WO2021193363A1 - Polyurethane foam and shoe sole member - Google Patents
Polyurethane foam and shoe sole member Download PDFInfo
- Publication number
- WO2021193363A1 WO2021193363A1 PCT/JP2021/011138 JP2021011138W WO2021193363A1 WO 2021193363 A1 WO2021193363 A1 WO 2021193363A1 JP 2021011138 W JP2021011138 W JP 2021011138W WO 2021193363 A1 WO2021193363 A1 WO 2021193363A1
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- WO
- WIPO (PCT)
- Prior art keywords
- polyurethane foam
- mass
- less
- isocyanate group
- polyol component
- Prior art date
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Classifications
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- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- A43B13/00—Soles; Sole-and-heel integral units
- A43B13/02—Soles; Sole-and-heel integral units characterised by the material
- A43B13/04—Plastics, rubber or vulcanised fibre
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
Definitions
- the present invention relates to polyurethane foam and shoe sole members.
- foams such as polyurethane foam and ethylene-vinyl acetate copolymer foam have been used as constituent members in various applications.
- a sole member made of polyurethane foam has excellent shock absorption, and is used as a component of the sole of athletic shoes such as walking shoes, running shoes, and trekking shoes as well as general-purpose shoes.
- the polyurethane foam is not limited to the use as a shoe sole member, but can also be used as a mat member such as a floor mat in a workplace or an underlay mat when installing a precision machine.
- the sole refers to the sole portion of the shoe
- the sole member refers to a constituent member (material) constituting the sole.
- the invention described in Patent Document 1 has an object of providing a polyurethane integral skin foam having a high rebound resilience in a wide temperature range and having excellent mechanical strength and productivity.
- the organic polyisocyanate composition (A), the polyol component (B), the catalyst (C), and the foaming agent (D) are used as raw materials, and the organic polyisocyanate composition (A) is diphenylmethane.
- the invention of polyurethane integral skin foam which is a urethane modified product of diisocyanate and polytetramethylene ether glycol having a number average molecular weight of 1000 to 3500 and is an organic polyisocyanate (a1) having an isocyanate group content of 7 to 25% by mass, is disclosed. ing.
- Patent Document 2 has an object of providing a polyurethane foam which is durable, has shock absorption and resilience at the same time, and also has bending resistance.
- Patent Document 2 describes a polyurethane raw material containing a polyol component, a polyisocyanate component, a foaming agent, a catalyst, and a foam stabilizer, and the polyol component has a number average molecular weight of 300 to 3000 and an average number of functional groups of 2 to. 3.
- polytetramethylene ether glycol having an average hydroxyl value of 50 to 200 mgKOH / g
- the polyisocyanate component contains a predetermined isocyanate group-terminated prepolymer and a predetermined modified MDI
- the prepolymer and the modified Polyurethane foams in which the MDI content, isocyanate index, and compression set are specified within a predetermined range are disclosed.
- the hardness of the polyurethane foam generally tends to increase.
- the sole is constructed using polyurethane foam having a high hardness, it is preferable that the sole has a relatively high hardness because the advanced running person has muscular strength. Therefore, advanced running users can run comfortably by taking advantage of the high impact resilience. However, beginners do not have enough muscle strength. Therefore, if a running beginner uses running shoes using a sole with high hardness, the impact on the knee is large, and the risk of causing a failure may increase.
- an object of the present invention is to provide a polyurethane foam that exhibits moderately low hardness and is also excellent in mechanical strength while maintaining good impact resilience, and a shoe sole member made of the polyurethane foam.
- the polyurethane foam of the present invention is a polyurethane foam made of a polyurethane raw material containing a polyol component, a polyisocyanate component, a foaming agent, a catalyst, and a foam stabilizer.
- the polyol component contains polytetramethylene ether glycol having a number average molecular weight of 600 or more and 3000 or less, and the ratio of the polytetramethylene ether glycol in the polyol component is 90% by mass or more.
- the polyisocyanate component is i) An isocyanate group-terminated prepolymer having a number average molecular weight of 500 or more and 2000 or less and an isocyanate group content of 3% by mass or more and 10% by mass or less. ii) Modified MDI having an isocyanate group content of 25% by mass or more and 33% by mass or less, Including The isocyanate group content in the polyisocyanate component is 11% by mass or more and 27% by mass or less
- shoe sole member of the present invention is characterized in that it is constructed by using the polyurethane foam of the present invention.
- the sole member made of the polyurethane foam of the present invention can be preferably used as a sole member constituting the sole of an athletic shoe, particularly an athletic shoe for beginners.
- the polyurethane foam of the present invention is composed of a polyurethane raw material containing a polyol component, a polyisocyanate component, a foaming agent, a catalyst, and a foam stabilizer.
- the polyol component contains polytetramethylene ether glycol (hereinafter, also referred to as PTMG) having a number average molecular weight of 600 or more and 3000 or less.
- PTMG polytetramethylene ether glycol
- the ratio of PTMG in the polyol component is adjusted to be 90% by mass or more.
- the polyisocyanate component contains an isocyanate group-terminated prepolymer having predetermined characteristics and a modified MDI having predetermined characteristics, so that the isocyanate group content in the polyisocyanate component is 11% by mass or more and 27% by mass or less. It will be adjusted.
- the isocyanate group-terminated prepolymer having predetermined characteristics is an isocyanate group-terminated prepolymer having a number average molecular weight of 500 or more and 2000 or less and an isocyanate group content of 3% by mass or more and 10% by mass or less.
- the modified MDI having a predetermined characteristic is a modified MDI having an isocyanate group content of 25% by mass or more and 33% by mass or less.
- the present invention can provide a polyurethane foam having both high impact resilience and low hardness, and also having excellent mechanical strength.
- the polyurethane foam of the present invention will be described in more detail below.
- the polyol component in the present invention contains 90% by mass or more of PTMG having a number average molecular weight of 600 or more and 3000 or less.
- PTMG number average molecular weight of 600 or more and 3000 or less.
- two or more types of PTMGs having different number average molecular weights may be mixed and used.
- the number average molecular weight of the mixture of PTMGs may be adjusted to be within the above range. If the number average molecular weight of PTMG is less than 600, good impact resilience may not be obtained.
- the obtained urethane foam may have a non-uniform cell size and may not easily exhibit low hardness, or may not have good mechanical strength.
- the number average molecular weight of PTMG is preferably in the range of 1000 or more and 2500 or less.
- the polyol component in the present invention contains 90% by mass or more of PTMG. Therefore, the number average molecular weight of the polyol component is greatly affected by the number average molecular weight of the contained PTMG.
- the number average molecular weight of the polyol component is adjusted to 600 or more and 3000 or less.
- the PTMG include a ring-opening polymer obtained by cation polymerization of tetrahydrofuran, an amorphous PTMG obtained by copolymerizing a dihydric alcohol with a polymerization unit of tetrahydrofuran, and the like.
- Amorphous means that it is liquid at room temperature (25 ° C.).
- Examples of the amorphous PTMG include a copolymer of tetrahydrofuran and alkyl-substituted tetrahydrofuran, a copolymer of tetrahydrofuran and branched glycol, and the like.
- Examples of the alkyl-substituted tetrahydrofuran include 3-methyltetrahydrofuran.
- branched glycol neopentyl glycol is exemplified.
- Polyurethane foam molded by using other polyol components in combination with PTMG may not have sufficient breaking strength and breaking point elongation, resulting in insufficient mechanical strength.
- the shoe sole member made of polyurethane foam having weak mechanical strength in this way is vulnerable to repeated use and may deteriorate quickly, or is exhibited by high impact resilience and low hardness for ease of running and resistance to fatigue. May not last long.
- the content of PTMG in the polyol component is 90% by mass or more. From the viewpoint of maintaining high mechanical strength more sufficiently, the content of PTMG in the polyol component is preferably 95% by mass or more, and more preferably 100% by mass.
- the polyurethane foam to be molded tends to be hard, and it is difficult to reduce the hardness.
- the isocyanate group content in the polyisocyanate component to be 11% by mass or more and 27% by mass or less, the machine exhibits high impact resilience while having an appropriately low hardness. It has made it possible to provide polyurethane foam with excellent physical strength.
- the isocyanate group content is specified in the above-mentioned preferable range, and the average cell diameter of the cells constituting the polyurethane foam described later is adjusted to the range of 100 ⁇ m or more and 150 ⁇ m or less. This can provide even better impact resilience, hardness, and mechanical strength.
- any component such as a cross-linking agent may be added to the above-mentioned polyol component.
- the cross-linking agent include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, neopentyl glycol, tetramethylene ether glycol, glycerin, pentaerythritol, trimethylolpropane, monoethanolamine, diethanolamine, isopropanolamine and amino.
- Alcohols such as ethylethanolamine, sucrose, sorbitol and glucose can be used. In particular, among these, those having three or more functionalities are preferable.
- the polyisocyanate components include i) an isocyanate group-terminated prepolymer having a number average molecular weight of 500 or more and 2000 or less and an isocyanate group content of 3% by mass or more and 10% by mass or less, and ii) an isocyanate group content of 25% by mass.
- modified MDI of 33% by mass or more.
- the modified MDI refers to a modified diphenylmethane diisocyanate.
- the ratio of the isocyanate group-terminated prepolymer to the modified MDI is not particularly limited, but is preferably 97/3 to 3/97 by mass ratio, and is 85/15 to 85/15. It is more preferably 15/85, and even more preferably 80/20 to 20/80.
- the isocyanate group-terminated prepolymer / modified MDI which is a mass ratio, is further 90/10 to 50/50 in the above range. It is preferably 85/15 to 55/45, more preferably 80/20 to 60/40.
- the modified MDI is contained in the polyisocyanate component in the same amount or less than the isocyanate group-terminated prepolymer in a predetermined range, the breaking strength and the breaking point elongation of the polyurethane foam tend to be high. Thereby, it is possible to provide a polyurethane foam more suitable for the shoe sole member to which the impact is repeatedly applied.
- Isocyanate group-terminated prepolymer As the above-mentioned i) isocyanate group-terminated prepolymer (hereinafter, also simply referred to as prepolymer), those having a number average molecular weight of 500 or more and 2000 or less and an isocyanate group content of 3% by mass or more and 10% by mass or less are used. When a prepolymer having a number average molecular weight of more than 2000 or an isocyanate group content of less than 3% by mass is used, the foamability of the produced polyurethane foam may be insufficient and the hardness may be increased.
- such a prepolymer may be inferior in the productivity of polyurethane foam because it has a high viscosity and tends to be difficult to mix with other materials.
- a prepolymer having a number average molecular weight of less than 500 or an isocyanate group content of more than 10% by mass is used, the produced polyurethane foam may foam too much and may not exhibit good impact resilience. be.
- the above-mentioned i) prepolymer is a prepolymer having an isocyanate group at the terminal, which is obtained by reacting a polyol and a polyisocyanate so that an isocyanate group (NCO group) becomes excessive.
- NCO group isocyanate group
- the excess isocyanate group means that the NCO group content in the prepolymer is in the range of 3% by mass or more and 10% by mass or less.
- polystyrene resin one kind of material selected from the following ⁇ , ⁇ , and ⁇ , or a mixed material of two or more kinds can be used.
- a polyether polyol is preferable, and a polytetramethylene ether glycol is more preferable.
- Polymer polyol for example, a polyether polyol obtained by graft-copolymerizing polyacrylonitrile, acrylonitrile-styrene copolymer, etc.
- ⁇ ) Of the alcohols listed above as examples of cross-linking agents bifunctional ones
- polyisocyanate examples include diphenylmethane diisocyanate (4,4'-MDI), polypeptide MDI (crude MDI), 2,4-tolylene diisocyanate (2,4-TDI), and 2,6-tolylene diisocyanate (2,6).
- aromatic isocyanates such as -TDI
- aliphatic diisocyanates such as tetramethylene diisocyanate and hexamethylene diisocyanate (HDI)
- alicyclic diisocyanates such as isophorone diisocyanate, hydrogenated TDI and hydrogenated MDI.
- 4,4'-MDI is preferable.
- the i) prepolymer those obtained by reacting polytetramethylene ether glycol as a polyol and 4,4′-MDI as a polyisocyanate are preferable.
- the prepolymer formed by reacting this polytetramethylene ether glycol with 4,4'-MDI has high crystallinity of the polytetramethylene ether glycol moiety. Therefore, by using such a prepolymer, urethane foam having high impact resilience can be easily obtained, and ii) modified MDI used in combination as a polyisocyanate component has good compatibility with the prepolymer.
- an isocyanate component containing a prepolymer and a modified MDI obtained by reacting polytetramethylene ether glycol with 4,4'-MDI is reacted with polytetramethylene ether glycol which is a polyol component.
- the mixing property is also good. Therefore, the molecular structure of the member tends to be uniform, and the quality of the obtained urethane foam can be stabilized.
- Modified MDI In the present invention, the modified MDI having an isocyanate group content of 25% by mass or more and 33% by mass or less is used. Within this range, the modified MDI can be treated as a liquid at room temperature.
- Prepolymers have a high molecular weight and therefore a high viscosity. However, by mixing the i) prepolymer and ii) modified MDI which is liquid at room temperature, the viscosity of the polyisocyanate component can be appropriately lowered. Therefore, the mixability of the polyisocyanate component and the polyol component can be improved. If the NCO group content in the modified MDI is less than 25% by mass, the foamability of the produced polyurethane foam may be insufficient.
- the amount of the modified MDI having an NCO group content of more than 33% by mass in the polyisocyanate component is reduced from the viewpoint of adjusting the NCO group content.
- the amount of the modified MDI is reduced in this way, it becomes difficult to adjust the polyisocyanate component containing the prepolymer having a large molecular weight to an appropriately low viscosity, and the mixing property when the polyisocyanate component and the polyol component are reacted with each other becomes difficult. May get worse.
- modified MDI that is liquid at room temperature
- a polymeric (crude MDI) urethane modified, urea modified, allophanate modified, biuret modified, carbodiimide modified, uretonimine modified, and uretdione.
- Modified products, isocyanurate modified products and the like can be mentioned.
- a polypeptide (crude MDI) and / or a modified carbodiimide is preferably selected as the modified MDI because the molecular (crosslinked) structure after the reaction with the polyol component is excellent.
- the polyisocyanate component containing the above-mentioned i) prepolymer and ii) modified MDI has an isocyanate group content of 11% by mass or more and 27% by mass or less.
- the isocyanate group content is less than 11% by mass, the bubble diameter of the obtained polyurethane foam becomes small and the hardness becomes high.
- the isocyanate group content exceeds 27% by mass, good impact resilience is not exhibited in the obtained polyurethane foam.
- the isocyanate group content is preferably 12% by mass or more and 25% by mass or less, more preferably 12% by mass or more and 21% by mass or less, and further preferably 12% by mass or more and 17% by mass or less. It is particularly preferably 12% by mass or more and 15% by mass or less.
- the polyisocyanate component in the present invention may further contain an isocyanate (third isocyanate) in addition to the above-mentioned i) prepolymer and ii) modified MDI.
- Foaming agent Water can be used as the foaming agent.
- the amount added is preferably 0.5 parts by mass or more and 3 parts by mass or less with respect to 100 parts by mass of the above-mentioned polyol component.
- Examples of the water include ion-exchanged water and distilled water, but ion-exchanged water is preferable. If the amount of the foaming agent added is less than 0.5 parts by mass, foaming may be insufficient. On the other hand, if the amount of the foaming agent added exceeds 3 parts by mass, foaming may proceed too much and the resulting polyurethane foam cell may become rough. In this case, problems such as the inside of the obtained polyurethane foam being easily cracked occur, and as a result, the foam state tends to be inferior and the resilience tends to be inferior.
- the catalyst may be any catalyst conventionally used in the production of polyurethane foam, and examples thereof include amine-based catalysts such as triethylenediamine and diethanolamine, and metal catalysts such as bismuth catalysts, but the catalysts are not particularly limited. No.
- the amount to be added is preferably 0.1 part by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the above-mentioned polyol component.
- urethane is formed by reacting the above-mentioned polyol component containing 90% by mass or more of PTMG with the above-mentioned polyisocyanate component containing an isocyanate group-terminated prepolymer and a modified MDI, and foaming and curing it in a mold.
- a polyurethane foam is formed by causing a reaction and foaming.
- a defoaming agent is contained in order to improve the cell size of the polyurethane foam obtained by such urethane foaming.
- the foam stabilizer is not particularly limited as long as it can be used in the production of urethane foam.
- the viscosity of the defoaming agent is preferably 300 mPa ⁇ s (25 ° C.) or more and 2000 mPa ⁇ s (25 ° C.) or less, and 800 mPa ⁇ s (25 ° C.) or more and 1000 mPa.
- -It is more preferably s (25 ° C.) or less.
- a silicone-based compound defoaming agent having such a suitable viscosity range is particularly preferable.
- the viscosity of the defoaming agent is less than 300 mPa ⁇ s (25 ° C.), the defoaming action is weak, the cells become coarse, and high impact resilience may not be obtained.
- the viscosity exceeds 2000 mPa ⁇ s (25 ° C.)
- the cell size of the obtained foam it is difficult for the cell size of the obtained foam to be uniform, and there is a risk that the physical properties will change locally.
- the silicone compound When a silicone compound having a suitable viscosity range is used as a defoaming agent, the silicone compound is added in a range of 0.5 parts by mass or more and 9 parts by mass or less with respect to 100 parts by mass of the above-mentioned polyol component. It is preferable, and it is more preferable to add it in the range of 0.5 parts by mass or more and 5 parts by mass or less. If it is less than 0.5 parts by mass, the foam regulating action is weak, the cell becomes coarse, and there is a possibility that high impact resilience cannot be obtained. On the other hand, if it exceeds 9 parts by mass, the impact resilience of the obtained polyurethane foam may be inferior.
- the raw material of the polyurethane foam of the present invention includes a polyol component, an isocyanate component, a foaming agent, a catalyst, a foam stabilizer, as well as a plasticizer, a filler, an antioxidant, a defoaming agent, and a compatibilizer, if necessary.
- a polyol component an isocyanate component
- a foaming agent a catalyst
- a foam stabilizer as well as a plasticizer
- a filler an antioxidant
- a defoaming agent e.g., a compatibilizer, if necessary.
- Colorants, stabilizers, UV absorbers and other additives commonly used in the production of polyurethane foam may be used as long as the effects of the present invention can be obtained.
