Manufacturing raw materials and method for manufacturing polyurethane foam

Abstract

To provide a raw material for producing polyurethane foam that can produce polyurethane foam having excellent load-bearing performance without causing troubles and that has a low environmental impact, and to provide a method for producing polyurethane foam.SOLUTION: According to embodiment, a raw material for producing a polyurethane foam having a 40% ILD hardness of 100 N or more is provided. The raw material for production comprises a polyol, an isocyanate, a first blowing agent, and a second blowing agent. The first blowing agent is water. The second blowing agent includes at least one selected from the group consisting of trans-1-chloro-3,3,3-trifluoropropene and cis-1-chloro-3,3,3-trifluoropropene. The contained amount of the second blowing agent in the raw material for production is 1 pts.wt. or more and less than 10 pts.wt. for 100 pts.wt. of the polyol.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a raw material for production and a method for producing polyurethane foam. [Background technology]

[0002] In addition to water as the main blowing agent, auxiliary blowing agents are also blended into the raw materials for low-density polyurethane foam. An example of an auxiliary blowing agent is dichloromethane (DCM). However, dichloromethane has been identified as being harmful to the environment and carcinogenic to humans, and is designated as a specified chemical substance. For these reasons, auxiliary blowing agents that can replace dichloromethane are being considered.

[0003] Liquefied carbon dioxide is one example of an auxiliary blowing agent that has been considered as a substitute for dichloromethane. However, when a reaction stock solution in which liquefied carbon dioxide and other polyurethane foam raw materials are mixed is discharged after mixing, the pressure may be suddenly reduced, causing bumping. This is undesirable because large bubbles are formed in the polyurethane foam produced from the reaction stock solution that has bumped. Furthermore, because liquefied carbon dioxide has a low boiling point, storage and use require equipment compatible with high-pressure gas.

[0004] Patent Document 1 describes a liquefied carbon dioxide foaming device that can prevent bumping. The liquefied carbon dioxide foaming device is equipped with a mesh-type pressure-varying device to prevent bumping by gradually reducing the pressure of the liquefied carbon dioxide. However, when the liquefied carbon dioxide foaming device is used to produce polyurethane foam containing a filler, the filler can clog the pressure-varying device, causing abnormal foaming. Fillers are powders added to impart functionality, such as flame retardants, pigments, antibacterial agents, and polymer particles in polymer polyols.

[0005] As an example of using another auxiliary blowing agent, Patent Document 2 describes a composition for producing polyurethane foam in which 10 to 30 parts by mass of liquid halogenated olefin is blended with 100 parts by mass of polyol. Paragraph 0033 of Patent Document 2 describes that if the content of liquid halogenated olefin is less than 10 parts by mass with respect to 100 parts by mass of polyol, the effect of the auxiliary blowing agent is not fully exerted, the apparent density of the foam increases, and the resulting polyurethane foam becomes hard. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] European Patent Application Publication No. 1332857 [Patent Document 2] International Publication No. 2018 / 225651 Summary of the Invention [Problem to be solved by the invention]

[0007] An object of the present invention is to provide a raw material for producing a polyurethane foam, which can produce a polyurethane foam having excellent load-bearing performance without causing any problems and which has a low environmental impact, and a method for producing a polyurethane foam. [Means for solving the problem]

[0008] According to one aspect of the present invention, Measured according to the method specified in JIS K 6400-2:2012 A manufacturing raw material for producing a polyurethane foam having a 40% ILD hardness of 100 N or more is provided. The manufacturing raw material includes a polyol, an isocyanate, a first blowing agent, and a second blowing agent. The polyol includes a polymer polyol containing a particulate polymer. The first blowing agent is water. The second blowing agent is , Shi bis-1-chloro-3,3,3-trifluoropropane N The content of the second blowing agent in the raw materials for production is 1 part by weight or more and less than 10 parts by weight per 100 parts by weight of the polyol.

[0009] According to another aspect of the present invention, there is provided a method for producing a polyurethane foam having a 40% ILD hardness of 100 N or more. The method includes a step of foaming the above-mentioned raw materials for production. [Effects of the Invention]

[0010] According to the present invention, it is possible to provide a raw material for producing a polyurethane foam and a method for producing a polyurethane foam that can produce a polyurethane foam having excellent load-bearing performance without causing any problems and that has a low environmental impact. [Brief explanation of the drawings]

[0011] [Figure 1] 1 is an explanatory diagram showing the configuration of a production facility for producing polyurethane foam from production raw materials according to an embodiment. [Figure 2] FIG. 2 is an explanatory diagram showing the configuration of a production facility for producing polyurethane foam from production raw materials according to a comparative example. DETAILED DESCRIPTION OF THE INVENTION

[0012] The following describes the embodiments with reference to the drawings as appropriate. Note that common components throughout the embodiments are designated by the same reference numerals, and redundant explanations will be omitted. The drawings are schematic diagrams for explaining and facilitating understanding of the embodiments, and the shapes, dimensions, ratios, etc. may differ from those of actual devices. However, these can be appropriately modified in design, taking into consideration the following explanation and known techniques.

