JP2023029435A - Foamed polyurethane resin composition, foamed polyurethane elastomer, and midsole - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a foamed polyurethane resin composition from which a foamed polyurethane elastomer having excellent impact resilience can be obtained, a foamed polyurethane elastomer which is excellent in impact resilience, and a midsole containing the foamed polyurethane elastomer.

SOLUTION: A foamed polyurethane resin composition contains a polyisocyanate component containing a terminal isocyanate group-containing prepolymer, a polyol component, water and a modifier. The modifier is organopolysiloxane modified with oxyalkylene. A content ratio of an Si atom to the total amount of the organopolysiloxane modified with oxyalkylene is 15 mass% or more. A content ratio of an oxyethylene group to the total amount of the oxyalkylene is 60 mass% or more.

SELECTED DRAWING: None

COPYRIGHT: (C)2023,JPO&INPIT

Description

The present invention relates to a foamed polyurethane resin composition, a foamed polyurethane elastomer and a midsole.

BACKGROUND ART Conventionally, foamed polyurethane elastomers have been used as cushioning materials, shock absorbing materials, vibration absorbing materials, cushion materials, mattress materials, sound absorbing materials, and the like.

As such foamed polyurethane elastomer, for example, a foamed polyurethane elastomer obtained by injecting a polyurethane resin composition containing a polyisocyanate component and a polyol component into a mold, followed by foaming and curing and molding into a desired shape is known. It is

For example, a polyisocyanate component containing an isocyanate group-terminated prepolymer obtained by reacting a polyphenylmethane polyisocyanate and a polyether polyol is mixed with a polyol component to prepare a polyurethane composition. A foamed polyurethane elastomer obtained by injecting into a mold and foaming has been proposed (see, for example, Patent Document 1).

JP 2016-204403 A

On the other hand, foamed polyurethane elastomers are sometimes required to have excellent impact resilience depending on the application.

The present invention provides a foamed polyurethane resin composition from which a foamed polyurethane elastomer having excellent impact resilience can be obtained, a foamed polyurethane elastomer having excellent impact resilience, and a midsole containing the foamed polyurethane elastomer.

The present invention [1] contains a polyisocyanate component containing a terminal isocyanate group-containing prepolymer that is a reaction product of an aromatic polyisocyanate and a polyol, a polyol component, water, and a modifier, The modifier is an oxyalkylene-modified organopolysiloxane, the content of Si atoms in the total amount of the oxyalkylene-modified organopolysiloxane is 15.0% by mass or more, and the total amount of the oxyalkylene A foamed polyurethane resin composition characterized in that the content of oxyethylene is 60% by mass or more.

In the present invention [2], the content of the modifier is 0.027 parts by mass or more and 1.375 parts by mass or less with respect to the total amount of 100 parts by mass of the polyisocyanate component, the polyol component and the water. The foamed polyurethane resin composition according to [1] is included.

The present invention [3] is the above-mentioned [1] or [2], wherein in the organopolysiloxane modified with oxyalkylene, the ratio of oxyethylene in the oxyalkylene at the molecular terminal is 50 mol% or more. A foamed polyurethane resin composition is included.

In the present invention [4], the polyol in the terminal isocyanate group-containing prepolymer is composed of a high molecular weight polyol having a number average molecular weight of 500 or more and 3000 or less and an average number of hydroxyl groups of 2, and the polyol component has a number average molecular weight of 500 or more and 3000 or less. , the foamed polyurethane resin composition according to any one of the above [1] to [3], which is composed of a high molecular weight polyol having an average number of hydroxyl groups of 2 to 3.

The present invention [5] includes a polyurethane foam elastomer comprising a foamed cured product of the polyurethane foam resin composition according to any one of [1] to [4] above.

The present invention [6] includes a midsole characterized by including the foamed polyurethane elastomer according to [5] above.

The foamed polyurethane resin composition of the present invention contains a modifier, the modifier is an oxyalkylene-modified organopolysiloxane, and the total amount of the oxyalkylene-modified organopolysiloxane is , and the content of oxyethylene units with respect to the total amount of oxyalkylene is the above ratio.

Therefore, according to such a foamed polyurethane resin composition, a foamed polyurethane elastomer having excellent impact resilience can be obtained.

In addition, the foamed polyurethane elastomer and the midsole of the present invention are obtained from the above foamed polyurethane resin composition, and are therefore excellent in impact resilience.

<Polyurethane foam resin composition>
The polyurethane foam resin composition of the present invention contains, as essential components, a polyisocyanate component, a polyol component, water, and a modifier.

1. Polyisocyanate Component The polyisocyanate component contains a prepolymer containing terminal isocyanate groups that is the reaction product of an aromatic polyisocyanate and a polyol.

Examples of aromatic polyisocyanates include aromatic polyisocyanate monomers and aromatic polyisocyanate derivatives.

Aromatic polyisocyanate monomers include, for example, m- or p-phenylene diisocyanate or mixtures thereof, 2,4- or 2,6-tolylene diisocyanate or mixtures thereof (TDI), 4,4′-, 2, 4'- or 2,2'-diphenylmethane diisocyanate or mixtures thereof (MDI), 4,4'-toluidine diisocyanate (TODI), 4,4'-diphenyl ether diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene aromatic diisocyanates such as diisocyanate (NDI);

Examples of aromatic polyisocyanate derivatives include oligomers of aromatic polyisocyanate monomers (e.g., dimers, trimers (e.g., isocyanurate modified products, iminooxadiazinedione modified products), pentamers, , heptamer, etc.), allophanate modified products (e.g., aromatic polyisocyanate monomers, allophanate modified products produced by reaction with monohydric alcohols (described later) and / or dihydric alcohols (described later)), polyols Modified products (e.g., aromatic polyisocyanate monomers and polyol modified products (alcohol adducts) produced by reaction with trihydric or higher alcohols (described later)), biuret modified products (e.g., aromatic polyisocyanate monomers Biuret modified product produced by reaction of monomer with water or amines), urea modified product (for example, urea modified product produced by reaction of aromatic polyisocyanate monomer and diamine), oxadiazine Modified trione (for example, oxadiazine trione generated by reaction of aromatic polyisocyanate monomer and carbon dioxide gas), modified carbodiimide (modified carbodiimide generated by decarboxylation condensation reaction of aromatic polyisocyanate monomer) and the like), modified uretdione, modified uretonimine, and the like.

Furthermore, examples of aromatic polyisocyanate derivatives include polymethylene polyphenyl polyisocyanate (crude MDI, polymeric MDI, polynuclear-containing diphenylmethane diisocyanate (p-MDI)), and the like.

These aromatic polyisocyanates can be used alone or in combination of two or more.

The aromatic polyisocyanate preferably includes aromatic polyisocyanate derivatives, more preferably polymethylene polyphenyl polyisocyanate (p-MDI).

