JP2021059704A - Foamable urethane resin composition - Google Patents

Abstract

To provide a foamable urethane resin composition for producing a polyurethane foam that is substantially free of inorganic fillers and has a property of not easily spreading the fire.SOLUTION: Provided is a foamable urethane resin composition, which is a foamable urethane resin composition containing a polyol compound, a polyisocyanate compound, a flame retardant liquid at room temperature, a foaming agent, and a catalyst, and in which the foamable urethane resin composition contains substantially no inorganic filler, and the sinking distance of a steel ball in the hot steel ball evaluation of a polyurethane foam made of said foamable urethane resin composition is 10 mm or less.SELECTED DRAWING: None

Description

The present invention relates to a foamable urethane resin composition.

Polyurethane foam has been put to practical use for heat insulating and preventing dew condensation on ceilings, roofs, walls and the like of condominiums and other condominiums, detached houses and commercial buildings by utilizing its excellent heat insulating properties. Although polyurethane foam is lightweight, it is easily burned because it is an organic substance. In order to improve this, a polyurethane foam having a flame retardant or the like contained in the polyurethane foam to improve the flame retardancy is used. For example, in Patent Document 1, a flame-retardant polyurethane foam obtained by using ammonium polyphosphate, a urea derivative, a polyol, and an isocyanate, wherein the flame-retardant polyurethane foam weighs 5 to 150 parts by weight based on 100 parts by weight of the polyol. Described are flame-retardant polyurethane foams obtained by using ammonium polyphosphate in the range of parts and urea derivatives in the range of 0.001 to 15 parts by weight.

JP-A-2015-151524

In recent years, a relatively large number of fires have been reported due to polyurethane foam used in buildings as a heat insulating material. In order to improve such a problem, it is expected to develop a polyurethane foam which not only has excellent flame retardancy but also has a property of being hard to spread when a fire breaks out.
On the other hand, for example, by blending a large amount of an inorganic filler such as a solid flame retardant, it is expected that the polyurethane foam can be imparted with the property of being hard to spread, but when the inorganic filler is blended, foaming for producing a polyurethane foam is performed. Problems such as the formation of precipitates during storage of the urethane resin composition and deterioration of handleability, or the tendency of the device used when spraying and using the foamable urethane resin composition to wear out occur.
Therefore, it is an object of the present invention to provide a foamable urethane resin composition for producing a polyurethane foam which does not substantially contain an inorganic filler and has a property of being hard to spread by burning.

As a result of diligent studies, the present inventor has found a foamable urethane resin composition containing a polyol compound, a polyisocyanate compound, a flame retardant liquid at room temperature, a foaming agent, and a catalyst, and substantially free of an inorganic filler. , The present invention has been completed by finding that the above-mentioned problems can be solved by a foamable urethane resin composition showing a specific value in the evaluation of hot steel balls. That is, the present invention provides the following [1] to [11].
[1] A foamable urethane resin composition containing a polyol compound, a polyisocyanate compound, a flame retardant liquid at room temperature, a foaming agent, and a catalyst, wherein the foamable urethane resin composition contains substantially an inorganic filler. A foamable urethane resin composition in which the sinking distance of the steel balls in the following thermal steel ball evaluation of the polyurethane foam composed of the foamable urethane resin composition is 10 mm or less.
(Evaluation of hot steel balls)
(1) A polyurethane foam is cut into a cube having a side of 50 mm and used as a test body.
(2) A wire mesh is placed 30 mm from the burner mouth of the Bunsen burner (outer flame length 70 mm), and a steel ball with a diameter of 10.0 mm and a weight of 4.15 g is placed on the wire mesh, and the entire steel ball turns red. Heat for at least 5 minutes until it changes to a steel ball temperature of 630 ° C.
(3) In an atmosphere of 23 ° C., the steel ball heated in (2) above is immediately placed on the center of the upper part of the test piece of (1) above, and left to stand until the subduction of the steel ball is completed. Next, the cross section of the sufficiently cooled test piece is cut, and the subduction distance and the melt diameter distance of the steel ball are measured.
[2] The foamable urethane resin composition according to the above [1], wherein the sinking distance of the steel ball in the evaluation of the hot steel ball is 5 mm or less and the molten diameter distance is 15 mm or less.
[3] The total calorific value when the polyurethane foam made of the foamable urethane resin composition is ^{heated for 5 minutes at a radiant heat intensity of 50 kW / m 2 in accordance with the test method of ISO-5660 is 8 MJ /} The foamable urethane resin composition according to the above [1] or [2], which is m ^{2 or less.}
[4] The maximum heat generation rate when the polyurethane foam composed of the foamable urethane resin composition is ^{heated for 5 minutes at a radiant heat intensity of 50 kW / m 2 in accordance with the test method of ISO-5660 is 100 kW /.} The foamable urethane resin composition according to any one of the above [1] to [3], which is m ^{2 or less.}
[5] The foamable urethane resin composition according to any one of the above [1] to [4], wherein the polyol compound contains a phthalic acid-based polyester polyol.
[6] The above-mentioned [1] to [5], wherein the polyol compound contains a polyether-based polyol and a phthalic acid-based polyester polyol, and the content of the phthalic acid-based polyester polyol is 60% by mass or more based on the total amount of the polyol compound. ] The foamable urethane resin composition according to any one of.
[7] The foam according to any one of [1] to [6] above, wherein the foaming agent contains water and the content of the water is 1.5 parts by mass or less with respect to 100 parts by mass of the polyol compound. Sexual urethane resin composition.
[8] The foamable urethane resin composition according to any one of the above [1] to [7], wherein the foaming agent contains a hydrofluoroolefin.
[9] The foamable urethane resin composition according to any one of the above [1] to [8], wherein the catalyst contains a trimerization catalyst.
[10] The foamable urethane resin composition according to any one of the above [1] to [9], which has an isocyanate index of 150 to 700.
[11] The foamable urethane resin composition according to any one of the above [1] to [10], which is used for spraying applications.