[0013] Polyurethane foams are used in load-bearing applications such as mattresses. If the polyurethane foam's load-bearing capacity is insufficient, it may be unable to support the weight of the user when used as a mattress, resulting in a feeling of bottoming out. Furthermore, raw materials for producing polyurethane foams are required to have a low environmental impact and be less susceptible to defects during production.

[0014] The manufacturing raw material according to the embodiment is a raw material for producing a polyurethane foam having a 40% ILD hardness of 100N or more. The manufacturing raw material contains a polyol, an isocyanate, a first blowing agent, and a second blowing agent. The first blowing agent is water. The second blowing agent contains at least one selected from the group consisting of trans-1-chloro-3,3,3-trifluoropropene and cis-1-chloro-3,3,3-trifluoropropene. The content of the second blowing agent in the manufacturing raw material is 1 part by weight or more and less than 10 parts by weight per 100 parts by weight of the polyol.

[0015] The raw materials contain polyol and isocyanate, which polymerize to produce polyurethane. The raw materials also contain a first blowing agent (water) and a second blowing agent. As the polyurethane polymerization reaction progresses, foaming occurs simultaneously to form polyurethane foam.

[0016] The density (apparent density) of the polyurethane foam can be adjusted by adjusting the content of the first blowing agent in the production raw materials. For example, a low-density polyurethane foam can be produced by foaming a production raw material containing a large amount of the first blowing agent. However, if the content of the first blowing agent in the production raw materials is excessively high, the heat of reaction may become too great, and the polyurethane foam may burn during production. Therefore, there is a limit to reducing the density of a polyurethane foam using only the first blowing agent. Because the production raw materials of the embodiment contain a second blowing agent in addition to the first blowing agent, the content of the first blowing agent can be kept low even when producing a low-density polyurethane foam, preventing excessive heat of reaction.

[0017] The second blowing agent comprises at least one selected from the group consisting of trans-1-chloro-3,3,3-trifluoropropene (HFO1233zd(E)) and cis-1-chloro-3,3,3-trifluoropropene (HFO1233zd(Z)).

[0018] Neither trans-1-chloro-3,3,3-trifluoropropene nor cis-1-chloro-3,3,3-trifluoropropene is designated as a specified chemical substance, which means that the environmental impact of manufacturing raw materials containing these substances can be reduced.

[0019] Furthermore, trans-1-chloro-3,3,3-trifluoropropene has a boiling point of 19°C, and cis-1-chloro-3,3,3-trifluoropropene has a boiling point of 39°C. Therefore, the raw material for production according to the embodiment is less likely to bump. Therefore, when producing a polyurethane foam, a pressure gradual change device is not required, and problems such as clogging of the discharge port are less likely to occur.

[0020] The content of the second blowing agent in the raw material for production is preferably 1 part by weight or more and less than 10 parts by weight per 100 parts by weight of polyol. A raw material for production in which the content of the second blowing agent is less than 10 parts by weight per 100 parts by weight of polyol is likely to produce a polyurethane foam with a 40% ILD hardness of 100N or more.

[0021] Polyurethane foams with a 40% ILD hardness of 100 N or more have excellent load-bearing performance. The 40% ILD hardness can be measured in accordance with the measurement method specified in JIS K 6400-2:2012.

[0022] The raw materials for production according to the embodiment will be further described.

[0023] The manufacturing raw materials according to the embodiment include a polyol, an isocyanate, a first blowing agent, and a second blowing agent. The manufacturing raw materials may be in a form in which the respective raw materials are present independently without being mixed, or may be in the form of a raw material mixture in which the respective raw materials are mixed. In addition to the above raw materials, the manufacturing raw materials may further include a catalyst, a foam stabilizer, an additive, etc.

[0024] Each raw material is described below.

[0025] (Polyol) Examples of the polyol include multifunctional polyols and polymer polyols. One or more types of polyols may be used.

[0026] Polymer polyol is a polyol in which a solid particulate polymer is dispersed. The particulate polymer can further improve the hardness of the polyurethane foam. The content of the polymer polyol is preferably 5 parts by weight or more and 100 parts by weight or less per 100 parts by total weight of the polyol. The median diameter of the particulate polymer contained in the polymer polyol is preferably 0.2 μm or more and 500 μm or less.

[0027] (Isocyanate) As the isocyanate, for example, tolylene diisocyanate is preferably used. The amount of isocyanate added to the raw materials for production is preferably an amount such that the isocyanate index (NCO index) of the entire raw materials for production is a value of 90 or more and 120 or less. The isocyanate index is an index of the reaction ratio between hydroxyl groups and isocyanate groups, and can be calculated using the following formula.

number

[0028] (First blowing agent) The first blowing agent is water. The preferred range of the content of the first blowing agent in the raw materials for production is 4 parts by weight or more and 6 parts by weight or less per 100 parts by weight of polyol. When the content of the first blowing agent is 4 parts by weight or more per 100 parts by weight of polyol, the foaming effect is easily obtained. When the content of the first blowing agent is 6 parts by weight or less per 100 parts by weight of polyol, the reaction heat does not become too large.