The isocyanate group content (NCO%) of the aromatic polyisocyanate is, for example, 10% by mass or more, preferably 20% by mass or more, and for example, 50% by mass or less, preferably 40% by mass or less. The isocyanate group content can be measured by the n-butylamine method according to JIS K-1603-1 (2007) using a potentiometric titrator (the same applies hereinafter).

Examples of polyols include low-molecular-weight polyols having a molecular weight of less than 250 and high-molecular-weight polyols having a molecular weight (number-average molecular weight) of 250 or more.

A low-molecular-weight polyol is a compound having two or more hydroxyl groups and having a molecular weight of 60 or more and less than 250, preferably 200 or less. Low-molecular-weight polyols include, for example, dihydric alcohols (e.g., ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butylene glycol, 1,3-butylene glycol, 1,2-butylene glycol, 1, 5-pentanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, dipropylene glycol, 3-methyl-1,5-pentanediol, isosorbide, 1,3- or 1,4-cyclohexanedimethanol and their mixture, 1,4-cyclohexanediol, hydrogenated bisphenol A, 1,4-dihydroxy-2-butene, 2,6-dimethyl-1-octene-3,8-diol, bisphenol A, etc.), trihydric alcohols (e.g. , glycerin, trimethylolpropane, etc.), tetrahydric alcohols (e.g., tetramethylolmethane (pentaerythritol), diglycerin, etc.), pentahydric alcohols (e.g., xylitol, etc.), hexahydric alcohols (e.g., sorbitol, etc.), heptahydric alcohols alcohols (eg, perseitol, etc.), and the like. These low-molecular-weight polyols can be used singly or in combination of two or more.

The high-molecular-weight polyol has a number average molecular weight having two or more hydroxyl groups (molecular weight in terms of standard polyoxyethylene by GPC, or a molecular weight calculated based on the average hydroxyl value and the average number of functional groups (hereinafter the same)) of 250 or more, preferably 400 or more, more preferably 500 or more, more preferably 600 or more, for example 10000 or less, preferably 5000 or less, more preferably 3000 or less, still more preferably 2000 or less.

Examples of high-molecular-weight polyols include polyether polyols, polyester polyols, polycarbonate polyols, polyurethane polyols, epoxy polyols, vegetable oil polyols, polyolefin polyols, acrylic polyols, silicone polyols, fluorine polyols, and vinyl monomer-modified polyols.

Examples of polyether polyols include polyoxy(C2-3) alkylene polyols (e.g., polyoxyethylene polyols, polyoxypropylene polyols, polyoxyethylene polyoxypropylene copolymers, polytrimethylene ether polyols, etc.), polytetramethylene ethers and polyols.

Examples of polyester polyols include adipate-based polyester polyols, phthalic acid-based polyester polyols, and lactone-based polyester polyols.

Polycarbonate polyols include, for example, a ring-opening polymer of ethylene carbonate using the low-molecular-weight polyol as an initiator, and an amorphous polycarbonate polyol obtained by copolymerizing the above-described dihydric alcohol and ring-opening polymer.

Examples of polyurethane polyols include polyester polyurethane polyols, polyether polyurethane polyols, polycarbonate polyurethane polyols, and polyester polyether polyurethane polyols.

Epoxy polyols include, for example, reaction products of the aforementioned low molecular weight polyols and polyfunctional halohydrins (eg, epichlorohydrin, β-methylepichlorohydrin, etc.).

Vegetable oil polyols include, for example, hydroxyl group-containing vegetable oils (eg, castor oil, coconut oil, etc.), ester-modified castor oil polyols, and the like.

Polyolefin polyols include, for example, polybutadiene polyols and partially saponified ethylene-vinyl acetate copolymers.

Examples of acrylic polyols include hydroxyl group-containing acrylates (e.g., 2-hydroxyethyl (meth)acrylate) and copolymerizable vinyl monomers (e.g., alkyl (meth)acrylates, aromatic vinyl monomers, etc.). and copolymers with.

Examples of silicone polyols include acrylic polyols in which a vinyl group-containing silicone compound (eg, γ-methacryloxypropyltrimethoxysilane, etc.) is blended as a copolymerizable vinyl monomer in the copolymerization of the acrylic polyols described above. be done.

Examples of fluoropolyols include acrylic polyols in which a vinyl group-containing fluorine compound (e.g., tetrafluoroethylene, chlorotrifluoroethylene, etc.) is blended as a copolymerizable vinyl monomer in the above-described acrylic polyol copolymerization. be done.

Examples of vinyl monomer-modified polyols include reaction products of the above-described high-molecular-weight polyols and vinyl monomers (eg, alkyl (meth)acrylates, etc.).

These high molecular weight polyols can be used alone or in combination of two or more.

High molecular weight polyols preferably include polyether polyols, more preferably polytetramethylene ether polyols.

The average number of hydroxyl groups (average number of functional groups) of the high-molecular-weight polyol is, for example, 2 or more, for example 5 or less, preferably 4 or less, more preferably 3 or less, still more preferably 2.5 or less, and particularly preferably. is 2. Incidentally, the average number of hydroxyl groups (average number of functional groups) can be calculated from the charged components (the same applies hereinafter).

The average hydroxyl value of the high-molecular-weight polyol is, for example, 28 mgKOH/g or more, preferably 37 mgKOH/g or more, and for example, 187 mgKOH/g or less, preferably 112 mgKOH/g or less. The average hydroxyl value can be measured by the acetylation method or phthalation method according to JIS K-1557-1 (2007) (the same shall apply hereinafter).

These polyols can be used alone or in combination of two or more.

Polyols preferably include high-molecular-weight polyols, more preferably polyether polyols, and still more preferably polytetramethylene ether polyols.

Thus, the polyol preferably comprises a high molecular weight polyol, more preferably a polyether polyol, even more preferably a polytetramethylene ether polyol.

When the polyol contains polytetramethylene ether polyol, it is possible to form soft segments generated by the reaction of aromatic polyisocyanate and polytetramethylene ether polyol in the foamed polyurethane elastomer (described later), thereby improving mechanical properties. can be planned.

As described above, the polyol may contain a low-molecular-weight polyol, but from the viewpoint of the mechanical properties of the foamed polyurethane elastomer (described later), it preferably does not contain a low-molecular-weight polyol and consists of a high-molecular-weight polyol.

The average number of hydroxyl groups (average number of functional groups) of the polyol is, for example, 2 or more, for example 5 or less, preferably 4 or less, more preferably 3 or less, still more preferably 2.5 or less, and particularly preferably 2.

Also, the average hydroxyl value of the polyol is, for example, 28 mgKOH/g or more, preferably 37 mgKOH/g or more, and for example, 187 mgKOH/g or less, preferably 112 mgKOH/g or less.

