JP2021113066A - Discharge container - Google Patents

Abstract

To provide a discharge container with excellent discharge stability when discharging a liquid.SOLUTION: The discharge container contains a liquid and has a valve. The valve is in contact with the liquid as it is discharged. A water absorption rate of a member constituting the valve is 1 mass % or less. Total water content is 2 mass% or less.SELECTED DRAWING: None

Description

The present invention relates to a discharge container and a two-component discharge container including the discharge container.

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 solution and a polyisocyanate solution filled in separate containers are mixed to form a foam is widely used.

Two-component polyurethane may be used as an aerosol because each liquid can be discharged from a container and mixed with a relatively simple structure (for example, Patent Document 1). Specifically, one discharge container is filled with polyisocyanate and a low boiling point organic solvent, and the other discharge container is filled with a polyol and a low boiling point organic solvent. From each discharge container, a polyisocyanate solution is prepared by the vapor pressure of the low boiling point solvent. Polyurethane foam can be formed by discharging the polyol liquid and the polyol liquid respectively and mixing them.
In this case, from the viewpoint of forming the polyurethane foam and stabilizing its physical properties, it is necessary to discharge the polyisocyanate solution and the polyol solution in specified amounts.

Japanese Unexamined Patent Publication No. 11-49837

However, it has been confirmed that the discharge amount tends to vary especially on the discharge container side containing the polyisocyanate solution, and injection defects may occur. Attempts were made to solve the problem caused by the variation in the discharge amount on the polyisocyanate solution side by adjusting the discharge amount on the polyol side, but the problem was not solved.
Therefore, an object of the present invention is to provide a discharge container that contains a liquid and that can stabilize the discharge amount of the liquid.

As a result of diligent studies, the present inventors have found that the above problems can be solved by keeping the water absorption rate and the total water content of the members constituting the valve provided in the discharge container below a certain level. The present invention has been completed. That is, the present invention provides the following [1] to [7].
[1] A discharge container having a valve containing a liquid agent, and the valve comes into contact with the liquid agent when the liquid agent is discharged to the outside, and the water absorption rate of a member constituting the valve is 1% by mass. A discharge container having the following content and a total water content of 2% by mass or less.
[2] The member constituting the valve is composed of at least one of a hydrophobic resin having no amide structure in the main chain and no hydroxyl group in the side chain, and a metal-based material [1]. ] The discharge container described in.
[3] The discharge according to the above [2], wherein the hydrophobic resin is a resin having neither an amide structure nor an ester structure in the main chain and neither a hydroxyl group nor an ester group in the side chain. container.
[4] The discharge container according to any one of [1] to [3] above, wherein the liquid agent contained in the discharge container contains an organic solvent, and the liquid agent is discharged by the vapor pressure of the organic solvent.
[5] The discharge container according to claim 4, wherein the organic solvent is a gas at 23 ° C. and 1 atm.
[6] The discharge container according to any one of [1] to [5] above, wherein the liquid preparation is a polyisocyanate liquid preparation containing a polyisocyanate.
[7] A two-component discharge container including a first discharge container including the discharge container according to the above [6] and a second discharge container containing a polyol liquid agent containing a polyol.

According to the present invention, it is possible to provide a discharge container having excellent discharge stability when discharging a liquid agent.

It is an overall view of the discharge container shown as one Embodiment of this invention. It is a partial cross-sectional view of the discharge container shown as one Embodiment of this invention. It is a partial cross-sectional view of the discharge container shown as one Embodiment of this invention. It is a partial cross-sectional view of the discharge container shown as another embodiment of this invention. It is a partial cross-sectional view of the discharge container shown as another embodiment of this invention. It is a perspective view of the spring 29 in FIG. It is a partial cross-sectional view of the discharge container shown as another embodiment of this invention. It is a partial cross-sectional view of the discharge container shown as another embodiment of this invention. It is a schematic diagram which shows one Embodiment of the mixing system of this invention. It is a schematic diagram which shows another embodiment of the mixing system of this invention.

Hereinafter, the present invention will be described in detail with reference to the embodiments.
[Discharge container]
The present invention is a discharge container having a valve containing a liquid agent, and the valve comes into contact with the liquid when the liquid is discharged to the outside, and the water absorption rate of the member constituting the valve is 1 mass. % Or less, and the total water content is 2% by mass or less.

FIG. 1 shows an overall view of a discharge container shown as an embodiment of the present invention. The discharge container of the present invention is not limited to the specific structure of the discharge container shown in the figure.
The discharge container 10 is a discharge container in which the liquid agent 13 is housed. The discharge container 10 is formed by a pressure-resistant container 12 filled with a liquid agent 13 and a sealing component 14 provided above the pressure-resistant container 12 and airtightly sealing the pressure-resistant container 12.
The sealing component 14 includes a mountain cup 115 provided so as to be airtight on the upper part of the pressure-resistant container 12, a valve 11 held in the cup 15, a dip tube 21 extending from the valve 11 to the lower part of the pressure-resistant container 12, and a valve. It is provided with an actuator 22 provided at the upper end of 11.