[0029] (Second blowing agent) The second blowing agent comprises at least one selected from the group consisting of trans-1-chloro-3,3,3-trifluoropropene (HFO1233zd(E)) and cis-1-chloro-3,3,3-trifluoropropene (HFO1233zd(Z)). In particular, cis-1-chloro-3,3,3-trifluoropropene has a high boiling point of 39°C and can therefore be stored and used in an environment at room temperature and atmospheric pressure. This makes it more preferable because it does not require equipment for high-pressure gas and allows polyurethane foam to be produced easily and at low cost.

[0030] (catalyst) The raw materials for production may further contain a catalyst. Examples of catalysts include tin catalysts and amine catalysts. The type of catalyst used may be one or more types.

[0031] (additives) The raw materials for production may further contain additives. Examples of additives include antioxidants, flame lamination modifiers, flame retardants, hygiene improvers, pigments, and natural products. Examples of flame retardants include melamine, urea, polyvinyl chloride (PVC), zinc oxide, antimony trioxide, expandable graphite, and phosphorus-based solid materials. Examples of hygiene improvers include antibacterial agents, anti-mite agents, anti-fungal agents, antiviral agents, and deodorizers. Examples of natural products include green tea powder, catechin, charcoal, needle leaf powder, and herbs. The additives used may be one or more types.

[0032] Adding additives to the manufacturing raw materials is preferable because it can impart properties to the polyurethane foam depending on the type of additive. For example, adding a flame retardant to the manufacturing raw materials can improve the flame retardancy of the polyurethane foam. Adding a hygiene improving agent can improve the hygiene of the polyurethane foam.

[0033] The preferred content of additives in the raw materials varies depending on the type of additive. For example, the content of the antibacterial agent is preferably 0.1 to 2 parts by weight per 100 parts by weight of polyol. The content of green tea powder is preferably 0.1 to 2 parts by weight per 100 parts by weight of polyol.

[0034] The additive may be in the form of a filler. Here, the filler is a powder added for the purpose of imparting functionality, etc. The median diameter of the filler contained in the additive is preferably 0.2 μm or more and 500 μm or less. Examples of filler forms include an antibacterial agent made up of particles with a median diameter of 5 μm, green tea powder made up of particles with a median diameter of 50 μm, and needle leaf powder made up of particles with a median diameter of 300 μm.

[0035] (Foam stabilizer) The type of foam stabilizer is not particularly limited, but may be a silicone-based foam stabilizer. In this case, the increased foam stabilizing power makes it easier to retain the foaming gas generated by the reaction, thereby improving moldability.

[0036] The content of the foam stabilizer in the raw materials for production is, for example, in the range of 0.5 to 15 parts by weight per 100 parts by weight of polyol. If the content of the foam stabilizer in the raw materials for production is too low, it becomes difficult to retain the foaming gas generated, and moldability tends to deteriorate. The content of the foam stabilizer in the raw materials for production is preferably in the range of 1.0 to 3.0 parts by weight per 100 parts by weight of polyol.

[0037] (nitrogen gas) The raw materials for production may be foamed in the presence of nitrogen gas. When comparing a polyurethane foam produced by foaming in the presence of nitrogen gas with a polyurethane foam produced without adding nitrogen gas, if the density of the polyurethane foam is the same, the polyurethane foam produced by foaming the raw materials for production in the presence of nitrogen gas will contain more small cells. Therefore, mixing and foaming the raw materials in the presence of nitrogen gas allows the production of a homogeneous polyurethane foam with fewer coarse cells.

[0038] (Method of manufacturing polyurethane foam) A method for producing polyurethane foam will now be described. Polyurethane foam can be produced, for example, by supplying raw materials at a desired ratio from a tank containing the raw materials to a mixer, mixing and stirring the materials, and then discharging the mixture from the discharge port of the mixer to cause foaming.

[0039] The raw materials may be stored in separate tanks. Alternatively, multiple types of raw materials may be mixed in advance and supplied from the tank in the form of a mixed liquid. The mixed liquid may consist of two or more raw materials. For example, raw materials such as polyol, catalyst, and foam stabilizer may be mixed in advance. Furthermore, solid raw materials may be dispersed in liquid raw materials such as polyol in advance and supplied from the tank in the form of a dispersion. The temperature and pressure inside the tank and piping may be adjusted according to the properties of each raw material, such as the boiling point and melting point.

[0040] The above-mentioned raw materials are mixed, and the raw material mixture is discharged from the discharge port of the mixer. The discharge port is preferably equipped with a mesh for removing foreign matter. A conveyor may be provided in the direction of discharge. Furthermore, a process sheet may be continuously fed onto the conveyor. The process sheet may be, for example, a paper surface agent or a plastic film. With this configuration, the discharged raw material mixture moves on the conveyor, allowing continuous foaming.

