odor, and problems such as deterioration of the spraying work environment will occur due to the volatilization of the amine-based catalyst during foaming. For this reason, from the viewpoint of odor, it is preferable to add a small amount of such amine-based catalyst. 【0037】 On the other hand, in composition B, which is composed of the foamable composition for polyurethane foam according to the present invention together with composition A described above, the main component polyisocyanate is blended with composition A and reacts with the polyol in composition A to produce polyurethane (resin). The polyisocyanate is an organic isocyanate compound having two or more isocyanate groups (NCO groups) in its molecule. Examples include aromatic polyisocyanates such as diphenylmethane diisocyanate, polymethylene polyphenylene polyisocyanate, tolylene diisocyanate, polytollene diisocyanate, xylylene diisocyanate, and naphthalene diisocyanate; aliphatic polyisocyanates such as hexamethylene diisocyanate; alicyclic polyisocyanates such as isophorone diisocyanate; as well as urethane prepolymers having isocyanate groups at the molecular ends, isocyanurate modified polyisocyanates, carbodiimide modified polyisocyanates, and the like. These polyisocyanate compounds may be used alone or in combination of two or more. Generally, from the viewpoint of reactivity, cost-effectiveness, and ease of handling, polymethylene polyphenylene polyisocyanate (crude MDI) is preferred. 【0038】 The mixing ratio of composition B, which mainly consists of the polyisocyanate, and composition A, which mainly consists of the polyol, will be appropriately determined depending on the type of foam formed (e.g., polyurethane, polyisocyanurate). Generally, the ratio will be appropriately determined so that the NCO / OH index (equivalent ratio), which indicates the ratio of isocyanate groups (NCO) of the polyisocyanate in composition B to hydroxyl groups (OH) of the polyol in composition A, is in the range of approximately 0.9 to 2.5. 【0039】 Incidentally, in addition to the above-mentioned compounding components or constituent components, compositions A and B, which constitute the foaming compositions for polyurethane foam according to the present invention, may also be further formulated with various conventionally known auxiliary agents, such as known flame retardants and foam stabilizers, as needed. 【0040】 The foam stabilizers used here are used to uniformly arrange the cell structure of the polyurethane foam, and silicone-based or nonionic surfactants are preferably used. Specific examples include polyoxyalkylene-modified dimethylpolysiloxane, polysiloxane-oxyalkylene copolymer, polyoxyethylene sorbitan fatty acid ester, castor oil ethylene oxide adduct, and lauryl fatty acid ethylene oxide adduct. One of these may be used alone, or two or more may be used in combination. The amount of foam stabilizer used is determined appropriately according to the desired foam characteristics and the type of foam stabilizer used, but is selected in the range of 0.1 to 10 parts by mass, preferably 1 to 8 parts by mass, per 100 parts by mass of the total polyol in composition A. 【0041】 Furthermore, as flame retardants, phosphate esters such as trischloroethyl phosphate, trischloropropyl phosphate, and triethyl phosphate are advantageously used because they have a low environmental impact and also function as a viscosity reducer for foamed compositions. When incorporating these phosphate esters, the amount can be appropriately determined depending on the desired foam characteristics and the type of flame retardant, but is generally selected in the range of 5 to 60 parts by mass, preferably 10 to 40 parts by mass, per 100 parts by mass of the total polyol in composition A. In addition to the above-mentioned phosphate esters, aluminum hydroxide and the like can also be suitably used as flame retardants. As mentioned above, phosphate esters such as trischloroethyl phosphate, trischloropropyl phosphate, and triethyl phosphate are advantageously used as flame retardants because they have a low environmental impact and also function as a viscosity reducer for foamed compositions. When this phosphate ester is incorporated, the amount can be appropriately determined depending on the desired foam properties and the type of flame retardant, but it is generally selected in the range of 5 to 60 parts by mass, preferably 10 to 40 parts by mass, per 100 parts by mass of the total polyol in composition A. 【0042】 Furthermore, the foaming composition for polyurethane foam according to the present invention may also contain, as needed, various conventionally known additives such as formaldehyde scavenging agents like urea and melamine, foam refining agents, plasticizers, and reinforcing substrates, selected and blended as appropriate. 