CN110114383B

CN110114383B - Soft polyurethane foam, material for clothing, bra pad, bra cup, and process for producing soft polyurethane foam

Info

Publication number: CN110114383B
Application number: CN201880005339.7A
Authority: CN
Inventors: 金山宏; 渡边实; 中川俊彦; 森田广一; 山崎聪
Original assignee: Mitsui Chemicals Inc
Current assignee: Mitsui Chemicals Inc
Priority date: 2017-03-31
Filing date: 2018-03-26
Publication date: 2021-09-17
Anticipated expiration: 2038-03-26
Also published as: TWI732112B; WO2018181151A1; JP6793249B2; CN110114383A; TW201841965A; JPWO2018181151A1

Abstract

A flexible polyurethane foam obtained by reacting and foaming a polyisocyanate component containing a derivative of an aliphatic polyisocyanate with a polyol component containing a polyoxyalkylene polyol, wherein the derivative contains an allophanate derivative of the aliphatic polyisocyanate, the content of the allophanate derivative of the aliphatic polyisocyanate is 70 mol% or more relative to the total amount of the derivatives of the aliphatic polyisocyanate, the polyoxyalkylene polyol contains both an oxyethylene unit and an oxypropylene unit, the oxyethylene unit is 5 to 20 mol% relative to the polyoxyalkylene polyol, and the primary hydroxyl group is 50 mol% or less relative to the total number of moles of terminal hydroxyl groups of the polyoxyalkylene polyol.

Description

Soft polyurethane foam, material for clothing, bra pad, bra cup, and process for producing soft polyurethane foam

Technical Field

The present invention relates to a flexible polyurethane foam, a material for clothing, a brassiere pad, a brassiere cup, and a method for producing a flexible polyurethane foam, and more particularly to a flexible polyurethane foam, a material for clothing including the flexible polyurethane foam, a brassiere pad as a molded product of the material for clothing, a brassiere cup provided with the brassiere pad, and a method for producing a flexible polyurethane foam.

Background

Flexible polyurethane foams are obtained by reacting a polyisocyanate component with a polyol component in the presence of a urethane-forming catalyst and a blowing agent, and have been used in a wide variety of fields.

As such a polyisocyanate component, it is known to use an aromatic polyisocyanate, but an aromatic flexible polyurethane foam obtained using an aromatic polyisocyanate may be exposed to ultraviolet rays or an oxygen-containing gas (for example, nitrogen oxide gas (NO))_x) Etc.) to cause discoloration.

Therefore, studies have been made on the use of an aliphatic polyisocyanate and/or a derivative thereof as a polyisocyanate component.

For example, the following schemes are proposed: in a flexible polyurethane foam obtained by reacting and foaming and curing a mixed liquid of an organic polyisocyanate (a), a polyol (B), a catalyst (C), a blowing agent (D) and a foam stabilizer (E), a mixture of an allophanate-modified organic polyisocyanate composition (a1) comprising a monool and an aliphatic and/or alicyclic diisocyanate, an allophanate-modified organic polyisocyanate composition (a2) comprising an alcohol having 2 or more hydroxyl groups and an aliphatic and/or alicyclic diisocyanate, and an organic polyisocyanate compound (A3) obtained by reacting an aliphatic and/or alicyclic diisocyanate with a polyol component (a1) is used as the isocyanate component (a). It has been proposed to use polypropylene glycol (PPG) as the polyol (B) in such a flexible polyurethane foam, and specifically, it has been proposed to use PPG having 2 to 3 functional groups and an OH value of 56 to 560 (see, for example, patent document 1 (preparation examples 44 to 47)).

Documents of the prior art

Patent document

Patent document 1: japanese laid-open patent publication No. 2012-224712

Disclosure of Invention

Problems to be solved by the invention

On the other hand, in recent years, a flexible polyurethane foam is required to have air permeability, and a flexible polyurethane foam obtained using a polyisocyanate composition and polypropylene glycol (PPG) described in patent document 1 has a disadvantage of insufficient air permeability.

In addition to air permeability, mechanical properties (deformation resistance (resistance to deformation), tear strength, elongation, and the like) are sometimes required of the flexible polyurethane foam.