According to the present invention, it is possible to provide a foamable urethane resin composition that is less likely to cause a precipitate during storage, is excellent in handleability, and can suppress wear of a spraying device or the like used during use. In addition to this, the foamable urethane resin composition can form a polyurethane foam having a property of being hard to spread in the event of a fire or the like.

[Effervescent urethane resin composition]
The foamable urethane resin composition of the present invention is a foamable urethane resin composition containing a polyol compound, a polyisocyanate compound, a flame retardant liquid at room temperature, a foaming agent, and a catalyst. , A foamable urethane resin composition that does not substantially contain an inorganic filler and has a steel ball sinking distance of 10 mm or less in the following thermal steel ball evaluation of a polyurethane foam composed of the foamable urethane resin composition. is there.
(Evaluation of hot steel balls)
(1) A polyurethane foam is cut into a cube having a side of 50 mm and used as a test body.
(2) A wire mesh is placed 30 mm from the burner mouth of the Bunsen burner (outer flame length 70 mm), and a steel ball with a diameter of 10.0 mm and a weight of 4.15 g is placed on the wire mesh, and the entire steel ball turns red. Heat for at least 5 minutes until it changes to a steel ball temperature of 630 ° C. The steel ball temperature was measured by moving the steel ball heated as described above from the wire mesh to another table that does not affect the radiation temperature measurement. For the steel ball temperature, a radiation thermometer (manufactured by KEYENCE: FT-H40K) was used, the radiation coefficient of the steel ball used was 0.45, and the value obtained by dividing the display value of the radiation thermometer by 0.45 was evaluated. (630 ° C.). A new steel ball was used.
(3) In an atmosphere of 23 ° C., the steel ball heated in (2) above is immediately placed on the center of the upper part of the test piece of (1) above, and left to stand until the subduction of the steel ball is completed. Next, the cross section of the sufficiently cooled test piece is cut, and the subduction distance and the melt diameter distance of the steel ball are measured.
In this thermal steel ball evaluation, the time from heating the steel ball to measuring the temperature is within 1 second, and the steel ball is placed on the test body immediately after the temperature measurement. Therefore, the steel ball temperature (630 ° C.) can be regarded as the temperature of the steel ball when the steel ball is placed on the test piece.

In the above hot steel ball evaluation, regarding the diameter and weight of the steel ball, the diameter is 10.0 ± 0.5 mm, the weight is 4.15 ± 0.3 g, and the steel ball temperature is measured by a radiation thermometer at 600 to 650 ° C. As long as it is within the range of, the same hot steel ball evaluation can be obtained by setting other conditions as described above. Therefore, it may be carried out within such a range of diameter, weight, and steel ball temperature.
The external flame length means the length of the flame in the direction directly above the center of the burner mouth.

By setting the steel ball subduction distance and the melt diameter distance in the evaluation of hot steel balls of the polyurethane foam made of the foamable urethane resin composition of the present invention within the above-mentioned predetermined ranges, the polyurethane foam is exposed to fire or the like. In that case, it can be made difficult to spread.

In the polyurethane foam made of the foamable urethane resin composition of the present invention, the sinking distance of the steel balls in the evaluation of hot steel balls is 10 mm or less. If the subduction distance of the steel ball exceeds 10 mm, the polyurethane foam easily burns and spreads when exposed to a fire or the like, and it becomes difficult to effectively prevent the spread of fire. From the viewpoint of effectively preventing the spread of fire, the subduction distance of the steel ball is preferably 5 mm or less, more preferably 3 mm or less, and further preferably 0 mm.

The polyurethane foam made of the foamable urethane resin composition of the present invention preferably has a melt diameter distance of 15 mm or less in the evaluation of steel ball subduction. When the melt diameter distance is 15 mm or less, the polyurethane foam is less likely to spread when exposed to a fire or the like, and the spread of fire can be effectively prevented. From the viewpoint of effectively preventing the spread of fire, the melt diameter distance is preferably 14 mm or less, more preferably 13 mm or less, still more preferably 12 mm or less. The melt diameter distance is 0 mm or more.

The steel ball subduction distance and the melt diameter distance can be adjusted to desired values by adjusting the type of the polyol compound contained in the foamable urethane resin composition, the content of water, and the like.

In the hot steel ball evaluation, a cavity is formed in the test body from the upper surface to the inside by the subduction of the steel ball. The subduction distance of the steel ball means the maximum distance of the cavity in the direction perpendicular to the upper surface of the test piece (the part that is discolored by heat but retains its shape is not covered). The molten diameter distance is the diameter of a hole formed by a heated steel ball on the upper surface of the test piece. The diameter of the hole means the diameter of the circle if the shape of the hole formed on the upper surface of the test piece is circular, and means the major axis if the shape of the hole is elliptical. .. If the shape of the hole is other than circular and elliptical, the maximum distance between any two points of that shape is defined as the diameter of the hole. If the test piece does not melt and no cavity is formed on the upper surface, the diameter of the carbonized or discolored part is measured in the same manner.

As the polyurethane foam in the evaluation of hot steel balls, those produced under the conditions described in the examples are used.

(Inorganic filler)
The foamable urethane resin composition of the present invention substantially does not contain an inorganic filler. By substantially not containing an inorganic filler, it is possible to provide a foamable urethane resin composition that is less likely to cause a precipitate during storage, is excellent in handleability, and can suppress wear of equipment and the like used during use. ..
Here, the fact that the inorganic filler is substantially not contained means that the content of the inorganic filler is 5% by mass or less, preferably 1% by mass or less, based on the total amount of the foamable urethane resin composition.