【0043】 Then, when reacting composition A and composition B obtained as described above in the presence of a catalyst to foam and harden, various known polyurethane foam manufacturing methods can be employed. For example, a continuous laminate foaming method in which a mixture of composition A and composition B is applied to a surface material and foamed and hardened into a plate-like form; an injection foaming method in which the mixture is injected and filled into spaces requiring thermal insulation, such as electric refrigerators, or into the honeycomb structure of lightweight, high-strength boards, and foamed and hardened; or a spray foaming method in which the mixture is sprayed from the spray gun head of an on-site foaming machine onto a predetermined adherend (structure) and foamed and hardened, thereby foaming and hardening the foamable composition according to the present invention and forming the desired polyurethane foam. In particular, in the present invention, a spray foaming method that is performed on-site at ambient temperature is preferably employed. By applying such an on-site spray foaming method, the features of the present invention are further advantageously demonstrated, and a polyurethane foam with excellent thermal insulation properties, strength properties, dimensional stability, and other properties can be advantageously obtained. [Examples] 【0044】 The following describes several embodiments of the present invention and compares them with comparative examples to further clarify the features of the present invention. However, it goes without saying that the present invention is not limited in any way by the description of such embodiments. Furthermore, it should be understood that, in addition to the embodiments described below and the specific descriptions above, various changes, modifications, and improvements can be made to the present invention based on the knowledge of those skilled in the art, as long as they do not depart from the spirit of the present invention. Note that the percentages (%) and parts shown below are all expressed on a mass basis unless otherwise specified. 【0045】 Furthermore, the boiling point of composition A (chemical solution) obtained in the following examples and comparative examples, as well as the initial thermal conductivity of the polyurethane foam, the thermal conductivity after 15 days, and the compressive strength were evaluated or measured as follows. 【0046】 (1) Measurement of boiling point Each 50 mL airtight transparent glass bottle was filled with 40 mL of the chemical solution, sealed, and then heated in a water bath at 30°C increments of 0.5°C for 30 minutes. After removing the bottle from the water bath and opening the lid, the temperature at which boiling occurred was measured. This measurement was performed for five samples, and the average value was defined as the boiling point. 【0047】 (2) Measurement of thermal conductivity at the initial stage and after 15 days For each foam obtained in the examples and comparative examples, the thermal conductivity of each foam was measured in accordance with JIS-A-9526 (2017) using a thermal conductivity measuring device (Auto Lambda HC-074 manufactured by Eiko Seiki Co., Ltd.). Specifically, a test specimen with dimensions of 200 mm (length) x 200 mm (width) x 25 mm (thickness) was cut from the core of the foam that had been left standing for 24 hours in an atmosphere of 23°C and 50% RH. The thermal conductivity of the test specimen was measured within one day of cutting, while the thermal conductivity of the test specimen stored for 15 days in an atmosphere of 25°C and 50% RH was also measured. These measured values ​​were defined as the initial thermal conductivity and the thermal conductivity after 15 days, respectively. 【0048】 (3) Measurement of compressive strength From the foam layer formed on the surface of a specified plywood according to a spraying method consisting of one undercoat and two topcoats, test specimens measuring 50mm x 50mm x 50mm were cut out, with one internal skin layer (skin layer from the first topcoat) present within each specimen. The 10% compressive strength of these test specimens was then measured using a universal testing machine in accordance with JIS-K-7220 to determine the compressive strength of each specimen. 【0049】 First, the following raw materials were prepared as components to be used in the following examples and comparative examples. Polyol: Phthalate-based polyester polyol (manufactured by Air Water Performance Chemicals Co., Ltd., RDK133) Polyol: Phthalate-based polyester polyol (manufactured by Air Water Performance Chemical Co., Ltd., RFK505) Polyol: Ethylenediamine-based polyether polyol (manufactured by AGC Inc., 75 0 ED) Catalyst: Quaternary ammonium salt (manufactured by Kao Corporation, Kaolizer No. 420) Catalyst: Imidazole-based catalyst (manufactured by Tosoh Corporation, TOYOCAT-DM70) Catalyst: Metal catalyst (manufactured by Toei Chemical Co., Ltd., hexoate lead) Foam stabilizer: Silicone-based foam stabilizer (Niax Silicone L-6100, manufactured by Momentive Performance Materials Japan LLC) Flame retardant: Phosphate ester [Wanshan Co., Ltd., Tris(1-chloro-2-propyl) phosphate, TCPP] Foaming agent: Water Foaming agent: HCFO-1233zd (manufactured by Honeywell, 1-chloro-3,3,3-trifluoropropene, E-isomer) Foaming agent: HCFO-1224yd (manufactured by AGC Inc., 1-chloro-2,3,3,3-tetrafluoropropene, Z-isomer) 【0050】 -Preparation of Composition A- The various raw materials prepared above, namely polyols, catalysts, foam stabilizers, flame retardants, and blowing agents, were uniformly mixed in the various combinations and proportions shown in Tables 1 and 2 below to prepare various liquid compositions A for Examples 1 to 6 and Comparative Examples 1 to 2. The boiling points of the obtained compositions A were then measured according to the measurement method described above, and the results are shown in Tables 1 and 2 below. 