JP2021127153A - Pouch like cartridge and mixing and discharging system - Google Patents

Abstract

To provide a cartridge capable of suppressing permeation of water vapor or the like from an outside into a polyol liquid and a polyisocyanate liquid filled in the cartridge and further preventing leakage of the polyol liquid containing a foaming agent during storage.SOLUTION: The present invention is a pouch like cartridge 10 that including a first pouch container 11A filled with a polyol liquid containing a polyol and a foaming agent, and a second pouch container 11B filled with a polyisocyanate liquid containing a polyisocyanate.SELECTED DRAWING: Figure 1

Description

The present invention relates to a pouch-shaped cartridge and a mixed discharge system.

Conventionally, polyurethane foam has been used as a heat insulating material in vehicles such as automobiles, railroad vehicles, and ships, and buildings. As the polyurethane foam, a two-component polyurethane in which a polyol liquid agent and a polyisocyanate liquid agent filled in separate containers are discharged and mixed to form a foam is widely used.

As a method of discharging the polyol liquid and the polyisocyanate liquid, these two liquids are filled in each container of a cartridge composed of two separate containers, and the piston provided in each container is driven by gas, electricity, or the like. The general method is to press the liquid using the above and discharge the two liquids. The cartridge is composed of two containers (housings) having a large opening into which a piston can be inserted and a discharge port, and the discharge port is sealed with a lid. For example, Patent Document 1 describes a method of forming a polyurethane foam using a two-component mixed cartridge system.

International Publication No. 2001/032389

However, in the conventional cartridge, since there is a slight gap between the piston and the container (housing), water vapor, gas, etc. are easily permeated into the container. Therefore, there is a concern about deterioration of the polyol solution and the polyisocyanate solution. Further, since water functions as a foaming agent for forming a polyurethane foam from a polyol liquid agent and a polyisocyanate liquid agent, there is a problem that when water is mixed in from the outside, the composition adjusted in advance changes and the foaming efficiency fluctuates. .. Further, when a foaming agent is mixed with the liquid agent, the internal pressure of the container increases, and therefore the piston is pushed out, which causes a problem such as leakage of the liquid agent during storage.

Therefore, the present invention can suppress the permeation of water vapor and the like from the outside into the polyol liquid and the polyisocyanate liquid filled in the cartridge, and further prevent leakage of the polyol liquid containing a foaming agent during storage. The challenge is to provide a variety of cartridges.

The present inventors have found that the above problems can be solved by using a pouch-shaped cartridge provided with a pouch container filled with each of a polyol liquid containing a polyol and a foaming agent, and a polyisocyanate liquid, and a discharge port. Completed the invention.
That is, the present invention is the following [1] to [10].
[1] A first pouch container filled with a polyol liquid containing a polyol and a foaming agent, a second pouch container filled with a polyisocyanate liquid containing a polyisocyanate, and a discharge port for discharging the liquid. A pouch-shaped cartridge to be equipped.
[2] The pouch-shaped cartridge according to the above [1], wherein the foaming agent has a boiling point of 50 ° C. or lower.
[3] The pouch-shaped cartridge according to the above [1] or [2], wherein the polyol liquid contains a filler.
[4] The pouch-shaped cartridge according to the above [3], wherein the filler contains a solid flame retardant.
[5] The solid flame retardant is a red phosphorus flame retardant, a boron-containing flame retardant, a bromine-containing flame retardant, a phosphate-containing flame retardant, a chlorine-containing flame retardant, an antimony-containing flame retardant, a metal hydroxide and a needle-like filler. The pouch-shaped cartridge according to the above [4], which is at least one selected from the group consisting of.
[6] The pouch-shaped cartridge according to any one of the above [1] to [5], which is provided with a hard case for storing the first and second pouch containers.
[7] A polyurethane composition containing a polyol solution and a polyisocyanate solution discharged from the pouch-shaped cartridge according to any one of the above [1] to [6].
[8] A polyurethane foam formed from the polyurethane composition according to the above [7].
[9] The polyurethane foam according to the above [8], which is used as a heat insulating material for vehicles or buildings.
[10] A mixing / discharging system including the pouch-shaped cartridge according to any one of the above [1] to [6] and a static mixer.

The pouch-shaped cartridge of the present invention can suppress the permeation of water vapor or the like from the outside into the polyol liquid agent and the polyisocyanate liquid agent filled in the cartridge. Therefore, deterioration of the liquid agent and fluctuation of the composition can be prevented. Further, it is possible to prevent leakage of the polyol liquid containing the foaming agent during storage.

It is a schematic diagram which shows one Embodiment of the pouch-shaped cartridge of this invention. It is a schematic diagram which shows another embodiment of the pouch-shaped cartridge of this invention. It is a schematic diagram which shows one Embodiment of the pouch-shaped cartridge provided with the hard case of this invention. It is a schematic diagram which shows one Embodiment of the mixed discharge system of this invention. It is a schematic diagram which shows one Embodiment of the caulking gun used for the mixed discharge system of this invention. It is a schematic diagram explaining the cartridge used in the comparative example.

[Pouch-shaped cartridge]
The pouch-shaped cartridge of the present invention is for discharging a first pouch container filled with a polyol liquid containing a polyol and a foaming agent, a second pouch container filled with a polyisocyanate liquid containing a polyisocyanate, and a liquid. Equipped with a discharge port.

FIG. 1 shows an embodiment of the pouch-shaped cartridge of the present invention. The content of the present invention is not limited to the drawings. The pouch-shaped cartridge 10 includes a first pouch container 11A filled with a polyol liquid containing a polyol and a foaming agent, a second pouch container 11B filled with a polyisocyanate liquid containing a polyisocyanate, and a polyol liquid and a polyisocyanate. A discharge port 14 for discharging a liquid agent is provided.

In the present invention, the pouch refers to a bag-shaped container that can be filled with a liquid agent. Specifically, the first pouch container 11A has a concave elongated bag-shaped film portion 12A having an open upper portion and a film 12A. It is composed of a lid member 13A formed so as to cover the upper part of the. Similarly, the second pouch container is composed of a concave elongated bag-shaped film portion 12B having an open upper portion and a lid member 13B formed so as to cover the upper portion of the film portion 12B. Further, the lid member 13A is formed with a hole communicating with the discharge port 14 so that the polyol liquid inside the first pouch container is sent to the discharge port 14. Similarly, the lid member 13B is formed with a hole communicating with the discharge port 14 so that the polyisocyanate liquid agent inside the second pouch container is sent to the discharge port 14. The film portions 12A and 12B are easily deformed by pressing from the lower part to the upper part (that is, pressing in the direction of the arrow in FIG. 1), whereby the liquids filled in the first and second pouch containers are discharged. The liquid is sent to the inside of the outlet 14 and discharged from the hole at the upper part of the discharge port 14.
The respective volumes of the first pouch container 11A and the second pouch container 12B are not particularly limited, but are, for example, 25 to 750 mL, preferably 50 to 300 mL.

The film portions 12A and 12B each include at least a gas barrier layer from the viewpoint of gas barrier properties that suppress the permeation of water vapor and the like. As the gas barrier layer, those used for general pouch containers can be used without limitation. For example, ethylene-vinyl alcohol copolymer (EVOH), polyvinylidene chloride (PVDC), nylon, metal foil, metal deposition can be used. Examples thereof include a gas barrier layer composed of a film or the like. Among these, a metal foil and a metal-deposited film are preferable because they have excellent light-shielding properties. Examples of the metal include aluminum, iron, copper, tin, and alloys thereof, but aluminum is preferable.

The film portions 12A and 12B are preferably multilayer films in which one or more other layers such as a base material layer and a sealant layer are laminated in addition to the gas barrier layer. As the layer other than the gas barrier layer, those used for general pouch containers can be used without limitation, and examples thereof include polyester films such as polyethylene terephthalate and polyolefin films such as polyethylene, polypropylene and polystyrene. Be done.

The thicknesses of the film portions 12A and 12B are not particularly limited, but are preferably 10 to 500 μm, more preferably 30 to 300 μm, from the viewpoint of improving the gas barrier property and improving the operability at the time of discharging the liquid agent.