The inorganic filler is an inorganic compound such as a particle or a fibrous compound, and examples thereof include metals, metal oxides, metal hydroxides, and ceramics. Inorganic compounds other than solid flame retardants and solid flame retardants. Examples include fillers.
The solid flame retardant is a solid flame retardant at 23 ° C., for example, an antimony-containing flame retardant such as antimonate oxide, antimonate, pyroantimonate, magnesium hydroxide, calcium hydroxide, aluminum hydroxide and the like. Examples thereof include metal hydroxide-based flame retardants, boron-containing flame retardants such as lithium borate and sodium borate, phosphinic acid-based flame retardants, phosphate-containing flame retardants, bromine-containing flame retardants, and red phosphorus.
Examples of inorganic fillers other than solid flame retardants include silica, diatomaceous earth, alumina, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, ferrites, basic magnesium carbonate, and calcium carbonate. Magnesium carbonate, barium carbonate, dosonite, hydrotalcite, calcium sulfate, barium sulfate, gypsum fiber, potassium salts such as calcium silicate, talc, clay, mica, montmorillonite, bentonite, active white clay, sepiolite, imogolite, cericite, glass Fibers, glass beads, silica parun, aluminum nitride, boron nitride, silicon nitride, carbon black, graphite, carbon fiber, carbon parun, charcoal powder, various metal powders, potassium titanate, magnesium sulfate, lead zirconate titanate, aluminum porate, Examples thereof include molybdenum sulfide, silicon carbide, stainless steel fibers, various magnetic powders, slag fibers, fly ash, silica-alumina fibers, alumina fibers, silica fibers, and zirconia fibers.

(Total calorific value)
When the polyurethane foam made of the foamable urethane resin composition of the present invention is ^{heated for 5 minutes at a radiant heat intensity of 50 kW / m 2} in accordance with the ISO-5660 test method, the total calorific value is 8 MJ / m ^2. The following is preferable. Since the total calorific value is 8 MJ / m ² or less, the polyurethane foam made of the foamable urethane resin composition of the present invention has a predetermined flame retardancy. A polyurethane foam having a predetermined flame retardancy and having flame retardancy and not spreading by having the steel ball sinking distance and the molten diameter distance being less than a certain value as described above. Therefore, it is possible to more effectively prevent the spread of fire in the event of a fire.
From the viewpoint of further improving the flame retardancy of the polyurethane foam, the gross calorific value is preferably at 7.8MJ / ^{m 2} or less, more preferably 7.5 mJ / ^{m 2} or less.

(Maximum heat generation rate)
The maximum heat generation rate when the polyurethane foam made of the foamable urethane resin composition of the present invention is ^{heated for 5 minutes at a radiant heat intensity of 50 kW / m 2 in accordance with the test method of ISO-5660 is 100 kW / m 2.} The following is preferable. Since the maximum heat generation rate is 100 kW / m ² or less, the polyurethane foam made of the foamable urethane resin composition of the present invention has a predetermined flame retardancy. Further, by adjusting both the maximum heat generation rate and the total heat generation amount as described above, the flame retardancy is further improved.
A polyurethane foam having a predetermined flame retardancy and having flame retardancy and not spreading by having the steel ball sinking distance and the molten diameter distance being less than a certain value as described above. Therefore, it is possible to more effectively prevent the spread of fire in the event of a fire.
From the viewpoint of further improving the flame retardancy of the polyurethane foam, the maximum heating rate is preferably 98kW / m ² or less, and more preferably 95kW / m ² or less.

The total calorific value and the maximum exothermic rate can be obtained by a cone calorimeter test, and can be measured in detail by the method described in Examples.
In the corn calorimeter test, it is preferable that the polyurethane foam used in the test has shape stability to the extent that it does not come into contact with the spark igniter of the corn calorimeter.

(Polyol compound)
The polyol compound contained in the foamable urethane resin composition of the present invention is not particularly limited, but a polyether polyol and a polyester polyol are preferable. Among them, aromatic polyester polyols are preferable, and phthalic acid-based polyester polyols are more preferable, as will be described later, from the viewpoint of enhancing the flame retardancy of the obtained polyurethane foam.

<Polyether polyol>
The polyether polyol is a polyoxyalkylene polyol obtained by ring-opening addition polymerization of an alkylene oxide to an initiator having two or more active hydrogen atoms. Specific examples of the initiator include aliphatic polyhydric alcohols (eg, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,4-butanediol, 1,3-butanediol, 1,6-hexane). Glycols such as diols, neopentyl glycols, cyclohexylene glycols and cyclohexanedimethanol, triols such as trimethylolpropane and glycerin, tetrafunctional alcohols such as pentaerythritol, sugars such as sucroses and sorbitols), aliphatics Amines (eg, alkylenediamines such as ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, neopentyldiamine, alkanolamines such as monoethanolamine, diethanolamine), aromatic amines (eg, aniline, tolylenediamine, xylylenediamine) , Diphenylmethanediamine, Mannig condensate, etc.), and these may be used alone or in combination of two or more.

As the polyether polyol, from the viewpoint of improving the moldability at the time of injection and the workability at the time of spraying during urethane foaming, a tolylenediamine-based polyether polyol, a Mannig-based polyether polyol, a Schroth-based polyether polyol, and a sorbitol-based poly. Ether polyols are preferred. From the viewpoint of achieving both moldability and flame retardancy, these polyol compounds are preferably used in combination with an aromatic polyester polyol described later, and are preferably 5 to 40% by mass, preferably 10 to 30% by mass, based on the total amount of the polyol compounds. More preferably. From this point of view, the polyol compound of the present invention more preferably contains a polyether polyol and a phthalic acid-based polyester polyol described later. The type and content of the phthalic acid-based polyester polyol will be described later.

The above-mentioned tolylenediamine-based polyether polyol is a polyether polyol obtained by using tolylenediamine as an initiator. The same applies to the sucrose-based polyether polyol and the sorbitol-based polyether polyol.
The Mannich-based polyether polyol is obtained by utilizing the Mannich reaction, and is obtained by adding an alkylene oxide to a Mannich condensate having two or more hydroxyl groups in the molecule, or such a Mannich condensation product. Polyether polyol. More specifically, at least one of phenol and an alkyl-substituted derivative thereof, a Mannich condensation obtained by a Mannich reaction of formaldehyde and an alkanolamine, or at least one of ethylene oxide and propylene oxide on this compound is ring-opened addition polymerized. It is a polyether polyol obtained by allowing it to grow.