【0051】 -Preparation of Composition B- As the polyisocyanate, polymeric MDI (Wannate PM-130, manufactured by Manka Chemical Japan Co., Ltd.) was prepared, and composition B was constructed using only this polyisocyanate. 【0052】 -Manufacturing of polyurethane foam- Various compositions A, mainly composed of polyols, and composition B, consisting of polyisocyanate, obtained above were sprayed onto a 910mm x 910mm flexible board to a thickness of 5mm or less using a foaming machine (Graco, A-25). These were then laminated to a thickness of 30mm or less to produce a foam (polyurethane foam) with a layer thickness of approximately 60mm. In this spray foaming process, the polyol-containing composition A and the polyisocyanate-containing composition B were mixed in a volume ratio of 1:1. 【0053】 Then, using the various polyurethane foams thus obtained, their initial thermal conductivity and thermal conductivity after 15 days were measured, and their compressive strength was also measured. The results obtained are shown in Tables 1 and 2 below. 【0054】 [Table 1] [Table 2] 【0055】 As is clear from the results in Tables 1 and 2, each of the polyol-containing compositions A prepared in Examples 1 to 6 according to the present invention yielded polyurethane foams with excellent initial and 15-day thermal conductivity, and all of the resulting polyurethane foams exhibited high compressive strength. Furthermore, the compositions A prepared in Examples 1 to 6 all had relatively high boiling points, which effectively contributed to suppressing deterioration and bumping due to boiling of the chemical solution in summer, and were found to be effective in terms of handling and foaming workability. 【0056】 In contrast, in the case of composition A in Comparative Example 1 and Comparative Example 2, since HCFO-1233zd and HCFO-1224yd are contained individually as blowing agents, it is difficult to exhibit sufficient properties in either the boiling point or thermal conductivity of the chemical solution. This causes problems when used in summer, or has inherent problems in terms of thermal insulation performance. In addition, it was found that the compressive strength of the polyurethane foam obtained using any of the compositions A was insufficient. 【0057】 - Examination of the effect of water as a foaming agent - In Examples 3 and 5 described above, composition A for Examples 7 and 8 was prepared in the same manner as in Examples 3 and 5, except that 20 parts of HCFO-1233zd and 20 parts of HCFO-1224yd were used as blowing agents, without adding water as a blowing agent. Next, the prepared composition A was reacted with composition B, which consists of the polyisocyanate described above, to produce a polyurethane foam. The initial thermal conductivity and thermal conductivity after 15 days were measured for the obtained polyurethane foam, and the results are shown in Table 3 below in comparison with the results for Examples 3 and 5. 【0058】 [Table 3] 【0059】 As is clear from the results in Table 3, in Examples 7 and 8, where no water was added as a blowing agent, better results were obtained in both the initial thermal conductivity of the polyurethane foam and the thermal conductivity after 15 days compared to Examples 3 and 5.

Claims

[Claim 1] A foaming composition is formed by the reaction, foaming, and curing of composition A, which mainly consists of a polyol and contains a catalyst and a blowing agent, and composition B, which mainly consists of a polyisocyanate, thereby forming a polyurethane foam. A foaming composition for polyurethane foam, characterized in that composition A contains both 1-chloro-3,3,3-trifluoropropene and 1-chloro-2,3,3,3-tetrafluoropropene as the foaming agent, and composition A contains an aromatic polyester polyol in proportion to 50% by mass or more of the polyol, and further contains an ethylenediamine-based polyether polyol as the polyol, and the water content in composition A is less than 1% by mass. [Claim 2] The foaming composition for polyurethane foam according to claim 1, characterized in that (E)-1-chloro-3,3,3-trifluoropropene is used as the 1-chloro-3,3,3-trifluoropropene. [Claim 3] The foaming composition for polyurethane foam according to claim 1 or 2, characterized in that (Z)-1-chloro-2,3,3,3-tetrafluoropropene is used as the 1-chloro-2,3,3,3-tetrafluoropropene. [Claim 4] The foaming composition for polyurethane foam according to any one of claims 1 to 3, characterized in that the ratio of 1-chloro-3,3,3-trifluoropropene to 1-chloro-2,3,3,3-tetrafluoropropene used is 20:80 to 60:40 by mass ratio.

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