The lid members 13A and 13B are harder than the film portions 12A and 12B, for example, members that do not deform when the liquid agent is discharged. Therefore, the pouch-shaped cartridge 10 can be easily fixed to the hard case described later, and the pressure at the time of discharge is increased. Since the pressure resistance of the liquid is also increased, stable discharge of the liquid agent becomes possible. The materials of the lid members 13A and 13B are not particularly limited and may be made of metal or plastic, but are preferably made of plastic from the viewpoint of moldability and weight reduction.
Further, as shown in FIG. 2, the lid members 13A and 13B may be provided with liquid agent introduction portions 13a and 13b, respectively. The liquid agent introduction portions 13a and 13b are provided with sealing members that shield the inside and the outside of the pouch container, respectively. By removing the sealing members, the liquid agent can be introduced into the pouch container, and after the liquid agent is introduced. Can be sealed by attaching a sealing member.

The pouch-shaped cartridge 10 is provided with a discharge port 14 capable of discharging a polyol liquid agent and a polyisocyanate liquid agent on the upper portions of the lid members 13A and 13B. The discharge port 14 is formed so as to communicate with each of the first pouch container 11A and the second pouch container 11B, and usually, the lid member 13A, the lid member 13B, and the discharge port 14 are integrally molded. Manufactured. As the discharge port 14, the port communicating with the lid member 13A and the port communicating with the lid member 13B can be separately molded and integrated at the time of storage or use. The upper part of the discharge port 14 is opened by providing a hole, and the polyol liquid agent and the polyisocyanate liquid agent can be discharged. The discharge port 14 may be sealed with a lid member or the like during storage, and may be removed from the lid member or the like during use. Further, a screw thread 14a may be formed at the discharge port 14, whereby a static mixer or the like capable of mixing a polyol liquid agent and a polyisocyanate liquid agent can be attached.

The film portion 12A, the lid member 13A and the discharge port 14, and the film portion 12B, the lid member 13B and the discharge port 14 may have a structure that can be attached to and detached from the lid member 13 or the discharge port 14. By making it removable, it is possible to manage each separately during manufacturing or storage. When having the above structure, it is preferable to combine them when loading and using the mixing system and use them as one body.

The pouch-shaped cartridge 10 has no opening other than the discharge port 14. Therefore, the mixing of water vapor and the like from the outside is suppressed. It is preferable that the opening of the discharge port 14 is closed by a lid or the like when the pouch-shaped cartridge is not in use, and is opened when the pouch-shaped cartridge is in use.

By pressing the pouch-shaped cartridge 10 in the direction of the arrow in FIG. 1, that is, from the lowermost portions 16A and 16B of the pouch container toward the upper part, the polyol liquid agent and the polyisocyanate liquid agent can be discharged from the discharge port 14. The pressing may be performed manually, but it is preferably performed by a piston (plunger) using compressed gas or electric power as a drive source. The polyol solution and the polyisocyanate solution are discharged from the first pouch container and the second pouch container, respectively, and mixed to produce a polyurethane composition containing the polyol solution and the polyisocyanate solution.

(Pouch-shaped cartridge with hard case)
FIG. 3 shows a pouch-shaped cartridge 20 including a hard case 15 in which the first and second pouch containers are stored. The hard case 15 is composed of a first hard case 15A in which the first pouch container is stored and a second hard case 15B in which the second pouch container is stored. The hard case 15 may be composed of an integral member in which the hard case 15A and the hard case 15B are connected, or may be composed of separate members in which the hard case 15A and the hard case 15B are not connected. May be good.
By providing the hard case 15 in the pouch-shaped cartridge 20, the pouch container can be easily compressed in one direction, and the liquid agent can be stably discharged. The hard case 15A has a cylindrical or substantially cylindrical shape so that the first pouch container can be stored. The inner diameter (r1) of the hard case 15A is larger than the outer diameter (r2) of the first pouch container 11A, but from the viewpoint of improving the discharge property, it is preferable that the difference between the two is small, and the inner diameter and the outer diameter are smaller. The difference (r1-r2) from the above is preferably 3 cm or less, and more preferably 1 cm or less. The shape of the hard case 15B is the same as that of the hard case 15A described above.
The hard case may be provided as a caulking gun structure.

Inside the hard case 15A, a piston 17A (indicated by a dotted line in FIG. 3) for pressing the first pouch container 11A is provided, and by moving the piston 17A, the lowermost portion of the first pouch container 11A is provided. The liquid agent filled in the pouch container may be discharged by pressing 16A upward. Similarly, the inside of the hard case 15B is also provided with a piston 17B (indicated by a dotted line in FIG. 3) for pressing the second pouch container 11B, and the inside of the pouch container is filled by moving the piston 17B. The liquid agent may be discharged.
The method of pressing the pistons 17A and 17B is not particularly limited, and external forces such as manual operation, compressed gas, and electric power may be used. However, as described later, a pouch-shaped cartridge provided with a hard case is set in the caulking gun. Then, a method of pressing with compressed gas, electric power, or the like is preferable.

(Mixed discharge system)
The mixed discharge system of the present invention includes a pouch-shaped cartridge and a mixer that mixes a polyol liquid agent and a polyisocyanate liquid agent discharged from the pouch-shaped cartridge. As described above, the pouch-shaped cartridge is preferably a pouch-shaped cartridge provided with a hard case.
As one embodiment of the mixing / discharging system, for example, as shown in FIG. 4, a mixing / discharging system 30 including a pouch-shaped cartridge 10 and a stationary mixer 18 can be mentioned. The stationary mixer 18 is attached, for example, by using the thread 14a of the discharge port 14 of the pouch-shaped cartridge 10. A polyurethane composition containing the polyol solution and the polyisocyanate solution is produced by mixing the polyol solution discharged from the first pouch container and the polyisocyanate solution extruded from the second pouch container by the static mixer 18. can do.
The stationary mixer 18 is a so-called static mixer, which is a mixer without a drive unit, and the fluid is mixed by passing the fluid through the inside of the pipe body. Examples of the stationary mixer 18 include a mixer element 18B in which the mixer element 18B is arranged inside the tube body 18A as shown in FIG. Examples of the mixer element 18B include those formed in a spiral shape and those in which a plurality of baffle plates are formed.
The stationary mixer 18 may also have the function of an injector. In this case, the mixture mixed inside the tube body 18A may be injected from the tip 18C of the tube body as shown in FIG.

It is preferable that the mixing / discharging system 30 including the pouch-shaped cartridge 10 and the stationary mixer 18 is used by incorporating it into a caulking gun.
Examples of the caulking gun include a caulking gun 40 including a main body portion 42, a mounting portion 44 to which the mixing system 30 can be mounted, and a grip portion 46 having a trigger 48, as shown in FIG. By incorporating the mixing discharge system 30 into the caulking gun and pressing the pouch containers 11A and 11B, the polyol liquid agent and the polyisocyanate liquid agent can be discharged, but the pressing of the pouch container is an external force such as compressed gas or electric power. It is preferable to use.
When using compressed gas, by pulling the trigger 48, air can be sent to the pouch-shaped cartridge 10 using a cylinder or compressor (not shown), and the pouch container can be pressed by a piston (plunger) or the like. be. That is, the polyol liquid agent and the polyisocyanate liquid agent can be discharged by pressing the pouch containers 11A and 11B using the gas pressure by air. Further, by pulling the trigger 48, the piston (plunger) is operated by electric power, and by pressing the pouch containers 11A and 11B, the polyol liquid agent and the polyisocyanate liquid agent can be discharged.
When a pouch-shaped cartridge provided with a hard case is used, the pouch container can be pressed by moving the pistons 17A and 17B provided in the hard case with gas pressure or electric power.

The secondary pressure of the cylinder or compressor when the gas pressure is used is not particularly limited, but is preferably 0.05 MPa or more and 1 MPa or less, and more preferably 0.1 MPa or more and 0.8 MPa or less. By setting the secondary pressure to the lower limit value or more, the pistons 17A and 17B can be reliably driven. Further, by setting the secondary pressure to the upper limit value or less, it is possible to prevent problems such as insufficient mixing of the liquids and damage to the pouch-shaped cartridge due to a rapid increase in the pressure.