The valve 11 will be described below with reference to FIG. 2, but the structure of the valve described below is not limited as long as the effect of the present invention is achieved.
FIG. 2 shows a partial cross-sectional view of the valve portion of the discharge container 10. The valve 11 is provided at the housing 16 held by the mountain cup 15, the stem 18 provided inside the housing 16, the rubber 17 provided so as to close the stem hole 18B of the stem 18, and the lower portion of the stem 18. The stem 18 is provided with a spring 19 that allows the stem 18 to move in the vertical direction.
When the actuator 22 provided on the upper portion of the valve 11 is not pressed, the stem 18 is pushed upward by the spring 19, and the opening portion of the stem hole 18B is closed by the rubber 17. As a result, the space inside the housing 16 communicating with the inside of the pressure-resistant container 12 is cut off from the stem passage 18A. In this case, the liquid agent 13 is not discharged to the outside of the discharge container 10.
On the other hand, when the stem 18 is pressed against the spring 19 by the actuator 22, the inner peripheral surface portion of the rubber 17 is curved downward, and the opening portion of the stem hole 18B is below the rubber 17. Since it is in a detached position, it is in a state of being communicated with the space inside the housing 16 (FIG. 3). As a result, the liquid agent 13 inside the discharge container 10 is discharged by the vapor pressure of the organic solvent filled in the container.

The arrow shown in FIG. 3 indicates the flow path of the liquid agent 13. The liquid agent 13 is discharged to the outside while being in contact with the housing 16, the spring 19, the rubber 17, and the stem 18 constituting the valve 11.

The valve provided in the discharge container is not limited to the above-described embodiment. FIG. 4 shows another embodiment of the valve. In FIG. 4, there is no member corresponding to the housing and rubber shown as the members constituting the valve in FIGS. 2 and 3, and the valve 21 is formed by the stem 28 and the spring 29 including the stem passage member 28X and the stem moving member 28Y. It is configured. The valve 21 shown in FIG. 4 includes a stem passage member 28X, a stem moving member 28Y that can move in the vertical direction, and a spring 29 that is arranged so as to come into contact with the lower portion of the stem moving member 28Y. The stem moving member 28Y is composed of a disk-shaped part and a rod-shaped part arranged vertically above the central portion of the disk-shaped part, and has a T-shaped cross section. These disk-shaped parts and rod-shaped parts are usually composed of the same type of members. A part of the upper surface of the disk-shaped part of the stem moving member 28Y is in contact with the lower part of the stem passage member 28X.
As shown in the perspective view of FIG. 6, the spring 29 is a single concave metal plate, and the bent portion 29A formed by making a U-shaped cut in the central portion of the metal plate and bending it upward. Has. By forming the bent portion 29A, a hollow portion 29Y communicating with the upper surface and the lower surface of the metal plate is formed in the central portion of the metal plate. Both ends of the spring 29 are supported by the mountain cup 15, and the bent portion 29A pushes up the stem moving member 28Y to close the stem hole 28B formed in the lower part of the stem passage member X.

When the stem moving member 28Y is pressed against the spring 29, the stem hole 28B is opened and the liquid agent inside the discharge container is discharged to the outside (FIG. 5). The arrow in FIG. 5 indicates the flow path of the liquid agent, and the liquid agent is discharged to the outside while being in contact with the spring 29, the stem moving member 28Y, and the stem passage member 28X constituting the valve 21.

Yet another embodiment of the valve is shown in FIG. In FIG. 7, the housing and the spring shown as the members constituting the valve in FIGS. 2 and 3 do not exist, and the valve is composed of the rubber and the stem.
The valve 31 in FIG. 7 includes a stem 38 and a rubber 37 that can move in the vertical direction. The stem 38 is formed of a disk-shaped member and a hollow tubular member arranged vertically above the central portion of the disk-shaped member, and a stem hole 38B is formed in the vicinity of the disk-shaped member of the hollow tubular member. ing. The rubber 37 has a donut-shaped shape and is arranged so as to be in contact with one surface of the disk-shaped member of the stem 38 and the outer peripheral portion of the hollow tubular member to close the stem hole 38B.
By moving the stem 38 downward, the blocked stem hole 38B is opened, so that the liquid agent inside the discharge container passes through the stem hole 38B and is discharged to the outside (FIG. 8). The arrow in FIG. 8 indicates the flow path of the liquid agent, and the liquid agent is discharged to the outside while contacting the rubber 37 and the stem 38 constituting the valve 31.

In the present invention, the water absorption rate of the members constituting the valve is 1% by mass or less, and the total water content is 2% by mass or less. As a result, the liquid agent is stably discharged. The reason for this is not clear, but it is presumed as follows. When the water absorption rate or the total water content of the members constituting the valve is large, the discharge property of the liquid agent deteriorates due to a chemical reaction or some interaction between the water and the liquid agent. On the other hand, when a member having a water absorption rate and a total water content of a certain level or less is used, it is considered that the chemical reaction between the water and the liquid agent is suppressed, and as a result, stable discharge is possible. In particular, when the liquid agent is a polyisocyanate liquid agent containing polyisocyanate, the discharge property due to the reaction product generated by the reaction between water and polyisocyanate is caused by lowering the water absorption rate and the total water supply amount of the members constituting the valve. It is considered that the deterioration of the above can be prevented.

(Water absorption rate)
In the discharge container of the present invention, the water absorption rate of the members constituting the valve is 1% by mass or less. If the water absorption rate of the members constituting the valve exceeds 1% by mass, the liquid agent cannot be discharged stably. From the viewpoint of stably discharging the liquid agent, the water absorption rate of the member constituting the valve is preferably 0.6% by mass or less, and more preferably 0.3% by mass or less.
In the present invention, "the water absorption rate of the members constituting the valve is X% by mass or less" means that the water absorption rate of all the members constituting the valve is X% by mass or less. In other words, it means that the water absorption rate of the member having the highest water absorption rate among the members constituting the valve is X mass% or less.
For example, when the members constituting the valve are a housing, a spring, a rubber, and a stem, the water absorption rate of all these members must be kept below a certain level. Since the spring is usually made of metal, the water absorption rate is 0 or a value close to 0, so that it is necessary to keep the water absorption rate of the housing, rubber and stem below a certain level. The water absorption rate can be adjusted by appropriately selecting the material of the member constituting the valve.