[0041] Thus, slab-blown polyurethane foam can be produced.

[0042] The method for producing a polyurethane foam using the production raw materials of the embodiment will be described below with reference to FIG.

[0043] FIG. 1 is a schematic diagram illustrating an example of a production facility for producing a polyurethane foam from raw materials according to an embodiment.

[0044] The production equipment includes a polyol supply section 1, an isocyanate supply section 2, a first auxiliary agent supply section 3, a second auxiliary agent supply section 4, a nitrogen gas supply section 5, a first pipe 11, a second pipe 12, a third pipe 14, a first branch pipe 13, a second branch pipe 15, and a mixer 6.

[0045] The polyol supply unit 1 is connected to the mixer 6 via a first pipe 11. The first pipe 11 branches into a first branch pipe 13. The first branch pipe 13 is connected to a first auxiliary agent supply unit 3. The isocyanate supply unit 2 is connected to the mixer 6 via a second pipe 12. The second pipe 12 branches into a second branch pipe 15. The nitrogen gas supply unit 5 is connected to the second branch pipe 15. The second auxiliary agent supply unit 4 is connected to the mixer 6 via a third pipe 14.

[0046] The polyol supply unit 1 is configured to be able to supply polyol to the first pipe 11. The polyol supply unit 1 can include, for example, one or more tanks that store polyol. Examples of polyols include those described above. When two or more types of polyols are supplied from the polyol supply unit 1, separate tanks may be used to store each type of polyol. The polyol containing polymer polyol is preferably kept at 20°C or higher.

[0047] Furthermore, the polyol supply unit 1 can accommodate raw materials other than polyol in addition to polyol. Examples of raw materials other than polyol include antibacterial agents and natural materials, which are listed as examples of additives. The polyol supply unit 1 can accommodate, for example, a dispersion liquid prepared by dispersing raw materials other than polyol in polyol. This method is suitable, for example, when blending powdered raw materials such as fillers with the manufacturing raw materials. The raw materials other than polyol dispersed in the polyol can be one type or two or more types.

[0048] The isocyanate supply unit 2 is configured to be able to supply isocyanate to the second pipe 12. For example, one or more tanks for storing isocyanate may be provided.

[0049] The first auxiliary supply section 3 is configured to supply the first auxiliary to the first branch pipe 13. Examples of the first auxiliary include an additive, an amine catalyst, a foam stabilizer, a first blowing agent, and a second blowing agent. The first auxiliary supply section 3 may include, for example, one or more tanks for storing the first auxiliary. When two or more types of first auxiliary are supplied from the first auxiliary supply section 3, separate tanks may be used for each type of first auxiliary. The interior of a tank for storing a first auxiliary with a low boiling point is preferably under high pressure or at a temperature lower than the boiling point of the raw material. The type of first auxiliary stored in the polyol supply section 1 does not need to be stored in the first auxiliary supply section 3.

[0050] The second auxiliary supply unit 4 is configured to be able to supply the second auxiliary to the third pipe 14. An example of the second auxiliary is a catalyst. Examples of catalysts include those described above. The second auxiliary supply unit 4 can be equipped with, for example, one or more tanks that store the second auxiliary. When two or more types of second auxiliary are supplied from the second auxiliary supply unit 4, separate tanks may be used to store each type of second auxiliary. Of the second auxiliary, raw materials of the type stored in the first auxiliary supply unit 3 (e.g., amine catalyst) do not need to be stored in the second auxiliary supply unit 4.

[0051] The nitrogen gas supply unit 5 is configured to be able to supply nitrogen gas to the second branch pipe 15. The nitrogen gas supply unit 5 can store, for example, nitrogen gas in a gaseous state.

[0052] The manufacturing equipment further includes a control unit (not shown) that is configured to be able to control the supply amount of each raw material, as well as the supply start and stop timings.

[0053] The flow of the method for producing polyurethane foam using the production equipment having the above configuration will be described below.

[0054] Polyol is supplied from polyol supply unit 1 into first pipe 11 and sent through first pipe 11 along the arrow. Furthermore, first auxiliary agent is supplied from first auxiliary agent supply unit 3 into first branch pipe 13 and sent through first branch pipe 13 along the arrow, and then supplied into first pipe 11. The polyol and first auxiliary agent are further sent through first pipe 11 along the arrow. Thus, the polyol and first auxiliary agent are supplied in a mixed state from first pipe 11 to mixer 6.

[0055] Furthermore, isocyanate is supplied from isocyanate supply unit 2 into second pipe 12 and sent through second pipe 12 along the arrow. Nitrogen gas is also supplied from nitrogen gas supply unit 5 into second branch pipe 15 and sent through second branch pipe 15 along the arrow, and then supplied into second pipe 12. The isocyanate and nitrogen gas are further sent through second pipe 12 along the arrow. Therefore, the isocyanate and nitrogen gas are supplied in a mixed state from second pipe 12 to mixer 6.