The present invention relates to a flexible polyurethane foam having both air permeability and mechanical properties, a material for clothing comprising the flexible polyurethane foam, a brassiere pad which is a molded article of the material for clothing, a brassiere cup provided with the brassiere pad, and a method for producing the flexible polyurethane foam.

Means for solving the problems

The present invention [1] comprises a flexible polyurethane foam obtained by reacting and foaming a polyisocyanate component containing a derivative of an aliphatic polyisocyanate with a polyol component containing a polyoxyalkylene polyol, wherein the derivative of the aliphatic polyisocyanate comprises an allophanate derivative of the aliphatic polyisocyanate, the content of the allophanate derivative of the aliphatic polyisocyanate is 70 mol% or more based on the total amount of the derivative of the aliphatic polyisocyanate, the polyoxyalkylene polyol has both an oxyethylene unit and an oxypropylene unit, the oxyethylene unit is 5 mol% or more and 20 mol% or less based on the polyoxyalkylene polyol, and the primary hydroxyl group is 50 mol% or less based on the total number of moles of terminal hydroxyl groups of the polyoxyalkylene polyol.

The invention [2] comprises the flexible polyurethane foam according to [1], wherein the content of the allophanate derivative of the aliphatic polyisocyanate is 75 to 99 mol% based on the total amount of the derivatives of the aliphatic polyisocyanate.

The invention [3] is the flexible polyurethane foam according to the above [1] or [2], wherein the aliphatic polyisocyanate contains pentamethylene diisocyanate and/or hexamethylene diisocyanate.

The invention [4] comprises the flexible polyurethane foam according to [3], wherein the polyisocyanate component further contains an alicyclic polyisocyanate.

The invention [5] comprises the flexible polyurethane foam according to any one of the above [1] to [4], wherein the derivative comprises an alcohol-modified allophanate derivative, and the alcohol contains a monohydric alcohol and a dihydric alcohol.

The invention [6] is a flexible polyurethane foam according to the above [5], wherein the alcohol contains a branched monohydric alcohol and a branched dihydric alcohol.

The invention [7] is a clothing material comprising the flexible polyurethane foam according to any one of the above [1] to [6 ].

The present invention [8] includes a brassiere pad which is a molded article of the clothing material according to [7 ].

The present invention [9] includes a brassiere cup provided with the brassiere pad according to [8 ].

The present invention [10] comprises a method for producing a flexible polyurethane foam, which comprises the steps of: a step for preparing a polyisocyanate component containing a derivative of an aliphatic polyisocyanate and a polyol component containing a polyoxyalkylene polyol; and a step of producing a flexible polyurethane foam by reacting and foaming the polyisocyanate component and the polyol component, wherein the derivative of the aliphatic polyisocyanate contains an allophanate derivative of the aliphatic polyisocyanate, the allophanate derivative of the aliphatic polyisocyanate is contained in a proportion of 70 mol% or more relative to the total amount of the derivative of the aliphatic polyisocyanate, the polyoxyalkylene polyol contains both an oxyethylene unit and an oxypropylene unit, the oxyethylene unit is 5 mol% or more and 20 mol% or less relative to the polyoxyalkylene polyol, and the primary hydroxyl group is 50 mol% or less relative to the total number of moles of terminal hydroxyl groups of the polyoxyalkylene polyol.

ADVANTAGEOUS EFFECTS OF INVENTION

In the flexible polyurethane foam and the process for producing the same according to the present invention, the polyisocyanate component contains an allophanate derivative of an aliphatic polyisocyanate in a predetermined ratio with respect to the derivative of the aliphatic polyisocyanate, and the polyol component contains a polyoxyalkylene polyol in which the ratio of oxyethylene units and the ratio of primary hydroxyl groups are in a predetermined ratio. Therefore, the flexible polyurethane foam of the present invention has both air permeability and mechanical properties.

Further, the material for clothing comprising the flexible polyurethane foam of the present invention, and the brassiere pad and the brassiere cup which are molded products of the material for clothing have both air permeability and mechanical properties.

Detailed Description

The flexible polyurethane foam of the present invention is a reaction product obtained by reacting and foaming a polyisocyanate component and a polyol component.