The hydroxyl value of the polyether polyol is preferably 200 to 1,000 mgKOH / g, more preferably 300 to 600 mgKOH / g. The hydroxyl value is a value measured in accordance with JIS K1557-1: 2007.

<Polyester polyol>
Examples of the polyester polyol include an aromatic polyester polyol and an aliphatic polyester polyol, but in consideration of the flame retardancy of the obtained polyurethane foam, it is preferable to use an aromatic polyester polyol. The aromatic polyester polyol is a condensate of an aromatic dicarboxylic acid such as o-phthalic acid (phthalic acid), m-phthalic acid (isophthalic acid), p-phthalic acid (terephthalic acid), and naphthalenedicarboxylic acid and glycol. Is preferable. Among them, the polyol compound is a condensation of phthalic acid and glycol from the viewpoint of improving the flame retardancy of the polyurethane foam, reducing the values of the steel ball sinking distance and the melt diameter distance described above, and improving the performance of not spreading. It is preferable to contain a phthalic acid-based polyester polyol which is a product, and more preferably to contain a p-phthalic acid-based polyester polyol which is a condensate of p-phthalic acid and glycol.
The glycol is not particularly limited, but it is preferable to use a known low molecular weight aliphatic glycol as a constituent component of a polyester polyol such as ethylene glycol, propylene glycol, and diethylene glycol.

From the viewpoint of reducing the values of the steel ball subduction distance and the melt diameter distance described above and enhancing the performance of not spreading, the content of the phthalic acid-based polyester polyol in the total amount of the polyol compound is preferably 60% by mass or more. It is preferably 70% by mass or more, more preferably 90% by mass or more, still more preferably 100% by mass.

The hydroxyl value of the polyester polyol is preferably 100 to 400 mgKOH / g, more preferably 150 to 350 mgKOH / g.

(Polyisocyanate compound)
As the polyisocyanate compound contained in the foamable urethane resin composition of the present invention, various polyisocyanate compounds such as aromatic, alicyclic, and aliphatic compounds having two or more isocyanate groups can be used. It is preferable to use liquid diphenylmethane diisocyanate (MDI) because it is easy to handle, the reaction speed is excellent, the physical characteristics of the obtained polyurethane foam are excellent, and the cost is low. Examples of the liquid MDI include crude MDI (also referred to as polypeptide MDI). Specific commercial products of liquid MDI include "44V-10", "44V-20" (manufactured by Sumika Covestro Urethane Co., Ltd.), "Millionate MR-200" (Nippon Polyurethane Industry Co., Ltd.) and the like. Further, MDI containing uretonimine (for example, "Millionate MTL" as a commercially available product: manufactured by Nippon Polyurethane Industry Co., Ltd.) may be used. In addition to the liquid MDI, another polyisocyanate compound may be used in combination, and as the polyisocyanate compound to be used in combination, a polyisocyanate compound known in the technical field of polyurethane can be used without limitation.

The range of the isocyanate index of the foamable urethane resin composition of the present invention is preferably 150 to 700, more preferably 200 to 650, and further preferably 250 to 600. When the isocyanate index is in such a range, it becomes easy to adjust the sinking distance and the molten diameter distance of the steel ball in the above-mentioned hot steel ball evaluation to a desired range.
The isocyanate index (INDEX) is calculated by the following method.

INDEX = isocyanate equivalent ÷ (poly polyol equivalent + water equivalent) x 100
here,
Equivalent number of isocyanate = Number of copies of polyisocyanate used x NCO content (%) x 100 / NCO molecular weight Equivalent number of polyol = OHV x Number of copies of polyol used ÷ Molecular weight of KOH, OHV is the hydroxyl value of polyol (mgKOH / g),
Equivalent number of water = number of copies of water used x number of OH groups of water / molecular weight of water. In the above formula, the unit of the number of copies used is the weight (g), the molecular weight of the NCO group is 42, and the NCO content is the ratio of the NCO group in the polyisocyanate compound expressed in mass%. For convenience of unit conversion, the molecular weight of KOH is 56,100, the molecular weight of water is 18, and the number of OH groups in water is 2.

(Liquid flame retardant)
The foamable urethane resin composition of the present invention contains a flame retardant that is liquid at room temperature. Here, room temperature means 23 ° C. By containing a liquid flame retardant, it becomes easy to adjust the above-mentioned steel ball subduction distance and melt diameter distance to a desired range, and by being a liquid, the equipment used when using the foamable urethane resin composition, etc. Wear can be suppressed.
Examples of the liquid flame retardant include phosphoric acid ester-based flame retardants such as monophosphate ester and condensed phosphoric acid ester.
The monophosphate ester is not particularly limited, and examples thereof include trimethyl phosphate, triethyl phosphate, tricresyl phosphate, cresyldiphenyl phosphate, and tris (β-chloropropyl) phosphate.
The condensed phosphoric acid ester is not particularly limited, and is, for example, resorcinol polyphenyl phosphate (trade name CR-733S), bisphenol A polycredyl phosphate (trade name CR-741), and aromatic condensed phosphoric acid ester (trade name CR747). ) And so on.
The content of the liquid flame retardant is preferably 5 to 100 parts by mass, more preferably 10 to 80 parts by mass, and further preferably 20 to 70 parts by mass with respect to 100 parts by mass of the polyol compound. preferable.

(Foaming agent)
The foamable urethane resin composition of the present invention contains a defoaming agent, if necessary. Examples of the defoaming agent include a polyoxyalkylene defoaming agent such as polyoxyalkylene alkyl ether and a surfactant such as a silicone defoaming agent such as organopolysiloxane. If it has a structure having a portion, a surface-active effect can be obtained, so that it is not caught by the above types. Further, the silicone foam stabilizer may contain a graft copolymer of polydimethylsiloxane and polyethylene glycol.
The content of the foam stabilizer is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 8 parts by mass, and 0.5 to 5 parts by mass with respect to 100 parts by mass of the polyol compound. It is more preferably a part. The foam stabilizer may be used alone or in combination of two or more.

