JP6917812B2 - Foamable composition for polyurethane foam and method for producing polyurethane foam using it - Google Patents

Description

The present invention relates to a foamable composition for polyurethane foam and a method for producing a polyurethane foam using the same, and in particular, a foamable composition for polyurethane foam having excellent workability and dimensional stability using the same. It relates to a method of producing an excellent polyurethane foam.

Conventionally, polyurethane foam has been used mainly as a heat insulating member to insulate interior and exterior wall materials for buildings, panels, etc., as well as heat insulation for metal siding, electric refrigerators, etc., by utilizing its excellent heat insulating properties and adhesiveness. It has been put to practical use for heat insulation and dew condensation prevention of building walls, ceilings, roofs, etc. of apartments and refrigerators, and heat insulation of infusion pipes, etc. In general, such polyurethane foam is mainly composed of a polyol compound, and a polyol compounding solution (premixed solution) in which a foaming agent and, if necessary, various auxiliary agents such as a catalyst, a defoaming agent, and a flame retardant are mixed. It is produced by continuously or intermittently mixing a polyol composition composed of a composition with a polyisocyanate with a mixing device, applying it to a foam forming site, reacting it, and foaming / curing it. ..

By the way, hydrofluorocarbons (HFCs) such as HFC-134a, HFC-245fa, and HFC-365mfc, which are relatively superior in global warming potential, are currently used as foaming agents for the production of such polyurethane foams. System foaming agents are known. Although this hydrofluorocarbon-based foaming agent is recognized as an alternative CFC with little or no ozone depletion, in the near future, strong demand for environmental destruction will limit the use of such alternative CFCs. Instead, halogenated hydroolefin-based foaming agents called hydrofluoroolefins (HFOs) and hydrochlorofluoroolefins (HCFOs), which have a low global warming potential due to their chemical instability, are available. , Has been developed.

For example, in Japanese Patent Application Laid-Open No. 2013-500386 (Patent Document 1), HCFO-1233zd, which is one of the halogenated hydroolefin-based foaming agents, is used, and at least one polyester polyol and at least one polyether polyol are used. A technique has been proposed in which a composition containing a polyurethane foam is formed by reacting, foaming and curing the composition with a polyisocyanate to form a polyurethane foam. The halogenated hydroolefin-based foaming agent used there has better compatibility with the polyol as compared with the above-mentioned HFC-based foaming agent, and has a property that the foaming agent is difficult to be desorbed from the system. Although it is a thing, if the polyester polyol and the polyether polyol proposed there are simply used together as a polyol component, the flame retardancy of the formed foam is low, and the workability and dimensional stability are good. It has been difficult to obtain a rigid polyurethane foam exhibiting various properties.

On the other hand, in Japanese Patent Application Laid-Open No. 7-25975 (Patent Document 2), a rigid polyurethane foam is prepared by using an ethylenediamine-based polyether polyol having a hydroxyl value (mgKOH / g) of 500 to 1000 as one of the polyol components. A manufacturing method has been proposed, and by adopting such a method, it is possible to prevent the lateral running phenomenon during spraying and the accompanying peeling of the rigid polyurethane foam from the surface to be constructed, and it is excellent in heat insulation and adhesion, and the flyer. It has been shown that it is possible to form a heat insulating layer of rigid polyurethane foam with low bitterness and no scorch.

However, when an ethylenediamine-based polyether polyol is used at a ratio as specified in Patent Document 2, a mixture of the polyol composition and the polyisocyanate is sprayed onto the object to obtain the desired hardness. During spraying to form a layer of polyurethane foam, foam formation progresses at the tip of the spray gun, causing a curing reaction, which causes a gun clogging phenomenon in which the tip of the spray gun is clogged. There is a problem that it cannot be done. Further, when a hydrofluorocarbon (HFC) -based or hydrochlorofluorocarbon (HCFC) -based foaming agent proposed therein is used as the foaming agent, its boiling point is low and its compatibility with the polyol is inferior. Since gas is likely to be desorbed from the foaming agent composition and the generated foam may exhibit abrupt foaming behavior, it is not possible to sufficiently prevent the lateral running phenomenon during spraying. There is also an inherent problem that the dimensional stability deteriorates due to insufficient strength of the produced foam, and further, when the blending amount of the ethylenediamine-based polyether polyol is increased, the flame retardancy decreases. There was also the problem of doing it.

Japanese Patent Application Laid-Open No. 2013-500386 Japanese Unexamined Patent Publication No. 7-25975

Here, the present invention has been made in the context of such circumstances, and the problem to be solved thereof is to provide a foaming composition for polyurethane foam having good spraying workability. It is also an object of the present invention to provide a polyurethane foam having excellent dimensional stability and an effervescent composition which provides the polyurethane foam.

Then, in order to solve the above-mentioned problems, the present invention can be preferably carried out in various aspects as listed below, and each of the aspects described below can be carried out in any combination. , Can be adopted. It should be noted that the aspects or technical features of the present invention are not limited to those described below, and can be recognized based on the description of the entire specification and the invention idea disclosed therein. Should be understood.