More specifically, the flexible polyurethane foam can be obtained by reacting and foaming a polyisocyanate component and a polyol component in the presence of a urethane-forming catalyst (described later) and a foaming agent (described later).

The polyisocyanate component contains a derivative of an aliphatic polyisocyanate.

Examples of the aliphatic polyisocyanate include chain (linear or branched: acyclic) aliphatic polyisocyanates, specifically, chain aliphatic diisocyanates such as ethylene diisocyanate, 1, 3-propylene diisocyanate, 1, 2-propylene diisocyanate, tetramethylene diisocyanate (1, 4-tetramethylene diisocyanate, 1, 2-tetramethylene isocyanate, 2, 3-tetramethylene isocyanate, 1, 3-tetramethylene isocyanate), 1, 5-Pentamethylene Diisocyanate (PDI), 1, 6-Hexamethylene Diisocyanate (HDI), 2, 4, 4-or 2, 2, 4-trimethylhexamethylene diisocyanate, 2, 6-diisocyanatomethyl hexanoate, and 1, 12-dodecane diisocyanate, and preferably, 1, 5-Pentamethylene Diisocyanate (PDI), 1, 6-Hexamethylene Diisocyanate (HDI).

Further, as the aliphatic polyisocyanate, alicyclic polyisocyanate can be also exemplified.

Examples of the alicyclic polyisocyanate include alicyclic diisocyanates such as 1, 3-cyclopentene diisocyanate, 1, 4-cyclohexane diisocyanate, 1, 3-cyclohexane diisocyanate, 3-isocyanatomethyl-3, 5, 5-trimethylcyclohexyl isocyanate (isophorone diisocyanate; IPDI), 4 ' -, 2, 4 ' -or 2, 2 ' -dicyclohexylmethane diisocyanate or a mixture thereof (hydrogenated MDI), methyl-2, 4-cyclohexane diisocyanate, methyl-2, 6-cyclohexane diisocyanate, 1, 3-or 1, 4-bis (isocyanatomethyl) cyclohexane or a mixture thereof (hydrogenated XDI), norbornane diisocyanate (NBDI) and the like.

These aliphatic polyisocyanates may be used alone or in combination of 2 or more.

The aliphatic polyisocyanate is preferably a chain aliphatic polyisocyanate, more preferably a chain aliphatic diisocyanate, and still more preferably pentamethylene diisocyanate or hexamethylene diisocyanate.

When the aliphatic polyisocyanate contains a chain aliphatic polyisocyanate (preferably a chain aliphatic diisocyanate), air permeability and mechanical properties can be improved. Further, when the aliphatic polyisocyanate contains pentamethylene diisocyanate and/or hexamethylene diisocyanate, the reactivity can be improved.

The aliphatic polyisocyanate is particularly preferably pentamethylene diisocyanate.

When the aliphatic polyisocyanate contains pentamethylene diisocyanate, the flexibility, air permeability and mechanical properties can be improved.

The derivative of the aliphatic polyisocyanate contains an allophanate derivative of the aliphatic polyisocyanate.

The allophanate derivative of an aliphatic polyisocyanate can be obtained, for example, by reacting the above-mentioned aliphatic polyisocyanate with an alcohol, followed by an allophanatization reaction in the presence of an allophanatization catalyst.

Examples of the alcohol include monohydric alcohol, dihydric alcohol, trihydric or higher alcohols, and the like.

Examples of the monohydric alcohol include straight chain monohydric alcohols and branched chain monohydric alcohols.

Examples of the linear monohydric alcohol include linear monohydric alcohols having 1 to 20 carbon atoms such as methanol, ethanol, n-propanol, n-butanol, n-pentanol, n-hexanol, n-heptanol, n-octanol, n-nonanol, n-decanol, n-undecanol, n-dodecanol (lauryl alcohol), n-tridecanol, n-tetradecanol, n-pentadecanol, n-hexadecanol, n-heptadecanol, n-octadecanol (stearyl alcohol), n-nonadecanol, and eicosanol.