The water absorption rate of the members constituting the valve is measured in accordance with JIS K 7209, and specifically, it is measured as follows. A member constituting the valve provided in the discharge container is sampled, and the sample is sufficiently dried (at 80 ° C. for 12 hours) to prepare a sample before immersion. The sample is immersed in distilled water at 23 ° C. for 12 hours, and the water absorption rate is determined by the following formula from the weight A of the sample before immersion and the weight B of the sample after immersion.
Water absorption rate = 100 x (BA) / A
The measurement is performed individually for each member constituting the valve.

(Total water content)
In the discharge container of the present invention, the total water content of the members constituting the valve is 2% by mass or less. If the total water content of the members constituting the valve exceeds 2% by mass, the liquid agent cannot be discharged stably. From the viewpoint of stable discharge of the liquid agent, the total water content of the members constituting the valve is preferably 1.5% by mass or less, and more preferably less than 1.0% by mass.
The total water content of the members that make up the valve is measured as follows. The total weight of each member constituting the valve before drying is measured. Next, each member is dried at 80 ° C. for 12 hours, the total weight of the members constituting the valve after drying is measured, and the total water content is calculated by the following formula.
Total water content = 100 x (total weight of the members that make up the valve before drying-total weight of the members that make up the valve after drying) / total weight of the members that make up the valve before drying

The member constituting the valve is preferably selected from materials that do not easily absorb water, and is at least one of a hydrophobic resin in which the main chain does not have an amide bond and no hydroxyl group in the side chain, and a metal-based material. It is preferably composed of.

(Hydrophobic resin)
The hydrophobic resin having no amide bond in the main chain and no hydroxyl group in the side chain is not particularly limited, but for example, a polyolefin resin, a fluorinated polyolefin resin, a polyester resin, an acrylic resin, etc. Examples thereof include polyacetal-based resins and rubber-based resins. Among these hydrophobic resins, from the viewpoint of reducing the water absorption rate and the total water content, there are resins having neither an amide bond nor an ester bond in the main chain and neither a hydroxyl group nor an ester group in the side chain. Preferably, such a resin includes, for example, a polyolefin resin, a fluorinated polyolefin resin, a polyacetal resin, a rubber resin and the like.

Examples of the polyolefin resin include polyethylene resin and polypropylene resin. Among these, polyethylene resin is preferable.
Examples of the fluorinated polyolefin resin include a fluorinated polyethylene resin and a fluorinated polypropylene resin. Among these, fluorinated polyethylene resin is preferable.

Examples of the polyester resin include polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate and the like. Of these, polybutylene terephthalate is preferable.

Examples of the acrylic resin include homopolymers of (meth) acrylic acid alkyl esters and copolymers of two or more types of (meth) acrylic acid alkyl esters. Examples of the (meth) acrylic acid alkyl ester include methyl acrylate, ethyl acrylate, propyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate and the like. Among them, as the acrylic resin, polymethyl methacrylate (PMMA), which is a homopolymer of methyl methacrylate, is preferable.

The polyacetal resin is a polymer compound having an oxymethylene group (-OCH2-) as a main structural unit, and has a polyacetal homopolymer consisting substantially only of repeating oximethylene and a comonomer unit other than the oximethylene unit. Examples include polyacetal copolymers.

Examples of the rubber-based resin include acrylonitrile-butadiene rubber (NBR), butyl rubber (IIR), ethylene-propylene-diene rubber (EPDM), fluororubber, silicon rubber, chloroprene rubber (CR), isoprene rubber (IR), and natural rubber. (NR), styrene-butadiene copolymer rubber (SBR), butadiene rubber (BR) and the like can be mentioned. Among these, butyl rubber (IIR), ethylene-propylene-diene rubber (EPDM), fluororubber, silicon rubber and the like are preferable.

(Metallic material)
Examples of the metal-based material include metals such as aluminum and iron, and alloys such as brass and stainless steel. Among these, aluminum and brass are preferable.

Examples of the member constituting the valve included in the discharge container of the present invention include a housing, a rubber, a stem, and a spring as described above. It is preferable that the material forming each of these members is appropriately selected from the viewpoint of reducing the water absorption rate and the total water content and from the viewpoint of exerting an appropriate function as one component of the discharge container.

Therefore, the housing and stem, which are members constituting the valve, are at least one selected from the group consisting of polyethylene, fluorinated polyethylene, polyacetal, polymethylmethacrylate, polybutylene terephthalate, aluminum, and brass, respectively. It is preferably formed from seeds. From the viewpoint of further reducing the water absorption rate and the total water content, the housing and the stem are preferably formed from at least one selected from the group consisting of polyethylene, fluorinated polyethylene, polyacetal, aluminum, and brass, respectively. Above all, the housing is preferably made of polyacetal from the viewpoint of low water absorption and weight reduction of the discharge container. The stem is preferably polyacetal or brass because of its low water absorption.

The rubber that is a member of the valve is made of a rubber-based material, and among them, a group consisting of acrylonitrile-butadiene rubber (NBR), butyl rubber (IIR), ethylene-propylene-diene rubber (EPDM), fluororubber, and silicon rubber. It is preferably formed from at least one selected from. From the viewpoint of further reducing the water absorption rate and the total water content, the rubber is formed from at least one selected from the group consisting of butyl rubber (IIR), ethylene-propylene-diene rubber (EPDM), fluororubber, and silicone rubber. Is preferable.