(Foaming agent)
The foamable urethane resin composition of the present invention contains a foaming agent. Specific examples of the foaming agent include water, low boiling point hydrocarbons, chlorinated aliphatic hydrocarbon compounds, fluorocarbon compounds, hydrochlorofluorocarbon compounds, hydrofluorocarbons, ether compounds, hydrofluoroolefins and the like. Further, examples of the foaming agent include organic physical foaming agents such as a mixture of these compounds, and inorganic physical foaming agents such as nitrogen gas, oxygen gas, argon gas and carbon dioxide gas.
Examples of the low boiling point hydrocarbon include propane, butane, pentane, hexane, heptane, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane and the like.
Examples of the chlorinated aliphatic hydrocarbon compound include dichloroethane, propyl chloride, isopropyl chloride, butyl chloride, isobutyl chloride, pentyl chloride, isopentyl chloride and the like.
Examples of the fluorine compound include CHF ₃ , CH ₂ F ₂ , CH ₃ F and the like.
Examples of the hydrochlorofluorocarbon compound include trichloromonofluoromethane, trichlorotrifluoroethane, dichloromonofluoroethane (for example, HCFC141b (1,1-dichloro-1-fluoroethane), HCFC22 (chlorodifluoromethane), HCFC142b (). 1-chloro-1,1-difluoroethane)) and the like can be mentioned.
Examples of the hydrofluorocarbon include HFC-245fa (1,1,1,3,3-pentafluoropropane) and HFC-365mfc (1,1,1,3,3-pentafluorobutane).
Examples of the ether compound include diisopropyl ether and the like.
Examples of the hydrofluoroolefin include HFO-1233zd (E) (trans-1-chloro-3,3,3-trifluoropropene) and HFO-1234yf (2,3,3,3-tetrafluoro-1-. Propene), HFO-1336mzz (Z) (cis-1,1,1,4,4,4, -hexafluorobut-2-ene) and the like.

In the present invention, the foaming agent preferably contains water, and more specifically, the above-mentioned low boiling point hydrocarbons, chlorinated aliphatic hydrocarbon compounds, fluorocarbon compounds, hydrochlorofluorocarbon compounds, hydrofluorocarbons, ether compounds, and the like. And a foaming agent in which water is used in combination with at least one compound selected from hydrofluoroolefins is preferable. As the water, for example, ion-exchanged water, distilled water and the like can be appropriately used. The amount of water with respect to 100 parts by mass of the polyol compound is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, still more preferably 0.1 parts by mass or more, and preferably 2.0 parts by mass. Hereinafter, it is more preferably 1.5 parts by mass or less, and further preferably 1.1 parts by mass or less. When the water content is at least these lower limit values, it becomes easy to foam the foamable urethane resin composition, and it becomes easy to adjust the density within a desired range. Further, when the water content is not more than these upper limit values, it becomes easy to adjust the sinking distance and the molten diameter distance of the steel balls in the evaluation of the hot steel balls of the polyurethane foam to the above-mentioned desired ranges.

In the present invention, the foaming agent preferably contains a hydrofluoroolefin, and more preferably contains both the hydrofluoroolefin and the above-mentioned water. The amount of hydrofluoroolefin to 100 parts by mass of the polyol compound is preferably 10 to 50 parts by mass, more preferably 15 to 45 parts by mass, further preferably 25 to 40 parts by mass, and even more preferably 28 to 40 parts by mass.

(catalyst)
The foamable urethane resin composition of the present invention contains a catalyst. The catalyst may contain, for example, one or both of the urethanization catalyst and the trimerization catalyst, and preferably contains both. The catalyst contained in the foamable urethane resin composition does not correspond to the inorganic filler in the present invention.

The urethanization catalyst is a catalyst that promotes the reaction between the polyol component and polyisocyanate. Specific examples thereof include amino compounds, tin compounds, bismuth compounds, and acetylacetone metal salts.
Examples of the amino compound include pentamethyldiethylenetriamine, triethylamine, N-methylmorpholinbis (2-dimethylaminoethyl) ether, bis (2-dimethylaminoethyl) ether, N, N, N', N ", N". -Pentamethyldiethylenetriamine, N, N, N'-trimethylaminoethyl-ethanolamine, bis (2-dimethylaminoethyl) ether, N-methyl-N', N'-dimethylaminoethyl piperazine, second in the imidazole ring Imidazole compounds in which the primary amine functional group is replaced with a cyanoethyl group, N, N-dimethylcyclohexylamine, diazabicycloundecene, triethylenediamine, tetramethylethylenediamine, tetramethylhexamethylenediamine, 1-methylimidazole, trimethylaminoethylpiperazine, Examples thereof include tripropylamine.
Examples of the tin compound include stannous octylate, dibutyltin diacetate, and dibutyltin dilaurate. Examples of the bismuth compound include bismuth neodecanoate and bismuth octylate.
Examples of the acetylacetone metal salt include acetylacetone aluminum, acetylacetone iron, acetylacetone copper, acetylacetone zinc, acetylacetone verylium, acetylacetone chromium, acetylacetone indium, acetylacetone manganese, acetylacetone molybdenum, acetylacetone titanium, acetylacetone cobalt, acetylacetone vanadium, acetylacetone zirconium and the like. ..
The urethanization catalyst may be used alone or in combination of two or more.

The blending amount of the urethanization catalyst in the foamable urethane resin composition is not particularly limited, but is preferably in the range of 0.3 to 10 parts by mass and 0.5 to 8 parts by mass with respect to 100 parts by mass of the urethane resin. It is more preferably in the range of parts, and even more preferably in the range of 1 to 5 parts by mass. Within the above range, the reaction between the polyol compound and the polyisocyanate compound can be promoted at an appropriate reaction rate. The urethane resin 100 parts by mass means a total of 100 parts by mass of the polyol compound and the polyisocyanate compound.