(1) A foamable composition composed of a polyol composition mainly composed of a polyol and a polyisocyanate, which gives a polyurethane foam by foaming with a foaming agent together with the reaction between the polyol and the polyisocyanate.
As the polyol in the polyol composition, the polyester polyol (A) and the polyether polyol (B) are used in a ratio of A: B = 70:30 to 40:60 in terms of mass ratio, and the polyether is used. A foamable composition for polyurethane foam, wherein 70% by mass or more of the polyol is composed of an ethylenediamine-based polyether polyol, and at least a halogenated hydroolefin is used as the foaming agent.
(2) The foamable composition for polyurethane foam according to the above aspect (1), wherein a halogenated hydroolefin and water are used in combination as the foaming agent.
(3) The effervescent composition for polyuretan foam according to the above aspect (2), wherein the halogenated hydroolefin and the water are used in a mass ratio of 80:20 to 95: 5. ..
(4) The embodiment (4), wherein the quaternary ammonium salt is contained in the polyol composition at a ratio of 0.1 to 5 parts by mass with respect to 100 parts by mass of the polyol as a catalyst. The foamable composition for polyurethane foam according to any one of 1) to (3) above.
(5) One of the above-mentioned modes (1) to (4), wherein the halogenated hydroolefin is selected from the group consisting of hydrofluoroolefins and hydrochlorofluoroolefins. The foamable composition for polyurethane foams described.
(6) The effervescent composition for a polyurethane foam according to any one of the above aspects (1) to (5), wherein the halogenated hydroolefin is HCFO-1233zd.
(7) The ethylenediamine-based polyether polyols are an ethylenediamine-based polyether polyol having a hydroxyl value of 400 mgKO H / g or more and less than 600 mgKOH / g, and an ethylenediamine-based polyether having a hydroxyl value: 600 mgKOH / g or more and 1000 mgKOH / g or less. The above-described embodiment, which comprises a polyol (the above-mentioned embodiment).
The foamable composition for polyurethane foam according to any one of 1) to (6) above.
(8) The hydroxyl value: an ethylenediamine-based polyether polyol having a hydroxyl value of 400 mgKOH / g or more and less than 600 mgKOH / g and an ethylenediamine-based polyether polyol having a hydroxyl value of 600 mgKOH / g or more and 1000 mgKOH / g or less have a mass ratio of 10: The foamable composition for polyurethane foam according to the above aspect (7), which is used in a ratio of 90 to 30:70.
(9) The polyurethane foam according to any one of the above aspects (1) to (8), wherein the polyether polyol is composed of an ethylenediamine-based polyether polyol and a Mannig-based polyether polyol. Foaming composition for.
(10) The effervescent composition for polyurethane foam according to any one of the above aspects (1) to (9), wherein the polyester polyol contains a phthalic acid-based polyester polyol.
(11) The aspect (1) to the above, wherein the amine-based catalyst is contained in the polyol composition at a ratio of 0.1 to 7 parts by mass with respect to 100 parts by mass of the polyol. The effervescent composition for polyurethane foam according to any one of aspects (10).
(12) Using the effervescent composition for polyurethane foam according to any one of the above aspects (1) to (11), the effervescent composition is sprayed onto the surface of a predetermined structure. A method for producing polyurethane foam, which is characterized by being attached and foamed and cured.

As described above, in the effervescent composition for polyurethane foam according to the present invention, at least a halogenated hydroolefin is used as the effervescent agent, and the polyol that is the main component of the polyol composition is defined as a polyester polyol and a polyether polyol. Since most of the polyether polyols are composed of ethylenediamine-based polyether polyols, workability, especially on-site spray foaming workability, is effective. It is improved and good dimensional stability of the obtained rigid polyurethane foam can be advantageously realized.

Further, by combining two kinds of ethylenediamine-based polyether polyols according to a preferred embodiment of the present invention, the curing rate can be adjusted, and the advantage that the foam strength of the obtained rigid polyurethane foam can be advantageously improved can be enjoyed. Furthermore, by using an ethylenediamine-based polyether polyol and a Mannig-based polyether polyol in combination as a polyether polyol, there is a feature that flame retardancy and reaction activity can be improved.

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

First, the foamable composition for polyurethane foam according to the present invention is composed of a polyol composition mainly composed of a polyol and a polyisocyanate, and the polyurethane foam is foamed by a foaming agent together with the reaction between the polyol and the polyisocyanate. The polyol which is a main component constituting the polyol composition used therein is composed of a polyester polyol (A) and a polyether polyol (B), but they are indispensable. In addition to the constituents of the above, various known polyol compounds (for example, polyolefin-based polyols, acrylic-based polyols, polymer polyols, etc.) that react with polyisocyanates to produce polyurethanes are used as long as they do not deviate from the object of the present invention. , Alone or in combination as appropriate. The proportion of the polyol in such a polyol composition is about 50 to 80% by mass, preferably about 60 to 70% by mass in total.

Then, among the above-mentioned polyester polyol (A) and polyether polyol (B) constituting the polyol in such a polyol composition, the polyester polyol (A) is a polyhydric alcohol-polyhydric carboxylic acid condensation system. Examples thereof include known polyols such as the polyols of the cyclic ester ring-opening polymerization system. Here, as the polyhydric alcohol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, glycerin, trimethylolpropane, pentaerythritol and the like can be used, and among them, the dihydric alcohol is preferably used. Examples of the polyvalent carboxylic acid include succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid, terephthalic acid, isophthalic acid, and anhydrides thereof. Be done. Further, examples of the cyclic ester include ε-caprolactone and the like.

Among them, as the polyester polyol, it is preferable to use an aromatic polyester polyol from the viewpoint of flame retardancy and compatibility, and specifically, it is preferable to use a phthalic acid polyester polyol, and further, such a polyester. It is also effective to combine two or more types of polyols. The phthalic acid-based polyester polyol is a phthalic acid composed of a condensate of phthalic acid, terephthalic acid, isophthalic acid and their anhydrides and dihydric alcohols such as ethylene glycol, propylene glycol, diethylene glycol and dipropylene glycol. A polyester polyol is preferably used. When such a phthalic acid-based polyester polyol is used, even if in-situ foaming is performed at a low temperature (about -10 to 5 ° C.), peeling from the building frame or the like is unlikely to occur, and the foam edge after in-situ foaming is not easily caused. There is an advantage that a rigid polyurethane foam having a degree of flexibility that is relatively easy to process can be obtained. In particular, when a hydrofluoroolefin-based foaming agent or a hydrochlorofluoroolefin-based foaming agent is contained, the composition is characterized by having excellent storage stability.