The spring, which is a member constituting the valve, is usually formed of a metal-based material. Since the water absorption rate and the total water content of the metal-based material are 0 or a value close to 0, in order to keep the water absorption rate and the total water content of the members constituting the valve within a desired range, the valve components other than the spring are used. It is necessary to properly select the materials that form the housing, stem and rubber.

(Liquid)
The liquid agent contained in the discharge container of the present invention is not particularly limited, but preferably contains a compound that easily reacts with water such as a polyisocyanate, an alkoxy group-containing compound, and a carboxylic acid halide, and particularly contains a polyisocyanate. Is more preferable. Hereinafter, the liquid preparation containing polyisocyanate is also referred to as a polyisocyanate liquid preparation.
When the discharge container of the present invention containing the polyisocyanate solution is used, the water absorption rate and the total water content of the members constituting the valve are below a certain level, so that the reaction between the polyisocyanate and the water is suppressed and the polyisocyanate is stable. Can be discharged to. Therefore, the polyisocyanate and the polyol discharged by the two-component discharge container consisting of the first discharge container containing the polyisocyanate liquid agent and the second discharge container containing the polyol liquid agent containing the polyol prepared separately, respectively. The reaction can be carried out at a constant ratio, and a polyurethane foam having stable physical properties can be formed.

(Polyisocyanate solution)
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 phenylenediisocyanate, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate (MDI), modified diphenylmethane diisocyanate (modified MDI), dimethyldiphenylmethane diisocyanate, triphenylmethane triisocyanate, naphthalene diisocyanate, and polymethylene. Examples thereof include polyphenyl polyisocyanate (polymeric MDI).

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 from the viewpoint of ease of use and availability, and diphenylmethane diisocyanate, polypeptide MDI, or a mixture thereof is more preferable. One type of polyisocyanate may be used alone, or two or more types may be mixed and used.

The polyisocyanate solution usually further contains an organic solvent. The organic solvent becomes a gas at 23 ° C. and 1 atm, and the vapor pressure of the organic solvent causes the polyisocyanate solution to be discharged and vaporized when the polyisocyanate solution is discharged, so that the polyisocyanate solution or described later will be described. Foam the polyurethane composition. The organic solvent has a vapor pressure of preferably 0.1 MPaG or more at 20 ° C. When the vapor pressure is 0.1 MPaG or more, it becomes possible to discharge at a relatively high discharge flow velocity, and it becomes easy to mix appropriately with the polyol liquid after discharge. In addition, the foamability at the time of discharging is also good. The discharge container of the present invention is preferably an aerosol discharge container that discharges the liquid agent by the vapor pressure of the organic solvent as described above.

The vapor pressure of the organic solvent at 20 ° C. is preferably 0.2 MPaG or more, more preferably 0.3 MPaG or more. By setting the vapor pressure to these lower limit values or more, the discharge flow velocity becomes high and the mixing property with the polyol liquid agent becomes excellent. Further, the foamability at the time of forming the polyurethane foam is also excellent.
The upper limit of the vapor pressure at 20 ° C. is not particularly limited, but is, for example, 10 MPaG. Further, in order to prevent the internal pressure inside the discharge container from becoming too high, the vapor pressure at 20 ° C. is preferably 3 MPaG or less, and more preferably 1 MPaG or less.

As the organic solvent, one type may be used alone, or two or more types may be used in combination. When two or more kinds are used in combination, the "vapor pressure at 20 ° C." means the vapor pressure of a mixture of the two or more kinds of organic solvents (mixed solvent) at 20 ° C. Therefore, when two or more types are used in combination, when the vapor pressure is 0.1 MPaG or more, an organic solvent having a vapor pressure of 0.1 MPaG or more at 20 ° C. and an organic solvent having a vapor pressure of less than 0.1 MPaG at 20 ° C. May be used in combination with.

The organic solvent used in the present invention is preferably selected from hydrocarbons having 2 to 5 carbon atoms and dimethyl ether. These organic solvents have a relatively high vapor pressure and have good compatibility with polyol compounds. Examples of the hydrocarbon having 2 to 5 carbon atoms include various butanes such as ethane, propane, isobutane, and normal butane, and various pentanes such as isopentane, normal pentane, and cyclopentane.
The above-mentioned hydrocarbons and dimethyl ethers may be used alone or in combination of two or more. For example, LPG containing propane and butanes as main components may be mentioned as suitable specific examples. Be done.
As the hydrocarbon and dimethyl ether, among the above, hydrocarbons having 3 or 4 carbon atoms such as propane, isobutane and normal butane, and dimethyl ether are preferable in order to keep the vapor pressure in a suitable range. Further, from the viewpoint of compatibility and the like, a mixed solvent of dimethyl ether, dimethyl ether and propane, isobutane or normal butane is more preferable.

As described above, the organic solvent preferably contains at least one selected from the above hydrocarbons and dimethyl ether, but in that case, other organic solvents other than these may or may not be contained. .. Examples of other organic solvents include hydrofluoroolefins.