[Polyform solution]
The polyol liquid agent in the present invention includes a polyol and a foaming agent. Hereinafter, each component contained in the polyol liquid preparation will be described.

(Polyol)
Examples of the polyol contained in the polyol solution include polylactone polyols, polycarbonate polyols, aromatic polyols, alicyclic polyols, aliphatic polyols, polyester polyols, polymer polyols, and polyether polyols.

Examples of the polylactone polyol include polypropiolactone glycol, polycaprolactone glycol, polyvalerolactone glycol and the like.
Examples of the polycarbonate polyol include a polyol obtained by dealcoholization of a hydroxyl group-containing compound such as ethylene glycol, propylene glycol, butanediol, pentandiol, hexanediol, octanediol, and nonanediol with ethylene carbonate, propylene carbonate, and the like. And so on.

Examples of the aromatic polyol include bisphenol A, bisphenol F, phenol novolac, cresol novolac and the like.
Examples of the alicyclic polyol include cyclohexanediol, methylcyclohexanediol, isophoronediol, dicyclohexylmethanediol, and dimethyldicyclohexylmethanediol.
Examples of the aliphatic polyol include ethylene glycol, propylene glycol, butanediol, pentanediol, and hexanediol.

As the polyester polyol, for example, a polymer obtained by dehydration condensation of a polybasic acid and a polyhydric alcohol, a polymer obtained by ring-opening polymerization of a lactone such as ε-caprolactone and α-methyl-ε-caprolactone. , And a condensate of hydroxycarboxylic acid and the polyhydric alcohol or the like.
Examples of the polybasic acid include adipic acid, azelaic acid, sebacic acid, isophthalic acid (m-phthalic acid), terephthalic acid (p-phthalic acid), succinic acid and the like. Examples of the polyhydric alcohol include bisphenol A, ethylene glycol, 1,2-propylene glycol, 1,4-butanediol, diethylene glycol, 1,6-hexane glycol, neopentyl glycol and the like.
Examples of the hydroxycarboxylic acid include castor oil, a reaction product of castor oil and ethylene glycol, and the like.

Examples of the polymer polyol include a polymer obtained by graft-polymerizing an ethylenically unsaturated compound such as acrylonitrile, styrene, methyl acrylate, and methacrylate with an aromatic polyol, an alicyclic polyol, an aliphatic polyol, a polyester polyol, or the like. , Polybutadiene polyols, modified polyols of polyhydric alcohols, hydrogenated compounds thereof and the like.

Examples of the modified polyol of the polyhydric alcohol include those modified by reacting the raw material polyhydric alcohol with an alkylene oxide.
Examples of the polyhydric alcohol include trihydric alcohols such as glycerin and trimethylolpropane, pentaerythritol, sorbitol, mannitol, sorbitan, diglycerin, dipentaerythritol and the like, sucrose, glucose, mannose, fructose, methyl glucoside and the like. 4 to 8 valent alcohols such as derivatives thereof, fluoroglycolsinol, cresol, pyrogallol, catechol, hydroquinone, bisphenol A, bisphenol F, bisphenol S, 1,3,6,8-tetrahydroxynaphthalene, and 1,4 , 5,8-Tetrahydroxyanthracene and other polyols, castor oil polyol, (co) polymer of hydroxyalkyl (meth) acrylate and polyfunctional (for example, 2 to 100 functional groups) polyols such as polyvinyl alcohol, condensation of phenol and formaldehyde Things (Novolak) can be mentioned.

The method for modifying the polyhydric alcohol is not particularly limited, but a method for adding an alkylene oxide (hereinafter, also referred to as “AO”) is preferably used. Examples of AO include AO having 2 to 6 carbon atoms, for example, ethylene oxide (hereinafter, also referred to as “EO”), 1,2-propylene oxide (hereinafter, also referred to as “PO”), 1,3-propyleneoxide, and the like. Examples thereof include 1,2-butylene oxide and 1,4-butylene oxide.
Among these, PO, EO and 1,2-butylene oxide are preferable, and PO and EO are more preferable, from the viewpoint of properties and reactivity. When two or more types of AO are used (for example, PO and EO), the addition method may be block addition, random addition, or a combination of these.

As the polyether polymer, for example, at least one kind of alkylene oxide such as ethylene oxide, propylene oxide and tetrahydrofuran is ring-opened in the presence of at least one kind such as a low molecular weight active hydrogen compound having two or more active hydrogens. Examples thereof include a polymer obtained by polymerization. Examples of the low molecular weight active hydrogen compound having two or more active hydrogens include diols such as bisphenol A, ethylene glycol, propylene glycol, butylene glycol and 1,6-hexanediol, and triols such as glycerin and trimethylolpropane. , Ethylenediamine, amines such as butylene diamine and the like.

As the polyol used in the present invention, polyester polyol and polyether polyol are preferable. Further, a polyol having two hydroxyl groups is preferable. Among them, polybasic acids having an aromatic ring such as isophthalic acid (m-phthalic acid) and terephthalic acid (p-phthalic acid), and dihydric alcohols such as bisphenol A, ethylene glycol, and 1,2-propylene glycol. The polyester polyol obtained by dehydration condensation of the above is more preferable.

The hydroxyl value of the polyol is preferably 20 to 300 mgKOH / g, more preferably 30 to 250 mgKOH / g, and even more preferably 50 to 220 mgKOH / g. When the hydroxyl value of the polyol is not more than the above upper limit value, the viscosity of the polyol solution does not become excessively large, which is preferable from the viewpoint of handleability and the like. On the other hand, when the hydroxyl value of the polyol is at least the above lower limit value, the crosslink density of the polyurethane foam is increased and the strength is increased.
The hydroxyl value of the polyol can be measured according to JIS K 1557-1: 2007.

(Foaming agent)
The polyol liquid agent in the present invention contains a foaming agent. As the foaming agent, a known foaming agent used when a polyol and a polyisocyanate are mixed and foamed to form a polyurethane foam can be used without limitation, but a foaming agent having a boiling point of 50 ° C. or lower may be used. preferable. When a foaming agent having a boiling point of 50 ° C. or lower is used, the foamability is increased and polyurethane foam is easily formed. In the case of a conventional cartridge (that is, a cartridge including a container filled with a liquid agent and a piston for directly pressing the liquid agent inside the container) without using the pouch-shaped cartridge of the present invention, the liquid agent has a boiling point of 50 ° C. or less. When the foaming agent is contained, the internal pressure of the container increases due to the vaporization of the foaming agent, the gap between the container and the piston widens, and there is a problem that the liquid agent leaks. On the other hand, when the pouch-shaped cartridge of the present invention is used, such a problem of leakage of the liquid agent does not occur.
The boiling point of the foaming agent is preferably 45 ° C. or lower, more preferably 40 ° C. or lower, from the viewpoint of facilitating the formation of polyurethane foam. The boiling point of the foaming agent is preferably 10 ° C. or higher from the viewpoint of suppressing vaporization during storage.

The foaming agent contained in the polyol solution is not particularly limited, and examples thereof include hydrocarbon compounds, chlorinated aliphatic hydrocarbon compounds, hydrofluorocarbons, hydrochlorofluorocarbon compounds, and hydrofluoroolefins.
Examples of the hydrocarbon compound 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 hydrofluorocarbon include CHF ₃ , CH ₂ F ₂ , CH ₃ F and the like.

Examples of the hydrochlorofluorocarbon compound include dichloromonofluoroethane (for example, HCFC141b (1,1-dichloro-1-fluoroethane), HCFC22 (chlorodifluoromethane), HCFC142b (1-chloro-1,1-difluoroethane)). , HFC-245fa (1,1,1,3,3-pentafluoropropane), HFC-365mfc (1,1,1,3,3-pentafluorobutane) and the like.