The terminal isocyanate group-containing prepolymer is prepared by reacting the aromatic polyisocyanate described above with the polyol described above in such a proportion that free isocyanate groups remain.

The terminal isocyanate group-containing prepolymer has free isocyanate groups at least at both ends of the molecule.

The average functional group number of isocyanate groups in the terminal isocyanate group-containing prepolymer is, for example, 2 or more, for example, 5 or less, preferably 4 or less, and more preferably 3 or less.

The isocyanate group content (NCO%) in the terminal isocyanate group-containing prepolymer is, for example, 1% by mass or more, preferably 5% by mass or more, for example, 30% by mass or less, preferably 20% by mass or less, more preferably , 15% by mass or less.

A commercially available product can also be used for such a terminal isocyanate group-containing prepolymer.

Such a polyisocyanate component can contain other isocyanates (e.g., carbodiimide-modified MDI derivatives, o-MDI, etc.) in addition to the terminal isocyanate group-containing prepolymer, but is preferably a terminal isocyanate group-containing prepolymer. consists of

2. Polyol Component Examples of the polyol component include the low-molecular-weight polyols described above and the high-molecular-weight polyols described above.

The polyol component can be used alone or in combination of two or more.

As the polyol component, a high molecular weight polyol is preferably used from the viewpoint of the mechanical properties of the foamed polyurethane elastomer (described later). The polyol component more preferably does not contain low molecular weight polyols and consists of high molecular weight polyols as described above.

As described above, the high-molecular-weight polyol has two or more hydroxyl groups and has a number average molecular weight (molecular weight in terms of standard polystyrene by GPC) of 250 or more, preferably 400 or more, more preferably 500 or more, and still more preferably 600 or more. , for example, 10000 or less, preferably 5000 or less, more preferably 3000 or less, still more preferably 1500 or less.

The high-molecular-weight polyols preferably include polyether polyols, more preferably polyoxy(C2-3) alkylene polyols and polytetramethylene ether polyols, and particularly preferably polyoxy(C2-3) alkylene polyols and , combined use with polytetramethylene ether polyol.

Polyoxyalkylene (C2-3) polyols include, for example, addition polymers of alkylene oxides having 2 to 3 carbon atoms using the aforementioned low-molecular-weight polyols and known polyamines as initiators.

Examples of alkylene oxides having 2 to 3 carbon atoms include ethylene oxide, propylene oxide (1,2-propylene oxide) and trimethylene oxide (1,3-propylene oxide). Moreover, these alkylene oxides can be used alone or in combination of two or more.

Examples of polyoxyalkylene (C2-3) polyols include polyoxyethylene polyols, polyoxypropylene polyols, polyoxytrimethylene polyols, polyoxyethylene polyoxypropylene copolymers (random and/or or block copolymer).

Polyoxyalkylene (C2-3) polyols preferably include polyoxyethylene polyols, polyoxypropylene polyols and polyoxyethylene polyoxypropylene copolymers, more preferably polyoxypropylene polyols.

Polyoxypropylene polyol can have ethylene oxide added to its molecular terminal, if necessary. That is, polyoxypropylene polyol can have oxyethylene at the molecular end.

Polyoxypropylene polyols preferably include polyoxypropylene polyols having oxyethylene at the molecular ends from the viewpoint of mechanical properties (in particular, mechanical strength and elongation properties).

These polyoxyalkylene (C2-3) polyols can be used alone or in combination of two or more.

The number average molecular weight of the polyoxy(C2-3)alkylene polyol is, for example, 250 or more, preferably 400 or more, more preferably 500 or more, and for example, 10000 or less, preferably 2000 or less, more preferably 1200. It is below.

Further, the average number of hydroxyl groups (average number of functional groups) of the polyoxy(C2-3)alkylene polyol is, for example, 2 or more, preferably 3 or more, for example, 5 or less, preferably 4 or less, more preferably 3 0.5 or less, particularly preferably 3.

The average hydroxyl value of the polyoxy(C2-3)alkylene polyol is, for example, 33 mgKOH/g or more, preferably 56 mgKOH/g or more, more preferably 84 mgKOH/g or more, still more preferably 112 mgKOH/g or more, especially Preferably, it is 132 mgKOH/g or more, for example, 210 mgKOH/g or less, preferably 187 mgKOH/g or less.

Polytetramethylene ether polyols include, for example, a ring-opening polymer obtained by cationic polymerization of tetrahydrofuran (polytetramethylene ether glycol (crystalline)), a polymerization unit such as tetrahydrofuran, an alkyl-substituted tetrahydrofuran, the above-described divalent Amorphous (non-crystalline) polytetramethylene ether glycol obtained by copolymerizing alcohol and the like can be mentioned.

These polytetramethylene ether polyols can be used alone or in combination of two or more.

The number average molecular weight of the polyoxy(C2-3)alkylene polyol is, for example, 250 or more, preferably 800 or more, more preferably 1,300 or more, and for example, 10,000 or less, preferably 5,000 or less, more preferably 2,000. It is below.

In addition, the average number of hydroxyl groups (average number of functional groups) of the polytetramethylene ether polyol is, for example, 2 or more, for example 5 or less, preferably 4 or less, more preferably 3 or less, still more preferably less than 3, and still more preferably is 2.5 or less, particularly preferably 2.

Further, the average hydroxyl value of the polytetramethylene ether polyol is, for example, 33 mgKOH/g or more, preferably 56 mgKOH/g or more, for example 168 mgKOH/g or less, preferably less than 112 mgKOH/g, more preferably 84 mgKOH/g. is less than

The combined ratio of polyoxy (C2-3) alkylene polyol and polytetramethylene ether polyol is not particularly limited, but from the viewpoint of mechanical properties, for example, the total amount of polyoxy (C2-3) alkylene polyol and polytetramethylene ether glycol is 100 mass. The polyoxy (C2-3) alkylene polyol is, for example, 10 parts by mass or more, preferably 15 parts by mass or more, and for example, 50 parts by mass or less, preferably 30 parts by mass or less. Polytetramethylene ether glycol is, for example, 50 parts by mass or more, preferably 70 parts by mass or more, and is, for example, 90 parts by mass or less, preferably 85 parts by mass or less.

If the combined ratio of polyoxy(C2-3)alkylene polyol and polytetramethylene ether glycol is within the above range, a foamed polyurethane elastomer (described later) having excellent mechanical properties can be obtained.

As the polyol component, preferably two or more high molecular weight polyols having different number average molecular weights are used in combination, more preferably two high molecular weight polyols having different number average molecular weights are used in combination.

In such a case, the number average molecular weight of one high molecular weight polyol is, for example, 400 or more, preferably 500 or more, and for example, 2000 or less, preferably 1200 or less.

The number average molecular weight of the other high-molecular-weight polyol is, for example, 800 or more, preferably 1,300 or more, and for example, 5,000 or less, preferably 2,000 or less.