When phthalic acid-based polyester polyols are used in combination, it is preferable to combine two types of phthalic anhydride-based polyester polyols and terephthalic acid-based polyester polyols. Phthalic anhydride can be obtained at a low cost, and the polyester polyol obtained from the phthalic anhydride can be produced at a low cost, and has a feature that is advantageous in terms of cost. In addition, since it has an aromatic ring, it has excellent flame retardancy and has excellent compatibility with halogenated hydroolefins used as foaming agents. Further, the terephthalic acid-based polyester polyol is more flame-retardant than the phthalic anhydride-based polyester polyol, and has a rigid structure, which contributes to the improvement of dimensional stability. Have. Therefore, by combining two polyester polyols, a phthalic anhydride type and a terephthalic acid type, a hard polyurethane foam having excellent flame retardancy is advantageous because the halogenated hydroolefin which is a foaming agent is moderately compatible. It becomes possible to manufacture it.

On the other hand, 70% by mass or more, preferably 80% by mass or more of the polyether polyol (B), which is another essential component of the polyol in the polyol composition used in the present invention, is an ethylenediamine-based polyether polyol. Must be composed of. If the proportion of the ethylenediamine-based polyether polyol in the polyether polyol is less than 70% by mass, the curing rate is lowered, and dripping and lateral running phenomenon are likely to occur during construction, and the foam end portion during spraying work. This is because problems such as peeling occur in the above. Here, as the ethylenediamine-based polyether polyol, ethylenediamine is used as the main reaction initiator, and an alkylene oxide is added thereto, so that the hydroxyl value thereof is 400 to 1000 mgKOH / g. The one adjusted to the above will be preferably used. Therefore, as the ethylenediamine, a normal one produced by the reaction of ethylene dichloride and ammonia can be used, and as the alkylene oxide, ethylene oxide, propylene oxide, butylene oxide and the like can be used alone or in combination of two or more. However, propylene oxide is advantageously used in view of the price of the raw material and the physical characteristics of the hard foam. If the hydroxyl value of the ethylenediamine-based polyether polyol is less than 400 mgKOH / g, the expression of foam strength becomes insufficient, a transverse phenomenon occurs during spraying, and the formed hard foam peels off from the construction surface. There is a risk of Further, when the amount exceeds 1000 mgKOH / g, the flyability becomes large and problems such as scorch generation are likely to occur.

In particular, in the present invention, as the ethylenediamine-based polyether polyol, an ethylenediamine-based polyether polyol having a hydroxyl value of 400 mgKOH / g or more and less than 600 mgKOH / g, and an ethylenediamine having a hydroxyl value of 600 mgKOH / g or more and 1000 mgKOH / g or less It is recommended to use it in combination with a based polyether polyol, which makes it possible to effectively suppress the residual unreacted hydroxyl groups while improving the curing rate, and improves dimensional stability. You can enjoy the benefits. The ethylenediamine-based polyether polyol having a hydroxyl value of 400 mgKOH / g or more and less than 600 mgKOH / g and the ethylenediamine-based polyether polyol having a hydroxyl value of 600 mgKOH / g or more and 1000 mgKOH / g or less are 10 in mass ratio. It is desirable that the mixture is blended at a ratio of: 90 to 30:70, preferably 15:85 to 25:75.

Further, in the present invention, the polyether polyol, which is one of the essential constituents of the polyol in the polyol composition, may be composed of the above-mentioned ethylenediamine-based polyether polyol, or such an ethylenediamine-based poly. It is also possible to use 70% by mass or more of the ether polyol and other polyether polyol other than this ethylenediamine-based polyether polyol in combination. As other polyether polyols used therein, Mannig-based polyether polyols, glycerin-based polyether polyols, aromatic polyether polyols, Schcros-based polyether polyols, sorbitol-based polyether polyols, and toluenediamine-based polyols. Examples thereof include ether polyols and tolylene diamine-based polyether polyols.

Above all, in the present invention, it is recommended to use a Mannig-based polyether polyol in combination as another polyether polyol component used together with the ethylenediamine-based polyether polyol. Since the Mannig-based polyether polyol has excellent reaction activity, its use contributes effectively to the promotion of the resinification reaction. Therefore, when sprayed, the curing reaction (resinization) and bubbles occur. It is advantageous to prevent the heat of reaction generated by the chemical reaction from being transferred to the adherend exposed to the low temperature environment and being taken away by the adherend, and as a result, the heat of reaction generated is further increased. It can be effectively used in the curing reaction and the foaming reaction, and the initial foaming property can be effectively improved.

The Mannich-based polyether polyol described above is obtained by utilizing the Mannich reaction, and an alkylene oxide is added to a Mannich condensate having two or more hydroxyl groups in the molecule, or such a Mannich condensate. The added Mannich-based polyether polyol or a mixture thereof. In addition, among them, phenols such as Mannich condensate obtained by reacting phenols, aldehydes and secondary amines, or Mannich-based polyether polyol in which an alkylene oxide is added to such a Mannich condensate are used as a base. The Mannich-based polyether polyol described above will be preferably used.

By the way, the polyester polyol (A) as described above and the polyether polyol (B) constituting the polyol in the polyol composition used in the present invention have a mass ratio of A: B = 70: 30 to 40:60. , Preferably 65: 35-45: 55, where the proportion of polyester polyol (A) is greater than 70% by mass [the proportion of polyether polyol (B) is 30. If it is less than% by mass], the curing speed will decrease, causing dripping and lateral running during spraying, and peeling will occur at the edges of the foam during spraying. May be evoked. Further, when the proportion of the polyether polyol (B) is more than 60% by mass [the proportion of the polyester polyol (A) is less than 40% by mass], the curing rate is too high and spraying is performed. During construction, the foam hardens at the tip of the spray gun, causing a gun clogging phenomenon in which spraying cannot be performed in a circular spray pattern, which may cause a problem that it becomes difficult to continue spraying.