Examples of the hydrofluoroolefin include fluoroalkenes having 3 to 6 carbon atoms. Further, the hydrofluoroolefin may be a hydrochlorofluoroolefin having a chlorine atom, and therefore may be a chlorofluoroalkene having 3 to 6 carbon atoms. The hydrofluoroolefin preferably has 3 or 4 carbon atoms.
More specifically, trifluoropropene, tetrafluoropropene such as HFO-1234, pentafluoropropene such as HFO-1225, chlorotrifluoropropene such as HFO-1233, chlorodifluoropropene, chlorotrifluoropropene, and chlorotetra. Fluoropropene and the like can be mentioned. More specifically, 1,3,3,3-tetrafluoropropene (HFO-1234ze), 1,1,3,3-tetrafluoropropene, 1,2,3,3,3-pentafluoropropene (HFO). -1225ye), 1,1,1-trifluoropropene, 1,1,1,3,3-pentafluoropropene (HFO-1225zc), 1,1,1,3,3,3-hexafluorobut-2 -En, 1,1,2,3,3-pentafluoropropene (HFO-1225yc), 1,1,1,2,3-pentafluoropropene (HFO-1225yz), (E) -1-chloro-3 , 3,3-Trifluoropropene (HFO-1233zd (E)), (Z) -1-chloro-3,3,3-trifluoropropene (HFO-1233zd (Z)) (Z) -1,1, 1,4,4,4-hexafluorobut-2-ene (HFO-1336mzz (Z)), (E) -1,1,1,4,4,4-hexafluorobut-2-ene (HFO-) 1336 mzz (E)), 2,3,3,3-tetrafluoropropene (HFO-1234yf), trifluoroethylene (HFO-1123), (E) -1-chloro-3,3,3-trifluoropropene (E) HCFO-1233zd (E)), (Z) -2,3,3,3-tetrafluoro-1-chloropropene (HCFO-1224yd (Z)) and the like can be mentioned.

Among these foaming agents, HFO-1233zd (E), HFO-1336mzz (Z), HFO-1336mzz (E), HFC-245fa and the like are preferable because the boiling point is 50 ° C. or lower and the handling property is excellent.
The foaming agent may be used alone, or may be used in combination of two or more.

The content of the foaming agent is preferably 5 to 60 parts by mass, more preferably 10 to 50 parts by mass, still more preferably 15 to 45 parts by mass with respect to 100 parts by mass of the polyol. When the content of the foaming agent is at least the lower limit value, foaming is promoted and the density of the obtained polyurethane foam can be reduced. On the other hand, when the content of the foaming agent is not more than the upper limit value, it is possible to suppress excessive progress of foaming.

(water)
The polyol solution may contain water. By containing water, the foamability when forming the polyurethane foam becomes good.
The blending amount of water is, for example, 0.1 to 10 parts by mass, preferably 0.2 to 5 parts by mass, and more preferably 0.3 to 3 parts by mass with respect to 100 parts by mass of the polyol. By setting the blending amount of water within these ranges, the polyurethane composition can be easily foamed appropriately.

[Polyisocyanate solution]
The polyisocyanate solution in the present invention contains a polyisocyanate. As the polyisocyanate contained in the polyisocyanate solution, a known polyisocyanate used for forming polyurethane foam can be used. Examples of the polyisocyanate include aromatic polyisocyanates, alicyclic polyisocyanates, and aliphatic polyisocyanates.
Examples of the aromatic polyisocyanate include phenylenediocyanate, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, dimethyldiphenylmethane diisocyanate, triphenylmethane triisocyanate, naphthalene diisocyanate, and polymethylene polyphenyl polyisocyanate.

Examples of the alicyclic polyisocyanate include cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and dimethyldicyclohexylmethane diisocyanate.

Examples of the aliphatic polyisocyanate include methylene diisocyanate, ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate and the like.

Among these, aromatic polyisocyanates are preferable, and diphenylmethane diisocyanates are more preferable, from the viewpoint of ease of use and availability. One type of polyisocyanate may be used alone, or two or more types may be mixed and used.

(Filler)
At least one of the polyol liquid and the polyisocyanate liquid may contain a filler, and it is preferable that the polyol liquid contains a filler. The filler preferably contains a flame retardant. By using a flame retardant as a filler, high flame retardant performance can be imparted to polyurethane foam.
The flame retardant used as the filler is a solid flame retardant. In the present invention, the flame retardancy can be more effectively enhanced by using the solid flame retardant. Further, the solid flame retardant is usually in a state of being dispersed as a solid component in a polyol solution or a polyisocyanate solution, and constitutes at least a part of the above-mentioned solid content (insoluble component).
The solid flame retardant is a flame retardant that becomes solid at normal temperature (23 ° C.) and normal pressure (1 atm).

From the viewpoint of effectively enhancing flame retardant, solid flame retardants include red phosphorus flame retardants, boron-containing flame retardants, bromine-containing flame retardants, phosphate-containing flame retardants, chlorine-containing flame retardants, and antimony-containing flame retardants. At least one selected from the group consisting of metal hydroxides and acicular fillers is preferred.

<Red phosphorus flame retardant>
The red phosphorus-based flame retardant may be composed of red phosphorus alone, may be red phosphorus coated with a resin, a metal hydroxide, a metal oxide, or the like, or red phosphorus may be coated with a resin, a metal hydroxide, or a metal. It may be mixed with an oxide or the like. The resin coated with red phosphorus or mixed with red phosphorus is not particularly limited, and examples thereof include thermosetting resins such as phenol resin, epoxy resin, unsaturated polyester resin, melamine resin, urea resin, aniline resin, and silicone resin. Be done. As the film or the compound to be mixed, a metal hydroxide is preferable from the viewpoint of flame retardancy. As the metal hydroxide, those described later may be appropriately selected and used.

The blending amount of the red phosphorus flame retardant is preferably 3 to 45 parts by mass, more preferably 10 to 40 parts by mass, and further preferably 15 to 25 parts by mass with respect to 100 parts by mass of the polyol or polyisocyanate. By setting the blending amount of the red phosphorus flame retardant to these lower limit values or more, the effect of containing the red phosphorus flame retardant can be easily exhibited. On the other hand, when the value is set to the upper limit or less, foaming is not hindered by the red phosphorus flame retardant.

<Boron-containing flame retardant>
Examples of the boron-containing flame retardant include borax, boron oxide, boric acid, borate and the like. Examples of the boron oxide include diboron trioxide, boron trioxide, diboron dioxide, tetraboron trioxide, tetraboron pentoxide and the like.
Examples of the borate include alkali metals, alkaline earth metals, elements of Groups 4, 12, and 13 of the periodic table, and ammonium borates. Specifically, alkali metal borate salts such as lithium borate, sodium borate, potassium borate, and cesium borate, alkaline earth metal borate salts such as magnesium borate, calcium borate, and barium borate, and borate. Examples thereof include zirconium acid, zinc borate, aluminum borate, and ammonium borate.
The boron-containing flame retardant may be used alone or in combination of two or more.
The boron-containing flame retardant is preferably borate, more preferably zinc borate.

The amount of the boron-containing flame retardant to be blended is not particularly limited, but is preferably 3 to 45 parts by mass, more preferably 10 to 40 parts by mass, and further preferably 15 to 25 parts by mass with respect to 100 parts by mass of the polyol or polyisocyanate. Is. By setting the blending amount of the boron-containing flame retardant to these lower limit values or more, the effect of containing the boron-containing flame retardant can be easily exerted, and the flame retardancy can be enhanced. On the other hand, when the value is set to the upper limit or less, the foaming is not hindered by the boron-containing flame retardant.

<Brominated flame retardant>
The bromine-containing flame retardant is not particularly limited as long as it is a compound containing bromine in its molecular structure and becomes a solid at normal temperature and pressure, and examples thereof include a brominated aromatic ring-containing aromatic compound.
Examples of the brominated aromatic ring-containing aromatic compound include hexabromobenzene, pentabromotoluene, hexabromobiphenyl, decabromobiphenyl, decabromodiphenyl ether, octabromodiphenyl ether, hexabromodiphenyl ether, bis (pentabromophenoxy) ethane, and ethylenebis (Pentabromophenoxy). Examples thereof include monomer-based organic bromine compounds such as pentabromophenyl), ethylene bis (tetrabromophthalimide), and tetrabromobisphenol A.