In addition, as the polyol component, preferably two or more types of high molecular weight polyols having mutually different average numbers of hydroxyl groups (average number of functional groups) are used in combination, more preferably two types having mutually different average numbers of hydroxyl groups (average number of functional groups). is used in combination with a high molecular weight polyol.

In such a case, the average number of hydroxyl groups of one of the high-molecular-weight polyols is, for example, 3 or more, for example, 5 or less, preferably 4 or less, and particularly preferably 3.

The average number of hydroxyl groups of the other high-molecular-weight polyol is, for example, 2 or more, but less than 3, preferably 2.5 or less, and particularly preferably 2.

As the polyol component, preferably two or more high molecular weight polyols having mutually different average hydroxyl values are used in combination, more preferably two kinds of high molecular weight polyols having mutually different average hydroxyl values are used together.

In such a case, the average hydroxyl value of one of the high molecular weight polyols is, for example, 112 mgKOH/g or more, preferably 132 mgKOH/g or more, and for example, 210 mgKOH/g or less, preferably 187 mgKOH/g or less.

The average hydroxyl value of the other high molecular weight polyol is, for example, 33 mgKOH/g or more, preferably 56 mgKOH/g or more, and is, for example, less than 112 mgKOH/g, preferably less than 84 mgKOH/g.

As described above, the polyol component may contain a low-molecular-weight polyol, but from the viewpoint of the mechanical properties of the foamed polyurethane elastomer (described later), it preferably does not contain a low-molecular-weight polyol and consists of a high-molecular-weight polyol. , more preferably polyether polyols, more preferably polyoxy(C2-3) alkylene polyols and polytetramethylene ether glycols.

The number average molecular weight of the polyol component (total amount) is, for example, 250 or more, preferably 400 or more, more preferably 500 or more, still more preferably 600 or more, for example 10000 or less, preferably 5000 or less, more preferably , 3000 or less, more preferably 1500 or less.

In addition, the average number of hydroxyl groups (average number of functional groups) of the polyol component is, for example, 2 or more and, for example, 5 or less, preferably 4 or less, more preferably 3 or less.

The average hydroxyl value of the polyol component is, for example, 33.7 mgKOH/g or more, preferably 56.1 mgKOH/g or more, and for example, 187 mgKOH/g or less, preferably 168.3 mgKOH/g or less.

3. Water Water is a chemical blowing agent that reacts with the isocyanate groups of the polyisocyanate component to produce carbon dioxide.

The content of water is, for example, 0.1 parts by mass or more, preferably 1.0 parts by mass or more, for example 5.0 parts by mass or less, preferably 3.0 parts by mass, with respect to 100 parts by mass of the polyol component. It is below the department.

4. Modifier A modifier is an additive for improving the impact resilience of a foamed polyurethane elastomer (described later), that is, an elasticity improver.

Modifiers include, more specifically, oxyalkylene-modified organopolysiloxanes (hereinafter referred to as oxyalkylene-modified organopolysiloxanes). In other words, the modifier consists of an oxyalkylene-modified organopolysiloxane.

Examples of the oxyalkylene-modified organopolysiloxane include, for example, an organopolysiloxane whose main chain end is modified with oxyalkylene, an organopolysiloxane whose side chain is modified with oxyalkylene, and an organopolysiloxane whose main chain end and side chain are both modified with oxyalkylene. Examples include modified organopolysiloxanes. When the main chain end is modified with oxyalkylene, for example, an organopolysiloxane in which only one end of the main chain is modified with oxyalkylene, or an organopolysiloxane in which both ends of the main chain are modified with oxyalkylene. etc. These oxyalkylene-modified organopolysiloxanes can be used alone or in combination of two or more.

In the oxyalkylene-modified organopolysiloxane, the number of oxyalkylene units may be singular or plural. In other words, oxyalkylene includes monooxyalkylene and polyoxyalkylene, and from the viewpoint of various mechanical properties and foamability, polyoxyalkylene is preferred.

The number of oxyalkylene units is, for example, 1 or more, preferably 2 or more, and is, for example, 100 or less, preferably 50 or less.

Oxyalkylenes contain, as an essential oxyalkylene unit, oxyalkylenes having 2 carbon atoms, ie, oxyethylene (OCH ₂ CH ₂ ).

In addition, oxyalkylene can contain oxyalkylene having 3 to 4 carbon atoms as an optional oxyalkylene unit, if necessary.

Examples of oxyalkylenes having 3 to 4 carbon atoms include secondary oxypropylene (OCH(CH ₃ )CH ₂ ), primary oxypropylene (OCH ₂ CH(CH ₃ )), oxytrimethylene (OCH ₂ CH ₂ CH ₂ ), oxytetramethylene ( _{OCH2CH2CH2CH2 ) ,} and the like _. These can be used alone or in combination of two or more.

In addition, in the oxyalkylene-modified organopolysiloxane, the oxyalkylene at the molecular terminal (main chain terminal and/or side chain terminal) is selected from the above oxyalkylenes.

The ratio of oxyethylene in the oxyalkylene at the molecular terminal (main chain terminal and/or side chain terminal) is, for example, 50 mol% or more, preferably 80 mol% or more, more preferably 80 mol% or more, relative to the total moles of oxyalkylene. is 90 mol % or more, more preferably 95 mol % or more, and most preferably 100 mol %.

If the ratio of oxyethylene in the oxyalkylene at the molecular terminal is within the above range, the impact resilience is excellent, and various mechanical properties such as hardness, tensile strength, elongation at break, tear strength, and compression set are excellent. A foamed polyurethane elastomer (described later) having an excellent appearance can be obtained.

The type of oxyalkylene at the molecular terminal of oxyalkylene can be specified according to the examples described later (the same applies hereinafter).

In addition, the content of oxyethylene is 60% by mass or more, preferably 65% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, particularly preferably 80% by mass or more, with respect to the total amount of oxyalkylene. is 90 mass % or more, for example, 100 mass % or less, preferably 99 mass %, more preferably 95 mass % or less.

In addition, the content of oxyethylene can be measured according to the examples described later (the same applies hereinafter).

If the content ratio of oxyethylene to the total amount of oxyalkylene is within the above range, the impact resilience is excellent, and various mechanical properties such as hardness, tensile strength, elongation at break, tear strength, and compression set are excellent. It is possible to obtain a foamed polyurethane elastomer (described later) which is also excellent in

The oxyalkylene may be directly bonded to the Si atom of the organopolysiloxane, or indirectly bonded to the Si atom of the organopolysiloxane via a divalent hydrocarbon group (e.g., methylene). may be

Also, the oxyalkylene-modified organopolysiloxane contains Si atoms.