- the polyurethane foam of the present invention preferably has an average cell diameter of 100 ⁇ m or more and 150 ⁇ m or less in the cells constituting the foam.
- the average cell diameter is less than 100 ⁇ m, the mechanical properties are impaired, and if the average cell diameter exceeds 150 ⁇ m, high impact resilience is unlikely to be exhibited.
- the average bubble diameter is more preferably more than 100 ⁇ m and 150 ⁇ m or less, further preferably more than 100 ⁇ m and 135 ⁇ m or less, further preferably more than 100 ⁇ m and 130 ⁇ m or less, and more than 100 ⁇ m. It is particularly preferably 120 ⁇ m or less.
- the average bubble diameter can be specified by the following method. First, the polyurethane foam is cut at a randomly selected position to expose the cut surface. On the cut surface, a region having a predetermined dimension is randomly selected as a selected region.
- the region having a predetermined dimension is, for example, a rectangular region having a length of 4 mm and a width of 3 mm.
- the number of cells (bubbles) existing in the selected region (the number of all cells) and the diameter of each cell (diameter of each bubble) are measured using a microscope. The arithmetic mean value of each cell diameter measured as described above is obtained, and this is used as the average cell diameter in the present invention.
- the method for adjusting the average cell size of the polyurethane foam is not particularly limited, but for example, a polyurethane foam showing an average cell size in a desired range can be formed by adjusting the amount of the catalyst or foaming agent added.
- the hardness of the polyurethane foam of the present invention is preferably less than 50, more preferably less than 47, from the viewpoint of exhibiting appropriate flexibility.
- a sole member made of polyurethane foam having a hardness of less than 50 is suitable for a sole member such as an athletic shoe for beginners. By using such a shoe sole member, the burden on the knee or the like at the time of touchdown can be reduced. From the viewpoint of maintaining good shock absorption, the hardness is preferably 35 or more, more preferably 40 or more. Polyurethane foam with too low hardness cannot absorb the impact and may cause a risk of failure when used as a shoe sole member. Even when the polyurethane foam of the present invention is used as a mat member, the hardness is preferably in the above range.
- the hardness of the polyurethane foam of the present invention is measured in accordance with JIS K 7312 using an Asker rubber hardness tester C type under a temperature condition of 23 ⁇ 2 ° C.
- the apparent density of the polyurethane foam of the present invention is not particularly limited, but is preferably in the range of 0.30 g / cm 3 or more and 0.35 g / cm 3 or less. Further, in the present invention, it is more preferable that the apparent density is in the above range and the average cell diameter is 100 ⁇ m or more and 150 ⁇ m or less.
- the apparent density of the polyurethane foam of the present invention is measured according to JIS K 7222.
- the elastic modulus of the polyurethane foam of the present invention is preferably 50% or more, preferably 55% or more, from the viewpoint of good kicking and smooth foot movement when the polyurethane foam is used for a shoe sole or a mat. Is more preferable, and 60% or more is further preferable.
- the upper limit of the rebound resilience is not particularly limited, but from the viewpoint of easily achieving a good balance with hardness and mechanical properties, it is preferably less than 80%, and preferably less than 75%. More preferably, it is less than 70%.
- the elastic modulus of the polyurethane foam of the present invention is measured in accordance with JIS K 6255.
- the polyurethane foam of the present invention has a hardness of less than 50 and a rebound resilience of 50% or more. With such a polyurethane foam, it is possible to provide an excellent sole that is easy to run even for a beginner, absorbs the impact at the time of touchdown well, and reduces the burden on the knee and the like.
- the breaking strength of the polyurethane foam of the present invention is preferably 1.0 MPa or more, more preferably 1.5 MPa or more, from the viewpoint of improving the durability of the article made of the polyurethane foam. It is preferably 2.0 MPa or more, and more preferably 2.0 MPa or more. In particular, when polyurethane foam having a breaking strength of 1.5 MPa or more is used as a sole member of exercise shoes, even if the sole is used in a harsh usage environment such as being repeatedly impacted or curved. Deterioration in a short period of time can be prevented.
- the method for measuring the breaking strength of the polyurethane foam of the present invention is measured in accordance with JIS K6251.
- Break point elongation The elongation at break point of the polyurethane foam of the present invention is not particularly limited, but is preferably 300% or more, preferably 350% or more, when used for applications where repeated bending is expected, such as soles. More preferably, it is more preferably 400% or more.
- the method for measuring the elongation at break of the polyurethane foam of the present invention is measured in accordance with JIS K6251.
- the maximum impact load of the polyurethane foam of the present invention is such that the maximum impact load measured as follows is 1.5 kN or less from the viewpoint of improving the impact absorption of the article made of the polyurethane foam. It is preferable to have.
- the maximum impact load is measured by a product manufactured by Instron when a bullet-shaped weight w (made of iron, 5.1 kg) is collided from a height of 50 mm in a drop impact test of a test piece cut to a thickness of 12.5 mm. It can be done using the name "dynatup GRC8200".
- the flexibility of the polyurethane foam of the present invention is not particularly limited, but when it is used for applications where repeated bending is expected, such as soles, the number of bendings until cracks occur in the following test is 10,000. It is preferably more than once.
- a test piece prepared by adhering a test piece cut to a thickness of 6 mm to a texon board (trade name "# 347" manufactured by Bontex) having a thickness of 2 mm was formed at an angle of 90 ° at a speed of 100 times / minute. It is done by bending.
- the polyurethane foam of the present invention described above is used for various purposes. Above all, the polyurethane foam of the present invention is preferably used as a shoe sole member because it exhibits good impact resilience, its hardness is suppressed to a low level, and its mechanical properties are also excellent.
- the sole made of the polyurethane foam of the present invention supports the user's kicking, facilitates leg movement, and exhibits good flexibility to provide good comfort. Not only that, the occurrence of failure can be reduced. Therefore, the shoes provided with the soles are excellent as various exercise shoes, and are particularly suitable for beginners and elderly people of exercise.
- the sole member of the present invention may be a constituent member that constitutes a part of the sole, or may be a constituent member that constitutes the entire sole.
- the sole may be a sole portion of the shoe and may have an integral structure, or may be composed of a plurality of parts such as an insole and / or a midsole and an outsole.
- the entire one or more parts constituting the sole such as the insole, the midsole, and the outsole may be composed of the sole member of the present invention, or any part of one part may be made of the sole member of the present invention. It can also be configured.
- the polyurethane foam of the present invention can be suitably used as a constituent member of a mat. That is, the polyurethane foam of the present invention exhibits excellent impact resilience, is suppressed to a low hardness, and is excellent in mechanical properties, and thus exhibits an excellent effect even in a mat, particularly a floor mat.
- a mat made of the polyurethane foam of the present invention is laid on the floor and the mat is used for a long time such as working, walking, or standing, the accumulation of fatigue is reduced.
- the polyol component, catalyst, defoaming agent, and foaming agent are mixed to prepare solution A, and the solution A and solution B (polyisocyanate component) are mixed at the compounding ratio shown in Table 1.
- the mixture was poured into a mold and reacted under the condition of a mold temperature of 40 ° C., and then demolded to obtain a polyurethane foam.
- the unit of the numerical value indicating the composition of the materials in Table 1 is a mass part.
- the polyurethane foams obtained in each Example and each Comparative Example were appropriately cut to prepare test pieces, and the measurements shown below were carried out.
- the measurement results are shown in Table 1.
- ⁇ Average cell diameter ( ⁇ m)> The resulting polyurethane foam was cut at randomly selected positions to expose the cut surface. A rectangular region of 4 mm ⁇ 3 mm was randomly selected as the selected region on the cut surface. The number of cells (bubbles) existing in the selected region (the number of all cells) and the diameter of each cell (diameter of each bubble) were measured using a microscope. The arithmetic mean value of each cell diameter measured as described above was calculated and used as the average cell diameter.
- the polyurethane foam of the present invention has excellent impact resilience, is maintained at a low hardness, and is also excellent in mechanical properties such as breaking strength and breaking point elongation.
- the polyurethane foam of the present invention is suitable as a shoe sole member because it has excellent shock absorption and flexibility.
- the polyurethane foam of the present invention requires shock absorption, impact resilience, moderate flexibility, good mechanical strength, etc. for mat members, helmet interiors, protectors, vehicle cushioning materials, flooring materials, etc. Widely used in applications that are used.
- a polyurethane foam made of a polyurethane raw material containing a polyol component, a polyisocyanate component, a foaming agent, a catalyst, and a foam stabilizer.
- the polyol component contains polytetramethylene ether glycol having a number average molecular weight of 600 or more and 3000 or less, and the ratio of the polytetramethylene ether glycol in the polyol component is 90% by mass or more.
- the polyisocyanate component is i) An isocyanate group-terminated prepolymer having a number average molecular weight of 500 or more and 2000 or less and an isocyanate group content of 3% by mass or more and 10% by mass or less.
- Modified MDI having an isocyanate group content of 25% by mass or more and 33% by mass or less, Including A polyurethane foam having an isocyanate group content of 11% by mass or more and 27% by mass or less in the polyisocyanate component.
- the hardness of the polyurethane foam measured using the Asker rubber hardness tester C type in accordance with JIS K 7312 is less than 50.
- the polyurethane foam according to any one of (1) to (3) above, wherein the rebound resilience of the polyurethane foam measured in accordance with JIS K 6255 is 60% or more.
- a shoe sole member comprising the polyurethane foam according to any one of (1) to (6) above.
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Abstract
The present invention provides: a polyurethane foam which has an adequately low hardness and excellent mechanical strength, while maintaining good rebound resilience; and a shoe sole member which is obtained using this polyurethane foam. This polyurethane foam is configured from a polyurethane starting material that contains a polyol component, a polyisocyanate component, a foaming agent, a catalyst and a foam stabilizer, while being configured such that: the polyol component contains a polytetramethylene ether glycol that has a number average molecular weight of from 600 to 3,000; the proportion of the polytetramethylene ether glycol in the polyol component is 90% by mass or more; the polyisocyanate component contains (i) an isocyanate group-terminated prepolymer that has a number average molecular weight of from 500 to 2,000, an average number of functional groups of 2 and an isocyanate group content of from 3% by mass to 10% by mass and (ii) a modified MDI that has an isocyanate group content of from 25% by mass to 33% by mass; and the isocyanate group content in the polyisocyanate component is from 11% by mass to 27% by mass. A shoe sole member is configured using this polyurethane foam.
Description
本発明は、ポリウレタンフォームおよび靴底部材に関する。
The present invention relates to polyurethane foam and shoe sole members.
従来から、種々の用途における構成部材としてポリウレタンフォームやエチレン-酢酸ビニル共重合体フォームなどの発泡体が使用されている。たとえばポリウレタンフォームからなる靴底部材は、衝撃吸収性に優れており、一般使用のシューズはもちろん、ウォーキングシューズ、ランニングシューズ、トレッキングシューズなどの運動用シューズの靴底の構成部材としても使用されている。また、上記ポリウレタンフォームは、靴底部材としての用途に限らず、作業場における床敷きのマットや精密機械を設置する際の下敷き用マットなどのマット部材としても使用することができる。
Conventionally, foams such as polyurethane foam and ethylene-vinyl acetate copolymer foam have been used as constituent members in various applications. For example, a sole member made of polyurethane foam has excellent shock absorption, and is used as a component of the sole of athletic shoes such as walking shoes, running shoes, and trekking shoes as well as general-purpose shoes. .. Further, the polyurethane foam is not limited to the use as a shoe sole member, but can also be used as a mat member such as a floor mat in a workplace or an underlay mat when installing a precision machine.
運動用シューズの靴底等に用いられる場合、ポリウレタンフォームは、衝撃吸収性に加え、良好な反発弾性が求められる。反発弾性に優れる靴底を用いた運動用シューズは、蹴り出しがサポートされ足運びが容易となるので、長時間のランニングやウォーキングにおいて、疲労の蓄積を軽減する効果が期待される。なお、本発明に関し、靴底とは、靴の底部分を指し、靴底部材とは、靴底を構成する構成部材(材料)を指す。
When used for the soles of exercise shoes, polyurethane foam is required to have good impact resilience in addition to shock absorption. Exercise shoes that use soles with excellent impact resilience are expected to have the effect of reducing the accumulation of fatigue during long-term running and walking because kicking is supported and foot movement is easy. In the present invention, the sole refers to the sole portion of the shoe, and the sole member refers to a constituent member (material) constituting the sole.
たとえば、特許文献1に記載の発明は、高反発弾性率を幅広い温度帯域で有し、機械的強度や生産性に優れるポリウレタンインテグラルスキンフォームの提供を課題としている。具体的には特許文献1には、有機ポリイソシアネート組成物(A)、ポリオール成分(B)、触媒(C)、発泡剤(D)を原料とし、有機ポリイソシアネート組成物(A)が、ジフェニルメタンジイソシアネートと数平均分子量1000~3500のポリテトラメチレンエーテルグリコールとのウレタン変性体であり、イソシアネート基含有率7~25質量%の有機ポリイソシアネート(a1)であるポリウレタンインテグラルスキンフォームの発明が開示されている。
For example, the invention described in Patent Document 1 has an object of providing a polyurethane integral skin foam having a high rebound resilience in a wide temperature range and having excellent mechanical strength and productivity. Specifically, in Patent Document 1, the organic polyisocyanate composition (A), the polyol component (B), the catalyst (C), and the foaming agent (D) are used as raw materials, and the organic polyisocyanate composition (A) is diphenylmethane. The invention of polyurethane integral skin foam, which is a urethane modified product of diisocyanate and polytetramethylene ether glycol having a number average molecular weight of 1000 to 3500 and is an organic polyisocyanate (a1) having an isocyanate group content of 7 to 25% by mass, is disclosed. ing.
また特許文献2に記載の発明は、耐久性があって、衝撃吸収性や反発性を同時に有し、さらに耐屈曲性をも備えたポリウレタンフォームの提供を課題としている。具体的には特許文献2には、ポリオール成分、ポリイソシアネート成分、発泡剤、触媒、整泡剤を含むポリウレタン原料からなり、ポリオール成分が、数平均分子量が300~3000、平均官能基数が2~3、及び平均水酸基価が50~200mgKOH/gのポリテトラメチレンエーテルグリコールであり、上記ポリイソシアネート成分が、所定のイソシアネート基末端プレポリマーと、所定の変性MDIとを含み、当該プレポリマーと当該変性MDIの含有比率、イソシアネートインデックス、および圧縮永久歪が所定範囲に特定されたポリウレタンフォームが開示されている。
Further, the invention described in Patent Document 2 has an object of providing a polyurethane foam which is durable, has shock absorption and resilience at the same time, and also has bending resistance. Specifically, Patent Document 2 describes a polyurethane raw material containing a polyol component, a polyisocyanate component, a foaming agent, a catalyst, and a foam stabilizer, and the polyol component has a number average molecular weight of 300 to 3000 and an average number of functional groups of 2 to. 3. And polytetramethylene ether glycol having an average hydroxyl value of 50 to 200 mgKOH / g, and the polyisocyanate component contains a predetermined isocyanate group-terminated prepolymer and a predetermined modified MDI, and the prepolymer and the modified Polyurethane foams in which the MDI content, isocyanate index, and compression set are specified within a predetermined range are disclosed.
ところでポリウレタンフォームの反発弾性を向上させた場合、一般的には、当該ポリウレタンフォームの硬度も上がる傾向にある。硬度が高いポリウレタンフォームを用いて靴底を構成した場合、ランニング上級者は、筋力がついているため、靴底の硬度が比較的高いことが好適に働く。そのため、ランニング上級者は、高い反発弾性を活かして快適に走ることが可能である。
しかしながら、ランニング初心者は、十分な筋力がついていない。そのため、ランニング初心者が、硬度が高い靴底を用いたランニングシューズを使用すると、膝にかかる衝撃が大きく、故障を引き起こすリスクが高まる可能性がある。 By the way, when the impact resilience of the polyurethane foam is improved, the hardness of the polyurethane foam generally tends to increase. When the sole is constructed using polyurethane foam having a high hardness, it is preferable that the sole has a relatively high hardness because the advanced running person has muscular strength. Therefore, advanced running users can run comfortably by taking advantage of the high impact resilience.
However, beginners do not have enough muscle strength. Therefore, if a running beginner uses running shoes using a sole with high hardness, the impact on the knee is large, and the risk of causing a failure may increase.
しかしながら、ランニング初心者は、十分な筋力がついていない。そのため、ランニング初心者が、硬度が高い靴底を用いたランニングシューズを使用すると、膝にかかる衝撃が大きく、故障を引き起こすリスクが高まる可能性がある。 By the way, when the impact resilience of the polyurethane foam is improved, the hardness of the polyurethane foam generally tends to increase. When the sole is constructed using polyurethane foam having a high hardness, it is preferable that the sole has a relatively high hardness because the advanced running person has muscular strength. Therefore, advanced running users can run comfortably by taking advantage of the high impact resilience.
However, beginners do not have enough muscle strength. Therefore, if a running beginner uses running shoes using a sole with high hardness, the impact on the knee is large, and the risk of causing a failure may increase.
また従来、反発弾性を上げつつ、硬度を適度な範囲に抑えるポリウレタンフォームの提供の試みもなされてはいる。しかし、この場合、高い機械的強度が維持され難いという問題があった。運動用シューズの靴底は繰り返しの使用に耐えうる十分な機械的強度が求められる。そのため、反発弾性が高く、かつ硬度が低くても、機械的強度が不足するポリウレタンフォームは、靴底部材として問題であった。
Also, conventionally, attempts have been made to provide polyurethane foam that suppresses hardness within an appropriate range while increasing impact resilience. However, in this case, there is a problem that it is difficult to maintain high mechanical strength. The soles of athletic shoes are required to have sufficient mechanical strength to withstand repeated use. Therefore, polyurethane foam, which has high impact resilience and low hardness but lacks mechanical strength, has been a problem as a shoe sole member.
なお、上述する反発弾性、硬度、および機械的強度のバランスの保たれたポリウレタンフォームの提供は、靴底部材としてだけでなく、たとえばマット部材としても期待される。上述する観点から、特許文献1、2に開示されるポリウレタンフォームはいずれも改善の余地がある。
It should be noted that the provision of the polyurethane foam in which the above-mentioned impact resilience, hardness, and mechanical strength are balanced is expected not only as a shoe sole member but also as a mat member, for example. From the above viewpoint, all of the polyurethane foams disclosed in Patent Documents 1 and 2 have room for improvement.