A trimerization catalyst is a catalyst that promotes trimerization to form an isocyanurate bond. The flame retardancy of the polyurethane foam is improved by promoting the triquantization of the polyurethane resin.
Examples of the trimerization catalyst include aromatic compounds such as tris (dimethylaminomethyl) phenol, 2,4-bis (dimethylaminomethyl) phenol, 2,4,6-tris (dialkylaminoalkyl) hexahydro-S-triazine, and acetic acid. Alkali metal salts such as potassium, sodium acetate, potassium 2-ethylhexanoate, sodium 2-ethylhexanoate, potassium octylate, sodium octylate, aziridines such as 2-ethylaziridine, lead naphthenate, lead octylate, etc. Lead compounds, alcoholate compounds such as sodium methoxydo, phenolate compounds such as potassium phenoxide, tertiary ammonium salts such as trimethylammonium salt, triethylammonium salt, and triphenylammonium salt, tetramethylammonium salt, tetraethylammonium, tetraphenylammonium salt, etc. Quaternary ammonium salt and the like can be used.
The trimerization catalyst may be used alone or in combination of two or more.

The blending amount of the trimerization catalyst is not particularly limited, but is preferably in the range of 0.3 to 10 parts by mass and more preferably in the range of 0.5 to 8 parts by mass with respect to 100 parts by mass of the urethane resin. It is preferably in the range of 0.8 to 5 parts by mass, more preferably in the range of 0.8 to 5 parts by mass. By setting the amount of the trimerization catalyst within the above range, isocyanurate bonds are appropriately formed and flame retardancy is improved.
The total amount of the catalyst is preferably 0.5 to 20 parts by mass, more preferably 1 to 16 parts by mass, based on 100 parts by mass of the urethane resin, from the viewpoint of improving the curing rate and flame retardancy of urethane. 2 to 10 parts by mass is more preferable.

The trimerization catalyst and the urethanization catalyst do not correspond to the inorganic filler in the present invention.

The foamable urethane resin composition can be used as an additive, for example, an antioxidant such as a phenol-based, amine-based, or sulfur-based agent, a heat / light stabilizer, a metal damage inhibitor, and an antistatic agent, as long as the effect of the present invention is not impaired. It can contain an inhibitor, a cross-linking agent, a lubricant, a softening agent, a pigment, a tackifier resin and the like.

Since the foamable urethane resin composition of the present invention is cured by reacting the polyol compound with the polyisocyanate compound, its viscosity changes with time. Therefore, before using the foamable urethane resin composition, the foamable urethane resin composition is divided into two or more to prevent the foamable urethane resin composition from reacting and curing. When using the foamable urethane resin composition, it is preferable to combine the foamable urethane resin compositions divided into two or more into one.

When the foamable urethane resin composition is divided into two or more, curing does not start by each component of the foamable urethane resin composition divided into two or more, and each component of the foamable urethane resin composition is used. Each component may be divided so that the curing reaction starts after mixing. Usually, the foamable urethane resin composition is divided into a polyol composition containing a polyol compound and a polyisocyanate composition containing a polyisocyanate compound.

The above-mentioned flame retardant, foaming agent, catalyst, and foam stabilizer to be blended as needed, which are liquid at room temperature, may be contained in the polyol composition or may be contained in the polyisocyanate composition. Although it may be provided separately from the polyol composition and the polyisocyanate composition, it is preferably contained in the polyol composition.

The method for producing the foamable urethane resin composition is not particularly limited, but a method for preparing a polyol composition and a polyisocyanate composition prepared by kneading in advance and mixing the two, and a foamable urethane resin composition can be obtained. Examples thereof include a method of kneading each constituent component, but it is usually produced by mixing a polyol composition and a polyisocyanate composition. Mixing of each component can be performed by a known method, and can be obtained by using a known device such as a high-pressure foaming machine, a low-pressure foaming machine, a spray foaming machine, and a hand mixer.

(Viscosity of polyol composition)
The viscosity of the polyol composition at 20 ° C. is not particularly limited, but is preferably 2,000 mPa · s or less, and preferably 1,000 mPa · s or less. By setting the viscosity of the polyol solution to the above upper limit or less, the fluidity of the foamable urethane resin composition is also improved, and poor mixing can be suppressed. The viscosity of the polyol composition can be appropriately adjusted depending on, for example, the molecular weight of the polyol compound used. The viscosity of the polyol composition was measured at a temperature of 20 ° C. using a B-type viscometer.

(Use)
The use of the foamable urethane resin composition of the present invention is not particularly limited, but it is used for filling cavities in structures such as buildings, furniture, automobiles, trains, and ships, and for spraying on the structures. It can be used for. Above all, it is preferable to use it as an application for spraying on a structure, that is, as a foamable urethane resin composition for spraying.
Spraying can be performed using a spraying device (for example, GRACO: A-25) and a spray gun (for example, Gasmer: D gun). In general spraying devices and spray guns, the volume ratio of isocyanate and polyol in the foaming stock solution is evenly reacted and sprayed. Therefore, the volume ratio of the foaming stock solution is 1.0 for isocyanate and 0.8 to 1 for polyol. It can react in the range of .2. The spraying can be carried out by adjusting the temperature of the polyol composition and the polyisocyanate composition contained in separate containers in a spraying device, colliding and mixing the two with the tip of a spray gun, and misting the mixed solution by air pressure. Spraying devices and spray guns are known, and commercially available products can be used.