In the oxyalkylene-modified organopolysiloxane, the content of Si atoms is 15.0% by mass or more, preferably 15.1% by mass or more, more preferably 15% by mass, based on the total mass of the oxyalkylene-modified organopolysiloxane. .2% by mass or more, more preferably 15.3% by mass or more, for example, 30.0% by mass or less, preferably 25.0% by mass or less, more preferably 20.0% by mass or less, and further It is preferably 18.0% by mass or less, particularly preferably 16.0% by mass or less.

In addition, the content ratio of Si atoms can be measured according to the examples described later (the same applies hereinafter).

If the content ratio of Si atoms in the oxyalkylene-modified organopolysiloxane is within the above range, the impact resilience is excellent, and various mechanical properties such as hardness, tensile strength, elongation at break, tear strength, and compression set are excellent. , a foamed polyurethane elastomer (described later) having an excellent appearance can be obtained.

Further, the content of oxyalkylene relative to the total amount of oxyalkylene-modified organopolysiloxane is, for example, 30% by mass or more, preferably 40% by mass or more, more preferably 50% by mass or more, and still more preferably 55% by mass. % by mass or more, particularly preferably 60% by mass or more and, for example, 90% by mass or less.

The content of oxyalkylene can be measured according to the examples described later (the same applies hereinafter).

If the oxyalkylene content is within the above range, the foamed polyurethane is excellent in rebound resilience, excellent in various mechanical properties such as hardness, tensile strength, elongation at break, tear strength, and compression set, and also excellent in appearance. Elastomers (described below) can be obtained.

In addition, the hydroxyl group equivalent of the oxyalkylene-modified organopolysiloxane is, from the viewpoint of the mechanical properties of the foamed polyurethane elastomer (described later), for example, 300 or more, preferably 400 or more, more preferably 500 or more, and for example, 1000 or less. , preferably 800 or less, more preferably 600 or less.

Such modifiers are available as commercial products. Commercially available products include, for example, L-1169, L1160 (manufactured by Momentive Performance Materials Japan LLC), B8545 (manufactured by Evonik), etc., preferably L-1169 and L1160 (manufactured by Momentive Performance Materials Japan LLC). manufactured by Momentive Performance Materials Japan LLC).

These oxyalkylene-modified organopolysiloxanes can be used alone or in combination of two or more.

The content of the modifier (oxyalkylene-modified organopolysiloxane) in the foamed polyurethane resin composition is appropriately set according to the purpose and application.

For example, the content of the modifier (oxyalkylene-modified organopolysiloxane) is, for example, 0.010 parts by mass or more, preferably 0.025 parts by mass, with respect to the total amount of 100 parts by mass of the polyisocyanate component, the polyol component and water. parts by mass or more, more preferably 0.027 parts by mass or more, more preferably 0.050 parts by mass or more, still more preferably 0.100 parts by mass or more, particularly preferably 0.300 parts by mass or more, For example, 5.000 parts by mass or less, preferably 2.000 parts by mass or less, more preferably 1.500 parts by mass or less, even more preferably 1.375 parts by mass or less, still more preferably 1.000 parts by mass Below, especially preferably, it is 0.500 mass parts or less.

If the content of the modifier is within the above range, the resulting foam has excellent impact resilience, excellent mechanical properties such as hardness, tensile strength, elongation at break, tear strength, and compression set, and also has excellent appearance. A polyurethane elastomer (described later) can be obtained.

5. Catalyst The foamed polyurethane resin composition may optionally contain a catalyst.

Examples of catalysts include known urethanization catalysts, more specifically amine catalysts, organometallic compounds, and the like.

Examples of amine catalysts include triethylamine, tripropylamine, polyisopropanolamine, tributylamine, trioctylamine, hexamethyldimethylamine, N-methylmorpholine, N-ethylmorpholine, N-octadecylmorpholine, monoethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N,N-dimethylethanolamine, diethylenetriamine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethylpropylenediamine, N, N,N',N'-tetramethylbutanediamine, N,N,N',N'-tetramethyl-1,3-butanediamine, N,N,N',N'-tetramethylhexamethylenediamine, bis [2-(N,N-dimethylamino)ethyl] ether, N,N-dimethylbenzylamine, N,N-dimethylcyclohexylamine, N,N,N',N'-pentamethyldiethylenetriamine, triethylenediamine, triethylenediamine formates and other salts of , oxyalkylene adducts of amino groups of primary and secondary amines, azacyclic compounds such as N,N-dialkylpiperazines, various N,N',N''-trialkyl Examples include aminoalkylhexahydrotriazines, and further examples include quaternary ammonium salt compounds such as tetraethylhydroxylammonium, and imidazole compounds such as imidazole and 2-ethyl-4-methylimidazole.

Examples of organometallic compounds include tin acetate, tin octoate, tin oleate, tin laurate, dibutyltin diacetate, dimethyltin dilaurate, dibutyltin dilaurate, dibutyltin dimercaptide, dibutyltin maleate, dibutyltin dilaurate, and dibutyltin. organotin compounds such as dineodecanoate, dioctyltin dimercaptide, dioctyltin dilaurate, and dibutyltin dichloride; organolead compounds such as lead octanoate and lead naphthenate; organonickel compounds such as nickel naphthenate; For example, organic cobalt compounds such as cobalt naphthenate, organic copper compounds such as copper octenate, organic bismuth compounds such as bismuth octylate and bismuth neodecanoate, organic zirconium compounds such as zirconium acetylacetone chelate, and titanium acetoacetate chelate. , organic titanium compounds such as bis(2-ethylhexanoic acid) titanium, and organic iron compounds such as iron acetylacetone chelate.

Furthermore, examples of urethanization catalysts include potassium salts such as potassium carbonate, potassium acetate, and potassium octylate.

These catalysts can be used alone or in combination of two or more.

The catalyst preferably includes an amine catalyst.

Note that the content of the catalyst is not particularly limited, and is appropriately set according to the purpose and application.

6. Additives The foamed polyurethane resin composition may further contain known additives as optional components.

Known additives include, for example, foam stabilizers (e.g., silicone foam stabilizers, etc.), reaction retardants, processing aids (e.g., acrylic copolymer solutions, etc.), antioxidants (e.g., hindered phenolic antioxidants, agents), heat stabilizers (for example, phosphites, etc.), antioxidants, ultraviolet absorbers, light stabilizers, flame retardants, colorants, and the like.

In addition, the content ratio of the additive is not particularly limited, and is appropriately set according to the purpose and application.

<Polyurethane foam elastomer>
Such a foamed polyurethane resin composition is, for example, configured as a two-component resin material having an A agent containing the above-described polyisocyanate component and a B agent containing the above-described polyol component. The modifier, catalyst and known additives may be contained in either the A agent or the B agent, but are preferably contained in the B agent. Moreover, water is contained in B agent.