Examples of the branched monoalcohol include branched monoalcohols having carbon number of 3 to 20 such as isopropyl alcohol, isobutyl alcohol (isobutyl alcohol), sec-butyl alcohol, tert-butyl alcohol, isopentyl alcohol, isohexyl alcohol, isoheptyl alcohol, isooctyl alcohol, 2-ethyl-1-hexanol, isononyl alcohol, isodecyl alcohol, 5-ethyl-2-nonyl alcohol, trimethylnonyl alcohol, 2-hexyldecyl alcohol, 3, 9-diethyl-6-tridecyl alcohol, 2-isoheptylisoundecyl alcohol, 2-octyldodecyl alcohol, and other branched alkanols (C5 to 20).

These monohydric alcohols may be used alone or in combination of 2 or more.

The monohydric alcohol is preferably a branched monohydric alcohol, more preferably a branched monohydric alcohol having a carbon number of 3 to 20, even more preferably isopropanol and isobutanol, and particularly preferably isobutanol, from the viewpoint of reducing the viscosity of the derivative of the aliphatic polyisocyanate.

Examples of the diol include straight-chain diols and branched diols.

Examples of the linear dihydric alcohol include ethylene glycol, 1, 3-propanediol, 1, 4-butanediol (butanediol), 1, 5-pentanediol, 1, 6-hexanediol, 1, 4-dihydroxy-2-butene, diethylene glycol, triethylene glycol, dipropylene glycol, and other linear alkane (C7 to 20) glycols.

Examples of the branched diol include C3 to 20 branched diols such as 1, 2-propanediol, 1, 3-butanediol, 1, 2-butanediol, neopentyl glycol, 3-methyl-1, 5-pentanediol, 2, 2, 2-trimethylpentanediol, 3-dimethylolheptane, 2, 6-dimethyl-1-octene-3, 8-diol, and other branched alkane (C7 to 20) diols.

These diols may be used alone or in combination of 2 or more.

The diol is preferably a branched diol, more preferably a branched diol having from C3 to C20, still more preferably 1, 3-butanediol or 3-methyl-1, 5-pentanediol, and particularly preferably 3-methyl-1, 5-pentanediol, from the viewpoint of reducing the viscosity of the derivative of the aliphatic polyisocyanate.

Examples of the trihydric or higher alcohol include trihydric alcohols such as glycerol, trimethylolpropane and triisopropanolamine, tetrahydric alcohols such as tetramethylolmethane (pentaerythritol) and diglycerol, pentahydric alcohols such as xylitol, hexahydric alcohols such as sorbitol, mannitol, allitol, iditol, dulcitol, altritol, inositol and dipentaerythritol, heptahydric alcohols such as avocado sugar alcohol, and octahydric alcohols such as sucrose.

These trihydric or higher alcohols may be used alone or in combination of 2 or more.

The alcohol preferably includes a monohydric alcohol and a dihydric alcohol, and more preferably includes a branched monohydric alcohol and a branched dihydric alcohol from the viewpoint of air permeability and mechanical properties.

In the production of the allophanate derivative of an aliphatic polyisocyanate, the proportion of the alcohol in the reaction between the aliphatic polyisocyanate and the alcohol is, for example, 3 parts by mass or more, preferably more than 3 parts by mass, more preferably 3.2 parts by mass or more, still more preferably 3.5 parts by mass or more, for example, 50 parts by mass or less, preferably 20 parts by mass or less, and more preferably 10 parts by mass or less, relative to 100 parts by mass of the aliphatic polyisocyanate.

In addition, in this reaction, the above-mentioned alcohol may be used in combination with an active hydrogen group-containing compound such as a thiol, an oxime, a lactam, a phenol, or a β diketone, as necessary, within a range that does not inhibit the excellent effects of the present invention.

The reaction conditions in the reaction of the aliphatic polyisocyanate and the alcohol are, for example, under an inert gas atmosphere such as nitrogen or under normal pressure (atmospheric pressure), and the reaction temperature is, for example, room temperature (for example, 25 ℃) or higher, preferably 40 ℃ or higher, for example, 100 ℃ or lower, preferably 90 ℃ or lower. The reaction time is, for example, 0.05 hours or more, preferably 0.2 hours or more, for example, 10 hours or less, preferably 6 hours or less.