[0056] Furthermore, the second auxiliary agent contained in the second auxiliary agent supply unit 4 is supplied into the third pipe 14 , sent along the arrow in the third pipe 14 , and supplied to the mixer 6 .

[0057] The mixer 6 mixes and stirs the raw materials supplied through the first pipe 11, the second pipe 12, and the third pipe 14, and discharges the raw material mixture from the discharge port 7. The discharged raw material mixture foams as a result of a polymerization reaction, forming a polyurethane foam.

[0058] The first pipe 11, the second pipe 12, the third pipe 14, the first branch pipe 13, and the second branch pipe 15 may be pipes compatible with high-pressure gas. If the pipes are compatible with high-pressure gas, the strength of the manufacturing equipment can be maintained even if the internal pressure becomes high. Therefore, raw materials with low boiling points can be blended in a liquid state. [Example]

[0059] Examples will be described below. The raw materials used in each of the examples and comparative examples are as follows. Polyol 1: Actcoal T-3000S (Mitsui Chemicals SKC Polyurethanes Co., Ltd.) Polyol 2: Sannix FA-375 (manufactured by Sanyo Chemical Industries, Ltd.) Polymer polyol: Sharp Flow FS-7301 (manufactured by Sanyo Chemical Industries, Ltd.) Isocyanate: Cosmonate T-80 (Mitsui Chemicals SKC Polyurethanes Co., Ltd.) Tin catalyst: KOSMOS T 9 (manufactured by Evonik Japan Co., Ltd.) Amine catalyst 1: DABCO® 33 LV (manufactured by Evonik Japan Co., Ltd.) Amine catalyst 2: DABCO (registered trademark) NE300 (manufactured by Evonik Japan Co., Ltd.) Amine catalyst 3: TOYOCAT-NP (manufactured by Tosoh Corporation) Foam stabilizer 1: Niax® silicone L-598 (manufactured by Momentive Performance Materials Japan, LLC) Foam stabilizer 2: TEGOSTAB B 8228 (manufactured by Evonik Japan Co., Ltd.) Foam stabilizer 3: VORASURF (registered trademark) SZ-1142 Fluid (manufactured by Dow Toray Industries, Inc.) Antioxidant: NIAX COLOR STABILIZER CS-17 (manufactured by Momentive Performance Materials Japan, LLC) Flame lamination modifier: Niax® flame lamination additive FLE-500LF (manufactured by Momentive Performance Materials Japan, LLC) Flame retardant: CR-504L (manufactured by Daihachi Chemical Industry Co., Ltd.) First foaming agent: Water (H2O) Second blowing agent 1: HFO1233zd(Z) / (cis-1-chloro-3,3,3-trifluoropropene, manufactured by UniPo Corporation) Second blowing agent 2: HFO1233zd(E) / (trans-1-chloro-3,3,3-trifluoropropene, manufactured by UniPo Corporation) Third blowing agent 3: methylene chloride (dichloromethane, manufactured by Shin-Etsu Chemical Co., Ltd.) Third foaming agent 4: Liquefied carbon dioxide (CO2, manufactured by Air Water Carbonate Co., Ltd.) Antibacterial agent: Bactekiller BM-102TG (median diameter: 5 μm, manufactured by Fuji Chemical Co., Ltd.) Natural ingredients: Green tea powder (median diameter: 50 μm, manufactured by Takada Tea Garden Co., Ltd.) The median particle size of the particulate polymer dispersed in the polymer polyol is 0.6 μm.

[0060] <Production of polyurethane foam> (Examples 1, 3, 5, 7, 9, Comparative Examples 11 and 13) Using the production equipment shown in FIG. 1, polyurethane foams were produced by the method described below.

[0061] 1, a polyol supply section 1 and a first auxiliary agent supply section 3 each equipped with a plurality of tanks were used. Nitrogen gas was not used.

[0062] An antibacterial agent dispersion was prepared by dispersing the antibacterial agent in polyol 1. Also, a natural material dispersion was prepared by dispersing a natural material in polyol 1.

[0063] Polyol 1, polyol 2, polymer polyol, antibacterial agent dispersion, and natural material dispersion were stored separately in multiple tanks provided in polyol supply unit 1. The polymer polyol was maintained at 27° C. The polyol supply unit 1 was connected to a first pipe 11 so that raw materials could be supplied from each tank.

[0064] Isocyanate was stored in a tank provided in the isocyanate supply unit 2, and the isocyanate supply unit 2 and the second pipe 12 were connected.

[0065] Amine catalyst 1, amine catalyst 2, amine catalyst 3, foam stabilizer 1, foam stabilizer 2, foam stabilizer 3, antioxidant, flame laminate modifier, flame retardant, first blowing agent, and second blowing agent 1 were stored separately in multiple tanks provided in first auxiliary agent supplying section 3. First auxiliary agent supplying section 3 was connected to first branch pipe 13 so that raw materials could be supplied from each tank.

[0066] A tin catalyst was placed in a tank provided in the second auxiliary agent supplying section 4, and the second auxiliary agent supplying section 4 and the third pipe 14 were connected.