A foamed polyurethane resin composition is a raw material for a foamed polyurethane elastomer, and is suitably used for producing a foamed polyurethane elastomer.

To produce a foamed polyurethane elastomer, for example, first, the above-described agents A and B are mixed to prepare a mixture thereof (a foamed polyurethane resin composition).

The A agent and/or the B agent are preferably mixed after being heated to have a low viscosity.

The heating temperature of agent A is, for example, 25° C. or higher, preferably 40° C. or higher, and for example, 120° C. or lower, preferably 100° C. or lower. The heating temperature of agent B is, for example, 25° C. or higher, preferably 30° C. or higher, and for example, 100° C. or lower, preferably 80° C. or lower. Moreover, the heating temperature of the B agent is preferably lower than the heating temperature of the A agent.

In addition, for A and B, for example, the isocyanate index (NCO/(OH+H ₂ O)) × 100 (that is, the ratio of the sum of the isocyanate groups of the polyisocyanate component to the sum of the hydroxyl groups and water of the polyol component) is as follows. are mixed so as to be in the range of

That is, the isocyanate index is, for example, 75 or more, preferably 90 or more, more preferably 95 or more, and for example 300 or less, preferably 200 or less, more preferably 150 or less.

Next, a mixture (polyurethane foam resin composition) of agent A and agent B is injected into a predetermined mold that is preheated as necessary.

The preheating temperature of the mold is, for example, 50° C. or higher, preferably 60° C. or higher, and for example, 130° C. or lower, preferably 100° C. or lower, more preferably 90° C. or lower.

Then, in the mold, the polyisocyanate component and the polyol component are reacted (urethanization reaction), and the mixture of agent A and agent B (polyurethane foam resin composition) is foamed.

Thereby, the foamed polyurethane resin composition is foamed and cured to form a foamed polyurethane elastomer, and the foamed polyurethane elastomer is molded into a predetermined shape.

The range of reaction temperature (molding temperature) is the same as the range of preheating temperature described above.

The reaction time (molding time) is, for example, 5 minutes or longer, preferably 10 minutes or longer, and for example, 60 minutes or shorter, preferably 30 minutes or shorter, and more preferably 15 minutes or shorter.

The foamed polyurethane elastomer is then removed from the mold. After that, if necessary, the foamed polyurethane elastomer may be thermally formed at the above reaction temperature within about 24 hours.

A foamed polyurethane elastomer is manufactured by the above.

The foamed polyurethane elastomer includes a foamed cured product of a foamed polyurethane resin composition, and preferably consists of a foamed cured product of a foamed polyurethane resin composition.

The foamed polyurethane elastomer preferably comprises a soft segment formed by the reaction of an aromatic polyisocyanate and a high molecular weight polyol, and a hard segment formed by the reaction of a terminal isocyanate group-containing prepolymer (aromatic polyisocyanate) and water. (Urea group).

The hardness (C hardness) of such foamed polyurethane elastomer is, for example, 30 N/100 cm ² or more, preferably 40 N/100 cm ^{2 or} more, and for example, 60 N/100 cm ² or less, preferably 50 N/100 cm ² or less. be. The hardness (C hardness) can be measured according to Asker C hardness based on JIS K7312 (1996) (the same applies hereinafter).

In addition, the density of the foamed polyurethane elastomer is higher than the density of the polyurethane foam (for example, less than 0.200 g/cm ³ ), for example, 0.200 g/cm ³ or more, preferably 0.210 g/cm ³ or more, or more. It is preferably 0.220 g/cm ³ or more, more preferably 0.230 g/cm ³ or more, still more preferably 0.240 g/cm ³ or more, particularly preferably 0.240 g/cm ³ or more. , preferably 0.800 g/cm ³ or less, preferably 0.600 g/cm ³ or less, more preferably 0.400 g/cm ³ or less, still more preferably 0.300 g/cm ³ or less, still more preferably 0. 280 g/cm ³ or less, particularly preferably 0.260 g/cm ³ or less.

<Effect>
The polyurethane foam resin composition described above contains the specific modifier described above. More specifically, the modifier is an oxyalkylene-modified organopolysiloxane in which the proportion of Si atoms contained in the total amount of the oxyalkylene-modified organopolysiloxane is the above proportion, and the oxyalkylene The content ratio of the oxyethylene unit with respect to the total amount of is a compound having the above ratio.

Therefore, according to such a foamed polyurethane resin composition, a foamed polyurethane elastomer having excellent impact resilience can be obtained.

In addition, since the foamed polyurethane elastomer is obtained from the foamed polyurethane resin composition, it has excellent impact resilience.

Therefore, foamed polyurethane elastomers can be used in various industrial fields. Uses of foamed polyurethane elastomers include, for example, cushioning materials, shock absorbing materials, vibration absorbing materials, cushion materials, mattress materials, and sound absorbing materials.

More specifically, the uses of foamed polyurethane elastomers include, for example, furniture items such as mattresses and sofas, clothing items such as brassieres and shoulder pads, medical supplies such as disposable diapers, napkins, and cushioning materials for medical tapes. For example, sanitary products such as cosmetics, facial puffs, and pillows, shoe products such as shoe outsoles, shoe inner soles, and shoe midsoles, footwear products (sandals, etc.) for various uses such as medical applications , For example, body pressure dispersion products such as vehicle pads and vehicle cushions, for example, door trims, instrument panels, gear knobs and other hand-touched members, for example, heat insulation materials in electric refrigerators and buildings, for example, shock absorbers Shock absorbing materials such as fillers, vehicle articles such as vehicle handles, automobile interior members, automobile exterior members, semiconductor manufacturing articles such as chemical mechanical polishing (CMP) pads, e.g. bats, grip core materials It can be used in a wide range of fields such as sports equipment such as poles.

Particularly preferably, the foamed polyurethane elastomer is used as a shoe midsole because of its excellent impact resilience.

EXAMPLES The present invention will be explained more specifically by showing Examples below, but the present invention is not limited to them. Specific numerical values such as the mixing ratio (content ratio), physical property values, and parameters used in the following description are described in the above "Mode for Carrying Out the Invention", the corresponding mixing ratio (content ratio ), physical property values, parameters, etc. can. "Parts" and "%" are based on mass unless otherwise specified.

<NMR measurement>
(1) Each modifier was dissolved in a deuterated solvent, trifluoroacetic anhydride was added, and hydroxyl groups at the ends of the molecules were esterified with trifluoroacetic acid. A measurement sample was thus obtained.

(2) Measurement samples were subjected to ¹ H-NMR measurement under the following conditions.
Device; JNM-AL400 (manufactured by JEOL)
Measurement frequency: 400MHz
Solvent; CDCL ₃
Solute concentration: 5% by mass
Chemical shift standard; tetramethylsilane (0 ppm)
(3) Each chemical shift in the obtained NMR chart was attributed and their integral ratio was calculated.