本発明は上述のような課題に鑑みてなされたものである。即ち、本発明は、良好な反発弾性を維持しつつ、適度に低い硬度を示し、かつ機械的強度にも優れるポリウレタンフォーム、および当該ポリウレタンフォームからなる靴底部材を提供することを課題とする。
The present invention has been made in view of the above-mentioned problems. That is, an object of the present invention is to provide a polyurethane foam that exhibits moderately low hardness and is also excellent in mechanical strength while maintaining good impact resilience, and a shoe sole member made of the polyurethane foam.
本発明のポリウレタンフォームは、ポリオール成分、ポリイソシアネート成分、発泡剤、触媒、整泡剤を含むポリウレタン原料からなるポリウレタンフォームであって、
上記ポリオール成分は、数平均分子量が600以上3000以下であるポリテトラメチレンエーテルグリコールを含み、上記ポリオール成分中の上記ポリテトラメチレンエーテルグリコールの比率が90質量%以上であり、
上記ポリイソシアネート成分は、
i)数平均分子量が500以上2000以下であり、イソシアネート基含有率が3質量%以上10質量%以下のイソシアネート基末端プレポリマーと、
ii)イソシアネート基含有率が25質量%以上33質量%以下の変性MDIと、
を含み、
上記ポリイソシアネート成分中のイソシアネート基含有率が11質量%以上27質量%以下であることを特徴とする。 The polyurethane foam of the present invention is a polyurethane foam made of a polyurethane raw material containing a polyol component, a polyisocyanate component, a foaming agent, a catalyst, and a foam stabilizer.
The polyol component contains polytetramethylene ether glycol having a number average molecular weight of 600 or more and 3000 or less, and the ratio of the polytetramethylene ether glycol in the polyol component is 90% by mass or more.
The polyisocyanate component is
i) An isocyanate group-terminated prepolymer having a number average molecular weight of 500 or more and 2000 or less and an isocyanate group content of 3% by mass or more and 10% by mass or less.
ii) Modified MDI having an isocyanate group content of 25% by mass or more and 33% by mass or less,
Including
The isocyanate group content in the polyisocyanate component is 11% by mass or more and 27% by mass or less.
上記ポリオール成分は、数平均分子量が600以上3000以下であるポリテトラメチレンエーテルグリコールを含み、上記ポリオール成分中の上記ポリテトラメチレンエーテルグリコールの比率が90質量%以上であり、
上記ポリイソシアネート成分は、
i)数平均分子量が500以上2000以下であり、イソシアネート基含有率が3質量%以上10質量%以下のイソシアネート基末端プレポリマーと、
ii)イソシアネート基含有率が25質量%以上33質量%以下の変性MDIと、
を含み、
上記ポリイソシアネート成分中のイソシアネート基含有率が11質量%以上27質量%以下であることを特徴とする。 The polyurethane foam of the present invention is a polyurethane foam made of a polyurethane raw material containing a polyol component, a polyisocyanate component, a foaming agent, a catalyst, and a foam stabilizer.
The polyol component contains polytetramethylene ether glycol having a number average molecular weight of 600 or more and 3000 or less, and the ratio of the polytetramethylene ether glycol in the polyol component is 90% by mass or more.
The polyisocyanate component is
i) An isocyanate group-terminated prepolymer having a number average molecular weight of 500 or more and 2000 or less and an isocyanate group content of 3% by mass or more and 10% by mass or less.
ii) Modified MDI having an isocyanate group content of 25% by mass or more and 33% by mass or less,
Including
The isocyanate group content in the polyisocyanate component is 11% by mass or more and 27% by mass or less.
また本発明の靴底部材は、本発明のポリウレタンフォームを用いて構成されることを特徴とする。
Further, the shoe sole member of the present invention is characterized in that it is constructed by using the polyurethane foam of the present invention.
上記構成を備える本発明によれば、良好な反発弾性を維持しつつ、適度に低い硬度を示し、かつ機械的強度にも優れるポリウレタンフォームの提供が可能である。
そのため、本発明のポリウレタンフォームから構成される靴底部材は、運動用シューズ、特には、初心者用の運動用シューズの靴底を構成する靴底部材として好ましく使用することができる。 According to the present invention having the above structure, it is possible to provide a polyurethane foam which exhibits moderately low hardness and is also excellent in mechanical strength while maintaining good impact resilience.
Therefore, the sole member made of the polyurethane foam of the present invention can be preferably used as a sole member constituting the sole of an athletic shoe, particularly an athletic shoe for beginners.
そのため、本発明のポリウレタンフォームから構成される靴底部材は、運動用シューズ、特には、初心者用の運動用シューズの靴底を構成する靴底部材として好ましく使用することができる。 According to the present invention having the above structure, it is possible to provide a polyurethane foam which exhibits moderately low hardness and is also excellent in mechanical strength while maintaining good impact resilience.
Therefore, the sole member made of the polyurethane foam of the present invention can be preferably used as a sole member constituting the sole of an athletic shoe, particularly an athletic shoe for beginners.
[ポリウレタンフォーム]
本発明のポリウレタンフォームは、ポリオール成分、ポリイソシアネート成分、発泡剤、触媒、整泡剤を含むポリウレタン原料を用いて構成される。
上記ポリオール成分は、数平均分子量600以上3000以下のポリテトラメチレンエーテルグリコール(以下、PTMGともいう)を含む。本発明において、ポリオール成分中のPTMGの比率は、90質量%以上となるよう調整される。
上記ポリイソシアネート成分は、所定の特徴を有するイソシアネート基末端プレポリマーと、所定の特徴を有する変性MDIとを含み、ポリイソシアネート成分中のイソシアネート基含有率が11質量%以上27質量%以下となるよう調整される。
ここで、所定の特徴を有するイソシアネート基末端プレポリマーとは、数平均分子量が500以上2000以下であり、イソシアネート基含有率が3質量%以上10質量%以下のイソシアネート基末端プレポリマーである。
また、所定の特徴を有する変性MDIとは、イソシアネート基含有率が25質量%以上33質量%以下の変性MDIである。 [Polyurethane foam]
The polyurethane foam of the present invention is composed of a polyurethane raw material containing a polyol component, a polyisocyanate component, a foaming agent, a catalyst, and a foam stabilizer.
The polyol component contains polytetramethylene ether glycol (hereinafter, also referred to as PTMG) having a number average molecular weight of 600 or more and 3000 or less. In the present invention, the ratio of PTMG in the polyol component is adjusted to be 90% by mass or more.
The polyisocyanate component contains an isocyanate group-terminated prepolymer having predetermined characteristics and a modified MDI having predetermined characteristics, so that the isocyanate group content in the polyisocyanate component is 11% by mass or more and 27% by mass or less. It will be adjusted.
Here, the isocyanate group-terminated prepolymer having predetermined characteristics is an isocyanate group-terminated prepolymer having a number average molecular weight of 500 or more and 2000 or less and an isocyanate group content of 3% by mass or more and 10% by mass or less.
The modified MDI having a predetermined characteristic is a modified MDI having an isocyanate group content of 25% by mass or more and 33% by mass or less.
本発明のポリウレタンフォームは、ポリオール成分、ポリイソシアネート成分、発泡剤、触媒、整泡剤を含むポリウレタン原料を用いて構成される。
上記ポリオール成分は、数平均分子量600以上3000以下のポリテトラメチレンエーテルグリコール(以下、PTMGともいう)を含む。本発明において、ポリオール成分中のPTMGの比率は、90質量%以上となるよう調整される。
上記ポリイソシアネート成分は、所定の特徴を有するイソシアネート基末端プレポリマーと、所定の特徴を有する変性MDIとを含み、ポリイソシアネート成分中のイソシアネート基含有率が11質量%以上27質量%以下となるよう調整される。
ここで、所定の特徴を有するイソシアネート基末端プレポリマーとは、数平均分子量が500以上2000以下であり、イソシアネート基含有率が3質量%以上10質量%以下のイソシアネート基末端プレポリマーである。
また、所定の特徴を有する変性MDIとは、イソシアネート基含有率が25質量%以上33質量%以下の変性MDIである。 [Polyurethane foam]
The polyurethane foam of the present invention is composed of a polyurethane raw material containing a polyol component, a polyisocyanate component, a foaming agent, a catalyst, and a foam stabilizer.
The polyol component contains polytetramethylene ether glycol (hereinafter, also referred to as PTMG) having a number average molecular weight of 600 or more and 3000 or less. In the present invention, the ratio of PTMG in the polyol component is adjusted to be 90% by mass or more.
The polyisocyanate component contains an isocyanate group-terminated prepolymer having predetermined characteristics and a modified MDI having predetermined characteristics, so that the isocyanate group content in the polyisocyanate component is 11% by mass or more and 27% by mass or less. It will be adjusted.
Here, the isocyanate group-terminated prepolymer having predetermined characteristics is an isocyanate group-terminated prepolymer having a number average molecular weight of 500 or more and 2000 or less and an isocyanate group content of 3% by mass or more and 10% by mass or less.
The modified MDI having a predetermined characteristic is a modified MDI having an isocyanate group content of 25% by mass or more and 33% by mass or less.
上述する構成を満たすことで、本発明は、高い反発弾性と、低い硬度とを併せ持ち、かつ機械的強度にも優れたポリウレタンフォームを提供することが可能である。以下に、本発明のポリウレタンフォームについてさらに詳細に説明する。
By satisfying the above-mentioned configuration, the present invention can provide a polyurethane foam having both high impact resilience and low hardness, and also having excellent mechanical strength. The polyurethane foam of the present invention will be described in more detail below.
(ポリオール成分)
本発明におけるポリオール成分は、数平均分子量が600以上3000以下であるPTMGを90質量%以上含む。本発明では、数平均分子量が異なる2種以上のPTMGを混合して用いてもよい。2種以上のPTMGを混合して用いた場合には、PTMGの混合物の数平均分子量が上記範囲となるよう調整されればよい。
PTMGの数平均分子量が600未満の場合には、良好な反発弾性が得られない虞がある。一方、PTMGの数平均分子量が3000を超える場合には、得られるウレタンフォームは、セルサイズが不均一になり低い硬度を示し難く、あるいは、良好な機械的強度が得られない虞がある。得られるポリウレタンフォームの硬度が低く良好な柔軟性を示すとともに良好な反発弾性を示しやすいという観点からは、PTMGの数平均分子量は、1000以上2500以下の範囲であることが好ましい。
本発明におけるポリオール成分は90質量%以上のPTMGを含有する。そのため、当該ポリオール成分の数平均分子量は、含有するPTMGの数平均分子量に大きく影響を受ける。本発明において、ポリオール成分の数平均分子量が、600以上3000以下に調整されることが好ましい。
なお、PTMGとしては、例えば、テトラヒドロフランのカチオン重合により得られる開環重合物や、テトラヒドロフランの重合単位に2価アルコールを共重合した非晶性PTMGなどが挙げられる。なお、非晶性とは、常温(25℃)において液状であることを示す。
非晶性PTMGは、テトラヒドロフランとアルキル置換テトラヒドロフランとの共重合体や、テトラヒドロフランと分岐状グリコールとの共重合体などが挙げられる。上記アルキル置換テトラヒドロフランとしては、例えば、3-メチルテトラヒドロフランが例示される。また上記分岐状グリコールとしては、ネオペンチルグリコールが例示される。 (Polyol component)
The polyol component in the present invention contains 90% by mass or more of PTMG having a number average molecular weight of 600 or more and 3000 or less. In the present invention, two or more types of PTMGs having different number average molecular weights may be mixed and used. When two or more kinds of PTMGs are mixed and used, the number average molecular weight of the mixture of PTMGs may be adjusted to be within the above range.
If the number average molecular weight of PTMG is less than 600, good impact resilience may not be obtained. On the other hand, when the number average molecular weight of PTMG exceeds 3000, the obtained urethane foam may have a non-uniform cell size and may not easily exhibit low hardness, or may not have good mechanical strength. From the viewpoint that the obtained polyurethane foam has low hardness and exhibits good flexibility and easily exhibits good impact resilience, the number average molecular weight of PTMG is preferably in the range of 1000 or more and 2500 or less.
The polyol component in the present invention contains 90% by mass or more of PTMG. Therefore, the number average molecular weight of the polyol component is greatly affected by the number average molecular weight of the contained PTMG. In the present invention, it is preferable that the number average molecular weight of the polyol component is adjusted to 600 or more and 3000 or less.
Examples of the PTMG include a ring-opening polymer obtained by cation polymerization of tetrahydrofuran, an amorphous PTMG obtained by copolymerizing a dihydric alcohol with a polymerization unit of tetrahydrofuran, and the like. Amorphous means that it is liquid at room temperature (25 ° C.).
Examples of the amorphous PTMG include a copolymer of tetrahydrofuran and alkyl-substituted tetrahydrofuran, a copolymer of tetrahydrofuran and branched glycol, and the like. Examples of the alkyl-substituted tetrahydrofuran include 3-methyltetrahydrofuran. Further, as the branched glycol, neopentyl glycol is exemplified.
本発明におけるポリオール成分は、数平均分子量が600以上3000以下であるPTMGを90質量%以上含む。本発明では、数平均分子量が異なる2種以上のPTMGを混合して用いてもよい。2種以上のPTMGを混合して用いた場合には、PTMGの混合物の数平均分子量が上記範囲となるよう調整されればよい。
PTMGの数平均分子量が600未満の場合には、良好な反発弾性が得られない虞がある。一方、PTMGの数平均分子量が3000を超える場合には、得られるウレタンフォームは、セルサイズが不均一になり低い硬度を示し難く、あるいは、良好な機械的強度が得られない虞がある。得られるポリウレタンフォームの硬度が低く良好な柔軟性を示すとともに良好な反発弾性を示しやすいという観点からは、PTMGの数平均分子量は、1000以上2500以下の範囲であることが好ましい。
本発明におけるポリオール成分は90質量%以上のPTMGを含有する。そのため、当該ポリオール成分の数平均分子量は、含有するPTMGの数平均分子量に大きく影響を受ける。本発明において、ポリオール成分の数平均分子量が、600以上3000以下に調整されることが好ましい。
なお、PTMGとしては、例えば、テトラヒドロフランのカチオン重合により得られる開環重合物や、テトラヒドロフランの重合単位に2価アルコールを共重合した非晶性PTMGなどが挙げられる。なお、非晶性とは、常温(25℃)において液状であることを示す。
非晶性PTMGは、テトラヒドロフランとアルキル置換テトラヒドロフランとの共重合体や、テトラヒドロフランと分岐状グリコールとの共重合体などが挙げられる。上記アルキル置換テトラヒドロフランとしては、例えば、3-メチルテトラヒドロフランが例示される。また上記分岐状グリコールとしては、ネオペンチルグリコールが例示される。 (Polyol component)
The polyol component in the present invention contains 90% by mass or more of PTMG having a number average molecular weight of 600 or more and 3000 or less. In the present invention, two or more types of PTMGs having different number average molecular weights may be mixed and used. When two or more kinds of PTMGs are mixed and used, the number average molecular weight of the mixture of PTMGs may be adjusted to be within the above range.
If the number average molecular weight of PTMG is less than 600, good impact resilience may not be obtained. On the other hand, when the number average molecular weight of PTMG exceeds 3000, the obtained urethane foam may have a non-uniform cell size and may not easily exhibit low hardness, or may not have good mechanical strength. From the viewpoint that the obtained polyurethane foam has low hardness and exhibits good flexibility and easily exhibits good impact resilience, the number average molecular weight of PTMG is preferably in the range of 1000 or more and 2500 or less.
The polyol component in the present invention contains 90% by mass or more of PTMG. Therefore, the number average molecular weight of the polyol component is greatly affected by the number average molecular weight of the contained PTMG. In the present invention, it is preferable that the number average molecular weight of the polyol component is adjusted to 600 or more and 3000 or less.
Examples of the PTMG include a ring-opening polymer obtained by cation polymerization of tetrahydrofuran, an amorphous PTMG obtained by copolymerizing a dihydric alcohol with a polymerization unit of tetrahydrofuran, and the like. Amorphous means that it is liquid at room temperature (25 ° C.).
Examples of the amorphous PTMG include a copolymer of tetrahydrofuran and alkyl-substituted tetrahydrofuran, a copolymer of tetrahydrofuran and branched glycol, and the like. Examples of the alkyl-substituted tetrahydrofuran include 3-methyltetrahydrofuran. Further, as the branched glycol, neopentyl glycol is exemplified.
PTMGに対し、他のポリオール成分を併用して成形されたポリウレタンフォームは、破断強度および破断点伸度が十分ではなく機械的強度が不足する虞がある。このように機械的強度が弱いポリウレタンフォームを用いて構成された靴底部材は、繰り返しの使用に弱く劣化が早い虞があり、あるいは、高い反発弾性および低い硬度によって発揮される走り易さや疲れ難さが長く持続しない虞がある。
Polyurethane foam molded by using other polyol components in combination with PTMG may not have sufficient breaking strength and breaking point elongation, resulting in insufficient mechanical strength. The shoe sole member made of polyurethane foam having weak mechanical strength in this way is vulnerable to repeated use and may deteriorate quickly, or is exhibited by high impact resilience and low hardness for ease of running and resistance to fatigue. May not last long.
上述のとおり本発明において、ポリオール成分におけるPTMGの含有率は90質量%以上である。高い機械的強度をより十分に維持するという観点からは、ポリオール成分におけるPTMGの含有率は、95質量%以上であることが好ましく、100質量%であることがより好ましい。
As described above, in the present invention, the content of PTMG in the polyol component is 90% by mass or more. From the viewpoint of maintaining high mechanical strength more sufficiently, the content of PTMG in the polyol component is preferably 95% by mass or more, and more preferably 100% by mass.
なお、一般的には、ポリオール成分におけるPTMGの含有率が高いと、成形されるポリウレタンフォームは硬くなり易く、硬度を下げることが難しい。これに対し、本発明は、ポリイソシアネート成分中のイソシアネート基含有率を11質量%以上27質量%以下となるよう調整することによって、適度に低い硬度でありながら、高い反発弾性を示し、かつ機械的強度にも優れるポリウレタンフォームの提供を可能とした。
PTMGの含有率が高い本発明のポリウレタンフォームは、イソシアネート基含有率が上述する好ましい範囲に特定されるとともに、後述するポリウレタンフォームを構成するセルの平均気泡径が100μm以上150μm以下の範囲に調整されることで、さらに優れた反発弾性、硬度、および機械的強度を示しうる。 In general, when the content of PTMG in the polyol component is high, the polyurethane foam to be molded tends to be hard, and it is difficult to reduce the hardness. On the other hand, in the present invention, by adjusting the isocyanate group content in the polyisocyanate component to be 11% by mass or more and 27% by mass or less, the machine exhibits high impact resilience while having an appropriately low hardness. It has made it possible to provide polyurethane foam with excellent physical strength.