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, and more preferably 3 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), 1-chloro-3,3,3 -Trifluoropropene (HFO-1233zd), 1,1,1,4,4,4-hexafluorobut-2-ene, (Z) -1,1,1,4,4,4-hexafluorobut- 2-En (HFO-1336mzz (Z)), (E) -1,1,1,4,4,4-hexafluorobut-2-ene (HFO-1336mzz (E)), 2,3,3 3-Tetrafluoropropene (HFO-1234yf), trifluoroethylene (HFO-1123), (E) -1-chloro-3,3,3-trifluoropropene (HCFO-1233zd (E)), (Z)- Examples thereof include 2,3,3,3-tetrafluoro-1-chloropropene (HCFO-1224yd (Z)).
Among these, 1,3,3,3-tetrafluoropropene (HFO-1234ze), (Z) -1,1,1,4,4,4-hexafluorobut-2-ene (HFO-1336mzz) (Z) )), (E) -1,1,1,4,4,4-hexafluorobut-2-ene (HFO-1336mzz (E)), 2,3,3,3-tetrafluoropropene (HFO-1234yf) ), Trifluoroethylene (HFO-1123) is preferable.
These hydrofluoroolefins may be used alone or in combination of two or more.
The hydrofluoroolefin may be used in combination with one or more selected from hydrocarbons and dimethyl ether so that the vapor pressure of the organic solvent is within the above range.

The amount of the organic solvent blended in the polyisocyanate solution is not particularly limited, but is preferably 3 to 50 parts by mass, and more preferably 5 to 20 parts by mass with respect to 100 parts by mass of polyisocyanate. By setting the blending amount of the organic solvent within these ranges, it becomes easy to improve the discharge flow velocity, foamability, and the like. Further, by setting the value to the upper limit or less, it is possible to prevent the amount of the organic solvent in the polyisocyanate solution from being added more than necessary.

The polyisocyanate solution is a phenol-based, amine-based, sulfur-based or other antioxidant, heat stabilizer, metal damage inhibitor, antistatic agent, stabilizer, as required, as long as the object of the present invention is not impaired. Additives such as cross-linking agents, lubricants, softeners, pigments and antistatic resins, and antistatic agents such as polybutene and petroleum resins can be included.

In the discharge container of the present invention containing the polyisocyanate solution, for example, each component other than the organic solvent is mixed as necessary using a disperser or the like, filled in the discharge container, and then the organic solvent is discharged into the discharge container. It may be manufactured by filling the inside and sealing it.

(Polyform solution)
In the present invention, a two-component discharge container including a first discharge container composed of a discharge container containing the above-mentioned polyisocyanate solution and a second discharge container containing a separately prepared polyol solution containing a polyol. can do. It is preferable that the first and second discharge containers are both discharge containers for aerosols.

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. The polyol usually becomes a liquid at normal temperature (23 ° C.) and normal pressure (1 atm).

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, pentanediol, 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 alkanediols such as 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. Tetra-octavalent alcohols such as its derivatives, 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 compound used in the present invention, polyester polyol and polyether polyol are 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. Aromatic polyester polyol obtained by dehydration condensation of the above is more preferable. Further, a polyol having two hydroxyl groups is preferable.

(Solid flame retardant)
The polyol liquid may contain a solid flame retardant. By using a solid flame retardant, flame retardancy can be effectively enhanced. Further, the solid flame retardant is usually in a state of being dispersed in a polyol liquid as a powder component. The solid flame retardant is a flame retardant that becomes solid at normal temperature (23 ° C.) and normal pressure (1 atm).

Specific examples of the solid flame retardant include a red phosphorus flame retardant, a phosphate-containing flame retardant, a bromine-containing flame retardant, a chlorine-containing flame retardant, an antimony-containing flame retardant, a boron-containing flame retardant, and a metal hydroxide. .. These may be used alone or in combination of two or more.

The red phosphorus-based flame retardant may be composed of red phosphorus alone, red phosphorus may be 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.

<Phosphate-containing flame retardant>
The phosphate-containing flame retardant is selected from, for example, 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 a type of metal or compound can be mentioned.
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 monophosphate, pyrophosphate, polyphosphate 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.

<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 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), ethylenebis (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 (brominated benzyl acrylate), brominated polyphenylene ether, brominated bisphenol A, and brominated phenol of cyanur chloride. Condensates of, 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.

<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.

<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.

<Boron-containing flame retardant>
Examples of the boron-containing flame retardant used in the present invention 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, borates of ammonium, and the like. 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, borate. Examples thereof include zirconium acid, zinc borate, aluminum borate, and ammonium borate.

<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 thereof include vanadium hydroxide and tin hydroxide.

When a solid flame retardant is used, one type may be used alone, or two or more types may be used in combination. When a solid flame retardant is used, its content is preferably 5 to 150 parts by mass, and more preferably 10 to 100 parts by mass with respect to 100 parts by mass of the polyol.

The polyol 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.

As the phosphoric acid ester, a monophosphate ester, a condensed phosphoric acid ester and the like can be used. The monophosphate ester is a phosphate ester having one phosphorus atom in the molecule. The monophosphate ester is not limited as long as it is liquid at normal temperature and pressure, but for example, trialkyl phosphate such as trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri (2-ethylhexyl) phosphate, and tris (β-chloro). Halogen-containing phosphates such as propyl) phosphate, trialkoxy phosphates such as tributoxyethyl phosphate, tricresyl phosphate, trixylenyl phosphate, tris (isopropylphenyl) phosphate, cresildiphenyl phosphate, diphenyl (2-ethylhexyl) phosphate Examples thereof include aromatic ring-containing phosphoric acid esters such as, monoisodecyl phosphate, and acidic phosphoric acid esters such as diisodecyl phosphate.

Examples of the condensed phosphoric acid ester include aromatic condensed phosphoric acid esters such as trialkylpolyphosphate, resorcinol polyphenyl phosphate, bisphenol A polycredyl 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. Etc.