Then, in the present invention, a polyol composition is prepared by using the above-mentioned polyester polyol (A) and a polyether polyol (B) composed of 70% by mass or more of the ethylenediamine-based polyether polyol in a predetermined ratio. In such polyol compositions, various additives traditionally used in the production of polyurethane foams, such as foaming agents (and / or sources thereof), catalysts, flame retardants, and conditioned agents. A foaming agent or the like is appropriately blended and contained. In the present invention, as a foaming agent, one or more organic halogenated hydroolefins such as HFO and HCFO are particularly organic. A foaming agent will be used at least.

Here, examples of the hydrofluoroolefin (HFO), which is one of the above-mentioned halogenated hydroolefins, include pentafluoropropenes such as 1,2,3,3,3-pentafluoropropene (HFO1225ye), 1,3. , 3,3-Tetrafluoropropene (HFO1234ze), 2,3,3,3-Tetrafluoropropene (HFO1234yf), 1,2,3,3-Tetrafluoropropene (HFO1234ye) and other tetrafluoropropenes, 3,3 , 3-Fluoropropene such as 3-trifluoropropene (HFO1243zf), tetrafluorobutene (HFO1345), pentafluorobutene isomer (HFO1354), 1,1,1,4,4,4-hexafluoro-2- Hexafluorobutene isomers (HFO1336) such as butene (HFO1336mzz), heptafluorobutene isomers (HFO1327), heptafluoropentene isomers (HFO1447), octafluoropentene isomers (HFO1438), nonafluoropentene isomers. The body (HFO1429) and the like can be mentioned. Examples of the hydrochlorofluoroolefin (HCFO) include 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd) and 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf). Dichlorotrifluoropropene (HCFO1223) and the like can be mentioned.

In particular, such hydrofluoroolefins (HFOs) and hydrochlorofluoroolefins (HCFOs) have a low global warming potential due to their chemical instability, and therefore have received attention as environmentally friendly foaming agents. However, there is also an inherent risk of decomposition by amine compounds used as catalysts. However, in the present invention, since the amount of the amine-based catalyst used can be reduced as much as possible, there is no fear of decomposition of such a foaming agent (especially HCFO-1233zd), and its foaming function Has the advantage of being able to exert the advantage.

Further, in the present invention, water as a foaming agent is advantageously used together with the above-mentioned halogenated hydroolefin. As described above, the presence of water in the polyol composition causes the polyol composition and the polyisocyanate to be mixed and reacted, and the water reacts with the polyisocyanate to generate carbon dioxide. At that time, heat of reaction is generated, so that the heat can effectively promote the urethanization reaction and the isocyanurate-forming reaction, and the compressive strength of the obtained polyurethane foam can be further increased. It becomes. Then, due to the presence of water in such a polyol composition, when the polyol composition and the polyisocyanate are mixed and reacted, carbon dioxide is generated by the reaction between the water and the polyisocyanate, and this carbon dioxide is generated. Carbon also contributes to the foaming of polyurethane. Moreover, the combined use of the halogenated hydroolefin and water causes an endothermic reaction when the halogenated hydroolefin volatilizes, but the reaction heat occurs when water reacts with polyisocyanate to generate carbon dioxide. There is an advantage that the halogenated hydroolefin is easily volatilized by such reaction heat, and thus there is also an advantage that the amount of the halogenated hydroolefin used can be reduced and the cost thereof can be reduced. It will be.

The amount of the above-mentioned halogenated hydroolefin used is preferably 15 to 50 parts by mass, more preferably 25 to 40 parts by mass, based on 100 parts by mass of the entire polyol in the polyol composition. When the amount of the halogenated hydroolefin used exceeds 50 parts by mass, the core density of the foam becomes low, which may cause a decrease in the strength of the foam and thus a deterioration in dimensional stability. There is also a problem that it is disadvantageous in terms of cost. On the other hand, if the amount of the halogenated hydroolefin used is less than 15 parts by mass, the characteristics as a foaming agent cannot be sufficiently exhibited, the density of the obtained foam may increase, and the polyol may be used. The viscosity of the composition becomes high, the mixing property with isocyanate deteriorates, and a problem that a good spray pattern cannot be obtained is caused.

The amount of water used as a foaming agent is 0.5 to 8 parts by mass, preferably 1 to 5 parts by mass with respect to 100 parts by mass of the entire polyol in the polyol composition. Is contained. If the amount of water used is more than 8 parts by mass with respect to 100 parts by mass of the entire polyol, the strength will rather decrease. This is because the urea bond generated by the reaction between water and polyisocyanate increases in the resin, and the polyisocyanate used in the isocyanurate-forming reaction is consumed in the reaction with water, so that the polyisocyanate in the reaction system decreases. Because. Further, if the amount of water used is less than 0.5 parts by mass, there is a problem that the effect as a foaming agent due to the inclusion of water cannot be sufficiently obtained.

Then, as described above, when the halogenated hydroolefin and water are used in combination, the halogenated hydroolefin and water have a mass ratio of 80:20 to 99: 1, preferably 85: 15 to 95: 5. It is desirable to use in proportion. If the proportion of water exceeds 20 outside this range, brittleness develops as the reaction progresses, the adhesiveness to the skeleton surface decreases, and problems such as peeling may occur. In addition, carbon dioxide generated by the reaction with isocyanate may reduce the thermal conductivity and form a foamed layer having an insufficient thermal conductivity.

By the way, in the present invention, the polyol composition and the polyisocyanate are mixed, reacted in the presence of a catalyst, foamed by a foaming agent, and cured to form a hard polyurethane foam. However, as one of the catalysts used there, a resinification catalyst is advantageously used in order to promote the reaction between the polyol and the polyisocyanate. This resinification catalyst is appropriately selected and used according to the type of foam. For example, a urethanization catalyst or an isocyanurate-forming catalyst may be used alone or in combination thereof. .. Here, examples of the urethanization catalyst include fatty acid bismuth salts such as dibutyltin dilaurate, bismuth octylate (bismuth 2-ethylhexylate), bismuth neodecanoate, bismuth neododecanoate, and bismuth naphthenate, and lead naphthenate. .. On the other hand, examples of the isocyanurate-forming catalyst include quaternary ammonium salts, fatty acid alkali metal salts such as potassium octylate and sodium acetate, and tris (dimethylaminopropyl) hexahydrotriazine. Of these, it is particularly preferable to use a quaternary ammonium salt.