Thereby, the aliphatic polyisocyanate and the alcohol are subjected to a urethanization reaction.

In the above-mentioned urethanization reaction, a known urethanization catalyst (for example, amines (described later), organic metal compounds (described later), etc.) may be added, if necessary. The mixing ratio of the urethane-forming catalyst is not particularly limited, and may be appropriately set according to the purpose and use.

In this method, an allophanation catalyst is added to the obtained reaction liquid, and the reaction product of an aliphatic polyisocyanate and an alcohol is subjected to an allophanation reaction.

Examples of the allophanation catalyst include bismuth salts of organic carboxylic acids such as bismuth octoate and bismuth tris (2-ethylhexanoate), and lead salts of organic carboxylic acids such as lead octoate.

These allophanation catalysts may be used singly or in combination of 2 or more.

The allophanation catalyst is preferably a bismuth salt of an organic carboxylic acid, and more preferably bismuth tris (2-ethylhexanoate).

The proportion of the allophanation catalyst added is, for example, 0.0005 parts by mass or more, preferably 0.001 parts by mass or more, for example, 0.3 parts by mass or less, preferably 0.05 parts by mass or less, and more preferably 0.03 parts by mass or less, relative to 100 parts by mass of the aliphatic polyisocyanate.

The reaction conditions for the allophanatization reaction are, for example, a reaction temperature of 0 ℃ or higher, preferably 20 ℃ or higher, for example, 160 ℃ or lower, preferably 120 ℃ or lower under an inert gas atmosphere such as nitrogen or normal pressure (atmospheric pressure). The reaction time is, for example, 30 minutes or more, preferably 60 minutes or more, for example 1200 minutes or less, preferably 600 minutes or less.

In the allophanatization reaction described above, at the time when a predetermined reaction rate (isocyanate group conversion rate) is reached, a reaction terminator such as phosphoric acid, monochloroacetic acid, benzoyl chloride, dodecylbenzenesulfonic acid, toluenesulfonic acid (o-or p-toluenesulfonic acid) and derivatives thereof (e.g., methyl o-or p-toluenesulfonate, etc.), toluenesulfonamide (o-or p-toluenesulfonamide), etc., is added to the reaction solution to deactivate the catalyst and terminate the allophanatization reaction. In this case, an adsorbent for adsorbing the catalyst, such as a chelate resin or an ion exchange resin, may be added to terminate the allophanatization reaction.

The conversion rate of the isocyanate group at the time of terminating the allophanatization reaction is, for example, 1 mass% or more, preferably 5 mass% or more, for example, 20 mass% or less, preferably 15 mass% or less.

The conversion of the isocyanate group can be determined in the examples described below.

This enables the aliphatic polyisocyanate to undergo allophanatization.

In the above-mentioned urethanation reaction and/or allophanation reaction, for example, a known organic phosphite or the like may be added as a co-catalyst for the adjustment of urethanation and allophanation. The organic phosphite can be used alone or in combination of 2 or more. The organic phosphite is preferably a monophosphite, more preferably a tridecyl phosphite.

The proportion of the organophosphite ester to be added is, for example, 0.01 part by mass or more, preferably 0.02 part by mass or more, more preferably 0.03 part by mass or more, for example, 0.2 part by mass or less, preferably 0.15 part by mass or less, more preferably 0.1 part by mass or less, relative to 100 parts by mass of the aliphatic polyisocyanate.

In the above-mentioned urethanation reaction and/or allophanation reaction, a hindered phenol-based antioxidant, for example, a reaction stabilizer such as 2, 6-di-tert-butyl-4-methylphenol (BHT), IRGANOX 1010, IRGANOX 1076, IRGANOX 1135, and IRGANOX 245 (trade name, manufactured by BASF Japan) may be added, if necessary.

The mixing ratio of the reaction stabilizer is, for example, 0.01 parts by mass or more, preferably 0.05 parts by mass or more, for example, 1.0 parts by mass or less, preferably 0.10 parts by mass or less, relative to 100 parts by mass of the aliphatic polyisocyanate.

In the above-mentioned urethanation reaction and/or allophanation reaction, a known reaction solvent may be blended in an appropriate ratio as required.