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 esters are preferable, and halogen-containing phosphoric acid esters such as tris (β-chloropropyl) phosphate are more preferable from the viewpoint of facilitating the appropriate viscosity of the polyol and improving the flame retardancy of polyurethane foam. preferable.

When the polyol liquid agent contains a liquid flame retardant, the blending amount of the liquid flame retardant is preferably 5 to 100 parts by mass, more preferably 10 to 60 parts by mass with respect to 100 parts by mass of the polyol.

(Organic solvent)
The polyol solution preferably contains an organic solvent. By containing an organic solvent, the polyol can be discharged by its vapor pressure. As the organic solvent contained in the polyol solution, those described as the organic solvent contained in the polyisocyanate solution can be used without limitation.

(catalyst)
The polyol solution preferably contains a catalyst. As the catalyst, for example, a trimerization catalyst, a resinification catalyst, or both may be contained, but it is preferable to contain both.
The trimerization catalyst is a catalyst that promotes the formation of isocyanurate rings by reacting the isocyanate groups contained in polyisocyanate to trimerize them. As the trimerization catalyst, 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, tetra A quaternary ammonium salt such as a phenylammonium salt or a triethylmonomethylammonium salt can be used. Examples of the ammonium salt include ammonium salts of carboxylic acids such as 2,2-dimethylpropanoic acid, and more specifically, quaternary ammonium salts of carboxylic acids.
These may be used alone or in combination of two or more.
Among these, one or more selected from carboxylic acid alkali metal salt and carboxylic acid quaternary ammonium salt are preferable, and an embodiment using both of them is also preferable.

The blending amount of the trimerization catalyst is preferably 1 to 25 parts by mass, more preferably 2 to 18 parts by mass, still more preferably 3 to 15 parts by mass with respect to 100 parts by mass of the polyol. When the blending amount of the trimerization catalyst is not more than these lower limit values, trimerization of polyisocyanate is likely to occur, and the flame retardancy of the obtained polyurethane foam is improved. On the other hand, when the blending amount of the trimerization catalyst is not more than the upper limit value, the reaction can be easily controlled.

The resinification catalyst is a catalyst that promotes the reaction between the polyol compound and the polyisocyanate. 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 may be used.
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, the resinification catalysts include pentamethyldiethylenetriamine, triethylamine, N-methylmorpholinbis (2-dimethylaminoethyl) ether, N, N, N', N ", N"-. Pentamethyldiethylenetriamine, N, N, N'-trimethylaminoethyl-ethanolamine, bis (2-dimethylaminoethyl) ether, N, N-dimethylcyclohexylamine, diazabicycloundecene, triethylenediamine, tetramethylhexamethylenediamine , Various tertiary amines such as tripropylamine and the like.

Examples of the metal catalyst include metal salts composed of lead, tin, bismuth, copper, zinc, cobalt, nickel and the like, and preferably organic acid metal salts composed of lead, tin, bismuth, copper, zinc, cobalt, nickel and the like. Is. More preferably, dibutyltin dilaurate, dioctyltin dilaurate, dioctyltin versatate, bismuth trioctate, bismastrioctate (2-ethylhexanoate), tin dioctylate, lead dioctylate and the like can be mentioned, and among them, the organic acid bismuth salt is more preferable. ..
The resinification catalyst may be used alone or in combination of two or more. Further, among the above, it is preferable to use one or more selected from the imidazole compound and the organic acid bismuth salt, and it is also preferable to use both of them.

The blending amount of the resinification catalyst is preferably 1 to 25 parts by mass, more preferably 2 to 18 parts by mass, still more preferably 3 to 15 parts by mass with respect to 100 parts by mass of the polyol. When the blending amount of the resinification catalyst is at least these lower limit values, urethane bonds are likely to be formed, and the reaction proceeds rapidly. On the other hand, if it is less than these upper limit values, the reaction rate can be easily controlled.

The total amount of the catalyst in the polyol solution is not particularly limited, but is preferably 2 to 40 parts by mass, more preferably 5 to 35 parts by mass, and further preferably 10 to 25 parts by mass. When it is more than these lower limit values, the formation of urethane bonds and the triquantization proceed appropriately, and the flame retardancy tends to be good. Further, when it is not more than these upper limit values, it becomes easy to control the urethanization and trimerization reaction.

(Foaming agent)
The polyol liquid agent of the present invention may contain a defoaming agent. 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, and even more preferably 1 to 5 parts by mass with respect to 100 parts by mass of the polyol. When the blending amount of the foam stabilizer is not less than these lower limit values, the polyurethane composition formed by the polyurethane composition raw material liquid agent and the isocyanate liquid agent can be easily foamed, and a homogeneous polyurethane foam can be easily obtained. 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.

(Anti-sedimentation agent)
In the present invention, the polyol solution may contain an anti-sedimentant. By using the anti-precipitation agent, it is possible to prevent the solid flame retardant dispersed in the polyol liquid agent from precipitating. Further, the use of the sedimentation inhibitor facilitates uniform dispersion of the solid flame retardant. The sedimentation inhibitor generally becomes a solid at normal temperature and pressure, and usually becomes a solid content (insoluble content) in a polyol solution.

The settling inhibitor is not particularly limited, but for example, it is preferable to use one or more selected from carbon black, powdered silica, hydrogenated castor oil wax, fatty acid amide wax, organic clay and the like. Of these, powdered silica is more preferable.
As the carbon black used as the settling inhibitor, one produced 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.
Further, 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.
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 amount of the sedimentation inhibitor is not particularly limited, but is, for example, 0.5 to 20 parts by mass, preferably 0.7 to 12 parts by mass, and more preferably 1.1 to 8 parts with respect to 100 parts by mass of the solid flame retardant. It is a mass part. By setting the blending amount of the sedimentation preventive agent within the above range, the solid flame retardant can be prevented from settling without increasing the solid content more than necessary, and the dispersibility of the solid flame retardant can be improved.