<Analysis method>
(1) The proportion of oxyethylene at the molecular terminal was obtained from the ratio of the integrated values of the attributed peaks corresponding to the oxyalkylene at the molecular terminal. The oxyalkylene peaks at the ends of the molecules were assigned as follows.

Molecular terminal primary oxypropylene: 4.3 ppm
Molecular terminal oxyethylene: 4.4 to 4.6 ppm
Molecular terminal secondary oxypropylene: 5 to 5.5 ppm
(2) From the ratio of the integrated value of each attributed peak to the total amount of integrated values of all attributed peaks of the measurement sample, the ratio of oxyalkylene to the total amount of the modifier was calculated. Also, the ratio of oxyethylene to the total amount of oxyalkylene of the modifier was calculated from the ratio of the integrated values of the attributed peaks.

When oxyalkylene includes both oxyethylene and oxypropylene, a peak derived from methylene in oxyethylene and a peak derived from methylene and methine in oxypropylene are obtained in overlap. Therefore, the integrated value of the peak derived from methylene in oxyethylene was calculated by subtracting the integrated value of the peak derived from methyl in oxypropylene from the integrated value of these overlapping peaks. Moreover, each peak was assigned as follows.

Methyl in oxypropylene: 0.9-1.3 ppm
Methylene and methine in oxypropylene + methylene in oxyethylene: 3-5.5 ppm
(3) The mass of the organopolysiloxane portion (0.1 to 0.5 ppm) was calculated from the ratio of the integrated value of each attributed peak to the total amount of integrated values of all attributed peaks of the measurement sample. Then, the content ratio of Si atoms in the modifier was obtained from the Si content in the organopolysiloxane (dimethylsiloxane).

<Preparation of raw materials>
<<Polyisocyanate Component>>
Preparation example 1 (isocyanate (1))
A prepolymer containing a terminal isocyanate group, which is a reaction product of polyphenylmethane polyisocyanate (p-MDI, trade name Cosmonate PH, manufactured by Mitsui Chemicals SKC Polyurethane) and polytetramethylene ether glycol (PTMEG2000) having a number average molecular weight of 2000. (commercial product, isocyanate group content=15 mass %, average functional group number=2) was prepared as isocyanate (1).

<<polyol component>>
Preparation Example 2 (high molecular weight polyol (1))
PTG1500 (commercial product, polytetramethylene ether glycol having a number average molecular weight of 1500, an average number of hydroxyl groups of 2, manufactured by Mitsubishi Chemical) was prepared as a high molecular weight polyol (1).

Preparation Example 3 (high molecular weight polyol (2))
EP550N (commercial product, oxyethylene-terminated polyoxypropylene triol having a number average molecular weight of 1000, an average number of hydroxyl groups of 3, manufactured by Mitsui Chemicals SKC Polyurethane) was prepared as a high molecular weight polyol (2).

<<Modifier>>
Preparation example 4
L-1169 (commercial product, oxyalkylene-modified dimethylpolysiloxane, hydroxyl equivalent 534, manufactured by Momentive Performance Materials Japan LLC) was prepared as a modifier (1).

The content of Si atoms in modifier (1) (L-1169) was 15.3% by mass with respect to the total amount of oxyalkylene-modified organopolysiloxane.

Modifier (1) (L-1169) was an oxyalkylene-modified organopolysiloxane, and the proportion of oxyethylene in the oxyalkylene at the molecular end was 100 mol %.

In addition, the content of oxyethylene in modifier (1) (L-1169) was 91.2% by mass with respect to the total amount of oxyalkylene.

The content of oxyalkylene in modifier (1) (L-1169) was 61% by mass with respect to the total amount of oxyalkylene-modified organopolysiloxane.

Preparation example 5
L-1160 (commercial product, oxyalkylene-modified dimethylpolysiloxane, hydroxyl equivalent 532, manufactured by Momentive Performance Materials Japan LLC) was prepared as a modifier (2).

The content of Si atoms in modifier (2) (L-1160) was 18.0% by mass with respect to the total amount of oxyalkylene-modified organopolysiloxane.

Modifier (2) (L-1160) was an oxyalkylene-modified organopolysiloxane, and the proportion of oxyethylene in the oxyalkylene at the molecular end was 100 mol %.

In addition, the content of oxyethylene in modifier (2) (L-1160) was 91.4% by mass with respect to the total amount of oxyalkylene.

The content of oxyalkylene in modifier (2) (L-1160) was 53% by mass with respect to the total amount of oxyalkylene-modified organopolysiloxane.

Preparation example 6
B8545 (commercial product, oxyalkylene-modified organopolysiloxane, hydroxyl equivalent 458, manufactured by Evonik) was prepared as modifier (3).

The content of Si atoms in modifier (3) (B8545) was 15.5% by mass with respect to the total amount of oxyalkylene-modified organopolysiloxane.

Modifier (3) (B8545) was an oxyalkylene-modified organopolysiloxane, and the proportion of oxyethylene in the oxyalkylene at the molecular end was 20.7 mol %.

In addition, the content of oxyethylene in modifier (3) (B8545) was 63.7% by mass with respect to the total amount of oxyalkylene.

The content of oxyalkylene in modifier (3) (B8545) was 60% by mass with respect to the total amount of oxyalkylene-modified organopolysiloxane.

Preparation example 7
L594plus (commercial product, oxyalkylene-modified organopolysiloxane, hydroxyl equivalent of 149, manufactured by Momentive Performance Materials Japan LLC) was prepared as modifier (4).

The content of Si atoms in modifier (4) (L594plus) was 4.7% by mass with respect to the total amount of oxyalkylene-modified organopolysiloxane.

Modifier (4) (L594plus) was an oxyalkylene-modified organopolysiloxane, and the proportion of oxyethylene in the oxyalkylene at the molecular end was 0.5 mol %.

In addition, the content of oxyethylene in modifier (4) (L594plus) was 25.6% by mass with respect to the total amount of oxyalkylene.

The content of oxyalkylene in modifier (4) (L594plus) was 88% by mass with respect to the total amount of oxyalkylene-modified organopolysiloxane.

Preparation example 8
B8002 (commercial product, oxyalkylene-modified organopolysiloxane, hydroxyl equivalent 1370, manufactured by Evonik) was prepared as a modifier (5).

The content of Si atoms in modifier (5) (B8002) was 3.8% by mass with respect to the total amount of oxyalkylene-modified organopolysiloxane.

Modifier (5) (B8002) was an oxyalkylene-modified organopolysiloxane, and the proportion of oxyethylene in the oxyalkylene at the molecular end was 1.1 mol %.

In addition, the content of oxyethylene in modifier (5) (B8002) was 50.8% by mass with respect to the total amount of oxyalkylene.