In the polyurethane foam of the present invention having a high PTMG content, the isocyanate group content is specified in the above-mentioned preferable range, and the average cell diameter of the cells constituting the polyurethane foam described later is adjusted to the range of 100 μm or more and 150 μm or less. This can provide even better impact resilience, hardness, and mechanical strength.
PTMGの含有率が高い本発明のポリウレタンフォームは、イソシアネート基含有率が上述する好ましい範囲に特定されるとともに、後述するポリウレタンフォームを構成するセルの平均気泡径が100μm以上150μm以下の範囲に調整されることで、さらに優れた反発弾性、硬度、および機械的強度を示しうる。 In general, when the content of PTMG in the polyol component is high, the polyurethane foam to be molded tends to be hard, and it is difficult to reduce the hardness. On the other hand, in the present invention, by adjusting the isocyanate group content in the polyisocyanate component to be 11% by mass or more and 27% by mass or less, the machine exhibits high impact resilience while having an appropriately low hardness. It has made it possible to provide polyurethane foam with excellent physical strength.
In the polyurethane foam of the present invention having a high PTMG content, the isocyanate group content is specified in the above-mentioned preferable range, and the average cell diameter of the cells constituting the polyurethane foam described later is adjusted to the range of 100 μm or more and 150 μm or less. This can provide even better impact resilience, hardness, and mechanical strength.
上述するポリオール成分には、必要に応じて、架橋剤などの任意の成分が添加されてもよい。
架橋剤としては、例えば、エチレングリコール、ジエチレングリコール、プロピレングリコール、ジプロピレングリコール、ブチレングリコール、ネオペンチルグリコール、テトラメチレンエーテルグリコール、グリセリン、ペンタエリスリトール、トリメチロールプロパン、モノエタノールアミン、ジエタノールアミン、イソプロパノールアミン、アミノエチルエタノールアミン、ショ糖、ソルビトール、グルコース等のアルコール類が使用できる。特に、これらのうち、3官能以上のものが好ましい。 If necessary, any component such as a cross-linking agent may be added to the above-mentioned polyol component.
Examples of the cross-linking agent include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, neopentyl glycol, tetramethylene ether glycol, glycerin, pentaerythritol, trimethylolpropane, monoethanolamine, diethanolamine, isopropanolamine and amino. Alcohols such as ethylethanolamine, sucrose, sorbitol and glucose can be used. In particular, among these, those having three or more functionalities are preferable.
架橋剤としては、例えば、エチレングリコール、ジエチレングリコール、プロピレングリコール、ジプロピレングリコール、ブチレングリコール、ネオペンチルグリコール、テトラメチレンエーテルグリコール、グリセリン、ペンタエリスリトール、トリメチロールプロパン、モノエタノールアミン、ジエタノールアミン、イソプロパノールアミン、アミノエチルエタノールアミン、ショ糖、ソルビトール、グルコース等のアルコール類が使用できる。特に、これらのうち、3官能以上のものが好ましい。 If necessary, any component such as a cross-linking agent may be added to the above-mentioned polyol component.
Examples of the cross-linking agent include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, neopentyl glycol, tetramethylene ether glycol, glycerin, pentaerythritol, trimethylolpropane, monoethanolamine, diethanolamine, isopropanolamine and amino. Alcohols such as ethylethanolamine, sucrose, sorbitol and glucose can be used. In particular, among these, those having three or more functionalities are preferable.
(ポリイソシアネート成分)
ポリイソシアネート成分としては、i)数平均分子量が500以上2000以下であり、イソシアネート基含有率が3質量%以上10質量%以下のイソシアネート基末端プレポリマーと、ii)イソシアネート基含有率が25質量%以上33質量%以下の変性MDIとを含む。なお、変性MDIとは、変性ジフェニルメタンジイソシアネートを指す。
上記イソシアネート基末端プレポリマーと上記変性MDIとの比率(イソシアネート基末端プレポリマー/変性MDI)は、特に限定されないが、質量比で97/3~3/97であることが好ましく、85/15~15/85であることがより好ましく、80/20~20/80であることがさらに好ましい。 (Polyisocyanate component)
The polyisocyanate components include i) an isocyanate group-terminated prepolymer having a number average molecular weight of 500 or more and 2000 or less and an isocyanate group content of 3% by mass or more and 10% by mass or less, and ii) an isocyanate group content of 25% by mass. Includes modified MDI of 33% by mass or more. The modified MDI refers to a modified diphenylmethane diisocyanate.
The ratio of the isocyanate group-terminated prepolymer to the modified MDI (isocyanate group-terminated prepolymer / modified MDI) is not particularly limited, but is preferably 97/3 to 3/97 by mass ratio, and is 85/15 to 85/15. It is more preferably 15/85, and even more preferably 80/20 to 20/80.
ポリイソシアネート成分としては、i)数平均分子量が500以上2000以下であり、イソシアネート基含有率が3質量%以上10質量%以下のイソシアネート基末端プレポリマーと、ii)イソシアネート基含有率が25質量%以上33質量%以下の変性MDIとを含む。なお、変性MDIとは、変性ジフェニルメタンジイソシアネートを指す。
上記イソシアネート基末端プレポリマーと上記変性MDIとの比率(イソシアネート基末端プレポリマー/変性MDI)は、特に限定されないが、質量比で97/3~3/97であることが好ましく、85/15~15/85であることがより好ましく、80/20~20/80であることがさらに好ましい。 (Polyisocyanate component)
The polyisocyanate components include i) an isocyanate group-terminated prepolymer having a number average molecular weight of 500 or more and 2000 or less and an isocyanate group content of 3% by mass or more and 10% by mass or less, and ii) an isocyanate group content of 25% by mass. Includes modified MDI of 33% by mass or more. The modified MDI refers to a modified diphenylmethane diisocyanate.
The ratio of the isocyanate group-terminated prepolymer to the modified MDI (isocyanate group-terminated prepolymer / modified MDI) is not particularly limited, but is preferably 97/3 to 3/97 by mass ratio, and is 85/15 to 85/15. It is more preferably 15/85, and even more preferably 80/20 to 20/80.
ポリウレタンフォームの用途の観点でさらに述べれば、ポリウレタンフォームを靴底部材として用いる場合には、質量比であるイソシアネート基末端プレポリマー/変性MDIは、上述の範囲において、さらに90/10~50/50であることが好ましく、85/15~55/45であることがより好ましく、80/20~60/40であることがさらに好ましい。このように、ポリイソシアネート成分において、イソシアネート基末端プレポリマーに対し変性MDIが同量または所定範囲で少なく含有される場合には、ポリウレタンフォームの破断強度および破断点伸度が高い値を示しやすい。これにより、繰り返し衝撃が付加される靴底部材により適したポリウレタンフォームを提供することができる。
Further stated from the viewpoint of the application of the polyurethane foam, when the polyurethane foam is used as a shoe sole member, the isocyanate group-terminated prepolymer / modified MDI, which is a mass ratio, is further 90/10 to 50/50 in the above range. It is preferably 85/15 to 55/45, more preferably 80/20 to 60/40. As described above, when the modified MDI is contained in the polyisocyanate component in the same amount or less than the isocyanate group-terminated prepolymer in a predetermined range, the breaking strength and the breaking point elongation of the polyurethane foam tend to be high. Thereby, it is possible to provide a polyurethane foam more suitable for the shoe sole member to which the impact is repeatedly applied.
i)イソシアネート基末端プレポリマー:
上述するi)イソシアネート基末端プレポリマー(以下、単にプレポリマーともいう)としては、数平均分子量が500以上2000以下、イソシアネート基含有率が3質量%以上10質量%以下のものを用いる。
数平均分子量が2000を超え、あるいはイソシアネート基含有率が3質量%未満のプレポリマーを用いた場合、製造されるポリウレタンフォームの発泡性が不十分となり硬度が高くなる虞がある。またそのようなプレポリマーは、粘度が大きく、他の材料との混合が困難になり易いため、ポリウレタンフォームの生産性に劣る場合がある。
一方、数平均分子量が500未満であり、あるいはイソシアネート基含有率が10質量%を超えるプレポリマーを用いた場合、製造されるポリウレタンフォームは発泡が進み過ぎて、良好な反発弾性が示されない虞がある。 i) Isocyanate group-terminated prepolymer:
As the above-mentioned i) isocyanate group-terminated prepolymer (hereinafter, also simply referred to as prepolymer), those having a number average molecular weight of 500 or more and 2000 or less and an isocyanate group content of 3% by mass or more and 10% by mass or less are used.
When a prepolymer having a number average molecular weight of more than 2000 or an isocyanate group content of less than 3% by mass is used, the foamability of the produced polyurethane foam may be insufficient and the hardness may be increased. Further, such a prepolymer may be inferior in the productivity of polyurethane foam because it has a high viscosity and tends to be difficult to mix with other materials.
On the other hand, when a prepolymer having a number average molecular weight of less than 500 or an isocyanate group content of more than 10% by mass is used, the produced polyurethane foam may foam too much and may not exhibit good impact resilience. be.
上述するi)イソシアネート基末端プレポリマー(以下、単にプレポリマーともいう)としては、数平均分子量が500以上2000以下、イソシアネート基含有率が3質量%以上10質量%以下のものを用いる。
数平均分子量が2000を超え、あるいはイソシアネート基含有率が3質量%未満のプレポリマーを用いた場合、製造されるポリウレタンフォームの発泡性が不十分となり硬度が高くなる虞がある。またそのようなプレポリマーは、粘度が大きく、他の材料との混合が困難になり易いため、ポリウレタンフォームの生産性に劣る場合がある。
一方、数平均分子量が500未満であり、あるいはイソシアネート基含有率が10質量%を超えるプレポリマーを用いた場合、製造されるポリウレタンフォームは発泡が進み過ぎて、良好な反発弾性が示されない虞がある。 i) Isocyanate group-terminated prepolymer:
As the above-mentioned i) isocyanate group-terminated prepolymer (hereinafter, also simply referred to as prepolymer), those having a number average molecular weight of 500 or more and 2000 or less and an isocyanate group content of 3% by mass or more and 10% by mass or less are used.
When a prepolymer having a number average molecular weight of more than 2000 or an isocyanate group content of less than 3% by mass is used, the foamability of the produced polyurethane foam may be insufficient and the hardness may be increased. Further, such a prepolymer may be inferior in the productivity of polyurethane foam because it has a high viscosity and tends to be difficult to mix with other materials.
On the other hand, when a prepolymer having a number average molecular weight of less than 500 or an isocyanate group content of more than 10% by mass is used, the produced polyurethane foam may foam too much and may not exhibit good impact resilience. be.
上記i)プレポリマーは、ポリオールとポリイソシアネートとを、イソシアネート基(NCO基)が過剰となるように反応させて得られる、末端にイソシアネート基を有するプレポリマーである。ここでイソシアネート基が過剰とは、プレポリマーにおけるNCO基含有率が3質量%以上10質量%以下の範囲である。
The above-mentioned i) prepolymer is a prepolymer having an isocyanate group at the terminal, which is obtained by reacting a polyol and a polyisocyanate so that an isocyanate group (NCO group) becomes excessive. Here, the excess isocyanate group means that the NCO group content in the prepolymer is in the range of 3% by mass or more and 10% by mass or less.
上記ポリオールとしては、下記α、β、およびγから選択された1種の材料また2種以上の混合材料を用いることができる。中でも、ポリオールとして、ポリエーテルポリオールが好ましく、ポリテトラメチレンエーテルグリコールがより好ましい。
α)ポリエーテルポリオール、またはポリエステルポリオール
β)ポリマーポリオール(例えば、ポリエーテルポリオールに、ポリアクリロニトリル、アクリロニトリル-スチレン共重合体などをグラフト共重合させたもの)
γ)上述にて架橋剤の例として挙げたアルコール類のうち、2官能のもの As the polyol, one kind of material selected from the following α, β, and γ, or a mixed material of two or more kinds can be used. Among them, as the polyol, a polyether polyol is preferable, and a polytetramethylene ether glycol is more preferable.
α) Polyester polyol or Polyester polyol β) Polymer polyol (for example, a polyether polyol obtained by graft-copolymerizing polyacrylonitrile, acrylonitrile-styrene copolymer, etc.)
γ) Of the alcohols listed above as examples of cross-linking agents, bifunctional ones
α)ポリエーテルポリオール、またはポリエステルポリオール
β)ポリマーポリオール(例えば、ポリエーテルポリオールに、ポリアクリロニトリル、アクリロニトリル-スチレン共重合体などをグラフト共重合させたもの)
γ)上述にて架橋剤の例として挙げたアルコール類のうち、2官能のもの As the polyol, one kind of material selected from the following α, β, and γ, or a mixed material of two or more kinds can be used. Among them, as the polyol, a polyether polyol is preferable, and a polytetramethylene ether glycol is more preferable.
α) Polyester polyol or Polyester polyol β) Polymer polyol (for example, a polyether polyol obtained by graft-copolymerizing polyacrylonitrile, acrylonitrile-styrene copolymer, etc.)
γ) Of the alcohols listed above as examples of cross-linking agents, bifunctional ones
上記ポリイソシアネートとしては、ジフェニルメタンジイソシアネート(4,4'-MDI)、ポリメリックMDI(クルードMDI)、2,4-トリレンジイソシアネート(2,4-TDI)、2,6-トリレンジイソシアネート(2,6-TDI)などの芳香族イソシアネート類、テトラメチレンジイソシアネート、ヘキサメチレンジイソシアネート(HDI)などの脂肪族ジイソシアネート、および、イソホロンジイソシアネート、水素添加TDI、水素添加MDIなどの脂環族ジイソシアネートなどが挙げられ、これらは単独でまたは2種以上を組み合わせて使用することもでき、中でも、4,4'-MDIが好ましい。
Examples of the polyisocyanate include diphenylmethane diisocyanate (4,4'-MDI), polypeptide MDI (crude MDI), 2,4-tolylene diisocyanate (2,4-TDI), and 2,6-tolylene diisocyanate (2,6). Examples thereof include aromatic isocyanates such as -TDI), aliphatic diisocyanates such as tetramethylene diisocyanate and hexamethylene diisocyanate (HDI), and alicyclic diisocyanates such as isophorone diisocyanate, hydrogenated TDI and hydrogenated MDI. Can be used alone or in combination of two or more, and among them, 4,4'-MDI is preferable.
すなわち、i)プレポリマーとしては、ポリオールとしてポリテトラメチレンエーテルグリコールを用い、ポリイソシアネートとして4,4'-MDIを用いて、これらを反応させて得られるものが好ましい。
このポリテトラメチレンエーテルグリコールに4,4'-MDIを反応させてなるプレポリマーは、ポリテトラメチレンエーテルグリコール部分の結晶性が高い。そのため、かかるプレポリマーを用いることで、反発弾性の高いウレタンフォームが得られやすく、かつポリイソシアネート成分として併用されるii)変性MDIと当該プレポリマーとの馴染み性が良好である。さらに、かかるプレポリマーを用いた場合、ポリテトラメチレンエーテルグリコールに4,4'-MDIを反応させてなるプレポリマーおよび変性MDIを含むイソシアネート成分と、ポリオール成分であるポリテトラメチレンエーテルグリコールとを反応させる際の混合性も良好である。そのため、部材の分子構造が均一になりやすく、得られるウレタンフォームの品質の安定化を図ることができる。 That is, as the i) prepolymer, those obtained by reacting polytetramethylene ether glycol as a polyol and 4,4′-MDI as a polyisocyanate are preferable.
The prepolymer formed by reacting this polytetramethylene ether glycol with 4,4'-MDI has high crystallinity of the polytetramethylene ether glycol moiety. Therefore, by using such a prepolymer, urethane foam having high impact resilience can be easily obtained, and ii) modified MDI used in combination as a polyisocyanate component has good compatibility with the prepolymer. Further, when such a prepolymer is used, an isocyanate component containing a prepolymer and a modified MDI obtained by reacting polytetramethylene ether glycol with 4,4'-MDI is reacted with polytetramethylene ether glycol which is a polyol component. The mixing property is also good. Therefore, the molecular structure of the member tends to be uniform, and the quality of the obtained urethane foam can be stabilized.
このポリテトラメチレンエーテルグリコールに4,4'-MDIを反応させてなるプレポリマーは、ポリテトラメチレンエーテルグリコール部分の結晶性が高い。そのため、かかるプレポリマーを用いることで、反発弾性の高いウレタンフォームが得られやすく、かつポリイソシアネート成分として併用されるii)変性MDIと当該プレポリマーとの馴染み性が良好である。さらに、かかるプレポリマーを用いた場合、ポリテトラメチレンエーテルグリコールに4,4'-MDIを反応させてなるプレポリマーおよび変性MDIを含むイソシアネート成分と、ポリオール成分であるポリテトラメチレンエーテルグリコールとを反応させる際の混合性も良好である。そのため、部材の分子構造が均一になりやすく、得られるウレタンフォームの品質の安定化を図ることができる。 That is, as the i) prepolymer, those obtained by reacting polytetramethylene ether glycol as a polyol and 4,4′-MDI as a polyisocyanate are preferable.