Examples of the tetraammonium salt advantageously used here include tetramethylammonium, methyltriethylammonium, ethyltrimethylammonium, propyltrimethylammonium, butyltrimethylammonium, pentyltrimethylammonium, hexyltrimethylammonium, heptyltrimethylammonium, octyltrimethylammonium, and nonyl. Aliphatic ammonium compounds such as trimethylammonium, decyltrimethylammonium, undecyltrimethylammonium, dodecyltrimethylammonium, tridecyltrimethylammonium, tetradecyltrimethylammonium, heptadecyltrimethylammonium, hexadecyltrimethylammonium, heptadecyltrimethylammonium, octadecyltrimethylammonium. , (2-Hydroxypropyl) trimethylammonium, hydroxyethyltrimethylammonium, hydroxyammonium compounds such as trimethylaminoethoxyethanol, 1-methyl-1-azania-4-azabicyclo [2,2,2] octanium, 1,1-dimethyl Examples thereof include alicyclic ammonium compounds such as -4-methylpiperidinium, 1-methylmorpholinium, and 1-methylpiperidinium. Among these, tetramethylammonium, methyltriethylammonium, ethyltrimethylammonium, butyltrimethylammonium, hexyltrimethylammonium, octyltrimethylammonium, decyltrimethylammonium, dodecyltrimethylammonium, because of their excellent catalytic activity and industrial availability, Tetradecyltrimethylammonium, hexadecyltrimethylammonium, octadecyltrimethylammonium, (2-hydroxypropyl) trimethylammonium, hydroxyethyltrimethylammonium, 1-methyl-1-azania-4-azabicyclo [2,2,2] octanium, and 1 , 1-Dimethyl-4-methylpiperidinium will be preferably used.

Examples of the organic acid group or inorganic acid group constituting the tetraammonium salt as described above include formic acid group, acetic acid group, octyl acid group, oxalic acid group, malonic acid group, succinic acid group, glutaric acid group and adipine. Organic acid groups such as acid groups, benzoic acid groups, toluic acid groups, ethyl benzoic acid groups, methyl carbonate groups, phenol groups, alkylbenzene sulfonic acid groups, toluene sulfonic acid groups, benzene sulfonic acid groups, phosphoric acid ester groups, and halogens. Examples thereof include inorganic acid groups such as groups, hydroxyl groups, hydrogen carbonate groups and carbonate groups. Among these, formic acid group, acetic acid group, octylate group, methyl carbonate group, halogen group, hydroxyl group, hydrogen carbonate group and carbonic acid group are preferable because they have excellent catalytic activity and are industrially available.

Further, as a catalyst composed of such a quaternary ammonium salt, various catalysts are commercially available, and for example, U-CAT 18X, U-CAT 2313 (manufactured by San Apro Co., Ltd.), Kao Riser No. 410, Kao Riser No. 420 (manufactured by Kao Corporation) and the like can be mentioned.

The amount of the resinification catalyst used as one of the catalysts is 0.1 to 100 parts by mass with respect to 100 parts by mass of the entire polyol in the polyol composition while effectively exerting the function as the catalyst. It will be selected within the range of 5 parts by mass, preferably 0.5 to 3 parts by mass. If the amount of this resinification catalyst used is less than 0.1 parts by mass, the obtained foam may become sticky, dust or the like may adhere to the resin, resulting in a poor appearance. In the spray foaming operation, the floor or the like may be used. Since the droplets adhering to the resin become sticky, there are problems such as poor workability. On the other hand, if the amount exceeds 5 parts by mass, heat generation increases during the resinification reaction, and the appearance is abnormal such as yellowing of the foam. The quaternary ammonium salt catalyst contained in the droplets generated during foaming may worsen the work environment at the work site where the spraying work is performed.

Further, in addition to the above-mentioned resinification catalyst, if necessary, a known catalyst conventionally used in the production of polyurethane foam is appropriately selected and contained in the polyol composition. .. For example, an amine-based catalyst can advantageously improve the initial foamability of polyurethane, and also has the effect of reducing the overall density of the foam without changing the density difference between the skin layer and the core layer, and further. It is possible to improve the stickiness of the foam and advantageously prevent the deterioration of the appearance due to the adhesion of dust, etc., and in the spray foaming method, it exhibits the feature of improving the deterioration of workability due to the stickiness of the droplets adhering to the floor, etc. Is what you do. As such an amine-based catalyst, it is recommended to use a reactive amine compound having an OH group or an NH group in the chemical structure or a cyclic amine compound having a cyclic structure. Among them, the reactive amine compound is used. By using it as a catalyst, the odor can be further reduced.

The reactive amine compound and the cyclic amine compound used as such an amine-based catalyst can be appropriately selected from known urethanization catalysts. For example, the reactive amine compound includes 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- (2-hydroxypropyl) imidazole , 3,3-Diamino-N-methyldipropylamine, N-methyl-N'-hydroxyethylpiperazine and the like. Examples of the cyclic amine compound include triethylenediamine, N, N'-dimethylcyclohexylamine, N, N-dicyclohexylmethylamine, methylenebis (dimethylcyclohexyl) amine, N, N-dimethylbenzylamine, morpholine, and N-methyl. Morpholine, N-ethylmorpholine, N- (2-dimethylaminoethyl) morpholine, 4,4'-oxydiethylenedimorpholine, N, N'-diethylpiperazine, N, N'-dimethylpiperazine, N- Methyl-N'-dimethylaminoethylpiperazine, 1,8-diazobicyclo (5,4,0) -undecene-7 and the like can be mentioned.