Further, the brominated aromatic ring-containing aromatic compound may be a bromine compound polymer. Specifically, a polycarbonate oligomer produced from brominated bisphenol A, a brominated polycarbonate such as a copolymer of this polycarbonate oligomer and bisphenol A, and a diepoxy compound produced by the reaction of brominated bisphenol A with epichlorohydrin. And so on. Furthermore, brominated epoxy compounds such as monoepoxy compounds obtained by the reaction of brominated phenols with epichlorohydrin, poly (bromineed benzyl acrylate), brominated polyphenylene ether, brominated bisphenol A, and brominated phenol of cyanur chloride. , Brominated (polystyrene), poly (bromineed styrene), brominated polystyrene such as crosslinked brominated polystyrene, crosslinked or non-crosslinked brominated poly (-methylstyrene) and the like.
Further, it may be a compound other than a brominated aromatic ring-containing aromatic compound such as hexabromocyclododecane.
These brominated flame retardants may be used alone or in combination of two or more. Further, among the above, a brominated aromatic ring-containing aromatic compound is preferable, and among them, a monomer-based organic bromine compound such as ethylene bis (pentabromophenyl) is preferable.

The blending amount of the bromine-containing flame retardant is preferably 3 to 45 parts by mass, more preferably 10 to 40 parts by mass, and further preferably 15 to 25 parts by mass with respect to 100 parts by mass of the polyol or polyisocyanate. By setting the blending amount of the bromine-containing flame retardant to these lower limit values or more, the effect of containing the bromine-containing flame retardant can be easily exhibited. On the other hand, when the value is set to the upper limit or less, the brominated flame retardant does not inhibit the foaming.

<Phosphate-containing flame retardant>
As the phosphate-containing flame retardant, for example, at least one selected from various phosphoric acids, metals of Group IA to IVB of the periodic table, ammonia, aliphatic amines, aromatic amines, and heterocyclic compounds containing nitrogen in the ring. Phosphates consisting of salts with the metal or compound of.
The phosphoric acid is not particularly limited, and examples thereof include monophosphoric acid, pyrophosphoric acid, and polyphosphoric acid.
Examples of the metals of Group IA to IVB of the periodic table include lithium, sodium, calcium, barium, iron (II), iron (III), and aluminum.
Examples of the aliphatic amine include methylamine, ethylamine, diethylamine, triethylamine, ethylenediamine, piperazine and the like. Examples of the aromatic amine include aniline, o-triidin, 2,4,6-trimethylaniline, anicidin, 3- (trifluoromethyl) aniline and the like. Examples of the heterocyclic compound containing nitrogen in the ring include pyridine, triazine, melamine and the like.

Specific examples of the phosphate-containing flame retardant include monophosphates such as aluminum tertiary phosphate, pyrophosphates, polyphosphates and the like. Here, the polyphosphate is not particularly limited, and examples thereof include ammonium polyphosphate, piperazine polyphosphate, melamine polyphosphate, ammonium polyphosphate, aluminum polyphosphate, and the like.
As the phosphate-containing flame retardant, one or more of the above-mentioned ones can be used.

The amount of the phosphate-containing flame retardant to be blended is not particularly limited, but is 3 to 40 parts by mass, more preferably 5 to 35 parts by mass, still more preferably 10 to 30 parts by mass with respect to 100 parts by mass of the polyol or polyisocyanate. Is. By setting the blending amount of the phosphate-containing flame retardant to these lower limit values or more, the effect of containing the phosphate-containing flame retardant can be easily exerted. On the other hand, when the value is set to the upper limit or less, the foaming is not inhibited by the phosphate-containing flame retardant.

<Chlorine-containing flame retardant>
Examples of the chlorine-containing flame retardant include those commonly used in flame-retardant resin compositions, for example, polychlorinated naphthalene, chlorendic acid, and dodecachlorododecahydrodimethanodibenzocyclo, which is sold under the trade name of "Dechloran Plus". Octene and the like can be mentioned.
The amount of the chlorine-containing flame retardant to be blended is not particularly limited, but is preferably 3 to 40 parts by mass, more preferably 5 to 35 parts by mass, and further preferably 10 to 30 parts by mass with respect to 100 parts by mass of the polyol or polyisocyanate. Is. By setting the blending amount of the chlorine-containing flame retardant to these lower limit values or more, the effect of containing the chlorine-containing flame retardant can be easily exhibited. On the other hand, when the value is set to the upper limit or less, the foaming is not hindered by the chlorine-containing flame retardant.

<Antimony-containing flame retardant>
Examples of the antimony-containing flame retardant include antimony oxide, antimonate, pyroantimonate and the like. Examples of antimony oxide include antimony trioxide and antimony pentoxide. Examples of the antimonate include sodium antimonate, potassium antimonate and the like. Examples of the pyroantimonate include sodium pyroantimonate, potassium pyroantimonate and the like.
The antimony-containing flame retardant may be used alone or in combination of two or more. The preferred antimony-containing flame retardant used in the present invention is antimony trioxide.

The amount of the antimony-containing flame retardant to be blended is not particularly limited, but is preferably 1 to 40 parts by mass, more preferably 2 to 35 parts by mass, and further preferably 3 to 30 parts by mass with respect to 100 parts by mass of the polyol or polyisocyanate. Is. By setting the blending amount of the antimony-containing flame retardant to these lower limit values or more, the effect of containing the antimony-containing flame retardant can be easily exerted, and the flame retardancy can be enhanced. On the other hand, when the value is set to the upper limit or less, the foaming is not hindered by the antimony-containing flame retardant.

<Metal hydroxide>
Examples of the metal hydroxide used in the present invention include magnesium hydroxide, calcium hydroxide, aluminum hydroxide, iron hydroxide, nickel hydroxide, zirconium hydroxide, titanium hydroxide, zinc hydroxide, and copper hydroxide. Examples include vanadium hydroxide and tin hydroxide. The metal hydroxide may be used alone or in combination of two or more.

The blending amount of the metal hydroxide is, for example, 0.1 to 50 parts by mass, preferably 0.2 to 30 parts by mass, and more preferably 0.3 to 20 parts by mass with respect to 100 parts by mass of the polyol or polyisocyanate. , More preferably 0.5 to 15 parts by mass. By setting the blending amount of the metal hydroxide to these lower limit values or more, the effect of containing the metal hydroxide is easily exerted, and the flame retardancy is enhanced. On the other hand, when the value is set to the upper limit or less, the foaming is not hindered by the metal hydroxide.

<Needle-shaped filler>
Examples of needle-shaped fillers include potassium titanate whisker, aluminum borate whisker, magnesium-containing whisker, silicon-containing whisker, wollastonite, sepiolite, zonolite, elestadite, boehmite, rod-shaped hydroxyapatite, glass fiber, carbon fiber, and graphite fiber. , Metal fiber, slag fiber, gypsum fiber, silica fiber, alumina fiber, silica-alumina fiber, zirconia fiber, boron nitride fiber, boron fiber, stainless steel fiber and the like.
These needle-shaped fillers may be used alone or in combination of two or more.

The range of the aspect ratio (length / diameter) of the needle-shaped filler used in the present invention is preferably in the range of 5 to 50, and more preferably in the range of 10 to 40. The aspect ratio can be obtained by observing the needle-shaped filler with a scanning electron microscope and measuring its length and width.

The blending amount of the needle-shaped filler is, for example, 10 to 100 parts by mass, preferably 20 to 90 parts by mass, more preferably 30 to 80 parts by mass, and further preferably 40 to 70 parts by mass with respect to 100 parts by mass of the polyol or polyisocyanate. It is a mass part. By setting the needle-shaped filler to these lower limit values or more, the shape of the polyurethane foam after combustion can be easily maintained. On the other hand, when these upper limit values or less are set, foaming is less likely to be inhibited by the needle-shaped filler.