After the reaction is completed, unreacted aliphatic polyisocyanate (including the catalyst, the reaction solvent and/or the catalyst deactivator in the case where the catalyst, the reaction solvent and/or the catalyst deactivator are blended) is removed from the obtained reaction mixture by a known method such as distillation or extraction, for example, thin film distillation (smith distillation), whereby an allophanate derivative of aliphatic polyisocyanate can be obtained. After removing the unreacted aliphatic polyisocyanate, a reaction terminator may be added as a stabilizer to the obtained allophanate derivative of the aliphatic polyisocyanate at an arbitrary ratio.

In addition, according to this method, an allophanate derivative of an aliphatic polyisocyanate, more specifically, an alcohol-modified allophanate derivative can be obtained.

In the alcohol-modified allophanate derivative, the alcohol preferably includes a monohydric alcohol and a dihydric alcohol, and more preferably includes a branched monohydric alcohol and a branched dihydric alcohol, as described above.

The alcohol is preferably a combination of a monohydric alcohol and a dihydric alcohol, and particularly preferably a combination of a branched monohydric alcohol and a branched dihydric alcohol.

When a monohydric alcohol (preferably a branched monohydric alcohol (hereinafter the same)) and a dihydric alcohol (preferably a branched dihydric alcohol (hereinafter the same)) are used in combination, a flexible polyurethane foam having excellent air permeability and mechanical properties can be obtained.

The mode of using the monohydric alcohol and the dihydric alcohol in combination is not particularly limited, and for example, a mixed alcohol of the monohydric alcohol and the dihydric alcohol may be used for producing the allophanate derivative.

For example, an allophanate derivative obtained using only a monohydric alcohol and an allophanate derivative obtained using only a dihydric alcohol may be prepared separately and mixed.

Further, for example, an allophanate derivative obtained by using only a monohydric alcohol, an allophanate derivative obtained by using only a dihydric alcohol and an allophanate derivative obtained by using a mixed alcohol of a monohydric alcohol and a dihydric alcohol may be prepared separately and mixed.

The ratio of the monohydric alcohol to the dihydric alcohol (based on the raw materials) is, for example, 10 parts by mass or more, preferably 50 parts by mass or more, for example, 90 parts by mass or less, and preferably 80 parts by mass or less, relative to 100 parts by mass of the total amount of the monohydric alcohol and the dihydric alcohol. The diol is, for example, 10 parts by mass or more, preferably 20 parts by mass or more, for example, 90 parts by mass or less, preferably 50 parts by mass or less.

The derivative of the aliphatic polyisocyanate may contain a derivative (hereinafter referred to as another derivative) other than the allophanate derivative of the aliphatic polyisocyanate described above at an appropriate ratio.

Examples of the other derivatives include polymers of aliphatic polyisocyanates (for example, dimers, trimers, pentamers, heptamers, etc.), biuret derivatives (for example, biuret derivatives produced by the reaction of the above-mentioned aliphatic polyisocyanates with water or amines), urea derivatives (for example, urea derivatives produced by the reaction of the above-mentioned aliphatic polyisocyanates with diamines), oxadiazinetrione derivatives (for example, oxadiazinetrione derivatives produced by the reaction of the above-mentioned aliphatic polyisocyanates with carbon dioxide), carbodiimide derivatives (for example, carbodiimide derivatives produced by the decarboxylative condensation reaction of the above-mentioned aliphatic polyisocyanates), polyol derivatives (for example, polyol derivatives (alcohol adducts) produced by the reaction of the above-mentioned aliphatic polyisocyanates with known low-molecular-weight polyols (preferably, low-molecular-weight triols), and the like, A polyol derivative produced by the reaction of the above-mentioned aliphatic polyisocyanate with a known low-molecular-weight polyol and/or a known high-molecular-weight polyol), and the like.

These other derivatives may be used alone or in combination of 2 or more.

As other derivatives, preferred are trimers of aliphatic polyisocyanates.

The trimer of the aliphatic polyisocyanate contains a symmetrical/asymmetrical isocyanurate group (hereinafter, the trimer of the aliphatic polyisocyanate is sometimes referred to as an isocyanurate derivative of the aliphatic polyisocyanate).