[0067] Next, the manufacturing equipment was operated, and raw materials were supplied to the mixer 6 from the polyol supply unit 1, isocyanate supply unit 2, first auxiliary supply unit 3, and second auxiliary supply unit 4, respectively. The blending amount of each raw material was controlled by the control unit so as to be the value shown in Tables 1 and 2. The values ​​shown in Tables 1 and 2 indicate the blending amount of each raw material in parts by weight when the total blending amount of polyol 1, polyol 2, and polymer polyol is 100 parts by weight. In the tables, raw materials marked with "-" indicate that they were not blended.

[0068] The supplied raw materials were mixed and stirred in a mixer 6. A process sheet was continuously fed onto a moving conveyor (not shown), and the raw material mixture was discharged from the discharge outlet 7 of the mixer 6 onto the process sheet. A mesh (not shown) for removing foreign matter was installed at the discharge outlet 7. By continuously discharging the raw material mixture and running the conveyor, the discharged raw material mixture was foamed while moving. In this manner, a foam was continuously molded. After foaming was completed, the process sheet was removed from the foam to obtain a polyurethane foam.

[0069] (Examples 2, 4, 6, 8, 10, Comparative Examples 12 and 14) A polyurethane foam was produced using the production equipment shown in FIG. 1 used in Example 1, with the following modifications:

[0070] The first auxiliary agent supplying section 3 contained the second blowing agent 2 instead of the second blowing agent 1. This allowed the second blowing agent 2 to be supplied to the first branch pipe 13. The temperature of the second blowing agent 2 was maintained at 10°C or less. Furthermore, the manufacturing equipment was made compatible with high-pressure gas. Other than that, the manufacturing equipment had the same configuration as the manufacturing equipment shown in FIG. 1 used in Example 1.

[0071] The blending amounts of each raw material were controlled by the control unit so as to be the values ​​shown in Tables 1 and 2.

[0072] A polyurethane foam was obtained in the same manner as in Example 1 except for the above.

[0073] (Comparative Examples 1, 3, 5, 7, and 9) A polyurethane foam was produced using the production equipment shown in FIG. 1 used in Example 1, with the following modifications:

[0074] The first auxiliary supplying section 3 accommodated the third foaming agent 3 instead of the second foaming agent 1. This allowed the third foaming agent 3 to be supplied to the first branch pipe 13. The rest of the configuration was the same as that of the manufacturing equipment shown in FIG. 1 used in Example 1.

[0075] The blending amounts of each raw material were controlled by the control unit so as to be the values ​​shown in Tables 1 and 2.

[0076] A polyurethane foam was obtained in the same manner as in Example 1 except for the above.

[0077] (Comparative Examples 2, 4, 6, 8, and 10) Using the production equipment shown in FIG. 2, polyurethane foams of Comparative Examples 2, 4, 6, 8 and 10 were produced by the method described below.

[0078] FIG. 2 shows a schematic diagram of a production facility for producing polyurethane foam from raw materials containing a third blowing agent 4 (liquefied carbon dioxide gas).

[0079] 2 further includes a liquefied carbon dioxide gas supply unit 8 and a third branch pipe 18 branched from the first pipe 11, in addition to the components of the manufacturing equipment described with reference to FIG. 1. The liquefied carbon dioxide gas supply unit 8 is connected to the third branch pipe 18. The liquefied carbon dioxide gas supply unit 8 is configured to be able to supply liquefied carbon dioxide gas to the third branch pipe 18.

[0080] The manufacturing equipment shown in FIG. 2 also includes a mixer 9 instead of the mixer 6. The mixer 9 mixes and stirs the raw materials supplied through the first pipe 11, the second pipe 12, and the third pipe 14, and discharges the raw material mixture from the discharge port 10. The mixer 9 further includes a liquefied carbon dioxide gas bubbling device (not shown). The liquefied carbon dioxide gas bubbling device includes a mesh-like pressure gradual change device, and is therefore able to gradually reduce the pressure of the raw material mixture. This makes it possible to prevent bumping due to a sudden decrease in pressure of the raw material mixture during discharge.

[0081] In addition, the manufacturing equipment in Figure 2 is compatible with high-pressure gas, so liquefied carbon dioxide gas with a low boiling point can be blended in liquid form.

[0082] The manufacturing equipment shown in Figure 2 was operated, and liquefied carbon dioxide gas was supplied from the liquefied carbon dioxide gas supply unit 8. The gas was then sent through the third branch pipe 18 and the first pipe 11 along the arrows and supplied to the mixer 9. Other raw materials were supplied to the mixer 9 from the polyol supply unit 1, the isocyanate supply unit 2, the first auxiliary agent supply unit 3, and the second auxiliary agent supply unit 4, respectively. The blending amounts of each raw material were controlled by the control unit to be the values ​​shown in Tables 1 and 2. The supplied raw materials were mixed and stirred in the mixer 9. A process sheet was continuously fed onto a moving conveyor (not shown), and the raw material mixture was discharged from the discharge port 10 of the mixer 9 onto the process sheet. During discharge, the pressure of the raw material mixture was gradually reduced using a pressure-varying device. By continuously discharging the raw material mixture and running the conveyor, the discharged raw material mixture was foamed while moving. Using this method, a foam was continuously molded. After foaming was completed, the process sheet was removed from the foam to obtain a polyurethane foam.