The amount of the amine-based catalyst used as one of the catalysts is such that the function as the catalyst is effectively exhibited, problems such as odor and deterioration of the working environment are reduced, and effective foam characteristics are obtained. In order to obtain, 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 with respect to 100 parts by mass of the entire polyol in the polyol composition. , Will be selected. If the amount of this amine-based catalyst used is less than 0.1 parts by mass, it becomes difficult to fully exert the function as a catalyst, and the obtained foam becomes sticky, dust and the like adhere to it, resulting in a poor appearance. In addition, in the spray foaming operation, the droplets adhering to the floor or the like become sticky, which causes problems such as poor workability. Further, when the amount of the amine-based catalyst used is more than 7 parts by mass, the odor of the obtained polyurethane foam becomes remarkable, and the amine-based catalyst volatilized during foaming causes a problem that the spraying work environment is deteriorated. Will be. Therefore, from the viewpoint of odor, it is preferable that the amount of the amine-based catalyst added is small.

On the other hand, the polyisocyanate constituting the effervescent composition for polyurethane foam according to the present invention together with the above-mentioned polyol composition is blended with the polyol composition and reacts with the polyol in the polyol composition. It is an organic isocyanate compound that produces polyurethane (resin) and has two or more isocyanate groups (NCO groups) in the molecule. For example, diphenylmethane diisocyanate, polymethylene polyphenylene polyisocyanate, tolylene diisocyanate, polytri In addition to aromatic polyisocyanates such as lentry isocyanate, xylylene diisocyanate, and naphthalene diisocyanate, aliphatic polyisocyanates such as hexamethylene diisocyanate, and alicyclic polyisocyanates such as isophorone diisocyanate, urethane prepolymers having an isocyanate group at the molecular terminal. , Isocyanurate modified product of polyisocyanate, carbodiimide modified product and the like. These polyisocyanate compounds may be used alone or in combination of two or more. In general, polymethylene polyphenylene polyisocyanate (Crude MDI) is preferably used from the viewpoints of reactivity, economy, handleability and the like.

The blending ratio of the polyisocyanate to the above-mentioned polyol composition will be appropriately determined depending on the type of foam to be formed (for example, polyurethane or polyisocyanurate), but generally, the isocyanate of the polyisocyanate The NCO / OH index (equivalent ratio) indicating the ratio of the group (NCO) to the hydroxyl group (OH) of the polyol in the polyol composition is appropriately determined so as to be in the range of about 0.9 to 2.5. The Rukoto.

By the way, in the polyol composition and the polyisocyanate constituting the effervescent composition for polyurethane foam according to the present invention, in addition to the above-mentioned compounding components or contained components, if necessary, a known flame retardant or defoaming agent It is also possible to appropriately select and blend various conventionally known auxiliary agents such as.

The foam stabilizer used here is used to uniformly arrange the cell structure of the polyurethane foam, and here, a silicone-based surfactant or a nonionic surfactant is preferably adopted. Specific examples include polyoxyalkylene-modified dimethylpolysiloxane, polysiloxaneoxyalkylene copolymer, polyoxyethylene sorbitan fatty acid ester, castor oil ethylene oxide adduct, lauryl fatty acid ethylene oxide adduct, and the like. One type is used alone, or two or more types are used in combination. The blending amount of this defoaming agent is appropriately determined according to the desired foam characteristics, the type of defoaming agent to be used, and the like, but it is determined in 100 parts by mass of the entire polyol in the polyol composition. On the other hand, it is selected in the range of 0.1 to 10 parts by mass, preferably 1 to 8 parts by mass.

Further, as a flame retardant, phosphoric acid esters such as trischloroethyl phosphate, trischloropropyl phosphate, and triethyl phosphate, which have less impact on the environment and also function as a thickener of the effervescent composition, are advantageous. Used for. When this phosphoric acid ester is blended, the blending amount thereof can be appropriately determined according to the desired foam characteristics, the type of flame retardant, etc., with respect to 100 parts by mass of the entire polyol in the polyol composition. Generally, it is selected in the range of 5 to 60 parts by mass, preferably 10 to 40 parts by mass. In addition to the above-mentioned phosphoric acid ester, aluminum hydroxide or the like can be preferably used as a flame retardant. As the flame retardant described above, phosphoric acid esters such as trischloroethyl phosphate, trischloropropyl phosphate, and triethyl phosphate, which have a low environmental load and also function as a thickener for the effervescent composition, are used. , Used advantageously. When this phosphoric acid ester is blended, the blending amount can be appropriately determined depending on the desired foam characteristics, the type of flame retardant, etc., but is generally based on 100 parts by mass of the entire polyol in the polyol composition. It is selected in the range of 5 to 60 parts by mass, preferably 10 to 40 parts by mass.

Further, in the foamable composition for polyurethane foam according to the present invention, if necessary, for example, formaldehyde scavengers such as urea and melamine, bubble micronizing agents, plasticizers, reinforcing base materials and the like have been conventionally known. It is also possible to appropriately select and blend the various additives described above.

Then, when the polyol composition obtained as described above and the polyisocyanate are reacted in the presence of a catalyst to foam and cure, various known methods for producing polyurethane foam can be adopted. By the way, for example, in a space where heat insulation is required, such as a laminated continuous foaming method in which a mixture of these polyol compositions and polyisocyanate is applied onto a face material to foam and cure in a plate shape, an electric refrigerator or the like. Injecting and filling into the honeycomb structure of a lightweight and high-strength board to foam and cure, or spraying from the spray gun head of an on-site foaming machine onto a predetermined adherend (structure) to foam and cure. By the spray foaming method, the foamable composition according to the present invention is foamed and cured to form the target polyurethane foam. In particular, in the present invention, the ambient temperature (ambient temperature). Below, the spray foaming method, which is foamed in the field, is preferably adopted. By applying to such an in-situ spray foaming method, the features of the present invention can be more advantageously exhibited, and a polyurethane foam having excellent properties such as dimensional stability can be advantageously obtained.