<Amount of solid flame retardant compounded>
From the viewpoint of dischargeability, the amount of the solid flame retardant to be blended may be, for example, 150 parts by mass or less, preferably 90 parts by mass or less, and more preferably 85 parts by mass or less, based on 100 parts by mass of the polyol or isocyanate. More preferably, it is 75 parts by mass or less.
On the other hand, by setting the blending amount of the solid flame retardant to a certain amount or more, the solid flame retardant can impart appropriate flame retardancy to the polyurethane foam. From such a viewpoint, the blending amount of the solid flame retardant is, for example, 20 parts by mass or more with respect to 100 parts by mass of the polyol or polyisocyanate, but it is preferable in order to sufficiently enhance the flame retardancy by the solid flame retardant. Is 30 parts by mass or more, more preferably 40 parts by mass or more, still more preferably 50 parts by mass or more.

Further, as the filler, an inorganic filler other than the above-mentioned flame retardant may be blended. As inorganic fillers, alumina, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, ferrites, basic magnesium carbonate, calcium carbonate, magnesium carbonate, zinc carbonate, barium carbonate, dosonite, hydrotalcite, calcium sulfate , Barium sulfate, calcium silicate, talc, clay, mica, montmorillonite, bentonite, active white clay, imogolite, cericite, glass beads, silica balun, aluminum nitride, boron nitride, silicon nitride, graphite, carbon balun, charcoal powder, various metals Powder, magnesium sulfate, lead zirconate titanate, molybdenum sulfide, silicon carbide, various magnetic powders, fly ash and the like can be appropriately used. The inorganic filler may be used alone or in combination of two or more.

(Liquid flame retardant)
At least one of the polyol liquid and the polyisocyanate liquid may contain a liquid flame retardant. The liquid flame retardant is a flame retardant that becomes liquid at normal temperature (23 ° C.) and normal pressure (1 atm). Specific examples of the liquid flame retardant include phosphoric acid ester. By containing the liquid flame retardant, the polyol liquid agent or the polyisocyanate liquid agent is less likely to cause precipitation during storage, and it becomes easier to improve the flame retardancy.

As the phosphoric acid ester, it is preferable to use a monophosphate ester, a condensed phosphoric acid ester, or the like. Examples of the monophosphate ester include trialkyl phosphates such as trimethyl phosphate, triethyl phosphate, tributyl phosphate and tri (2-ethylhexyl) phosphate, halogen-containing phosphate esters such as tris (β-chloropropyl) phosphate, and tributoxyethyl phosphate. Arocyclic-containing phosphates such as trialkoxy phosphate, tricredyl phosphate, trixylenyl phosphate, tris (isopropylphenyl) phosphate, cresyldiphenyl phosphate, diphenyl (2-ethylhexyl) phosphate, monoisodecyl phosphate, diisodecyl Examples thereof include acidic phosphoric acid esters such as phosphate.

Examples of the condensed phosphate ester include aromatic condensed phosphate esters such as trialkylpolyphosphate, resorcinol polyphenyl phosphate, bisphenol A polycresyl phosphate, and bisphenol A polyphenyl phosphate.
Examples of commercially available condensed phosphate esters include "CR-733S", "CR-741", and "CR747" manufactured by Daihachi Chemical Industry Co., Ltd., and "ADEKA STUB PFR" and "FP-600" manufactured by ADEKA. And so on.

As the liquid flame retardant, one of the above-mentioned ones may be used alone, or two or more of them may be used in combination. Among these, monophosphate ester is preferable, and tris (β-chloropropyl) phosphate is more preferable, from the viewpoint of facilitating the production of polyurethane foam and improving the flame retardancy of polyurethane foam.

When the liquid flame retardant is contained, the blending amount thereof is preferably 5 to 70 parts by mass, more preferably 10 to 60 parts by mass, still more preferably 20 to 50 parts by mass with respect to 100 parts by mass of the polyol or polyisocyanate. By setting the blending amount of the liquid flame retardant to these lower limit values or more, the effect of containing the liquid flame retardant can be easily exerted. Further, when the value is set to the upper limit or less, the foaming of the polyurethane foam is not hindered by the liquid flame retardant.

Among the above-mentioned solid flame retardants, it is preferable to use a red phosphorus flame retardant, a boron-containing flame retardant, and a bromine-containing flame retardant.
Further, as the solid flame retardant, it is also preferable to use a plurality of solid flame retardants in combination. In this case, it is preferable to use a red phosphorus flame retardant, a boron-containing flame retardant and a bromine-containing flame retardant in combination. By using these in combination, it becomes easier to further improve the flame retardancy. Further, in the present invention, it is also preferable to use a solid flame retardant and a liquid flame retardant in combination.

(Precipitation inhibitor)
At least one of the polyol liquid and the polyisocyanate liquid may contain a sedimentation inhibitor. The precipitation inhibitor suppresses the precipitation of the filler dispersed in the polyol solution or the polyisocyanate solution during long-term storage at room temperature or low temperature, and makes it easy to uniformly disperse the filler simply by shaking the solution by hand. The sedimentation inhibitor generally becomes a solid at normal temperature and pressure, and usually becomes a solid content (insoluble content) in a liquid agent.

The sedimentation inhibitor is not particularly limited. Specific examples of the sedimentation inhibitor are powdered silica, organic clay, carbon black, hydrogenated castor oil wax, fatty acid amide wax and the like. One or more of these are used.
As the powdered silica, fumed silica, colloidal silica, silica gel and the like can be used. Among these, fumed silica is preferable, and hydrophobic fumed silica is particularly preferable. As fumed silica, Aerosil (registered trademark) manufactured by Aerosil Japan Co., Ltd. can be used.
As the organic clay, an organic substance-affinity phyllosilicate or the like can be used.
As the carbon black, those manufactured by a method such as a furnace method, a channel method, or a thermal method can be used. As for carbon black, a commercially available product may be appropriately selected and used.
Hydrogenated castor oil wax, fatty acid amide wax and the like form a swollen gel structure in a liquid.
These are generally marketed under the names of thixotropic agent, thickener, anti-sediment agent, anti-sagging agent, etc., and commercially available products can be appropriately selected and used.

The preferred sedimentation inhibitor is a sedimentation inhibitor having a thickening action, and among them, those containing Si as an element constituting the sedimentation inhibitor are more preferable. Specific examples of the sedimentation inhibitor having a thickening action are fumed silica and an organic substance-affinity phyllosilicate, and fumed silica is more preferable.

When the precipitation inhibitor is contained, the content thereof is not particularly limited, but is, for example, 1 to 20 parts by mass, preferably 2 to 12 parts by mass, and more preferably 3.5 parts by mass with respect to 100 parts by mass of the polyol or polyisocyanate. ~ 8 parts by mass. By setting the content of the sedimentation inhibitor to the above lower limit value or more, the polyol solution or the polyisocyanate solution can be thickened, the sedimentation of the filler can be suppressed, and the dispersibility thereof can be improved. Further, by setting the content of the sedimentation inhibitor to the above upper limit value or less, it is possible to prevent a decrease in handleability due to an excessively high viscosity of the liquid agent.

(catalyst)
At least one of the polyol solution and the polyisocyanate solution preferably contains a catalyst. As the catalyst, for example, a resinification catalyst, a quantification catalyst, or both may be contained, but it is preferable to contain both. These catalysts are preferably contained in the polyol solution.
<Resinization catalyst>
The resinification catalyst is a catalyst that promotes the reaction between the polyol and the polyisocyanate. In the present invention, a foaming catalyst that catalyzes the reaction between water and polyisocyanate is also included in the resinification catalyst. Examples of the resinification catalyst include amine-based catalysts such as imidazole compounds and piperazine compounds, and metal-based catalysts.
Examples of the imidazole compound include a tertiary amine in which the secondary amine at the 1-position of the imidazole ring is replaced with an alkyl group, an alkenyl group or the like. Specifically, N-methylimidazole, 1,2-dimethylimidazole, 1-ethyl-2-methylimidazole, 1-methyl-2-ethylimidazole, 1,2-diethylimidazole, and 1-isobutyl-2-methyl. Examples include imidazole. Further, an imidazole compound in which the secondary amine in the imidazole ring is replaced with a cyanoethyl group can also be mentioned.
Examples of the piperazine compound include tertiary amines such as N-methyl-N', N'-dimethylaminoethylpiperazine, and trimethylaminoethylpiperazine.
In addition to imidazole compounds and piperazine compounds, amine-based catalysts include pentamethyldiethylenetriamine, triethylamine, N-methylmorpholinbis (2-dimethylaminoethyl) ether, N, N, N', N ", N" -pentamethyl. Diethylenetriamine, N, N, N'-trimethylaminoethyl-ethanolamine, bis (2-dimethylaminoethyl) ether, N, N-dimethylcyclohexylamine, diazabicycloundecene, triethylenediamine, tetramethylhexamethylenediamine, tri Examples thereof include various tertiary amines such as propylamine.