[Polyurethane foam]
The polyurethane foam of the present invention is formed from the above-mentioned foamable urethane resin composition, and specifically, it is obtained by foaming and curing the foamable urethane resin composition.
The polyurethane foam has a steel ball subduction distance of 10 mm or less in the evaluation of hot steel balls. If the subduction distance of the steel ball exceeds 10 mm, the polyurethane foam easily burns and spreads when exposed to a fire or the like, and it becomes difficult to effectively prevent the spread of fire. From the viewpoint of effectively preventing the spread of fire, the subduction distance of the steel ball is preferably 5 mm or less, more preferably 3 mm or less, still more preferably 2 mm or less, still more preferably 0 mm. The subduction distance of the steel ball is 0 mm or more. The method for evaluating the steel ball subduction distance is as described above.

The polyurethane foam preferably has a melt diameter distance of 15 mm or less in the evaluation of hot steel balls. If the melt diameter distance exceeds 15 mm, the polyurethane foam tends to spread when exposed to a fire or the like, and it becomes difficult to effectively prevent the spread of fire. From the viewpoint of effectively preventing the spread of fire, the melt diameter distance is preferably 14 mm or less, more preferably 13 mm or less, still more preferably 12 mm or less. The melt diameter distance is 0 mm or more.

By the way, fires caused by polyurethane foams are largely due to sparks and fireballs (lumps of iron heated to high temperatures) during welding and fusing. According to the findings of the present inventors, it has been found that, in particular, when a fireball comes into contact with a polyurethane foam, it advances to the inside while melting the resin, and as a result, there is a risk of ignition and spread of fire from the inside of the polyurethane foam. did. The hot steel ball evaluation reproduces and evaluates a fire caused by a polyurethane foam during welding and fusing, and can evaluate whether or not the polyurethane foam is difficult to burn and spread.

The density of the polyurethane foam is not particularly limited, but is preferably in the range of ^{20 to 200 kg / m 3.} By setting the density to 200 kg / m ³ or less, the polyurethane foam becomes lightweight and the workability on the structure is improved. Further, when the weight is 20 kg / m ³ or more, the desired flame retardancy can be easily exhibited. From these viewpoints, the density of the polyurethane foam, more preferably in the range of 25~100kg / ^{m 3,} more preferably in the range of 25~80kg / ^{m 3.} The density of the polyurethane foam can be measured according to JIS K7222.

The present invention will be described in more detail by way of examples, but the present invention is not limited to these examples.

Details of each component used in each Example and Comparative Example are as follows.
(1) Polyester compound ・ p-phthalic acid polyester polyol (manufactured by Kawasaki Kasei Chemicals, product name: RFK-509, hydroxyl value = 200 mgKOH / g)
-P-Phthalic acid polyester polyol (manufactured by Hitachi Kasei Co., Ltd., product name: SV-208, hydroxyl value = 235 mgKOH / g)
-Mannich-based polyether polyol (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., product name: DK3776, hydroxyl value = 350 mgKOH / g)
-Trine diamine-based polyether polyol (manufactured by Mitsui Chemicals, product name: GR-40A, hydroxyl value = 400 mgKOH / g)
-Sucrose-based polyether polyol (manufactured by AGC, product name: EL-100S, hydroxyl value = 450 mgKOH / g)
-Sorbitol-based polyether polyol (manufactured by Mitsui Chemicals, product name: Actol SOR400, hydroxyl value = 400 mgKOH / g)
-Ethylenediamine-based polyether polyol (manufactured by AGC, product name: Excelol 750ED, hydroxyl value = 760 mgKOH / g)
(2) Liquid flame retardant / phosphate ester flame retardant <Tris (β-chloropropyl) phosphate>, (manufactured by Daihachi Chemical Co., Ltd., product name: TMCPP)
(3) Defoaming agent / silicone-based defoaming agent (manufactured by Toray Dow Corning, product name: SH-193)
(4) Catalyst (i) Trimerization catalyst, quaternary ammonium salt (manufactured by Evonik Japan, product name: TMR-7)
(Ii) Urethane catalyst / imidazole compound, (manufactured by Kao Corporation, product name: KL No. 390)
・ Bismuth compound, (manufactured by Nitto Kasei Co., Ltd., product name: Neostan U-600)
(5) Foaming agent, water, HFO-1233zd <hydrofluoroolefin> (manufactured by Honeywell, product name: Solstice LBA)
(6) Polyisocyanate compound / MDI (manufactured by Sumika Covestro Urethane Co., Ltd., product name: 44V-20)

The methods for measuring each physical property and property are as follows.

[Evaluation of hot steel balls]
For the polyurethane foams produced in each Example and Comparative Example, the subduction distance and the melt diameter distance of the steel balls were measured by the following procedures (1) to (3).
(1) A polyurethane foam was cut into a cube having a side of 50 mm and used as a test body.
(2) A wire mesh is placed at a point 30 mm from the burner mouth of the Bunsen burner (outer flame length 70 mm), and a steel ball (SUS304) having a diameter of 10.0 mm and a weight of 4.15 g is placed on the wire mesh, and the entire steel ball is placed. The steel ball was heated to 630 ° C. for 7 minutes until it turned red. The steel ball temperature was measured by moving the steel ball heated as described above from the wire mesh to another table that does not affect the radiation temperature measurement. The steel ball temperature is measured using a radiation thermometer (manufactured by KEYENCE: FT-H40K) with the radiation coefficient of the steel ball used as 0.45, and the value displayed by the radiation thermometer divided by 0.45. Was the evaluation temperature (630 ° C.). A new steel ball was used.
(3) In an atmosphere of 23 ° C., the steel ball heated in (2) above was immediately placed on the center of the upper part of the test piece of (1) above, and left to stand until the subduction of the steel ball was completed. Then, the cross section of the test piece sufficiently cooled by leaving it at 23 ° C. for 30 minutes was cut, and the subduction distance and the melt diameter distance of the steel ball were measured.
From the subduction distance and the molten diameter distance of the obtained steel balls, the quality of the property of not spreading was judged as follows.