Hereinafter, the features of the present invention will be clarified more concretely by showing some examples of the present invention and comparing them with the comparative examples. Needless to say, it is not subject to any restrictions. In addition to the following examples, the present invention is further modified in various ways based on the knowledge of those skilled in the art, as long as it does not deviate from the gist of the present invention, in addition to the specific description described above. It should be understood that modifications, improvements, etc. can be made. Unless otherwise specified, the percentages (%) and parts shown below are all shown on a mass basis.

In addition, the density, foaming characteristics (curing rate), workability, and dimensional change rate of the polyurethane foams obtained in the following Examples and Comparative Examples were evaluated or measured as follows, respectively.

(1) Measurement of Density For the rigid polyurethane foams obtained in each Example and Comparative Example, the respective densities were measured in accordance with JIS-K-7222. That is, five or more test pieces having a cubic shape of 5 cm square are cut out from a polyurethane foam that has been foamed for 72 hours or more after foaming and has been allowed to stand at 23 ° C. ± 2 ° C. for 16 hours or more before measurement. rice field. Next, for each test piece, each dimension of length, width, and height was measured three times or more using a caliper, the average value was obtained, and the volume of each test piece was calculated. Then, the mass of each test piece was measured, and the density (ρ) of the test piece was calculated from the following formula. If the density is too high, the polyurethane foam becomes hard and the stability deteriorates. Therefore, 30 kg / cm ³ or less was accepted.
ρ (kg / m ³ ) = [m (g) / V (mm ³ )] × 10 ⁶
Here, ρ: density, m: mass of the test piece, V: volume of the test piece.

(2) Measurement of Foaming Characteristics (Curing Rate) Polyol composition and crude MDI (Millionate MR-100: manufactured by Toso Co., Ltd.) as polyisocyanate are mixed, and the volume ratio of the polyol composition and polyisocyanate is a polyol. Weigh in a paper cup (capacity: 500 ml) so that the composition / polyisocyanate = 100/100, and then use a homodisper (manufactured by Tokushu Kika Kogyo Co., Ltd.) to stir and mix at high speed for 1 second. To prepare an effervescent mixed solution for rigid polyurethane foam. Then, the effervescent mixed solution prepared in such a paper cup was foamed and cured as it was at room temperature to obtain a rigid polyurethane foam.

Then, at the time of such foaming and curing, cream time (CT) and rise time (RT) were measured in order to judge the reactivity of the foaming mixed solution. Here, CT is the time from the start of mixing the polyol composition and the polyisocyanate to the start of foaming, and RT is the time from the start of mixing of the components to the end of foaming. There is. It should be noted that such CT may not be too early or too late, and it is said that 2 to 5 seconds is passed, and that RT should be early.

(3) Evaluation of workability The polyol composition and Crude MDI in each Example and Comparative Example are stirred and mixed using an on-site spray foaming machine (trade name: A-25, manufactured by Graco) to foam. Along with forming the sex mixture, the effervescent mixture was sprayed onto the surface of a concrete plate of a predetermined size, which is a skeleton, under the condition of an ambient temperature of 15 ° C. to form a foam layer made of hard polyurethane foam. .. Then, the "workability" at the time of forming the foamed layer was judged from the "initial foamability" and the "shape of the spray pattern" according to the following evaluation criteria.
×: The surface is not smooth because the spray pattern is not circular due to dripping. Δ: Slight dripping occurs, the pattern shape changes slightly, and the surface is not smooth. ○: Dripping occurs. The pattern shape does not change, and the surface is smooth.

(4) Measurement of Dimensional Change Rate The dimensional change rate was measured according to the following method according to ASTM-D-2126. First, as a test piece, from the foam layer formed in each Example or Comparative Example, length: 100 ± 1 mm, width: 100 ± 1 mm, thickness: 25 ± 0.5 mm so as to include one intermediate skin layer. It was cut out with the dimensions of. The cut test piece was then allowed to stand under the conditions of 23 ° C. and 50 RH% for 20 hours, then exposed to the conditions of 70 ° C. and 95 RH%, and the test piece was taken out after 48 hours. Then, the dimensions of the test piece were measured at 5 points for thickness and 3 points for width / length, average values were obtained for each, and the rate of change for each was calculated according to the following formula.
The length of the change rate _{= 100 × (l t -l 0} ) / l 0
Width change rate = 100 × (b _t − b ₀ ) / b ₀
Thickness change rate = 100 × (δ _{t −} δ ₀ ) / δ ₀
[L ₀ , b ₀ and δ ₀ : average value of the first dimension, l _t , b _t and δ _t : average value of the final dimension after 48 hours]

When the three rate of change calculated by the above formula is 10% or more even at one point, it is marked as "x" because good dimensional stability cannot be maintained, and even one point is 5% or more and less than 10%. Some of them were evaluated as "Δ", and those with less than 5% were evaluated as "○".

-Preparation of polyol composition-
As polyols, 750ED (manufactured by Asahi Glass Co., Ltd.), which is an ethylenediamine-based polyether polyol, 500ED (manufactured by Asahi Glass Co., Ltd.), which is an ethylenediamine-based polyether polyol, RDK133 (manufactured by Kawasaki Kasei Kogyo Co., Ltd.), which is a phthalic acid-based polyester polyol, RFK505 (manufactured by Kawasaki Kasei Kogyo Co., Ltd.), which is a phthalic acid-based polyester polyol, and DK polyol 3776 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), which is a Mannig-based polyether polyol, are prepared, respectively, and a tetraammonium salt is used as a catalyst. A certain U-CAT 18X (manufactured by Sun Appro Co., Ltd.) and Polycat 12 (manufactured by Ebony Japan Co., Ltd.), which is a tertiary amine N-methyldicyclohexylamine, were prepared respectively. In addition, Tris (1-chloro-2-propyl) phosphate (TCPP: manufactured by Wanshan Co., Ltd.) is prepared as a flame retardant, and Tegostave B8450 (manufactured by Ebonic Japan Co., Ltd.), which is a silicone-based defoaming agent, is prepared as a defoaming agent. Prepared. Further, as a foaming agent, 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd: manufactured by Honeywell), 1,1,1,4,4,4-hexafluoro-2-butane (HFO-). 1336mzz: manufactured by The Chemours), 1,1,1,3,3-pentafluoropropane (HFC245fa: manufactured by Central Glass Co., Ltd.), 1,1,1,3,3-pentafluorobutane (HFC365mfc: manufactured by SOLVAY) , And water were prepared respectively.