(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.
Further, the polyol liquid may further contain one or more selected from nitrogen gas, oxygen gas, argon gas, carbon dioxide gas and the like as the foaming agent in addition to water.

(Other ingredients)
The polyol solution may contain components other than the above-mentioned components as long as the effects of the present invention are not impaired. Examples of such a component include inorganic fillers other than the above-mentioned sedimentation inhibitor and solid flame retardant.
Inorganic fillers include alumina, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, ferrites, basic magnesium carbonate, calcium carbonate, magnesium carbonate, zinc carbonate, barium carbonate, dosonite, hydrotal. Sight, calcium sulfate, barium sulfate, gypsum fiber, calcium silicate, talc, clay, mica, montmorillonite, bentonite, active white clay, sebiolite, imogolite, cericite, glass fiber, glass beads, silica balun, aluminum oxide, boron nitride, nitride Silicon, graphite, carbon fiber, carbon balun, charcoal powder, various metal powders, potassium titanate, magnesium sulfate, lead zirconate titanate, molybdenum sulfide, silicon carbide, stainless fiber, various magnetic powders, slag fibers, fly ash, silica Alumina fiber, alumina fiber, silica fiber, zirconia fiber and the like can be mentioned. The inorganic filler is a solid component that becomes solid at normal temperature and pressure.
The inorganic filler may be used alone or in combination of two or more.

Further, the polyol liquid agent is an antioxidant such as phenol-based, amine-based, sulfur-based, heat stabilizer, metal damage inhibitor, antistatic agent, stabilizer, if necessary, as long as the object of the present invention is not impaired. , Crosslinking agents, lubricants, softeners, pigments, additives such as antistatic resins, and antistatic agents such as polybutene and petroleum resins.

In the discharge container in which the polyol liquid is second, for example, each component other than the organic solvent is mixed as necessary using a disperser or the like, and then the discharge container is filled, and then the organic solvent is filled inside the discharge container. Then, it is good to manufacture by sealing.

(Polyurethane composition)
A polyisocyanate solution and a polyol solution are discharged from the first and second discharge containers to be mixed and reacted to form a polyurethane composition. The polyurethane composition is formed while foaming with an organic solvent contained in the above-mentioned polyisocyanate solution, an organic solvent contained in a polyol solution, or the like, and becomes a polyurethane foam. As will be described later, the polyol solution and the isocyanate solution may be mixed in a mass ratio so that the isocyanate index falls within a predetermined range.

The isocyanate index of the polyurethane composition is preferably 250 or more. When the isocyanate index is 250 or more, the amount of polyisocyanate with respect to the polyol becomes excessive, and isocyanurate bonds due to the trimerated polyisocyanate are likely to be formed, and as a result, the flame retardancy of the polyurethane foam is improved. In order to further improve the flame retardancy, the isocyanate index is more preferably 300 or more, further preferably 340 or more.
The isocyanate index is preferably 1000 or less, more preferably 650 or less, and even more preferably 500 or less. When the isocyanate index is not more than these upper limit values, 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.

The present invention also provides a mixing system for mixing isocyanate liquids and polyol liquids. As shown in FIG. 9, the mixing system 40 includes a first discharge container 41 containing a polyisocyanate liquid agent and a second discharge container 42 containing a polyol liquid agent. The first and second discharge containers 41 and 42 are discharge containers for aerosols, and the polyisocyanate liquid agent contained in the first discharge container 41 is the liquid agent due to the vapor pressure of the organic solvent contained in the liquid agent. Is discharged. The polyol liquid agent sealed in the second discharge container 42 discharges the polyol liquid agent by the vapor pressure of the organic solvent contained in the polyol liquid agent. Inside the first discharge container 41, a part of the organic solvent is vaporized to form a gas phase. The same applies to the inside of the second discharge container 42.
The polyisocyanate liquid and the polyol liquid discharged from the first and second discharge containers 41 and 42 are mixed while being foamed by an organic solvent or the like, and the polyisocyanate reacts with the polyol to form a polyurethane foam (polyurethane composition). Thing) is formed.

The mixing system 40 may include a mixer 43. The discharge ports 41A and 42A of the first and second discharge containers 41 and 42 are connected to the mixer 43 via the supply lines 41B and 42B, respectively. The polyisocyanate solution and the polyol solution discharged from the first and second spray cans 41 and 42 are supplied to the mixer 43 via the supply lines 41B and 42B, respectively, and these are mixed in the mixer 43. The mixer 43 is a stationary mixer, and the mixer element 43B is arranged inside the tube body 43A. Examples of the mixer element 43B include those formed in a spiral shape and those in which a plurality of baffle plates are formed. The polyisocyanate solution and the polyol solution mixed in the mixer 43 are sprayed onto the construction target surface by an injector or the like. For example, the polyisocyanate solution and the polyol solution are mixed inside the tube body 43A of the mixer 43, and the mixture is injected from the tip 43C of the tube body.