Examples of the metal catalyst include metal salts such as lead, tin, bismuth, copper, zinc, cobalt and nickel, and preferably organic acid metal salts such as lead, tin, bismuth, copper, zinc, cobalt and nickel. .. More preferably, organic acid tin salts such as dibutyltin dilaurate, dioctyltin dilaurate and dioctyltin versatete, and organic acid bismuth salts such as bismastrioctate and bismastrioctate (2-ethylhexanoate) can be mentioned, and among them, organic acid bismuth. Salt is preferred.
The resinification catalyst may be used alone or in combination of two or more. Among the above, it is preferable to use one or more selected from 1,2-dimethylimidazole and bismuthtris (2-ethylhexanoate).

The content of the resinification catalyst is 1 to 15 parts by mass, preferably 2 to 10 parts by mass, and more preferably 3 to 8 parts by mass with respect to 100 parts by mass of the polyol. When the content of the resinification catalyst is at least the above lower limit value, a urethane bond is formed and the reaction proceeds rapidly. On the other hand, if it is equal to or less than the upper limit value, the reaction rate can be easily controlled.

<Triquantifier catalyst>
The trimerization catalyst is a catalyst that promotes the formation of an isocyanurate ring by reacting an isocyanate group contained in polyisocyanate to trirectify it. Examples of the trimerization catalyst include nitrogen-containing aromatic compounds such as tris (dimethylaminomethyl) phenol, 2,4-bis (dimethylaminomethyl) phenol, and 2,4,6-tris (dialkylaminoalkyl) hexahydro-S-triazine. , Carboxylic acid alkali metal salts such as potassium acetate, potassium 2-ethylhexanoate, potassium octylate, tertiary ammonium salts such as trimethylammonium salt, triethylammonium salt, triphenylammonium salt, tetramethylammonium salt, tetraethylammonium salt, etc. A quaternary ammonium salt such as a tetraphenylammonium salt, a triethylmonomethylammonium salt, or a quaternary ammonium salt of a carboxylic acid can be used. These may be used alone or in combination of two or more.
Among these, one or more selected from the group consisting of carboxylic acid alkali metal salts and carboxylic acid quaternary ammonium salts is preferable.

The content of the trimerization catalyst is 1 to 20 parts by mass, preferably 3 to 15 parts by mass, and more preferably 5 to 13 parts by mass with respect to 100 parts by mass of the polyol. When the content of the trimerization catalyst is at least the above lower limit value, trimerization of polyisocyanate is likely to occur, and the flame retardancy of the obtained polyurethane foam is improved. On the other hand, when the content of the trimerization catalyst is not more than the above upper limit value, the reaction can be easily controlled.

The total content of the trimerization catalyst and the resinification catalyst is not particularly limited, but is preferably 2 to 35 parts by mass, more preferably 5 to 25 parts by mass, and further preferably 8 to 8 parts by mass with respect to 100 parts by mass of the polyol. It is 21 parts by mass. When the total content of both catalysts is equal to or higher than these lower limit values, the formation of urethane bonds and triquantization proceed appropriately, and the flame retardancy of the polyurethane foam tends to be good. Further, when the total content of both catalysts is not more than these upper limit values, it becomes easy to control the urethanization and triquantification reactions.

(Foaming agent)
At least one of the polyol solution and the polyisocyanate solution preferably contains a foam stabilizer. The foam stabilizer improves the foamability of the polyurethane composition obtained from the polyol solution and the polyisocyanate solution.
Examples of the defoaming agent include a polyoxyalkylene-based defoaming agent such as polyoxyalkylene alkyl ether and a surfactant such as a silicone-based defoaming agent such as organopolysiloxane. These foam stabilizers may be used alone or in combination of two or more.
The blending amount of the foam stabilizer is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 8 parts by mass, still more preferably 1 to 5 parts by mass with respect to 100 parts by mass of the polyol or isocyanate. When the blending amount of the defoaming agent is not more than these lower limit values, it becomes easy to foam the polyurethane composition, and it becomes easy to obtain a homogeneous polyurethane foam. Further, when the blending amount of the defoaming agent is not more than these upper limit values, the balance between the manufacturing cost and the obtained effect becomes good.

(Other ingredients)
At least one of the polyol liquid and the polyisocyanate liquid is an antioxidant such as a phenol-based, amine-based, or sulfur-based antioxidant, a heat stabilizer, and a metal damage inhibitor as necessary without impairing the object of the present invention. , Antistatic agents, stabilizers, cross-linking agents, lubricants, softeners, pigments, additives such as tackifier resins, tackifiers such as polybutene and petroleum resins, and the like.
However, it is desirable that the liquid agent does not contain more solid components that become solid at normal temperature and pressure. The blending amount of solid components other than the above-mentioned components is preferably as small as possible, and is preferably smaller than the total blending amount of the solid flame retardant and the sedimentation inhibitor. The amount of solid content of the components other than the above components (that is, polyol, isocyanate, filler, flame retardant, sedimentation inhibitor, catalyst, foaming agent, water and foam stabilizer) is 100 parts by mass of the polyol or polyisocyanate. For example, it is 10 parts by mass or less, preferably 5 parts by mass or less, and more preferably 1 part by mass or less.

[Polyurethane composition]
The polyurethane composition of the present invention is a polyurethane composition containing a polyol solution and a polyisocyanate solution discharged from a pouch-shaped cartridge. Specifically, it is a composition in which a polyol solution and a polyisocyanate solution are discharged and mixed from the first pouch container and the second pouch container described above. As will be described later, each liquid may be mixed in a mass ratio so that the isocyanate index falls within a predetermined range. In the polyurethane composition, the polyol reacts with the polyisocyanate and further foams with a foaming agent to form a polyurethane foam.

(Isocyanate index)
The isocyanate index of the polyurethane composition of the present invention is not particularly limited, but is preferably 200 or more. When the isocyanate index is at least the above lower limit value, the amount of polyisocyanate with respect to the polyol becomes excessive, and isocyanurate bonds are easily formed by the trimeric of polyisocyanate, and as a result, the flame retardancy of the polyurethane foam is improved. Further, when it is at least the above lower limit value, it is easy to manufacture a polyurethane foam having an isocyanurate bond, that is, a polyurethane foam having both flame retardancy and heat insulating property at a high level. From these viewpoints, the isocyanate index is more preferably 250 or more, further preferably 300 or more, and particularly preferably 350 or more.
The isocyanate index is preferably 1000 or less, more preferably 800 or less, and particularly preferably 500 or less. When the isocyanate index is not more than the upper limit value, the balance between the flame retardancy of the obtained polyurethane foam and the manufacturing cost is improved.

The isocyanate index can be calculated by the following method.
Isocyanate index = equivalent number of polyisocyanate ÷ (equivalent number of polyol + equivalent number of water) × 100
Here, each equivalent number can be calculated as follows.
Equivalent number of polyisocyanate = amount of polyisocyanate used (g) x NCO content (mass%) / molecular weight of NCO (mol) x 100
-Equivalent number of polyol = OHV x amount of polyol used (g) ÷ molecular weight of KOH (mmol)
OHV is the hydroxyl value (mgKOH / g) of the polyol.
Equivalent number of water = molecular weight of water (g) / molecular weight of water (mol) x number of OH groups of water In each of the above formulas, the molecular weight of NCO is 42 (mol) and the molecular weight of KOH is 56100 (mmol). The molecular weight of water is 18 (mol), and the number of OH groups in water is 2.