The prepolymer formed by reacting this polytetramethylene ether glycol with 4,4'-MDI has high crystallinity of the polytetramethylene ether glycol moiety. Therefore, by using such a prepolymer, urethane foam having high impact resilience can be easily obtained, and ii) modified MDI used in combination as a polyisocyanate component has good compatibility with the prepolymer. Further, when such a prepolymer is used, an isocyanate component containing a prepolymer and a modified MDI obtained by reacting polytetramethylene ether glycol with 4,4'-MDI is reacted with polytetramethylene ether glycol which is a polyol component. The mixing property is also good. Therefore, the molecular structure of the member tends to be uniform, and the quality of the obtained urethane foam can be stabilized.
ii)変性MDI:
本発明では、変性MDIとして、イソシアネート基含有率が25質量%以上33質量%以下のものを用いる。かかる範囲であれば、変性MDIは常温で液体として取り扱うことができる。
i)プレポリマーは、分子量が大きいため粘度が高い。しかし、当該i)プレポリマーと常温で液体であるii)変性MDIとを混合させることにより、ポリイソシアネート成分の粘度を適度に下げることができる。そのため、当該ポリイソシアネート成分とポリオール成分との混合性を良好なものとすることができる。
変性MDIにおけるNCO基含有率が25質量%未満の場合、製造されるポリウレタンフォームの発泡性が不十分となる虞がある。一方、上記NCO基含有率が33質量%を超える変性MDIは、NCO基含有率の調整の観点からポリイソシアネート成分中に含有される量は少なくなる。このように変性MDIの量が少なくなると、分子量が大きいi)プレポリマーを含むポリイソシアネート成分を適度に低い粘度に調整することが困難となり、ポリイソシアネート成分とポリオール成分とを反応させる際の混合性が悪くなる虞がある。 ii) Modified MDI:
In the present invention, the modified MDI having an isocyanate group content of 25% by mass or more and 33% by mass or less is used. Within this range, the modified MDI can be treated as a liquid at room temperature.
i) Prepolymers have a high molecular weight and therefore a high viscosity. However, by mixing the i) prepolymer and ii) modified MDI which is liquid at room temperature, the viscosity of the polyisocyanate component can be appropriately lowered. Therefore, the mixability of the polyisocyanate component and the polyol component can be improved.
If the NCO group content in the modified MDI is less than 25% by mass, the foamability of the produced polyurethane foam may be insufficient. On the other hand, the amount of the modified MDI having an NCO group content of more than 33% by mass in the polyisocyanate component is reduced from the viewpoint of adjusting the NCO group content. When the amount of the modified MDI is reduced in this way, it becomes difficult to adjust the polyisocyanate component containing the prepolymer having a large molecular weight to an appropriately low viscosity, and the mixing property when the polyisocyanate component and the polyol component are reacted with each other becomes difficult. May get worse.
本発明では、変性MDIとして、イソシアネート基含有率が25質量%以上33質量%以下のものを用いる。かかる範囲であれば、変性MDIは常温で液体として取り扱うことができる。
i)プレポリマーは、分子量が大きいため粘度が高い。しかし、当該i)プレポリマーと常温で液体であるii)変性MDIとを混合させることにより、ポリイソシアネート成分の粘度を適度に下げることができる。そのため、当該ポリイソシアネート成分とポリオール成分との混合性を良好なものとすることができる。
変性MDIにおけるNCO基含有率が25質量%未満の場合、製造されるポリウレタンフォームの発泡性が不十分となる虞がある。一方、上記NCO基含有率が33質量%を超える変性MDIは、NCO基含有率の調整の観点からポリイソシアネート成分中に含有される量は少なくなる。このように変性MDIの量が少なくなると、分子量が大きいi)プレポリマーを含むポリイソシアネート成分を適度に低い粘度に調整することが困難となり、ポリイソシアネート成分とポリオール成分とを反応させる際の混合性が悪くなる虞がある。 ii) Modified MDI:
In the present invention, the modified MDI having an isocyanate group content of 25% by mass or more and 33% by mass or less is used. Within this range, the modified MDI can be treated as a liquid at room temperature.
i) Prepolymers have a high molecular weight and therefore a high viscosity. However, by mixing the i) prepolymer and ii) modified MDI which is liquid at room temperature, the viscosity of the polyisocyanate component can be appropriately lowered. Therefore, the mixability of the polyisocyanate component and the polyol component can be improved.
If the NCO group content in the modified MDI is less than 25% by mass, the foamability of the produced polyurethane foam may be insufficient. On the other hand, the amount of the modified MDI having an NCO group content of more than 33% by mass in the polyisocyanate component is reduced from the viewpoint of adjusting the NCO group content. When the amount of the modified MDI is reduced in this way, it becomes difficult to adjust the polyisocyanate component containing the prepolymer having a large molecular weight to an appropriately low viscosity, and the mixing property when the polyisocyanate component and the polyol component are reacted with each other becomes difficult. May get worse.
このように常温で液体である変性MDIの具体例としては、たとえば、ポリメリック体(クルードMDI)、ウレタン変性体、ウレア変性体、アロファネート変性体、ビウレット変性体、カルボジイミド変性体、ウレトンイミン変性体、ウレトジオン変性体、イソシアヌレート変性体などが挙げられる。中でも、ポリオール成分との反応後の分子(架橋)構造が優れる点から、変性MDIとして、ポリメリック体(クルードMDI)および/またはカルボジイミド変性体が選択されることが好ましい。
Specific examples of the modified MDI that is liquid at room temperature include, for example, a polymeric (crude MDI), urethane modified, urea modified, allophanate modified, biuret modified, carbodiimide modified, uretonimine modified, and uretdione. Modified products, isocyanurate modified products and the like can be mentioned. Among them, a polypeptide (crude MDI) and / or a modified carbodiimide is preferably selected as the modified MDI because the molecular (crosslinked) structure after the reaction with the polyol component is excellent.
(ポリイソシアネート成分中のイソシアネート基含有率)
本発明において、上述するi)プレポリマーおよびii)変性MDIを含むポリイソシアネート成分は、イソシアネート基含有率が11質量%以上27質量%以下である。当該イソシアネート基含有率が11質量%未満であると、得られるポリウレタンフォームの気泡径が小さくなり、硬度が高くなる。一方、当該イソシアネート基含有率が27質量%を超えた場合、得られるポリウレタンフォームにおいて良好な反発弾性が示されない。上記観点からは、当該イソシアネート基含有率は、好ましくは12質量%以上25質量%以下であり、より好ましくは12質量%以上21質量%以下であり、さらに好ましくは12質量%以上17質量%以下であり、特に好ましくは12質量%以上15質量%以下である。
なお、本発明におけるポリイソシアネート成分は、上述するi)プレポリマーおよびii)変性MDIに加え、さらにイソシアネート(第三のイソシアネート)を含んでいてもよい。 (Isocyanate group content in polyisocyanate component)
In the present invention, the polyisocyanate component containing the above-mentioned i) prepolymer and ii) modified MDI has an isocyanate group content of 11% by mass or more and 27% by mass or less. When the isocyanate group content is less than 11% by mass, the bubble diameter of the obtained polyurethane foam becomes small and the hardness becomes high. On the other hand, when the isocyanate group content exceeds 27% by mass, good impact resilience is not exhibited in the obtained polyurethane foam. From the above viewpoint, the isocyanate group content is preferably 12% by mass or more and 25% by mass or less, more preferably 12% by mass or more and 21% by mass or less, and further preferably 12% by mass or more and 17% by mass or less. It is particularly preferably 12% by mass or more and 15% by mass or less.
The polyisocyanate component in the present invention may further contain an isocyanate (third isocyanate) in addition to the above-mentioned i) prepolymer and ii) modified MDI.
本発明において、上述するi)プレポリマーおよびii)変性MDIを含むポリイソシアネート成分は、イソシアネート基含有率が11質量%以上27質量%以下である。当該イソシアネート基含有率が11質量%未満であると、得られるポリウレタンフォームの気泡径が小さくなり、硬度が高くなる。一方、当該イソシアネート基含有率が27質量%を超えた場合、得られるポリウレタンフォームにおいて良好な反発弾性が示されない。上記観点からは、当該イソシアネート基含有率は、好ましくは12質量%以上25質量%以下であり、より好ましくは12質量%以上21質量%以下であり、さらに好ましくは12質量%以上17質量%以下であり、特に好ましくは12質量%以上15質量%以下である。
なお、本発明におけるポリイソシアネート成分は、上述するi)プレポリマーおよびii)変性MDIに加え、さらにイソシアネート(第三のイソシアネート)を含んでいてもよい。 (Isocyanate group content in polyisocyanate component)
In the present invention, the polyisocyanate component containing the above-mentioned i) prepolymer and ii) modified MDI has an isocyanate group content of 11% by mass or more and 27% by mass or less. When the isocyanate group content is less than 11% by mass, the bubble diameter of the obtained polyurethane foam becomes small and the hardness becomes high. On the other hand, when the isocyanate group content exceeds 27% by mass, good impact resilience is not exhibited in the obtained polyurethane foam. From the above viewpoint, the isocyanate group content is preferably 12% by mass or more and 25% by mass or less, more preferably 12% by mass or more and 21% by mass or less, and further preferably 12% by mass or more and 17% by mass or less. It is particularly preferably 12% by mass or more and 15% by mass or less.
The polyisocyanate component in the present invention may further contain an isocyanate (third isocyanate) in addition to the above-mentioned i) prepolymer and ii) modified MDI.
(発泡剤)
発泡剤としては、水を用いることができる。添加量は、上述するポリオール成分100質量部に対し、0.5質量部以上3質量部以下であることが好ましい。上記水としては、イオン交換水、蒸留水などが挙げられるが、イオン交換水が好ましい。
発泡剤の添加量が0.5質量部未満の場合、発泡が不十分となる虞がある。一方、発泡剤の添加量が3質量部を超える場合、発泡が進み過ぎ、得られるポリウレタンフォームのセルが荒れる虞がある。この場合、得られるポリウレタンフォームの内部が割れやすいなどの問題が発生し、その結果、フォーム状態が劣り、また、反発性に劣る傾向にある。 (Foaming agent)
Water can be used as the foaming agent. The amount added is preferably 0.5 parts by mass or more and 3 parts by mass or less with respect to 100 parts by mass of the above-mentioned polyol component. Examples of the water include ion-exchanged water and distilled water, but ion-exchanged water is preferable.
If the amount of the foaming agent added is less than 0.5 parts by mass, foaming may be insufficient. On the other hand, if the amount of the foaming agent added exceeds 3 parts by mass, foaming may proceed too much and the resulting polyurethane foam cell may become rough. In this case, problems such as the inside of the obtained polyurethane foam being easily cracked occur, and as a result, the foam state tends to be inferior and the resilience tends to be inferior.
発泡剤としては、水を用いることができる。添加量は、上述するポリオール成分100質量部に対し、0.5質量部以上3質量部以下であることが好ましい。上記水としては、イオン交換水、蒸留水などが挙げられるが、イオン交換水が好ましい。
発泡剤の添加量が0.5質量部未満の場合、発泡が不十分となる虞がある。一方、発泡剤の添加量が3質量部を超える場合、発泡が進み過ぎ、得られるポリウレタンフォームのセルが荒れる虞がある。この場合、得られるポリウレタンフォームの内部が割れやすいなどの問題が発生し、その結果、フォーム状態が劣り、また、反発性に劣る傾向にある。 (Foaming agent)
Water can be used as the foaming agent. The amount added is preferably 0.5 parts by mass or more and 3 parts by mass or less with respect to 100 parts by mass of the above-mentioned polyol component. Examples of the water include ion-exchanged water and distilled water, but ion-exchanged water is preferable.
If the amount of the foaming agent added is less than 0.5 parts by mass, foaming may be insufficient. On the other hand, if the amount of the foaming agent added exceeds 3 parts by mass, foaming may proceed too much and the resulting polyurethane foam cell may become rough. In this case, problems such as the inside of the obtained polyurethane foam being easily cracked occur, and as a result, the foam state tends to be inferior and the resilience tends to be inferior.
(触媒)
触媒としては、従来からポリウレタンフォームの製造に使用されているものであればよく、例えば、トリエチレンジアミン、ジエタノールアミンなどのアミン系触媒、ビスマス触媒などの金属触媒が挙げられるが、特に限定されるものではない。
添加量は、上述するポリオール成分100質量部に対して、0.1質量部以上5質量部以下が好ましい。 (catalyst)
The catalyst may be any catalyst conventionally used in the production of polyurethane foam, and examples thereof include amine-based catalysts such as triethylenediamine and diethanolamine, and metal catalysts such as bismuth catalysts, but the catalysts are not particularly limited. No.
The amount to be added is preferably 0.1 part by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the above-mentioned polyol component.
触媒としては、従来からポリウレタンフォームの製造に使用されているものであればよく、例えば、トリエチレンジアミン、ジエタノールアミンなどのアミン系触媒、ビスマス触媒などの金属触媒が挙げられるが、特に限定されるものではない。
添加量は、上述するポリオール成分100質量部に対して、0.1質量部以上5質量部以下が好ましい。 (catalyst)
The catalyst may be any catalyst conventionally used in the production of polyurethane foam, and examples thereof include amine-based catalysts such as triethylenediamine and diethanolamine, and metal catalysts such as bismuth catalysts, but the catalysts are not particularly limited. No.
The amount to be added is preferably 0.1 part by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the above-mentioned polyol component.
(整泡剤)
本発明は、PTMGを90質量%以上含む上記ポリオール成分と、イソシアネート基末端プレポリマーおよび変性MDIを含む上記ポリイソシアネート成分とを反応させて、モールド(成形型)内で発泡硬化させることで、ウレタン反応を生じせしめるとともに発泡させ、ポリウレタンフォームが成形される。
このようなウレタン発泡により得られるポリウレタンフォームのセルサイズを良好なものとするために、整泡剤が含有される。整泡剤は、ウレタンフォームの製造で使用できるものであれば特に限定されない。良好な反発弾性が得られやすいという観点からは、整泡剤の粘度は300mPa・s(25℃)以上2000mPa・s(25℃)以下であることが好ましく、800mPa・s(25℃)以上1000mPa・s(25℃)以下であることがより好ましい。かかる好適な粘度範囲であるシリコーン系化合物の整泡剤が特に好ましい。
整泡剤の粘度が300mPa・s(25℃)未満であると、整泡作用が弱く、セルが粗大化してしまい、高い反発弾性が得られない虞がある。一方、粘度が2000mPa・s(25℃)を超えると、ポリウレタン原料中に整泡剤が均一に分散し難くなる。その結果、得られるフォームのセルサイズが均一になり難く、また、局所的に物性が変化してしまう虞がある。 (Foaming agent)
In the present invention, urethane is formed by reacting the above-mentioned polyol component containing 90% by mass or more of PTMG with the above-mentioned polyisocyanate component containing an isocyanate group-terminated prepolymer and a modified MDI, and foaming and curing it in a mold. A polyurethane foam is formed by causing a reaction and foaming.
A defoaming agent is contained in order to improve the cell size of the polyurethane foam obtained by such urethane foaming. The foam stabilizer is not particularly limited as long as it can be used in the production of urethane foam. From the viewpoint that good impact resilience can be easily obtained, the viscosity of the defoaming agent is preferably 300 mPa · s (25 ° C.) or more and 2000 mPa · s (25 ° C.) or less, and 800 mPa · s (25 ° C.) or more and 1000 mPa. -It is more preferably s (25 ° C.) or less. A silicone-based compound defoaming agent having such a suitable viscosity range is particularly preferable.
If the viscosity of the defoaming agent is less than 300 mPa · s (25 ° C.), the defoaming action is weak, the cells become coarse, and high impact resilience may not be obtained. On the other hand, if the viscosity exceeds 2000 mPa · s (25 ° C.), it becomes difficult for the defoaming agent to be uniformly dispersed in the polyurethane raw material. As a result, it is difficult for the cell size of the obtained foam to be uniform, and there is a risk that the physical properties will change locally.
本発明は、PTMGを90質量%以上含む上記ポリオール成分と、イソシアネート基末端プレポリマーおよび変性MDIを含む上記ポリイソシアネート成分とを反応させて、モールド(成形型)内で発泡硬化させることで、ウレタン反応を生じせしめるとともに発泡させ、ポリウレタンフォームが成形される。
このようなウレタン発泡により得られるポリウレタンフォームのセルサイズを良好なものとするために、整泡剤が含有される。整泡剤は、ウレタンフォームの製造で使用できるものであれば特に限定されない。良好な反発弾性が得られやすいという観点からは、整泡剤の粘度は300mPa・s(25℃)以上2000mPa・s(25℃)以下であることが好ましく、800mPa・s(25℃)以上1000mPa・s(25℃)以下であることがより好ましい。かかる好適な粘度範囲であるシリコーン系化合物の整泡剤が特に好ましい。
整泡剤の粘度が300mPa・s(25℃)未満であると、整泡作用が弱く、セルが粗大化してしまい、高い反発弾性が得られない虞がある。一方、粘度が2000mPa・s(25℃)を超えると、ポリウレタン原料中に整泡剤が均一に分散し難くなる。その結果、得られるフォームのセルサイズが均一になり難く、また、局所的に物性が変化してしまう虞がある。 (Foaming agent)
In the present invention, urethane is formed by reacting the above-mentioned polyol component containing 90% by mass or more of PTMG with the above-mentioned polyisocyanate component containing an isocyanate group-terminated prepolymer and a modified MDI, and foaming and curing it in a mold. A polyurethane foam is formed by causing a reaction and foaming.
A defoaming agent is contained in order to improve the cell size of the polyurethane foam obtained by such urethane foaming. The foam stabilizer is not particularly limited as long as it can be used in the production of urethane foam. From the viewpoint that good impact resilience can be easily obtained, the viscosity of the defoaming agent is preferably 300 mPa · s (25 ° C.) or more and 2000 mPa · s (25 ° C.) or less, and 800 mPa · s (25 ° C.) or more and 1000 mPa. -It is more preferably s (25 ° C.) or less. A silicone-based compound defoaming agent having such a suitable viscosity range is particularly preferable.
If the viscosity of the defoaming agent is less than 300 mPa · s (25 ° C.), the defoaming action is weak, the cells become coarse, and high impact resilience may not be obtained. On the other hand, if the viscosity exceeds 2000 mPa · s (25 ° C.), it becomes difficult for the defoaming agent to be uniformly dispersed in the polyurethane raw material. As a result, it is difficult for the cell size of the obtained foam to be uniform, and there is a risk that the physical properties will change locally.
上記好適な粘度範囲のシリコーン系化合物を整泡剤として用いる場合は、当該シリコーン系化合物を、上述するポリオール成分100質量部に対して、0.5質量部以上9質量部以下の範囲で添加することが好ましく、0.5質量部以上5質量部以下の範囲で添加することがより好ましい。
0.5質量部未満であると、整泡作用が弱く、セルが粗大化してしまい、高い反発弾性が得られない虞がある。
一方、9質量部を超えると、得られるポリウレタンフォームの反発弾性が劣る虞がある。その上、9質量部を超えると、得られるポリウレタンフォームの表面から整泡剤が染み出すブリードアウトが生じる虞があり、その結果、ポリウレタンフォームと他部材との接着が阻害されるなど、取扱い性も劣る場合がある。上記好適な粘度範囲のシリコーン系化合物の添加量を、上述するポリオール成分100質量部に対して、5質量部以下とすることで、ポリウレタンフォームの表面にべたつきが発生することがなく、高品質なポリウレタンフォームを提供することができる。 When a silicone compound having a suitable viscosity range is used as a defoaming agent, the silicone compound is added in a range of 0.5 parts by mass or more and 9 parts by mass or less with respect to 100 parts by mass of the above-mentioned polyol component. It is preferable, and it is more preferable to add it in the range of 0.5 parts by mass or more and 5 parts by mass or less.