[0083] <Measurement> The various polyurethane foams obtained as described above were measured for apparent density, 40% ILD hardness and load-bearing capacity.

[0084] (Method for measuring apparent density) The apparent density was measured in accordance with the measurement method specified in JIS K 7222:2005.

[0085] (40% ILD hardness measurement method) The 40% ILD hardness was measured in accordance with the measurement method specified in JIS K 6400-2:2012.

[0086] (Method for measuring load-bearing capacity) The load-bearing capacity of the polyurethane foam was measured by a sensory evaluation of the bottoming out feeling. The polyurethane foams produced from the raw materials for production of the Examples and Comparative Examples were cut into samples of 200 cm length x 100 cm width x 7 cm thickness, each of which was used as a sample for each formulation.

[0087] The feeling of hitting the floor was evaluated by the subject lying on the center of a single layer of the sample on the floor. The evaluation was conducted by 12 male and female subjects in two sleeping positions: lying on their back and lying on their side. The evaluation criteria for feeling of hitting the floor were as follows: if the subject felt that they were touching the floor, they were given a score of 0, if they felt that they were not touching the floor at all, they were given a score of 2, if they felt that they were not touching the floor at all, they were given a score of 1, if they felt that they were somewhere between feeling of hitting the floor and not feeling of hitting the floor, they were given a score of 1, if they felt that they were slightly touching the floor. The evaluation was conducted as an absolute evaluation, not a relative evaluation with other samples.

[0088] For each sample, the average score for the feeling of bottoming out when lying on one's back and the average score for the feeling of bottoming out when lying on one's side are shown in Tables 3 and 4. The load-bearing capacity was evaluated based on the average score for the feeling of bottoming out when lying on one's back. In Tables 3 and 4, an average score of 1 or more is marked with a circle, an average score of 0 but less than 1 is marked with a triangle, and an average score of 0 is marked with an cross.

[0089] [result] The experimental results will be explained below with reference to Tables 1 to 4.

[0090] [Table 1]

[0091] [Table 2]

[0092] [Table 3]

[0093] [Table 4]

[0094] Examples 1 to 10 are manufacturing raw materials containing, as the second blowing agent, Second Blowing Agent 1 (cis-1-chloro-3,3,3-trifluoropropene) or Second Blowing Agent 2 (trans-1-chloro-3,3,3-trifluoropropene) in an amount of 1 part by weight or more but less than 10 parts by weight per 100 parts by weight of polyol. These manufacturing raw materials do not contain any specific chemical substances, so they have a low environmental impact. In addition, no clogging of the discharge outlet occurred during foaming. The polyurethane foams manufactured from the manufacturing raw materials of Examples 1 to 10 all had a 40% ILD hardness of 100 N or more.

[0095] The evaluation results for bottoming out in Tables 3 and 4 show that, overall, the average score for bottoming out was lower and the feeling of bottoming out tended to be stronger when sleeping on one's side compared to when sleeping on one's back. However, the average scores for bottoming out for polyurethane foams with a 40% ILD hardness of 100 N or more were all higher than those for Comparative Examples 11 to 14, both when sleeping on one's back and on one's side. Therefore, it was revealed that the polyurethane foams produced from the raw materials for production in Examples 1 to 10 were polyurethane foams with a low bottoming out feeling and excellent load-bearing performance.

[0096] This is thought to be due to the fact that the amount of second blowing agent 1 (cis-1-chloro-3,3,3-trifluoropropene) or second blowing agent 2 (trans-1-chloro-3,3,3-trifluoropropene) in the raw materials used for production is 1 part by weight or more but less than 10 parts by weight. When the amount of second blowing agent 1 or second blowing agent 2 is less than 10 parts by weight, the apparent density of the polyurethane foam does not become too low, and the 40% ILD hardness is maintained at 100 N or more. This is thought to be why the foam is less likely to bottom out and has good load-bearing performance.

[0097] Therefore, it was revealed that the raw materials for production of the examples are raw materials for producing polyurethane foams that can produce polyurethane foams with excellent load-bearing performance without causing any problems and that have a low environmental impact.

[0098] Comparative Examples 1, 3, 5, 7, and 9, which contained third blowing agent 3 (dichloromethane), contained specific chemical substances and therefore became raw materials for production that had a large environmental impact. Furthermore, Comparative Examples 2, 4, 6, 8, and 10, which contained third blowing agent 4 (liquefied carbon dioxide gas) and were produced using the production equipment shown in Figure 2, experienced a problem during production in which the gradual pressure change device provided in the production equipment shown in Figure 2 was clogged.