The symmetric/asymmetric isocyanurate group is defined as a symmetric isocyanurate group and/or an asymmetric isocyanurate group.

The symmetrical isocyanurate group is an isocyanurate group and is contained in a symmetrical trimer (trimer) of the aliphatic polyisocyanate.

In addition, the asymmetric isocyanurate group is an iminooxadiazinedione group and is contained in an asymmetric trimer (trimer) of the aliphatic polyisocyanate.

The mode of containing the other derivative is not particularly limited, and for example, in the production of the allophanate derivative of the above-mentioned aliphatic polyisocyanate, the other derivative (for example, an isocyanurate derivative of an aliphatic polyisocyanate) is produced as a by-product in each reaction (urethane reaction, allophanate reaction, etc.), and the other derivative may be contained in the derivative of the aliphatic polyisocyanate.

For example, another derivative (for example, an isocyanurate derivative of an aliphatic polyisocyanate) prepared separately may be mixed with the allophanate derivative of the aliphatic polyisocyanate to be contained in the derivative of the polyisocyanate.

The derivative of the aliphatic polyisocyanate preferably contains an allophanate derivative of the aliphatic polyisocyanate and an isocyanurate derivative of the aliphatic polyisocyanate, and more preferably contains an allophanate derivative of the aliphatic polyisocyanate and an isocyanurate derivative of the aliphatic polyisocyanate produced as a by-product in the production of the allophanate derivative.

The content ratio of the allophanate derivative of the aliphatic polyisocyanate is, for example, 70 mol% or more, preferably 75 mol% or more, more preferably 80 mol% or more, further preferably 85 mol% or more, further preferably 90 mol% or more, particularly preferably 95 mol% or more, and usually less than 100 mol%, preferably 99 mol% or less, and more preferably 98 mol% or less, relative to the total amount of the derivatives of the aliphatic polyisocyanate.

The content of the isocyanurate derivative of the aliphatic polyisocyanate is, for example, more than 0 mol%, preferably 1 mol% or more, more preferably 2 mol% or more, and for example, 30 mol% or less, preferably 25 mol% or less, more preferably 20 mol% or less, further preferably 15 mol% or less, further preferably 10 mol% or less, and particularly preferably 5 mol% or less.

When the content ratio of the allophanate derivative of the aliphatic polyisocyanate to the isocyanurate derivative of the aliphatic polyisocyanate is in the above range, a flexible polyurethane foam having excellent air permeability and mechanical properties can be obtained.

In addition, it is preferable that the derivative of the aliphatic polyisocyanate does not contain a dimer of the aliphatic polyisocyanate or contains a trace amount of the other derivative.

The dimer of the aliphatic polyisocyanate contains a uretdione group (hereinafter, the dimer of the aliphatic polyisocyanate is sometimes referred to as a uretdione derivative of the aliphatic polyisocyanate).

The content of the uretdione derivative of the aliphatic polyisocyanate is, for example, less than 10 mol%, preferably 5 mol% or less, more preferably 3 mol% or less, still more preferably 1 mol% or less, and particularly preferably 0 mol% based on the total amount of the derivatives of the aliphatic polyisocyanate.

When the content ratio of the uretdione derivative of the aliphatic polyisocyanate is in the above range, a flexible polyurethane foam having excellent air permeability and mechanical properties can be obtained.

As the derivative of the aliphatic polyisocyanate, an allophanate derivative containing only the aliphatic polyisocyanate and an isocyanurate derivative containing the aliphatic polyisocyanate are particularly preferable.

The content of the allophanate derivative, isocyanurate derivative and uretdione derivative in the derivatives of aliphatic polyisocyanates can be used in accordance with the examples described below¹Molar ratio of allophanate groups to symmetrical/asymmetrical isocyanurate groups obtained from NMR chart obtained by H-NMR method, and use thereof¹³The molar ratio of the uretdione group to the symmetrical/asymmetrical isocyanurate group obtained from the NMR chart obtained by the C-NMR method was calculated.

More specifically, in this method, first, the utilization of the derivative of the aliphatic polyisocyanate is calculated according to the examples described later¹The NMR chart obtained by the H-NMR method shows the molar ratio of allophanate groups to symmetrical/asymmetrical isocyanurate groups.