If it is less than 0.5 parts by mass, the foam regulating action is weak, the cell becomes coarse, and there is a possibility that high impact resilience cannot be obtained.
On the other hand, if it exceeds 9 parts by mass, the impact resilience of the obtained polyurethane foam may be inferior. In addition, if it exceeds 9 parts by mass, bleed-out may occur in which the foam stabilizer exudes from the surface of the obtained polyurethane foam, and as a result, the adhesion between the polyurethane foam and other members is hindered, and the handleability is improved. May also be inferior. By setting the addition amount of the silicone compound in the above-mentioned suitable viscosity range to 5 parts by mass or less with respect to 100 parts by mass of the above-mentioned polyol component, the surface of the polyurethane foam does not become sticky and is of high quality. Polyurethane foam can be provided.
0.5質量部未満であると、整泡作用が弱く、セルが粗大化してしまい、高い反発弾性が得られない虞がある。
一方、9質量部を超えると、得られるポリウレタンフォームの反発弾性が劣る虞がある。その上、9質量部を超えると、得られるポリウレタンフォームの表面から整泡剤が染み出すブリードアウトが生じる虞があり、その結果、ポリウレタンフォームと他部材との接着が阻害されるなど、取扱い性も劣る場合がある。上記好適な粘度範囲のシリコーン系化合物の添加量を、上述するポリオール成分100質量部に対して、5質量部以下とすることで、ポリウレタンフォームの表面にべたつきが発生することがなく、高品質なポリウレタンフォームを提供することができる。 When a silicone compound having a suitable viscosity range is used as a defoaming agent, the silicone compound is added in a range of 0.5 parts by mass or more and 9 parts by mass or less with respect to 100 parts by mass of the above-mentioned polyol component. It is preferable, and it is more preferable to add it in the range of 0.5 parts by mass or more and 5 parts by mass or less.
If it is less than 0.5 parts by mass, the foam regulating action is weak, the cell becomes coarse, and there is a possibility that high impact resilience cannot be obtained.
On the other hand, if it exceeds 9 parts by mass, the impact resilience of the obtained polyurethane foam may be inferior. In addition, if it exceeds 9 parts by mass, bleed-out may occur in which the foam stabilizer exudes from the surface of the obtained polyurethane foam, and as a result, the adhesion between the polyurethane foam and other members is hindered, and the handleability is improved. May also be inferior. By setting the addition amount of the silicone compound in the above-mentioned suitable viscosity range to 5 parts by mass or less with respect to 100 parts by mass of the above-mentioned polyol component, the surface of the polyurethane foam does not become sticky and is of high quality. Polyurethane foam can be provided.
本発明のポリウレタンフォームの原料には、ポリオール成分、イソシアネート成分、発泡剤、触媒、整泡剤の他に、必要に応じて、可塑剤、充填剤、酸化防止剤、脱泡剤、相溶化剤、着色剤、安定剤、紫外線吸収剤など、ポリウレタンフォームの製造に際して一般的に使用される添加剤を、本発明の効果が得られる範囲内において使用してもよい。
The raw material of the polyurethane foam of the present invention includes a polyol component, an isocyanate component, a foaming agent, a catalyst, a foam stabilizer, as well as a plasticizer, a filler, an antioxidant, a defoaming agent, and a compatibilizer, if necessary. , Colorants, stabilizers, UV absorbers and other additives commonly used in the production of polyurethane foam may be used as long as the effects of the present invention can be obtained.
(ポリウレタンフォーム)
セルの平均気泡径:
本発明のポリウレタンフォームは、フォームを構成するセルの平均気泡径が100μm以上150μm以下の範囲であることが好ましい。このように意図的にやや大きな気泡径となるよう調整することによって、高反発弾性であって硬度も低く、かつ破断強度や破断点伸度といった機械的物性にも優れるポリウレタンフォームを提供しやすい。
上記平均気泡径が100μm未満であると、機械的物性が損なわれ、また上記平均気泡径が150μmを超えると、高い反発弾性が示され難い。上記平均気泡径は、100μmを超えて150μm以下であることがより好ましく、100μmを超えて135μm以下であることがさらに好ましく、100μmを超えて130μm以下であることがよりさらに好ましく、100μmを超えて120μm以下であることが特に好ましい。 (Polyurethane foam)
Average cell diameter:
The polyurethane foam of the present invention preferably has an average cell diameter of 100 μm or more and 150 μm or less in the cells constituting the foam. By intentionally adjusting the bubble diameter to be slightly large in this way, it is easy to provide a polyurethane foam having high rebound resilience, low hardness, and excellent mechanical properties such as breaking strength and breaking point elongation.
If the average cell diameter is less than 100 μm, the mechanical properties are impaired, and if the average cell diameter exceeds 150 μm, high impact resilience is unlikely to be exhibited. The average bubble diameter is more preferably more than 100 μm and 150 μm or less, further preferably more than 100 μm and 135 μm or less, further preferably more than 100 μm and 130 μm or less, and more than 100 μm. It is particularly preferably 120 μm or less.
セルの平均気泡径:
本発明のポリウレタンフォームは、フォームを構成するセルの平均気泡径が100μm以上150μm以下の範囲であることが好ましい。このように意図的にやや大きな気泡径となるよう調整することによって、高反発弾性であって硬度も低く、かつ破断強度や破断点伸度といった機械的物性にも優れるポリウレタンフォームを提供しやすい。
上記平均気泡径が100μm未満であると、機械的物性が損なわれ、また上記平均気泡径が150μmを超えると、高い反発弾性が示され難い。上記平均気泡径は、100μmを超えて150μm以下であることがより好ましく、100μmを超えて135μm以下であることがさらに好ましく、100μmを超えて130μm以下であることがよりさらに好ましく、100μmを超えて120μm以下であることが特に好ましい。 (Polyurethane foam)
Average cell diameter:
The polyurethane foam of the present invention preferably has an average cell diameter of 100 μm or more and 150 μm or less in the cells constituting the foam. By intentionally adjusting the bubble diameter to be slightly large in this way, it is easy to provide a polyurethane foam having high rebound resilience, low hardness, and excellent mechanical properties such as breaking strength and breaking point elongation.
If the average cell diameter is less than 100 μm, the mechanical properties are impaired, and if the average cell diameter exceeds 150 μm, high impact resilience is unlikely to be exhibited. The average bubble diameter is more preferably more than 100 μm and 150 μm or less, further preferably more than 100 μm and 135 μm or less, further preferably more than 100 μm and 130 μm or less, and more than 100 μm. It is particularly preferably 120 μm or less.
上記平均気泡径は、以下の方法で特定することができる。まず、ポリウレタンフォームから無作為に選択された位置で切断して切断面を露出させる。切断面において、所定寸法の領域を無作為に選択して選択領域とする。所定寸法の領域は、例えば、縦4mm、横3mmの矩形領域である。選択領域内に存在するセル(気泡)の個数(全セルの個数)、及び各セル径(各気泡の直径)を、マイクロスコープを用いて計測する。上述のとおり計測された各セル径の算術平均値を求め、これを本発明における平均気泡径とする。
The average bubble diameter can be specified by the following method. First, the polyurethane foam is cut at a randomly selected position to expose the cut surface. On the cut surface, a region having a predetermined dimension is randomly selected as a selected region. The region having a predetermined dimension is, for example, a rectangular region having a length of 4 mm and a width of 3 mm. The number of cells (bubbles) existing in the selected region (the number of all cells) and the diameter of each cell (diameter of each bubble) are measured using a microscope. The arithmetic mean value of each cell diameter measured as described above is obtained, and this is used as the average cell diameter in the present invention.
ポリウレタンフォームの平均気泡径の調整方法は特に限定されないが、たとえば、触媒や発泡剤の添加量などを調整することで所望の範囲の平均気泡径を示すポリウレタンフォームを成形することができる。
The method for adjusting the average cell size of the polyurethane foam is not particularly limited, but for example, a polyurethane foam showing an average cell size in a desired range can be formed by adjusting the amount of the catalyst or foaming agent added.
硬度:
本発明のポリウレタンフォームの硬度は、適度な柔軟性を発揮するという観点から50未満であることが好ましく、47未満であることがより好ましい。硬度が50未満であるポリウレタンフォームを用いて構成される靴底部材は、初心者用の運動シューズ等の靴底の構成部材に適している。このような靴底部材を用いることで、接地時における膝などへの負担が軽減される。
また良好な衝撃吸収性を維持するという観点からは、上記硬度は35以上であることが好ましく、40以上であることがより好ましい。硬度が低すぎるポリウレタンフォームは、衝撃が吸収しきれず、靴底部材として用いられた場合に、故障を引き起こすリスクが生じうる。本発明のポリウレタンフォームをマット部材として使用する場合にも、硬度は、上述する範囲であることが好適である。
本発明のポリウレタンフォームの硬度は、JIS K 7312に準拠し、温度条件23±2℃の条件下で、アスカーゴム硬度計C型を用いて測定される。 hardness:
The hardness of the polyurethane foam of the present invention is preferably less than 50, more preferably less than 47, from the viewpoint of exhibiting appropriate flexibility. A sole member made of polyurethane foam having a hardness of less than 50 is suitable for a sole member such as an athletic shoe for beginners. By using such a shoe sole member, the burden on the knee or the like at the time of touchdown can be reduced.
From the viewpoint of maintaining good shock absorption, the hardness is preferably 35 or more, more preferably 40 or more. Polyurethane foam with too low hardness cannot absorb the impact and may cause a risk of failure when used as a shoe sole member. Even when the polyurethane foam of the present invention is used as a mat member, the hardness is preferably in the above range.
The hardness of the polyurethane foam of the present invention is measured in accordance with JIS K 7312 using an Asker rubber hardness tester C type under a temperature condition of 23 ± 2 ° C.
本発明のポリウレタンフォームの硬度は、適度な柔軟性を発揮するという観点から50未満であることが好ましく、47未満であることがより好ましい。硬度が50未満であるポリウレタンフォームを用いて構成される靴底部材は、初心者用の運動シューズ等の靴底の構成部材に適している。このような靴底部材を用いることで、接地時における膝などへの負担が軽減される。
また良好な衝撃吸収性を維持するという観点からは、上記硬度は35以上であることが好ましく、40以上であることがより好ましい。硬度が低すぎるポリウレタンフォームは、衝撃が吸収しきれず、靴底部材として用いられた場合に、故障を引き起こすリスクが生じうる。本発明のポリウレタンフォームをマット部材として使用する場合にも、硬度は、上述する範囲であることが好適である。
本発明のポリウレタンフォームの硬度は、JIS K 7312に準拠し、温度条件23±2℃の条件下で、アスカーゴム硬度計C型を用いて測定される。 hardness:
The hardness of the polyurethane foam of the present invention is preferably less than 50, more preferably less than 47, from the viewpoint of exhibiting appropriate flexibility. A sole member made of polyurethane foam having a hardness of less than 50 is suitable for a sole member such as an athletic shoe for beginners. By using such a shoe sole member, the burden on the knee or the like at the time of touchdown can be reduced.
From the viewpoint of maintaining good shock absorption, the hardness is preferably 35 or more, more preferably 40 or more. Polyurethane foam with too low hardness cannot absorb the impact and may cause a risk of failure when used as a shoe sole member. Even when the polyurethane foam of the present invention is used as a mat member, the hardness is preferably in the above range.
The hardness of the polyurethane foam of the present invention is measured in accordance with JIS K 7312 using an Asker rubber hardness tester C type under a temperature condition of 23 ± 2 ° C.
見かけ密度:
本発明のポリウレタンフォームの見かけ密度は特に限定されないが、0.30g/cm3以上0.35g/cm3以下の範囲であることが好ましい。また本発明において、見かけ密度が上記範囲であって、かつ平均セル径が100μm以上150μm以下であることがより好ましい。
本発明のポリウレタンフォームの見かけ密度は、JIS K 7222に準拠して測定される。 Apparent density:
The apparent density of the polyurethane foam of the present invention is not particularly limited, but is preferably in the range of 0.30 g / cm 3 or more and 0.35 g / cm 3 or less. Further, in the present invention, it is more preferable that the apparent density is in the above range and the average cell diameter is 100 μm or more and 150 μm or less.
The apparent density of the polyurethane foam of the present invention is measured according to JIS K 7222.
本発明のポリウレタンフォームの見かけ密度は特に限定されないが、0.30g/cm3以上0.35g/cm3以下の範囲であることが好ましい。また本発明において、見かけ密度が上記範囲であって、かつ平均セル径が100μm以上150μm以下であることがより好ましい。
本発明のポリウレタンフォームの見かけ密度は、JIS K 7222に準拠して測定される。 Apparent density:
The apparent density of the polyurethane foam of the present invention is not particularly limited, but is preferably in the range of 0.30 g / cm 3 or more and 0.35 g / cm 3 or less. Further, in the present invention, it is more preferable that the apparent density is in the above range and the average cell diameter is 100 μm or more and 150 μm or less.
The apparent density of the polyurethane foam of the present invention is measured according to JIS K 7222.
反発弾性率:
本発明のポリウレタンフォームの反発弾性率は、当該ポリウレタンフォームを靴底やマットに用いた場合に、蹴り出しが良く足運びがスムーズであるという観点から50%以上であることが好ましく、55%以上であることがより好ましく、60%以上であることがさらに好ましい。
一方、本発明において反発弾性率の上限は特に限定されないが、硬度や機械的物性とのバランスを良好に図りやすいという観点からは、80%未満であることが好ましく、75%未満であることがより好ましく、70%未満であることがさらに好ましい。 Modulus of impact:
The elastic modulus of the polyurethane foam of the present invention is preferably 50% or more, preferably 55% or more, from the viewpoint of good kicking and smooth foot movement when the polyurethane foam is used for a shoe sole or a mat. Is more preferable, and 60% or more is further preferable.
On the other hand, in the present invention, the upper limit of the rebound resilience is not particularly limited, but from the viewpoint of easily achieving a good balance with hardness and mechanical properties, it is preferably less than 80%, and preferably less than 75%. More preferably, it is less than 70%.
本発明のポリウレタンフォームの反発弾性率は、当該ポリウレタンフォームを靴底やマットに用いた場合に、蹴り出しが良く足運びがスムーズであるという観点から50%以上であることが好ましく、55%以上であることがより好ましく、60%以上であることがさらに好ましい。
一方、本発明において反発弾性率の上限は特に限定されないが、硬度や機械的物性とのバランスを良好に図りやすいという観点からは、80%未満であることが好ましく、75%未満であることがより好ましく、70%未満であることがさらに好ましい。 Modulus of impact:
The elastic modulus of the polyurethane foam of the present invention is preferably 50% or more, preferably 55% or more, from the viewpoint of good kicking and smooth foot movement when the polyurethane foam is used for a shoe sole or a mat. Is more preferable, and 60% or more is further preferable.
On the other hand, in the present invention, the upper limit of the rebound resilience is not particularly limited, but from the viewpoint of easily achieving a good balance with hardness and mechanical properties, it is preferably less than 80%, and preferably less than 75%. More preferably, it is less than 70%.
本発明のポリウレタンフォームの反発弾性率は、JIS K 6255に準拠して測定される。
The elastic modulus of the polyurethane foam of the present invention is measured in accordance with JIS K 6255.
本発明のポリウレタンフォームは、硬度が50未満であり、かつ、反発弾性率が50%以上であることが特に好ましい。かかるポリウレタンフォームであれば、初心者でも走り易く、かつ接地時の衝撃が良好に吸収され膝などへの負担が軽減される優れた靴底を提供することができる。
It is particularly preferable that the polyurethane foam of the present invention has a hardness of less than 50 and a rebound resilience of 50% or more. With such a polyurethane foam, it is possible to provide an excellent sole that is easy to run even for a beginner, absorbs the impact at the time of touchdown well, and reduces the burden on the knee and the like.
破断強度:
本発明のポリウレタンフォームの破断強度は、当該ポリウレタンフォームを用いてなる物品の耐久性を良好なものとするという観点から、1.0MPa以上であることが好ましく、1.5MPa以上であることがより好ましく、2.0MPa以上であることがさらに好ましい。特に破断強度が1.5MPa以上であるポリウレタンフォームを運動用シューズの靴底部材として用いた場合、靴底が、繰り返し衝撃を負荷され、あるいは湾曲するなどの厳しい使用環境下で使用されても、短期間で劣化することが防止されうる。 Breaking strength:
The breaking strength of the polyurethane foam of the present invention is preferably 1.0 MPa or more, more preferably 1.5 MPa or more, from the viewpoint of improving the durability of the article made of the polyurethane foam. It is preferably 2.0 MPa or more, and more preferably 2.0 MPa or more. In particular, when polyurethane foam having a breaking strength of 1.5 MPa or more is used as a sole member of exercise shoes, even if the sole is used in a harsh usage environment such as being repeatedly impacted or curved. Deterioration in a short period of time can be prevented.
本発明のポリウレタンフォームの破断強度は、当該ポリウレタンフォームを用いてなる物品の耐久性を良好なものとするという観点から、1.0MPa以上であることが好ましく、1.5MPa以上であることがより好ましく、2.0MPa以上であることがさらに好ましい。特に破断強度が1.5MPa以上であるポリウレタンフォームを運動用シューズの靴底部材として用いた場合、靴底が、繰り返し衝撃を負荷され、あるいは湾曲するなどの厳しい使用環境下で使用されても、短期間で劣化することが防止されうる。 Breaking strength:
The breaking strength of the polyurethane foam of the present invention is preferably 1.0 MPa or more, more preferably 1.5 MPa or more, from the viewpoint of improving the durability of the article made of the polyurethane foam. It is preferably 2.0 MPa or more, and more preferably 2.0 MPa or more. In particular, when polyurethane foam having a breaking strength of 1.5 MPa or more is used as a sole member of exercise shoes, even if the sole is used in a harsh usage environment such as being repeatedly impacted or curved. Deterioration in a short period of time can be prevented.