≪Thermal steel ball evaluation criteria≫
〇 ・ ・ The subduction distance of the steel ball is 5 mm or less and the molten diameter distance is 15 mm or less △ ・ ・ The subduction distance of the steel ball is more than 5 mm and 10 mm or less × ・ ・ When other than the above "○" and "△"

[Maximum heat generation rate, total heat generation amount]
The maximum heat generation rate and the total heat generation amount of the polyurethane foams produced in each Example and Comparative Example were evaluated by the following methods. In a polypropylene beaker, a mixture obtained by mixing a polyol compound, a liquid flame retardant, a foam stabilizer, a catalyst, and a foaming agent according to the formulation shown in Table 1 and a polyisocyanate compound (total amount: 200 g, liquid temperature: 10 ° C.). And stir in a lab disper for 3 seconds. Immediately thereafter, it is sprayed on a gypsum board having a thickness of 12.5 mm to obtain a polyurethane foam. A polyurethane foam adhered using a gypsum board as a base is cut into a length of 10 cm, a width of 10 cm, and a thickness of 3.25 cm (inner gypsum board 12.5 mm) to prepare a sample for a corn calorimeter test. The test was conducted. The maximum heat generation rate and the total heat generation amount when the test sample was heated at a radiant heat intensity of 50 kW / m ^{2 for 5 minutes according to the test method of ISO-5660 were measured.} In addition to the above method, the method for producing the polyurethane foam was obtained by spraying the foamable urethane resin composition onto the structure using a spraying device and a spray gun.

[Example 1]
According to the formulation shown in Table 1, the polyol compound, the liquid flame retardant, the defoaming agent, the catalyst, and the foaming agent were weighed in a 1000 mL polypropylene beaker and stirred with a hand mixer at 20 ° C. for 10 seconds to prepare a polyol composition. After that, a polyisocyanate composition (polyisocyanate compound) whose temperature was also adjusted to 10 ° C. was added to the polyol composition cooled to 10 ° C. to obtain a foamable urethane resin composition, and the composition was stirred with a lab disper for 3 seconds. Then, a polyurethane foam was prepared. The above-mentioned hot steel ball evaluation was performed using the polyurethane foam. The maximum heat generation rate and total heat generation amount were also evaluated by the above procedure. The results of various evaluations are shown in Table 1.

[Examples 2 to 17, Comparative Example 1]
A polyurethane foam was obtained in the same manner as in Example 1 except that the formulation was changed as shown in Table 1. The above-mentioned hot steel ball evaluation was performed using the polyurethane foam. The maximum heat generation rate and total heat generation amount were also evaluated by the above procedure. The results of various evaluations are shown in Table 1.

As shown in each example, the polyurethane foam formed by the foamable urethane resin composition of the present invention has a property that it is difficult to spread due to the short steel ball subduction distance and melt diameter distance. It turned out. Further, since the foamable urethane resin composition of the present invention does not substantially contain an inorganic filler, it is difficult for a precipitate to form during storage, it is excellent in handleability, and it is possible to suppress wear of a spraying device used during use. Can be done.
On the other hand, it was found that the polyurethane foam formed by the foamable urethane resin composition of the comparative example had a hot steel ball evaluation outside the range specified in the present invention and was easily burned and spread.

Claims (11)

A foamable urethane resin composition containing a polyol compound, a polyisocyanate compound, a flame retardant liquid at room temperature, a foaming agent, and a catalyst.
The foamable urethane resin composition substantially does not contain an inorganic filler and does not contain an inorganic filler.
A foamable urethane resin composition in which the sinking distance of the steel balls in the following thermal steel ball evaluation of the polyurethane foam composed of the foamable urethane resin composition is 10 mm or less.
(Evaluation of hot steel balls)
(1) A polyurethane foam is cut into a cube having a side of 50 mm and used as a test body.
(2) A wire mesh is placed 30 mm from the burner mouth of the Bunsen burner (outer flame length 70 mm), and a steel ball with a diameter of 10.0 mm and a weight of 4.15 g is placed on the wire mesh, and the entire steel ball turns red. Heat for at least 5 minutes until it changes to a steel ball temperature of 630 ° C.
(3) In an atmosphere of 23 ° C., the steel ball heated in (2) above is immediately placed on the center of the upper part of the test piece of (1) above, and left to stand until the subduction of the steel ball is completed. Next, the cross section of the sufficiently cooled test piece is cut, and the subduction distance and the melt diameter distance of the steel ball are measured. The foamable urethane resin composition according to claim 1, wherein the sinking distance of the steel ball in the evaluation of the hot steel ball is 5 mm or less and the molten diameter distance is 15 mm or less. When the polyurethane foam made of the foamable urethane resin composition is ^{heated for 5 minutes at a radiant heat intensity of 50 kW / m 2} in accordance with the ISO-5660 test method, the total calorific value is 8 MJ / m ² or less. The foamable urethane resin composition according to claim 1 or 2. The maximum heat generation rate when the polyurethane foam made of the foamable urethane resin composition is ^{heated for 5 minutes at a radiant heat intensity of 50 kW / m 2 in accordance with the test method of ISO-5660 is 100 kW / m 2} or less. The foamable urethane resin composition according to any one of claims 1 to 3. The foamable urethane resin composition according to any one of claims 1 to 4, wherein the polyol compound contains a phthalic acid-based polyester polyol. Any one of claims 1 to 5, wherein the polyol compound contains a polyether polyol and a phthalic acid polyester polyol, and the content of the phthalic acid polyester polyol is 60% by mass or more based on the total amount of the polyol compound. The foamable urethane resin composition according to. The foamable urethane resin composition according to any one of claims 1 to 6, wherein the foaming agent contains water and the content of the water is 1.5 parts by mass or less with respect to 100 parts by mass of the polyol compound. Stuff. The foamable urethane resin composition according to any one of claims 1 to 7, wherein the foaming agent contains a hydrofluoroolefin. The foamable urethane resin composition according to any one of claims 1 to 8, wherein the catalyst contains a trimerization catalyst. The foamable urethane resin composition according to any one of claims 1 to 9, wherein the isocyanate index is 150 to 700. The foamable urethane resin composition according to any one of claims 1 to 10, which is used for spraying applications.