The content of oxyalkylene in modifier (5) (B8002) was about 88% by mass with respect to the total amount of oxyalkylene-modified organopolysiloxane.

<<Additives>>
Preparation example 9
Y-10366 (commercial product, silicone foam stabilizer, hydroxyl equivalent 1667, manufactured by Momentive Performance Materials Japan LLC) was prepared as a foam stabilizer.

The content of Si atoms in the foam stabilizer (Y-10366) was 5.3% by mass with respect to the total amount of the oxyalkylene-modified organopolysiloxane.

The foam stabilizer (Y-10366) was an oxyalkylene-modified organopolysiloxane, and the proportion of oxyethylene in the oxyalkylene at the molecular end was 81.0 mol %.

Also, the content of oxyethylene in the foam stabilizer (Y-10366) was 23.3% by mass with respect to the total amount of oxyalkylene.

The content of oxyalkylene in the foam stabilizer (Y-10366) was 86% by mass with respect to the total amount of oxyalkylene-modified organopolysiloxane.

Preparation example 10
Irganox 245 (commercial product, hindered phenol-based antioxidant, manufactured by BASF) was prepared as an antioxidant.

<Production of foamed polyurethane resin composition and foamed polyurethane elastomer>
Examples 1-9 and Comparative Examples 1-3
(1) Preliminary Preparation Polyisocyanate components were weighed according to the formulation shown in Table 1 to prepare agent A.

Then, agent A was preheated to 40°C.

In addition, the mold was coated with a release agent and preheated to 60°C.

(2) Preparation of resin premix The polyol components (polyol (1), polyol (2)) were preheated to 50°C.

Then, the polyol component, the modifier and the additive were weighed in proportions shown in Table 1, and stirred and mixed in a cup with a rotation or revolution stirrer (1600 rpm×1 minute). When the antioxidant did not dissolve, the mixture was heated to 80°C and mixed with stirring.

Next, water and a catalyst (commercial product, Dabco 33LV, amine catalyst, manufactured by Evonik) were added to the resulting mixed liquid at the ratio shown in Table 1, and mixed by stirring with a rotation-revolution stirrer (1600 rpm × 1 minute). .

Thus, a resin premix (agent B) was prepared. The obtained resin premix was preheated to 40°C.

(3) Casting and foaming Pre-warmed isocyanate (agent A) is weighed into a cup containing resin premix (agent B) at the ratio shown in Table 1, and stirred with a hand mixer (7000 rpm x 5 seconds). Mixed. As a result, a foamed polyurethane resin composition was obtained as a mixture.

The resulting mixture was then cast into a preheated mold, quickly sealed, and heated at 60° C. for 6 minutes or more.

Thereby, the foamed polyurethane resin composition was foamed to obtain a foamed polyurethane elastomer.

(4) Demolding and Curing After 10 minutes, the foamed polyurethane elastomer was demolded from the mold. After that, the resulting foamed polyurethane elastomer was heat-cured at 70° C. for 3 hours or more.

The foamed polyurethane elastomer after curing was punched into the following shapes and used for each evaluation.

<Evaluation>
Foamed polyurethane elastomers were evaluated by the following methods. The results are shown in Table 1.

(1) Appearance The upper and lower surfaces of the foamed polyurethane elastomer were observed with the naked eye to evaluate the appearance.

"○" indicates that the molding was good, and "loose skin" indicates that the surface was sagging due to molding failure. "Crater" indicates that the surface had irregularities, and "cell roughness" indicates that the cells of the foamed polyurethane elastomer were non-uniform.

(2) Density A measurement sample was cut out from the foamed polyurethane elastomer, and the apparent density was measured according to JIS K7222 (2005).

(3) Tensile strength and elongation at break A measurement sample (No. 1 dumbbell shape, thickness 10 mm) was punched from the foamed polyurethane elastomer, and the tensile strength and elongation at break (maximum value) were measured according to JIS K6400-5 (2012).

(4) C hardness The Asker C hardness of the foamed polyurethane elastomer was measured according to JIS K7312-7 (1996). Note that the C hardness was measured twice.

(5) Tear strength A measurement sample (15 mm x 100 mm x 10 mm) was cut out from the foamed polyurethane elastomer, a cut of 25 mm was made, and the tear strength (average value) was measured by pulling at 100 mm/min according to JIS K6252.

(6) Compression permanent set A disc-shaped measurement sample with a diameter of 29 mm and a thickness of 10 mm is cut out from the foamed polyurethane elastomer, and according to JIS K6262 (2013), the compression permanent deformation of the measurement sample is measured under the conditions of 50 ° C. x 6 hours and 50% compression. Strain was measured. Results are shown in each table.

(7) Impact resilience The impact resilience of the foamed polyurethane elastomer was measured by ball rebound according to JIS K6400-3 (2011). Note that the impact resilience was measured twice.

It should be noted that although the above invention has been provided as an exemplary embodiment of the present invention, this is merely an illustration and should not be construed as a limitation. Variations of the invention that are obvious to those skilled in the art are included in the following claims.

The foamed polyurethane resin composition, foamed polyurethane elastomer and midsole of the present invention are used in various industrial fields such as cushioning materials, shock absorbing materials, vibration absorbing materials, cushioning materials, mattress materials and sound absorbing materials, especially in the field of shoe midsoles. , is preferably used.

Claims (6)

a polyisocyanate component containing a terminal isocyanate group-containing prepolymer that is a reaction product of an aromatic polyisocyanate and a polyol;
a polyol component;
water and,
containing a modifier,
The modifier is
Organopolysiloxane modified with oxyalkylene,
The content of Si atoms is 15.0% by mass or more relative to the total amount of the oxyalkylene-modified organopolysiloxane,
A foamed polyurethane resin composition, characterized in that the content of oxyethylene relative to the total amount of oxyalkylene is 60% by mass or more. Claim 1, characterized in that the content ratio of the modifier is 0.027 parts by mass or more and 1.375 parts by mass or less with respect to 100 parts by mass of the total amount of the polyisocyanate component, the polyol component and the water. The foamed polyurethane resin composition according to 1. In the organopolysiloxane modified with oxyalkylene,
2. The foamed polyurethane resin composition according to claim 1, wherein the ratio of oxyethylene in the oxyalkylene at the molecular terminal is 50 mol % or more. The polyol in the terminal isocyanate group-containing prepolymer is
Consisting of a high molecular weight polyol having a number average molecular weight of 500 or more and 3000 or less and an average number of hydroxyl groups of 2,
The polyol component is
2. The polyurethane foam resin composition according to claim 1, comprising a high molecular weight polyol having a number average molecular weight of 500 or more and 3000 or less and an average number of hydroxyl groups of 2 to 3. A foamed polyurethane elastomer comprising a foamed cured product of the foamed polyurethane resin composition according to claim 1 . A midsole comprising the foamed polyurethane elastomer according to claim 5 .