本発明のポリウレタンフォームの破断強度の測定方法は、JIS K 6251に準拠して測定される。
The method for measuring the breaking strength of the polyurethane foam of the present invention is measured in accordance with JIS K6251.
破断点伸度:
本発明のポリウレタンフォームの破断点伸度は、特に限定されないが、例えば靴底など繰り返しの屈曲が予想される用途に用いられる場合には、300%以上であることが好ましく、350%以上であることがより好ましく、400%以上であることがさらに好ましい。 Break point elongation:
The elongation at break point of the polyurethane foam of the present invention is not particularly limited, but is preferably 300% or more, preferably 350% or more, when used for applications where repeated bending is expected, such as soles. More preferably, it is more preferably 400% or more.
本発明のポリウレタンフォームの破断点伸度は、特に限定されないが、例えば靴底など繰り返しの屈曲が予想される用途に用いられる場合には、300%以上であることが好ましく、350%以上であることがより好ましく、400%以上であることがさらに好ましい。 Break point elongation:
The elongation at break point of the polyurethane foam of the present invention is not particularly limited, but is preferably 300% or more, preferably 350% or more, when used for applications where repeated bending is expected, such as soles. More preferably, it is more preferably 400% or more.
本発明のポリウレタンフォームの破断点伸度の測定方法は、JIS K 6251に準拠して測定される。
The method for measuring the elongation at break of the polyurethane foam of the present invention is measured in accordance with JIS K6251.
最大衝撃荷重:
本発明のポリウレタンフォームの最大衝撃荷重は、当該ポリウレタンフォームを用いてなる物品の衝撃吸収性を良好なものとするという観点から、下記のとおり測定された最大衝撃荷重の値が1.5kN以下であることが好ましい。最大衝撃荷重の測定は、厚み12.5mmにカットした試験片の落下衝撃試験において、砲弾状の錘w(鉄製、5.1kg)を50mmの高さから衝突させた際に、Instron社製 商品名「dynatup GRC8200」を用いて行うことができる。 Maximum impact load:
The maximum impact load of the polyurethane foam of the present invention is such that the maximum impact load measured as follows is 1.5 kN or less from the viewpoint of improving the impact absorption of the article made of the polyurethane foam. It is preferable to have. The maximum impact load is measured by a product manufactured by Instron when a bullet-shaped weight w (made of iron, 5.1 kg) is collided from a height of 50 mm in a drop impact test of a test piece cut to a thickness of 12.5 mm. It can be done using the name "dynatup GRC8200".
本発明のポリウレタンフォームの最大衝撃荷重は、当該ポリウレタンフォームを用いてなる物品の衝撃吸収性を良好なものとするという観点から、下記のとおり測定された最大衝撃荷重の値が1.5kN以下であることが好ましい。最大衝撃荷重の測定は、厚み12.5mmにカットした試験片の落下衝撃試験において、砲弾状の錘w(鉄製、5.1kg)を50mmの高さから衝突させた際に、Instron社製 商品名「dynatup GRC8200」を用いて行うことができる。 Maximum impact load:
The maximum impact load of the polyurethane foam of the present invention is such that the maximum impact load measured as follows is 1.5 kN or less from the viewpoint of improving the impact absorption of the article made of the polyurethane foam. It is preferable to have. The maximum impact load is measured by a product manufactured by Instron when a bullet-shaped weight w (made of iron, 5.1 kg) is collided from a height of 50 mm in a drop impact test of a test piece cut to a thickness of 12.5 mm. It can be done using the name "dynatup GRC8200".
屈曲性:
本発明のポリウレタンフォームの屈曲性は、特に限定されないが、例えば靴底など繰り返しの屈曲が予想される用途に用いられる場合には、下記の試験において亀裂が発生するまでの屈曲の回数が1万回以上であることが好ましい。試験は、厚み6mmにカットした試験片を厚さ2mmのテキソンボード(ボンテックス社製 商品名「#347」)に接着して作成された試験体を、角度90°、100回/分の速度で屈曲することで行われる。 Flexibility:
The flexibility of the polyurethane foam of the present invention is not particularly limited, but when it is used for applications where repeated bending is expected, such as soles, the number of bendings until cracks occur in the following test is 10,000. It is preferably more than once. In the test, a test piece prepared by adhering a test piece cut to a thickness of 6 mm to a texon board (trade name "# 347" manufactured by Bontex) having a thickness of 2 mm was formed at an angle of 90 ° at a speed of 100 times / minute. It is done by bending.
本発明のポリウレタンフォームの屈曲性は、特に限定されないが、例えば靴底など繰り返しの屈曲が予想される用途に用いられる場合には、下記の試験において亀裂が発生するまでの屈曲の回数が1万回以上であることが好ましい。試験は、厚み6mmにカットした試験片を厚さ2mmのテキソンボード(ボンテックス社製 商品名「#347」)に接着して作成された試験体を、角度90°、100回/分の速度で屈曲することで行われる。 Flexibility:
The flexibility of the polyurethane foam of the present invention is not particularly limited, but when it is used for applications where repeated bending is expected, such as soles, the number of bendings until cracks occur in the following test is 10,000. It is preferably more than once. In the test, a test piece prepared by adhering a test piece cut to a thickness of 6 mm to a texon board (trade name "# 347" manufactured by Bontex) having a thickness of 2 mm was formed at an angle of 90 ° at a speed of 100 times / minute. It is done by bending.
[靴底部材]
上述する本発明のポリウレタンフォームは、種々の用途に用いられる。中でも本発明のポリウレタンフォームは、良好な反発弾性を示すとともに硬度も低く抑えられ、かつ機械的物性にも優れるという点から、靴底部材として用いられることが好ましい。
本発明のポリウレタンフォームからなる靴底部材を用いて構成された靴底は、使用者の蹴り出しをサポートし、脚運びを容易なものとし、かつ良好な柔軟性を示し良好な履き心地を与えるだけでなく故障の発生を低減させることができる。したがって、上記靴底を備える靴は、多様な運動用シューズとして優れ、特に運動の初心者や高齢者に対し、好適である。
なお、本発明の靴底部材は、靴底の一部を構成する構成部材であってもよいし、靴底全体を構成するものであってもよい。ここで靴底とは、靴の底部分であって一体的な構成であってもよいし、インソールおよび/またはミッドソールと、アウトソールといった複数のパーツから構成されたものであってもよい。たとえばインソール、ミッドソール、アウトソールといった靴底を構成するいずれか1以上のパーツ全体を本発明の靴底部材で構成してもよいし、1パーツにおける任意の部分を本発明の靴底部材で構成することもできる。 [Shoe sole member]
The polyurethane foam of the present invention described above is used for various purposes. Above all, the polyurethane foam of the present invention is preferably used as a shoe sole member because it exhibits good impact resilience, its hardness is suppressed to a low level, and its mechanical properties are also excellent.
The sole made of the polyurethane foam of the present invention supports the user's kicking, facilitates leg movement, and exhibits good flexibility to provide good comfort. Not only that, the occurrence of failure can be reduced. Therefore, the shoes provided with the soles are excellent as various exercise shoes, and are particularly suitable for beginners and elderly people of exercise.
The sole member of the present invention may be a constituent member that constitutes a part of the sole, or may be a constituent member that constitutes the entire sole. Here, the sole may be a sole portion of the shoe and may have an integral structure, or may be composed of a plurality of parts such as an insole and / or a midsole and an outsole. For example, the entire one or more parts constituting the sole such as the insole, the midsole, and the outsole may be composed of the sole member of the present invention, or any part of one part may be made of the sole member of the present invention. It can also be configured.
上述する本発明のポリウレタンフォームは、種々の用途に用いられる。中でも本発明のポリウレタンフォームは、良好な反発弾性を示すとともに硬度も低く抑えられ、かつ機械的物性にも優れるという点から、靴底部材として用いられることが好ましい。
本発明のポリウレタンフォームからなる靴底部材を用いて構成された靴底は、使用者の蹴り出しをサポートし、脚運びを容易なものとし、かつ良好な柔軟性を示し良好な履き心地を与えるだけでなく故障の発生を低減させることができる。したがって、上記靴底を備える靴は、多様な運動用シューズとして優れ、特に運動の初心者や高齢者に対し、好適である。
なお、本発明の靴底部材は、靴底の一部を構成する構成部材であってもよいし、靴底全体を構成するものであってもよい。ここで靴底とは、靴の底部分であって一体的な構成であってもよいし、インソールおよび/またはミッドソールと、アウトソールといった複数のパーツから構成されたものであってもよい。たとえばインソール、ミッドソール、アウトソールといった靴底を構成するいずれか1以上のパーツ全体を本発明の靴底部材で構成してもよいし、1パーツにおける任意の部分を本発明の靴底部材で構成することもできる。 [Shoe sole member]
The polyurethane foam of the present invention described above is used for various purposes. Above all, the polyurethane foam of the present invention is preferably used as a shoe sole member because it exhibits good impact resilience, its hardness is suppressed to a low level, and its mechanical properties are also excellent.
The sole made of the polyurethane foam of the present invention supports the user's kicking, facilitates leg movement, and exhibits good flexibility to provide good comfort. Not only that, the occurrence of failure can be reduced. Therefore, the shoes provided with the soles are excellent as various exercise shoes, and are particularly suitable for beginners and elderly people of exercise.
The sole member of the present invention may be a constituent member that constitutes a part of the sole, or may be a constituent member that constitutes the entire sole. Here, the sole may be a sole portion of the shoe and may have an integral structure, or may be composed of a plurality of parts such as an insole and / or a midsole and an outsole. For example, the entire one or more parts constituting the sole such as the insole, the midsole, and the outsole may be composed of the sole member of the present invention, or any part of one part may be made of the sole member of the present invention. It can also be configured.
[マット]
また本発明のポリウレタンフォームは、マットの構成部材としても好適に使用されうる。即ち、本発明のポリウレタンフォームの、良好な反発弾性を示すとともに硬度も低く抑えられ、かつ機械的物性にも優れるという点は、マット、特には床敷マットにおいても優れた効果を発揮する。
本発明のポリウレタンフォームで製造されたマットを床に敷き、その上で長時間、作業、歩行、または起立などを行った場合、疲労の蓄積が軽減される。 [mat]
Further, the polyurethane foam of the present invention can be suitably used as a constituent member of a mat. That is, the polyurethane foam of the present invention exhibits excellent impact resilience, is suppressed to a low hardness, and is excellent in mechanical properties, and thus exhibits an excellent effect even in a mat, particularly a floor mat.
When a mat made of the polyurethane foam of the present invention is laid on the floor and the mat is used for a long time such as working, walking, or standing, the accumulation of fatigue is reduced.
また本発明のポリウレタンフォームは、マットの構成部材としても好適に使用されうる。即ち、本発明のポリウレタンフォームの、良好な反発弾性を示すとともに硬度も低く抑えられ、かつ機械的物性にも優れるという点は、マット、特には床敷マットにおいても優れた効果を発揮する。
本発明のポリウレタンフォームで製造されたマットを床に敷き、その上で長時間、作業、歩行、または起立などを行った場合、疲労の蓄積が軽減される。 [mat]
Further, the polyurethane foam of the present invention can be suitably used as a constituent member of a mat. That is, the polyurethane foam of the present invention exhibits excellent impact resilience, is suppressed to a low hardness, and is excellent in mechanical properties, and thus exhibits an excellent effect even in a mat, particularly a floor mat.
When a mat made of the polyurethane foam of the present invention is laid on the floor and the mat is used for a long time such as working, walking, or standing, the accumulation of fatigue is reduced.
表1に示す配合で、ポリオール成分、触媒、整泡剤、および発泡剤を混合してA液を調製し、上記A液とB液(ポリイソシアネート成分)とを表1に示す配合比で混合させながら、モールド内に注入し、モールド温度40℃の条件下で反応させた後、脱型してポリウレタンフォームを得た。
なお、表1中の材料の配合を示す数値の単位は、質量部である。 With the formulation shown in Table 1, the polyol component, catalyst, defoaming agent, and foaming agent are mixed to prepare solution A, and the solution A and solution B (polyisocyanate component) are mixed at the compounding ratio shown in Table 1. The mixture was poured into a mold and reacted under the condition of a mold temperature of 40 ° C., and then demolded to obtain a polyurethane foam.
The unit of the numerical value indicating the composition of the materials in Table 1 is a mass part.
なお、表1中の材料の配合を示す数値の単位は、質量部である。 With the formulation shown in Table 1, the polyol component, catalyst, defoaming agent, and foaming agent are mixed to prepare solution A, and the solution A and solution B (polyisocyanate component) are mixed at the compounding ratio shown in Table 1. The mixture was poured into a mold and reacted under the condition of a mold temperature of 40 ° C., and then demolded to obtain a polyurethane foam.
The unit of the numerical value indicating the composition of the materials in Table 1 is a mass part.
<ポリオール成分>
・PTMG2000:ポリテトラメチレンエーテルグリコール(数平均分子量2000、水酸基価57.2mgKOH/g、平均官能基数2)
<触媒>
・アミン系触媒:トリエチレンジアミン
<整泡剤>
・シリコーン系化合物:粘度:900mPa・s(25℃)
<発泡剤>
・イオン交換水
<ポリイソシアネート成分>
・イソシアネート基末端プレポリマー(PTMG2000に4、4'-MDIを反応させ
たプレポリマー;数平均分子量1000、平均官能基数2、イソシアネート基含有率8.01質量%)
・カルボジイミド変性MDI(カルボジイミド変性体、平均官能基数2、イソシアネート基含有率28.2%) <Polyol component>
-PTMG2000: Polytetramethylene ether glycol (number average molecular weight 2000, hydroxyl value 57.2 mgKOH / g, average number of functional groups 2)
<Catalyst>
・ Amine-based catalyst: Triethylenediamine <foaming agent>
-Silicone compound: Viscosity: 900 mPa · s (25 ° C)
<foaming agent>
・ Ion-exchanged water <polyisocyanate component>
-Isocyanate group-terminated prepolymer (prepolymer obtained by reacting PTMG2000 with 4, 4'-MDI; number average molecular weight 1000, average number of functional groups 2, isocyanate group content 8.01% by mass)
-Carbodiimide-modified MDI (carbodiimide-modified product, average number of functional groups 2, isocyanate group content 28.2%)
・PTMG2000:ポリテトラメチレンエーテルグリコール(数平均分子量2000、水酸基価57.2mgKOH/g、平均官能基数2)
<触媒>
・アミン系触媒:トリエチレンジアミン
<整泡剤>
・シリコーン系化合物:粘度:900mPa・s(25℃)
<発泡剤>
・イオン交換水
<ポリイソシアネート成分>
・イソシアネート基末端プレポリマー(PTMG2000に4、4'-MDIを反応させ
たプレポリマー;数平均分子量1000、平均官能基数2、イソシアネート基含有率8.01質量%)
・カルボジイミド変性MDI(カルボジイミド変性体、平均官能基数2、イソシアネート基含有率28.2%) <Polyol component>
-PTMG2000: Polytetramethylene ether glycol (number average molecular weight 2000, hydroxyl value 57.2 mgKOH / g, average number of functional groups 2)
<Catalyst>
・ Amine-based catalyst: Triethylenediamine <foaming agent>
-Silicone compound: Viscosity: 900 mPa · s (25 ° C)
<foaming agent>
・ Ion-exchanged water <polyisocyanate component>
-Isocyanate group-terminated prepolymer (prepolymer obtained by reacting PTMG2000 with 4, 4'-MDI; number average molecular weight 1000, average number of functional groups 2, isocyanate group content 8.01% by mass)
-Carbodiimide-modified MDI (carbodiimide-modified product, average number of functional groups 2, isocyanate group content 28.2%)
各実施例および各比較例で得られたポリウレタンフォームを適宜カットし、試験片を作成し、以下に示す測定を行った。測定結果は表1に示す。
<平均セル径(μm)>
得られたポリウレタンフォームを、無作為に選択した位置で切断して切断面を露出させた。当該切断面において、4mm×3mmの矩形領域を無作為に選択して選択領域とした。選択領域内に存在するセル(気泡)の個数(全セルの個数)、及び各セル径(各気泡の直径)を、マイクロスコープを用いて計測した。上述のとおり計測された各セル径の算術平均値を求め、平均気泡径とした。
<見かけ密度(g/cm3)>
15mm×15mm×10mmの直方体にカットした試験片を用い、JIS K 7222に準拠して見かけ密度を測定した。
<硬度>
アスカーC硬度
厚み12.5mmにカットした試験片を用い、JIS K 7312に準拠し、アスカーゴム硬度計C型を用いてポリウレタンフォームの硬度(アスカーC硬度)を測定した。<反発弾性率(%)>
厚み12.5mmにカットした試験片を用い、JIS K 6255に準拠して反発弾性率を測定した。
<破断強度(MPa)>
ダンベル状(2号形)にカットした試験片を用い、JIS K 6251に準拠し、ポリウレタンフォームの破断強度を測定した。
<破断点伸度(%)>
ダンベル状(2号形)にカットした試験片を用い、JIS K 6251に準拠し、ポリウレタンフォームの破断点伸度を測定した。
<最大衝撃荷重(kN)>
厚み12.5mmにカットした試験片の落下衝撃試験において、砲弾状の錘w(鉄製、5.1kg)を50mmの高さから衝突させた際に、Instron社製 商品名「dynatup GRC8200」を用いて、測定した最大衝撃荷重の値を指標とする。最大衝撃荷重は、値が小さいほど、衝撃が吸収されていることを示すものであり、本発明においては、1.5kN以下であれば衝撃吸収性が良好であると判断した。
<屈曲性試験(万回)>
厚み6mmにカットした試験片を厚さ2mmのテキソンボード(ボンテックス社製 商品名「#347」)に接着して作成された試験体を用いた。上記試験体を角度90°、100回/分の速度で屈曲させ、亀裂が発生するまでの回数をカウントした。本発明においては、1万回以上であれば屈曲性が良好であると判断した。 The polyurethane foams obtained in each Example and each Comparative Example were appropriately cut to prepare test pieces, and the measurements shown below were carried out. The measurement results are shown in Table 1.
<Average cell diameter (μm)>
The resulting polyurethane foam was cut at randomly selected positions to expose the cut surface. A rectangular region of 4 mm × 3 mm was randomly selected as the selected region on the cut surface. The number of cells (bubbles) existing in the selected region (the number of all cells) and the diameter of each cell (diameter of each bubble) were measured using a microscope. The arithmetic mean value of each cell diameter measured as described above was calculated and used as the average cell diameter.