[0099] The polyurethane foams produced from the manufacturing raw materials of Comparative Examples 11 to 14, in which the amount of Second Blowing Agent 1 or Second Blowing Agent 2 was 10 parts by weight or more, even though the manufacturing raw materials contained Second Blowing Agent 1 (cis-1-chloro-3,3,3-trifluoropropene) or Second Blowing Agent 2 (trans-1-chloro-3,3,3-trifluoropropene), were inferior in load-bearing performance to the polyurethane foams produced from the manufacturing raw materials of the Examples.

[0100] As shown in Table 4, the 40% ILD hardness of the polyurethane foams in Comparative Examples 11 to 14 was less than 100 N. In the evaluation of bottoming out feeling, the polyurethane foams with a 40% ILD hardness of less than 100 N had an average score of less than 1 in both the supine and side positions.

[0101] As described above, in Comparative Examples 11 to 14, the content of the second blowing agent in the raw materials for production was 10 parts by weight or more per 100 parts by weight of polyol. This resulted in an insufficient 40% ILD hardness of the polyurethane foam, which meant that the weight of the subject could not be supported, resulting in a strong bottoming-out sensation felt by the subject, which is thought to have resulted in a low evaluation of the load-bearing performance.

[0102] In Examples 1, 2, 5 to 8 and Comparative Examples 1, 5, and 7, the production raw material contained polymer polyol, but no clogging occurred during foaming. In contrast, clogging of the discharge port occurred in Comparative Examples 2, 6, and 8. The following is thought to be the cause. Comparative Examples 2, 6, and 8 contained a third blowing agent 4 (liquefied carbon dioxide gas) in addition to the polymer polyol, and were produced using the production equipment shown in Figure 2. Therefore, it is thought that the particulate polymer clogged the pressure-varying device provided in the production equipment shown in Figure 2.

[0103] In Examples 3 to 6, 9, and 10, the raw materials used contained antibacterial agents or natural materials as additives, but no clogging occurred during foaming. In particular, in Examples 5 and 6, the raw materials used contained natural materials with a large median diameter of 50 μm, but they were able to foam without any problems. In contrast, in Comparative Examples 4, 6, and 10, which contained antibacterial agents or natural materials as additives and also contained the third foaming agent 4 (liquefied carbon dioxide), clogging occurred in the gradual pressure change device.

[0104] Examples 1, 3, 5, 7, and 9 are compared with Examples 2, 4, 6, 8, and 10. When producing Examples 2, 4, 6, 8, and 10, it was necessary to control the pressure and temperature of the second blowing agent 2 (trans-1-chloro-3,3,3-trifluoropropene). Therefore, equipment for high-pressure gas was required. In contrast, Examples 1, 3, 5, 7, and 9 contained the second blowing agent 1 (cis-1-chloro-3,3,3-trifluoropropene), which has a high boiling point of 39°C, and therefore could be produced at room temperature and normal pressure. Therefore, equipment for high-pressure gas was not required. Therefore, production could be carried out using simpler equipment, which was advantageous in terms of cost.

[0105] As described above, the production method including the step of foaming the production raw materials of Examples 1 to 10 is a method that can produce polyurethane foams with excellent load-bearing performance without causing any problems and that has a low environmental impact.

[0106] The present invention is not limited to the above-described embodiments, and various modifications can be made in the implementation stage without departing from the spirit of the invention. Furthermore, the embodiments may be implemented in appropriate combinations, in which case the combined effects can be obtained. Furthermore, the above-described embodiments include various inventions, and various inventions can be extracted by combining selected elements from the disclosed elements. For example, if the problem can be solved and the desired effect can be obtained even if some elements are deleted from all elements shown in the embodiments, the configuration from which these elements are deleted can be extracted as an invention. [Explanation of symbols]

[0107] 1...polyol supply section, 2...isocyanate supply section, 3...first auxiliary agent supply section, 4...second auxiliary agent supply section, 5...nitrogen gas supply section, 6, 9...mixer, 7, 10...discharge port, 8...liquefied carbon dioxide gas supply section, 11...first pipe, 12...second pipe, 13...first branch pipe, 14...third pipe, 15...second branch pipe, 18...third branch pipe.

Claims

1. A raw material for producing a polyurethane foam having a 40% ILD hardness of 100 N or more as measured by the measurement method specified in JIS K 6400-2:2012, The manufacturing raw materials include a polyol, an isocyanate, a first blowing agent, and a second blowing agent; the polyol comprises a polymer polyol containing a particulate polymer; the first blowing agent comprises water; the second blowing agent comprises cis-1-chloro-3,3,3-trifluoropropene; The content of the second blowing agent in the manufacturing raw material is 1 part by weight or more and less than 10 parts by weight per 100 parts by weight of the polyol.

2. The raw material for production according to claim 1, further comprising at least one additive selected from the group consisting of a flame retardant, a hygiene improving agent, and a natural product.

3. A method for producing a polyurethane foam having an ILD hardness of 100 N or more, comprising a step of foaming the raw material for production according to claim 1 or 2.

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