Then, these various polyols, catalysts, flame retardants, defoaming agents and foaming agents are uniformly mixed in various combinations and blending ratios shown in Tables 1 and 2 below, and compared with Examples 1 to 8. Various polyol compositions according to Examples 1 to 6 were prepared.

-Preparation of polyisocyanate-
Crude MDI (Millionate MR-100: manufactured by Tosoh Corporation) was prepared as a polyisocyanate.

-Manufacturing of polyurethane foam-
The various polyol compositions obtained above and polyisocyanate are used in a volume ratio of 1: 1 and mixed by stirring with an in-situ spray foaming machine (trade name: A-25, manufactured by Graco) to obtain a foaming stock solution. By spraying this onto the surface of the inorganic flexible board as an adherend multiple times under the condition of an atmospheric temperature of 15 ° C. to foam and cure it, Examples 1 to 8 and Comparative Examples 1 to 6 are obtained. The various rigid polyurethane foams described above were produced, respectively.

Then, using the various polyurethane foams thus obtained, the density, workability and dimensional stability of the polyurethane foams were measured, and the reaction times (CT, RT) at the time of forming the polyurethane foams were determined, respectively. The measurement results are shown in Tables 1 and 2 below, respectively.

As is clear from the results in Table 1, in the foaming agent composition composed of the combination of the polyol composition and the polyisocyanate adopted in Examples 1 to 8 according to the present invention, an appropriate cream is used for the reaction. It has a thyme (CT), the desired reaction characteristics can be advantageously realized, and a foamed layer having a smooth surface and a pattern shape that does not change is formed without causing dripping. In addition, the dimensional stability required from the dimensional change rate is such that the dimensional change rate is 5% or less, and a polyurethane foam having excellent dimensional stability can be obtained. Is recognized.

On the other hand, as shown in the results of Table 2, the reaction time (CT) was too short in Comparative Example 1 in which polyester polyol was not used as one of the polyol components and Comparative Example 2 in which the amount used was small. In Comparative Example 3 in which there is a problem in workability and dimensional stability and the amount of ethylenediamine-based polyether polyol used as one of the polyol components is small and Comparative Example 4 in which it is not used, the reaction time becomes too long. , There is a problem in dimensional stability or workability, and in Comparative Example 5 in which halogenated hydroolefin is not used as the foaming agent, the workability and dimensional stability are lacking, and in addition, only water is used as the foaming agent. In the case of Comparative Example 6, it was confirmed that the density of the obtained foam became too high, and the workability and dimensional stability were significantly lacking.

Claims (12)

A foamable composition composed of a polyol composition mainly composed of a polyol and a polyisocyanate, which gives a polyurethane foam by foaming with a foaming agent together with the reaction of the polyol and the polyisocyanate.
As the polyol in the polyol composition, the polyester polyol (A) and the polyether polyol (B) are used in a ratio of A: B = 65:35 to 40:60 in terms of mass ratio, and the polyether polyol is used. A foamable composition for polyurethane foam, characterized in that 80 % by mass or more of the above is composed of an ethylenediamine-based polyether polyol and at least a halogenated hydroolefin is used as the foaming agent.
The foamable composition for polyurethane foam according to claim 1, wherein a halogenated hydroolefin and water are used in combination as the foaming agent. The foamable composition for polyurethane foam according to claim 2, wherein the halogenated hydroolefin and the water are used in a mass ratio of 80:20 to 95: 5. Claims 1 to 3 are characterized in that the quaternary ammonium salt is contained in the polyol composition at a ratio of 0.1 to 5 parts by mass with respect to 100 parts by mass of the polyol as a catalyst. The foamable composition for polyurethane foam according to any one of the above items. The foamable composition for polyurethane foam according to any one of claims 1 to 4, wherein the halogenated hydroolefin is selected from the group consisting of hydrofluoroolefins and hydrochlorofluoroolefins. .. The foamable composition for polyurethane foam according to any one of claims 1 to 5, wherein the halogenated hydroolefin is HCFO-1233zd. The ethylenediamine-based polyether polyol contains an ethylenediamine-based polyether polyol having a hydroxyl value of 400 mgKOH / g or more and less than 600 mgKOH / g, and an ethylenediamine-based polyether polyol having a hydroxyl value of 600 mgKOH / g or more and 1000 mgKOH / g or less. The effervescent composition for polyurethane foam according to any one of claims 1 to 6, wherein the foaming composition is characterized by. The ethylenediamine-based polyether polyol having a hydroxyl value: 400 mgKOH / g or more and less than 600 mgKOH / g and the ethylenediamine-based polyether polyol having a hydroxyl value: 600 mgKOH / g or more and 1000 mgKOH / g or less have a mass ratio of 10:90 to 30: The foamable composition for polyurethane foam according to claim 7, wherein the foaming composition is used in a ratio of 70. The foamable composition for polyurethane foam according to any one of claims 1 to 8, wherein the polyether polyol is composed of an ethylenediamine-based polyether polyol and a Mannig-based polyether polyol. The foamable composition for polyurethane foam according to any one of claims 1 to 9, wherein the polyester polyol contains a phthalic acid-based polyester polyol. Any one of claims 1 to 10, wherein the polyol composition contains an amine-based catalyst in a proportion of 0.1 to 7 parts by mass with respect to 100 parts by mass of the polyol. The foamable composition for polyurethane foam according to the item. The foaming composition for polyurethane foam according to any one of claims 1 to 11 is used, and the foaming composition is sprayed onto the surface of a predetermined structure to be foamed and cured. Manufacturing method of polyurethane foam.