<Appearance density (g / cm 3 )>
The apparent density was measured according to JIS K 7222 using a test piece cut into a rectangular parallelepiped of 15 mm × 15 mm × 10 mm.
<Hardness>
Asker C hardness Using a test piece cut to a thickness of 12.5 mm, the hardness of polyurethane foam (Asker C hardness) was measured using an Asker rubber hardness tester C type in accordance with JIS K 7312. <Repulsive modulus (%)>
The elastic modulus was measured according to JIS K 6255 using a test piece cut to a thickness of 12.5 mm.
<Breaking strength (MPa)>
Using a test piece cut into a dumbbell shape (No. 2 type), the breaking strength of the polyurethane foam was measured according to JIS K 6251.
<Elongation at breaking point (%)>
Using a test piece cut into a dumbbell shape (No. 2 type), the break point elongation of the polyurethane foam was measured according to JIS K 6251.
<Maximum impact load (kN)>
In the drop impact test of a test piece cut to a thickness of 12.5 mm, when a bullet-shaped weight w (made of iron, 5.1 kg) was made to collide from a height of 50 mm, the product name "dynatup GRC8200" manufactured by Instron was used. Then, the measured maximum impact load value is used as an index. The smaller the value of the maximum impact load, the more the impact is absorbed, and in the present invention, it is judged that the impact absorption is good when the value is 1.5 kN or less.
<Flexibility test (10,000 times)>
A test piece prepared by adhering a test piece cut to a thickness of 6 mm to a texton board having a thickness of 2 mm (trade name “# 347” manufactured by Bontex Co., Ltd.) was used. The test piece was bent at an angle of 90 ° and a speed of 100 times / minute, and the number of times until a crack occurred was counted. In the present invention, it was determined that the flexibility is good if the number of times is 10,000 or more.
<平均セル径(μm)>
得られたポリウレタンフォームを、無作為に選択した位置で切断して切断面を露出させた。当該切断面において、4mm×3mmの矩形領域を無作為に選択して選択領域とした。選択領域内に存在するセル(気泡)の個数(全セルの個数)、及び各セル径(各気泡の直径)を、マイクロスコープを用いて計測した。上述のとおり計測された各セル径の算術平均値を求め、平均気泡径とした。
<見かけ密度(g/cm3)>
15mm×15mm×10mmの直方体にカットした試験片を用い、JIS K 7222に準拠して見かけ密度を測定した。
<硬度>
アスカーC硬度
厚み12.5mmにカットした試験片を用い、JIS K 7312に準拠し、アスカーゴム硬度計C型を用いてポリウレタンフォームの硬度(アスカーC硬度)を測定した。<反発弾性率(%)>
厚み12.5mmにカットした試験片を用い、JIS K 6255に準拠して反発弾性率を測定した。
<破断強度(MPa)>
ダンベル状(2号形)にカットした試験片を用い、JIS K 6251に準拠し、ポリウレタンフォームの破断強度を測定した。
<破断点伸度(%)>
ダンベル状(2号形)にカットした試験片を用い、JIS K 6251に準拠し、ポリウレタンフォームの破断点伸度を測定した。
<最大衝撃荷重(kN)>
厚み12.5mmにカットした試験片の落下衝撃試験において、砲弾状の錘w(鉄製、5.1kg)を50mmの高さから衝突させた際に、Instron社製 商品名「dynatup GRC8200」を用いて、測定した最大衝撃荷重の値を指標とする。最大衝撃荷重は、値が小さいほど、衝撃が吸収されていることを示すものであり、本発明においては、1.5kN以下であれば衝撃吸収性が良好であると判断した。
<屈曲性試験(万回)>
厚み6mmにカットした試験片を厚さ2mmのテキソンボード(ボンテックス社製 商品名「#347」)に接着して作成された試験体を用いた。上記試験体を角度90°、100回/分の速度で屈曲させ、亀裂が発生するまでの回数をカウントした。本発明においては、1万回以上であれば屈曲性が良好であると判断した。 The polyurethane foams obtained in each Example and each Comparative Example were appropriately cut to prepare test pieces, and the measurements shown below were carried out. The measurement results are shown in Table 1.
<Average cell diameter (μm)>
The resulting polyurethane foam was cut at randomly selected positions to expose the cut surface. A rectangular region of 4 mm × 3 mm was randomly selected as the selected region on the cut surface. The number of cells (bubbles) existing in the selected region (the number of all cells) and the diameter of each cell (diameter of each bubble) were measured using a microscope. The arithmetic mean value of each cell diameter measured as described above was calculated and used as the average cell diameter.
<Appearance density (g / cm 3 )>
The apparent density was measured according to JIS K 7222 using a test piece cut into a rectangular parallelepiped of 15 mm × 15 mm × 10 mm.
<Hardness>
Asker C hardness Using a test piece cut to a thickness of 12.5 mm, the hardness of polyurethane foam (Asker C hardness) was measured using an Asker rubber hardness tester C type in accordance with JIS K 7312. <Repulsive modulus (%)>
The elastic modulus was measured according to JIS K 6255 using a test piece cut to a thickness of 12.5 mm.
<Breaking strength (MPa)>
Using a test piece cut into a dumbbell shape (No. 2 type), the breaking strength of the polyurethane foam was measured according to JIS K 6251.
<Elongation at breaking point (%)>
Using a test piece cut into a dumbbell shape (No. 2 type), the break point elongation of the polyurethane foam was measured according to JIS K 6251.
<Maximum impact load (kN)>
In the drop impact test of a test piece cut to a thickness of 12.5 mm, when a bullet-shaped weight w (made of iron, 5.1 kg) was made to collide from a height of 50 mm, the product name "dynatup GRC8200" manufactured by Instron was used. Then, the measured maximum impact load value is used as an index. The smaller the value of the maximum impact load, the more the impact is absorbed, and in the present invention, it is judged that the impact absorption is good when the value is 1.5 kN or less.
<Flexibility test (10,000 times)>
A test piece prepared by adhering a test piece cut to a thickness of 6 mm to a texton board having a thickness of 2 mm (trade name “# 347” manufactured by Bontex Co., Ltd.) was used. The test piece was bent at an angle of 90 ° and a speed of 100 times / minute, and the number of times until a crack occurred was counted. In the present invention, it was determined that the flexibility is good if the number of times is 10,000 or more.
本発明のポリウレタンフォームは、反発弾性に優れるものでありながら、硬度も低く維持され、かつ破断強度や破断点伸度といった機械的物性にも優れる。また、衝撃吸収性や屈曲性も優れるため、本発明のポリウレタンフォームは、靴底部材として好適である。加えて、本発明のポリウレタンフォームは、マット部材、ヘルメットの内部、プロテクター、車両用の緩衝材料、床材など、衝撃吸収性、反発弾性、適度な柔軟性、良好な機械的強度等が必要とされる用途に広く用いられる。
The polyurethane foam of the present invention has excellent impact resilience, is maintained at a low hardness, and is also excellent in mechanical properties such as breaking strength and breaking point elongation. In addition, the polyurethane foam of the present invention is suitable as a shoe sole member because it has excellent shock absorption and flexibility. In addition, the polyurethane foam of the present invention requires shock absorption, impact resilience, moderate flexibility, good mechanical strength, etc. for mat members, helmet interiors, protectors, vehicle cushioning materials, flooring materials, etc. Widely used in applications that are used.
上述する本発明は、下記の技術的思想を包含する。
(1)ポリオール成分、ポリイソシアネート成分、発泡剤、触媒、整泡剤を含むポリウレタン原料からなるポリウレタンフォームであって、
上記ポリオール成分は、数平均分子量が600以上3000以下であるポリテトラメチレンエーテルグリコールを含み、上記ポリオール成分中の上記ポリテトラメチレンエーテルグリコールの比率が90質量%以上であり、
上記ポリイソシアネート成分は、
i)数平均分子量が500以上2000以下であり、イソシアネート基含有率が3質量%以上10質量%以下のイソシアネート基末端プレポリマーと、
ii)イソシアネート基含有率が25質量%以上33質量%以下の変性MDIと、
を含み、
上記ポリイソシアネート成分中のイソシアネート基含有率が11質量%以上27質量%以下であることを特徴とするポリウレタンフォーム。
(2)上記ポリウレタンフォームを構成するセルの平均気泡径が100μm以上150μm以下である上記(1)に記載のポリウレタンフォーム。
(3)上記ポリオール成分中のポリテトラメチレンエーテルグリコールの比率が95質量%以上である上記(1)または(2)に記載のポリウレタンフォーム。
(4)JIS K 7312に準拠し、アスカーゴム硬度計C型を用いて測定されたポリウレタンフォームの硬度が50未満であり、
JIS K 6255に準拠して測定されたポリウレタンフォームの反発弾性率が60%以上である上記(1)から(3)のいずれか一項に記載のポリウレタンフォーム。
(5)JIS K 6251に準拠して測定されたポリウレタンフォームの破断強度が1.0Mpa以上である上記(1)から(4)のいずれか一項に記載のポリウレタンフォーム。
(6)JIS K 6251に準拠して測定されたポリウレタンフォームの破断点伸度が400%以上である上記(1)から(5)のいずれか一項に記載のポリウレタンフォーム。
(7)上記(1)から(6)のいずれか一項に記載のポリウレタンフォームを用いて構成されることを特徴とする靴底部材。 The present invention described above includes the following technical ideas.
(1) A polyurethane foam made of a polyurethane raw material containing a polyol component, a polyisocyanate component, a foaming agent, a catalyst, and a foam stabilizer.
The polyol component contains polytetramethylene ether glycol having a number average molecular weight of 600 or more and 3000 or less, and the ratio of the polytetramethylene ether glycol in the polyol component is 90% by mass or more.
The polyisocyanate component is
i) An isocyanate group-terminated prepolymer having a number average molecular weight of 500 or more and 2000 or less and an isocyanate group content of 3% by mass or more and 10% by mass or less.
ii) Modified MDI having an isocyanate group content of 25% by mass or more and 33% by mass or less,
Including
A polyurethane foam having an isocyanate group content of 11% by mass or more and 27% by mass or less in the polyisocyanate component.
(2) The polyurethane foam according to (1) above, wherein the average cell diameter of the cells constituting the polyurethane foam is 100 μm or more and 150 μm or less.
(3) The polyurethane foam according to (1) or (2) above, wherein the ratio of polytetramethylene ether glycol in the polyol component is 95% by mass or more.
(4) The hardness of the polyurethane foam measured using the Asker rubber hardness tester C type in accordance with JIS K 7312 is less than 50.
The polyurethane foam according to any one of (1) to (3) above, wherein the rebound resilience of the polyurethane foam measured in accordance with JIS K 6255 is 60% or more.
(5) The polyurethane foam according to any one of (1) to (4) above, wherein the breaking strength of the polyurethane foam measured in accordance with JIS K 6251 is 1.0 Mpa or more.
(6) The polyurethane foam according to any one of (1) to (5) above, wherein the breaking point elongation of the polyurethane foam measured in accordance with JIS K 6251 is 400% or more.
(7) A shoe sole member comprising the polyurethane foam according to any one of (1) to (6) above.
(1)ポリオール成分、ポリイソシアネート成分、発泡剤、触媒、整泡剤を含むポリウレタン原料からなるポリウレタンフォームであって、
上記ポリオール成分は、数平均分子量が600以上3000以下であるポリテトラメチレンエーテルグリコールを含み、上記ポリオール成分中の上記ポリテトラメチレンエーテルグリコールの比率が90質量%以上であり、
上記ポリイソシアネート成分は、
i)数平均分子量が500以上2000以下であり、イソシアネート基含有率が3質量%以上10質量%以下のイソシアネート基末端プレポリマーと、
ii)イソシアネート基含有率が25質量%以上33質量%以下の変性MDIと、
を含み、
上記ポリイソシアネート成分中のイソシアネート基含有率が11質量%以上27質量%以下であることを特徴とするポリウレタンフォーム。
(2)上記ポリウレタンフォームを構成するセルの平均気泡径が100μm以上150μm以下である上記(1)に記載のポリウレタンフォーム。
(3)上記ポリオール成分中のポリテトラメチレンエーテルグリコールの比率が95質量%以上である上記(1)または(2)に記載のポリウレタンフォーム。
(4)JIS K 7312に準拠し、アスカーゴム硬度計C型を用いて測定されたポリウレタンフォームの硬度が50未満であり、
JIS K 6255に準拠して測定されたポリウレタンフォームの反発弾性率が60%以上である上記(1)から(3)のいずれか一項に記載のポリウレタンフォーム。
(5)JIS K 6251に準拠して測定されたポリウレタンフォームの破断強度が1.0Mpa以上である上記(1)から(4)のいずれか一項に記載のポリウレタンフォーム。
(6)JIS K 6251に準拠して測定されたポリウレタンフォームの破断点伸度が400%以上である上記(1)から(5)のいずれか一項に記載のポリウレタンフォーム。
(7)上記(1)から(6)のいずれか一項に記載のポリウレタンフォームを用いて構成されることを特徴とする靴底部材。 The present invention described above includes the following technical ideas.
(1) A polyurethane foam made of a polyurethane raw material containing a polyol component, a polyisocyanate component, a foaming agent, a catalyst, and a foam stabilizer.
The polyol component contains polytetramethylene ether glycol having a number average molecular weight of 600 or more and 3000 or less, and the ratio of the polytetramethylene ether glycol in the polyol component is 90% by mass or more.
The polyisocyanate component is
i) An isocyanate group-terminated prepolymer having a number average molecular weight of 500 or more and 2000 or less and an isocyanate group content of 3% by mass or more and 10% by mass or less.
ii) Modified MDI having an isocyanate group content of 25% by mass or more and 33% by mass or less,
Including
A polyurethane foam having an isocyanate group content of 11% by mass or more and 27% by mass or less in the polyisocyanate component.
(2) The polyurethane foam according to (1) above, wherein the average cell diameter of the cells constituting the polyurethane foam is 100 μm or more and 150 μm or less.
(3) The polyurethane foam according to (1) or (2) above, wherein the ratio of polytetramethylene ether glycol in the polyol component is 95% by mass or more.
(4) The hardness of the polyurethane foam measured using the Asker rubber hardness tester C type in accordance with JIS K 7312 is less than 50.
The polyurethane foam according to any one of (1) to (3) above, wherein the rebound resilience of the polyurethane foam measured in accordance with JIS K 6255 is 60% or more.
(5) The polyurethane foam according to any one of (1) to (4) above, wherein the breaking strength of the polyurethane foam measured in accordance with JIS K 6251 is 1.0 Mpa or more.
(6) The polyurethane foam according to any one of (1) to (5) above, wherein the breaking point elongation of the polyurethane foam measured in accordance with JIS K 6251 is 400% or more.
(7) A shoe sole member comprising the polyurethane foam according to any one of (1) to (6) above.
Claims (7)
- ポリオール成分、ポリイソシアネート成分、発泡剤、触媒、整泡剤を含むポリウレタン原料からなるポリウレタンフォームであって、
前記ポリオール成分は、数平均分子量が600以上3000以下であるポリテトラメチレンエーテルグリコールを含み、前記ポリオール成分中の前記ポリテトラメチレンエーテルグリコールの比率が90質量%以上であり、
前記ポリイソシアネート成分は、
i)数平均分子量が500以上2000以下であり、イソシアネート基含有率が3質量%以上10質量%以下のイソシアネート基末端プレポリマーと、
ii)イソシアネート基含有率が25質量%以上33質量%以下の変性MDIと、
を含み、
前記ポリイソシアネート成分中のイソシアネート基含有率が11質量%以上27質量%以下であることを特徴とするポリウレタンフォーム。 A polyurethane foam made of a polyurethane raw material containing a polyol component, a polyisocyanate component, a foaming agent, a catalyst, and a foam stabilizer.
The polyol component contains polytetramethylene ether glycol having a number average molecular weight of 600 or more and 3000 or less, and the ratio of the polytetramethylene ether glycol in the polyol component is 90% by mass or more.
The polyisocyanate component is
i) An isocyanate group-terminated prepolymer having a number average molecular weight of 500 or more and 2000 or less and an isocyanate group content of 3% by mass or more and 10% by mass or less.
ii) Modified MDI having an isocyanate group content of 25% by mass or more and 33% by mass or less,
Including
A polyurethane foam having an isocyanate group content of 11% by mass or more and 27% by mass or less in the polyisocyanate component. - 前記ポリウレタンフォームを構成するセルの平均気泡径が100μm以上150μm以下である請求項1に記載のポリウレタンフォーム。 The polyurethane foam according to claim 1, wherein the average cell diameter of the cells constituting the polyurethane foam is 100 μm or more and 150 μm or less.
- 前記ポリオール成分中のポリテトラメチレンエーテルグリコールの比率が95質量%以上である請求項1または2に記載のポリウレタンフォーム。 The polyurethane foam according to claim 1 or 2, wherein the ratio of polytetramethylene ether glycol in the polyol component is 95% by mass or more.
- JIS K 7312に準拠し、アスカーゴム硬度計C型を用いて測定されたポリウレタンフォームの硬度が50未満であり、
JIS K 6255に準拠して測定されたポリウレタンフォームの反発弾性率が60%以上である請求項1から3のいずれか一項に記載のポリウレタンフォーム。 According to JIS K 7312, the hardness of the polyurethane foam measured using the Asker rubber hardness tester C type is less than 50.
The polyurethane foam according to any one of claims 1 to 3, wherein the elastic modulus of the polyurethane foam measured according to JIS K 6255 is 60% or more. - JIS K 6251に準拠して測定されたポリウレタンフォームの破断強度が1.0Mpa以上である請求項1から4のいずれか一項に記載のポリウレタンフォーム。 The polyurethane foam according to any one of claims 1 to 4, wherein the breaking strength of the polyurethane foam measured in accordance with JIS K6251 is 1.0 Mpa or more.
- JIS K 6251に準拠して測定されたポリウレタンフォームの破断点伸度が400%以上である請求項1から5のいずれか一項に記載のポリウレタンフォーム。 The polyurethane foam according to any one of claims 1 to 5, wherein the breaking point elongation of the polyurethane foam measured in accordance with JIS K6251 is 400% or more.
- 請求項1から6のいずれか一項に記載のポリウレタンフォームを用いて構成されることを特徴とする靴底部材。 A shoe sole member comprising the polyurethane foam according to any one of claims 1 to 6.
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