(Use of polyurethane foam)
Although the polyurethane foam of the present invention formed from the above-mentioned polyurethane composition can be used for various purposes, it is preferably used as a heat insulating material. Polyurethane foam has a large number of air bubbles, which provides a heat insulating effect.
Polyurethane foam is more preferably used as a heat insulating material for vehicles or buildings. Vehicles include railroad vehicles, automobiles, ships, aircraft and the like.

Further, the polyurethane foam of the present invention is preferably formed by using, for example, the above-mentioned caulking gun, and is particularly suitable when the surface to be constructed is relatively small. Therefore, for example, it is preferable to spray a polyurethane composition containing a polyol solution and a polyisocyanate solution onto a portion where the existing heat-resistant material has deteriorated or damaged to form a polyurethane foam for repair. As described above, the polyurethane foam can be used for repair purposes, but it is not limited to such applications and may be used for forming a new heat-resistant material.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.
Each component used in Examples and Comparative Examples is shown below, and the content (parts by mass) of each component is shown in Table 1.

<Polyol compound>
(1) Polyester polyol (Maximole RLK-087 manufactured by Kawasaki Kasei Chemicals, hydroxyl value 200 mgKOH / g)
(2) Polyester polyol (PHANTOR SV-208 manufactured by Hitachi Kasei Co., Ltd., hydroxyl value 235 mgKOH / g)
<foaming agent>
(1) HFO-1233zd (E) (Solstice LBA manufactured by Central Glass Co., Ltd.) Boiling point 18.3 ° C.
(2) HFO-1336mzz (Z) (Opteon 1100 manufactured by Mitsui Chemours Fluoroproducts) Boiling point 33 ° C.
(3) HFO-1336mzz (E) (Opteon 1150 manufactured by Mitsui Chemours Fluoroproducts) Boiling point 7.5 ° C.
(4) HFC-245fa (GENETRON245FA manufactured by Honeywell) Boiling point 15 ° C.

<Filler>
(1) Needle-shaped filler Wollastonite (SH-1250 manufactured by Kinsei Matek Co., Ltd.)
(2) Red phosphorus flame retardant (Nova Excel 140 manufactured by Rinkagaku Kogyo Co., Ltd., metal hydroxide coating, red phosphorus content 94% by mass or more)
(3) Zinc borate (Firebreak ZB manufactured by Hayakawa Shoji Co., Ltd.)
(4) Ethylene bis (pentabromophenyl) (SAYTEX 8010 manufactured by Albemarle Corporation)
<Precipitation inhibitor>
(1) Fumed Silica (Aerosil R976S manufactured by Aerosil Japan)
<Liquid flame retardant>
(1) Tris (β-chloropropyl) phosphate (TMCPP manufactured by Daihachi Chemical Co., Ltd.)

<Catalyst>
(1) Trimerization catalyst: quaternary ammonium salt of carboxylic acid (DABCO TMR-7 manufactured by Evonik Japan Co., Ltd., active ingredient amount 45 to 55% by mass, diluted product with ethylene glycol)
(2) Resinification catalyst: Imidazole compound (TOYOCAT-DM70 manufactured by Tosoh Corporation, active ingredient amount 65-75% by mass, diluted with ethylene glycol)
(3) Resinification catalyst: Carboxylic acid bismuth salt (U-600 manufactured by Nitto Kasei Co., Ltd., active ingredient 55-58% by mass, 2-ethylhexanoic acid dilution)

<Foaming agent>
Polyoxyalkylene-based defoaming agent (SH-193 manufactured by Toray Dow Corning)
<Water>
water

(Pouch-shaped cartridge A of the present invention used in the examples)
The pouch-shaped cartridge of the present invention shown in FIG. 1 was prepared. The film portion of the first pouch container of the pouch-shaped cartridge includes a gas barrier layer made of aluminum foil. The volume of each of the first pouch container and the second pouch container is 300 mL.
(Conventional cartridge B used in the comparative example)
As shown in FIG. 6, a conventional cartridge B including a first container 51, a second container 52, and a discharge port 53 provided so as to connect each of these containers was prepared. Pistons (not shown) are provided inside the first container 51 and the second container 52 so as to press the liquid agent filled in each container and push it out from the discharge port 53. The volume of each of the first container 51 and the second container 52 is 300 mL.

(Examples 1 to 7)
In the formulation shown in Table 1, the components other than the foaming agent were measured in a 1000 ml polypropylene beaker, mixed at 1500 rpm for 5 minutes using a disper, and then the foaming agent was added and further mixed. The amount of foaming agent remaining in the mixed solution was finally adjusted to be as shown in Table 1 to obtain a polyol solution. The first pouch container of the pouch-shaped cartridge A was filled with a polyol solution, the discharge port was sealed, and the container was allowed to stand at 50 ° C. for 1 day. The case where the polyol liquid was leaked from the part other than the discharge port was evaluated as “x”, and the case where no leakage was confirmed was evaluated as “〇”.

(Reference example 1)
The polyol compound shown in Table 1 was measured in a 1000 ml polypropylene beaker and stirred at 1500 rpm for 5 minutes using a disper to obtain a polyol solution. The first pouch container of the pouch-shaped cartridge A was filled with a polyol solution, the discharge port was sealed, and the container was allowed to stand at 40 ° C. for 1 day. The case where the polyol liquid was leaked from the part other than the discharge port was evaluated as “x”, and the case where no leakage was confirmed was evaluated as “〇”.

(Comparative Examples 1 to 3)
In the formulation shown in Table 1, the components other than the foaming agent were measured in a 1000 ml polypropylene beaker, mixed at 1500 rpm for 5 minutes using a disper, and then the foaming agent was added and further mixed. The amount of foaming agent remaining in the mixed solution was finally adjusted to be as shown in Table 1 to obtain a polyol solution. The first container of the cartridge B was filled with a polyol solution, the discharge port was sealed, and the container B was allowed to stand at 40 ° C. for 1 day. The case where the polyol liquid was leaked from the part other than the discharge port was evaluated as “x”, and the case where no leakage was confirmed was evaluated as “〇”.

In the pouch-shaped cartridge of the present invention, leakage of the polyol liquid was not confirmed even when the polyol liquid contained a foaming agent. On the other hand, in the conventional cartridge, leakage of the polyol liquid was confirmed.

10 Pouch-shaped cartridge 11A First pouch container 11B Second pouch container 12A, 12B Film part 13A, 13B Lid member 13a, 13b Liquid agent introduction part 14 Discharge port
15 Hard case 15A First hard case 15B Second hard case 16A, 16B Bottom 17A, 17B Piston 18 Static mixer 18A Tube 18B Mixer element 18C Tip of tube 20 Pouch-shaped cartridge 30 with hard case 30 Mixing Discharge system 40 Caulking gun 42 Main body 44 Mounting 46 Grip 48 Trigger 51 First container 52 Second container 53 Discharge port

Claims (10)

A pouch including a first pouch container filled with a polyol liquid containing a polyol and a foaming agent, a second pouch container filled with a polyisocyanate liquid containing a polyisocyanate, and a discharge port for discharging the liquid. Liquid cartridge. The pouch-shaped cartridge according to claim 1, wherein the foaming agent has a boiling point of 50 ° C. or lower. The pouch-shaped cartridge according to claim 1 or 2, wherein the polyol liquid contains a filler. The pouch-shaped cartridge according to claim 3, wherein the filler contains a solid flame retardant. A group in which the solid flame retardant comprises a red phosphorus flame retardant, a boron-containing flame retardant, a bromine-containing flame retardant, a phosphate-containing flame retardant, a chlorine-containing flame retardant, an antimony-containing flame retardant, a metal hydroxide and a needle-like filler. The pouch-shaped cartridge according to claim 4, which is at least one selected from. The pouch-shaped cartridge according to any one of claims 1 to 5, wherein a hard case for storing the first and second pouch containers is provided. A polyurethane composition containing a polyol solution and a polyisocyanate solution, which is discharged from the pouch-shaped cartridge according to any one of claims 1 to 6. A polyurethane foam formed from the polyurethane composition according to claim 7. The polyurethane foam according to claim 8, which is used as a heat insulating material for vehicles or buildings. A mixing / discharging system comprising the pouch-shaped cartridge according to any one of claims 1 to 6 and a static mixer.

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