In addition to the above aspects, the mixing system may be the mixing system 50 shown in FIG. The mixing system 50 includes a two-liquid discharge device 53 having a first discharge container 41 and a second discharge container 42, supply lines 41B and 42B, a discharge gun 54, and a mixer 43. The first discharge container 41 and the second discharge container 42 are as described above, and contain a polyisocyanate liquid agent and a polyol liquid agent, respectively. From the first and second discharge containers, the polyisocyanate liquid agent and the polyol liquid agent are sent to the discharge gun 54 via the supply lines 41B and 42B, respectively. The discharge gun 54 includes a lever 54A and has an ON-OFF mechanism for feeding liquid. Specifically, when the lever 54A is pulled, the polyisocyanate solution and the polyol solution are sent to the mixer 43, and when the lever 54A is released, the delivery of the polyisocyanate solution and the polyol solution to the mixer 43 is stopped. By using the mixing system 50 provided with the discharge gun 54, the liquid can be fed as needed, so that the workability when forming the polyurethane foam is improved.

Although the polyurethane composition can be used for various purposes, it is preferably used as a heat insulating material. Since the polyurethane composition has a large number of bubbles by forming the polyurethane foam, it has a heat insulating effect.
The polyurethane composition is more preferably used as a heat insulating material for vehicles or buildings in particular. Vehicles include railroad vehicles, automobiles, ships, aircraft and the like. The polyurethane composition of the present invention has high flame retardancy by using the above-mentioned polyurethane composition raw material liquid. Therefore, from the viewpoint of disaster prevention and safety, it can be suitably used for vehicles or buildings.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.

Various measurement methods are as follows.
[Water absorption and total water content]
The water absorption rate and the total water content of the members constituting the valve were measured based on the method described in the specification.
・ Evaluation criteria for water absorption rate 〇 ・ ・ Water absorption rate of the members that make up the valve is 1% by mass or less × ・ ・ Water absorption rate of the members that make up the valve is over 1% by mass ・ Evaluation criteria for total water content 〇 ・ ・ Valve The total water content of the constituent members is less than 1% by mass △ ・ ・ The total water content of the members constituting the valve is 1% by mass or more and 2% by mass or less × ・ ・ The total water content of the members constituting the valve exceeds 2% by mass

[Evaluation of discharge stability]
The discharge stability of the polyisocyanate solution was evaluated using the discharge containers prepared in each Example and Comparative Example. Specifically, 10 same discharge containers are prepared, and 50% by mass or more can be injected based on the amount of the polyisocyanate liquid agent introduced into the discharge container (total of polyisocyanate and organic solvent). Evaluated in.
The experiment was carried out in an environment of 25 ° C., and the discharge container used was immersed in a hot water bath at 25 ° C. for 30 minutes.
〇 ・ ・ The number of polyisocyanate solutions that could be injected by 50% by mass or more was 7 or more × ・ ・ The number of polyisocyanate solutions that could be injected by 50% by mass or more was 6 or less

[Example 1]
A discharge container in which the members constituting the valve are a housing (material: polyethylene), a stem (material: polyethylene), a rubber (material: NBR), and a spring (material: SUS) was prepared. The container was filled with 400 g of polyisocyanate (MDI: diphenylmethane diisocyanate) and 40 g of an organic solvent to obtain a discharge container containing a polyisocyanate solution. The organic solvent is a mixture of DME (dimethyl ether) and LPG (mixed gas of propane and butane) in a ratio of 6: 4 (mass ratio). This discharge container is a discharge container having the configuration shown in FIG.

[Examples 2 to 10, Comparative Examples 1 to 14]
A discharge container was obtained in the same manner as in Example 1 except that the members constituting the valve were changed as shown in Table 1. In addition, in Table 1, it means that among the members constituting a valve, the member marked with ◯ was used.

As shown in the above examples, it was found that the discharge container in which the water absorption rate and the total water content of the members constituting the valve are 1% by mass or less is excellent in the discharge stability of the polyisocyanate liquid agent.

10 Discharge container 11 Valve 12 Pressure-resistant container 13 Liquid agent 14 Sealing part 15 Mountain cup 16 Housing 17 Rubber 18 Stem 19 Spring 21 Dip tube 22 Actuator 28 Stem 28B Stem hole 28X Stem passage member 28Y Stem moving member 29 Spring 29A Bending part 29Y Cavity part 31 Valve 37 Rubber 38 Stem 38B Stem hole 40 Mixing system 41 First discharge container 42 Second discharge container 41A, 42A Discharge port 41B, 42B Supply line 43 Mixer 43A Tube 43B Mixer element 43C Tip 50 Mixing system 53 2 Liquid discharge device 54 Discharge gun 54A Lever

Claims (7)

A discharge container having a valve containing a liquid agent, wherein the valve comes into contact with the liquid agent when the liquid agent is discharged to the outside, and the water absorption rate of a member constituting the valve is 1% by mass or less. A discharge container having a total water content of 2% by mass or less. The first aspect of the present invention, wherein the member constituting the valve is composed of at least one of a hydrophobic resin having no amide structure in the main chain and no hydroxyl group in the side chain, and a metal-based material. Discharge container. The discharge container according to claim 2, wherein the hydrophobic resin is a resin having neither an amide structure nor an ester structure in the main chain and neither a hydroxyl group nor an ester group in the side chain. The discharge container according to any one of claims 1 to 3, wherein the liquid agent contained in the discharge container contains an organic solvent, and the liquid agent is discharged by the vapor pressure of the organic solvent. The discharge container according to claim 4, wherein the organic solvent is a gas at 23 ° C. and 1 atm. The discharge container according to any one of claims 1 to 5, wherein the liquid agent is a polyisocyanate liquid agent containing a polyisocyanate. A two-component discharge container including a first discharge container including the discharge container according to claim 6 and a second discharge container containing a polyol liquid agent containing a polyol.

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