For example in derivatives of aliphatic polyisocyanates¹H-NMR measurement (400MHz, solvent: D)⁶DMSO (solute: 5 mass%), standard substance: tetramethylsilane), 8.3 to 8.7ppm was defined as the peak ascribed to protons in allophanate groups (NH groups in allophanate groups) of the aliphatic polyisocyanate, and 3.8ppm was defined as the peak ascribed to protons in symmetric/asymmetric isocyanurate groups (directly bonded to symmetric/asymmetric isocyanurate groups) of the aliphatic polyisocyanateMethylene group (CH) known as isocyanurate group₂Radix)) of the proton. Further, the peak area ratio (integrated ratio) thereof was calculated as the content ratio of the allophanate group to the symmetrical/asymmetrical isocyanurate group by the following formula.

Integral value of peak assignment of proton to allophanate group/(integral value of peak assignment of proton to symmetric/asymmetric isocyanurate group/6)

In this method, the use of the derivative of the aliphatic polyisocyanate was calculated according to the examples described later¹³The NMR chart obtained by the C-NMR method shows the molar ratio of the uretdione groups to the symmetrical/asymmetrical isocyanurate groups.

For example in derivatives of aliphatic polyisocyanates¹³C-NMR measurement (100MHz, solvent: CDCL)₃(solute: 50 mass%), standard substance: tetramethylsilane), 157.8ppm of the peak was assigned to the carbon of the uretdione group (CO group in uretdione group) of the aliphatic polyisocyanate, and 149.1ppm of the peak was assigned to the carbon of the symmetrical/asymmetrical isocyanurate group (CO group in symmetrical/asymmetrical isocyanurate group) of the aliphatic polyisocyanate. Further, the peak area ratio (integral ratio) thereof was calculated as the content ratio of the uretdione group to the symmetrical/asymmetrical isocyanurate group by the following formula.

Molar ratio of uretdione group/symmetrical/asymmetrical isocyanurate group (integrated value of peak ascribed to carbon of uretdione group/2)/(integrated value of peak ascribed to carbon of symmetrical/asymmetrical isocyanurate group/3)

Then, the number of moles of allophanate groups and the number of moles of uretdione groups were calculated with respect to 100 moles of symmetric/asymmetric isocyanurate groups. Then, the molar ratio of each group to the total amount of the symmetrical/asymmetrical isocyanurate group, allophanate group and uretdione group was calculated.

In this case, the molar ratio of allophanate groups to the total amount of symmetric/asymmetric isocyanurate groups, allophanate groups and uretdione groups is defined as the content of the allophanate derivative of the aliphatic polyisocyanate in the aliphatic polyisocyanate derivative.

The molar ratio of the symmetrical/asymmetrical isocyanurate groups to the total amount of the symmetrical/asymmetrical isocyanurate groups, allophanate groups and uretdione groups is defined as the content of the isocyanurate derivative of the aliphatic polyisocyanate in the derivative of the aliphatic polyisocyanate.

The molar ratio of uretdione groups to the total amount of symmetrical/asymmetrical isocyanurate groups, allophanate groups and uretdione groups is defined as the content of uretdione derivatives of aliphatic polyisocyanates in the aliphatic polyisocyanate derivatives.

The polyisocyanate component may contain other polyisocyanate and/or a derivative thereof in addition to the derivative of the aliphatic polyisocyanate (i.e., the allophanate derivative of the aliphatic polyisocyanate (and other derivatives added as needed)).

Examples of the other polyisocyanate and/or derivative thereof include a polyisocyanate monomer and a polyisocyanate derivative (excluding a derivative of an aliphatic polyisocyanate).

Examples of the polyisocyanate monomer include polyisocyanates such as the above-mentioned aliphatic polyisocyanates (including alicyclic polyisocyanates), aromatic polyisocyanates, and araliphatic polyisocyanates.

Examples of the aromatic polyisocyanate include aromatic diisocyanates such as m-and p-phenylene diisocyanate or a mixture thereof, 2, 4-or 2, 6-tolylene diisocyanate or a mixture Thereof (TDI), 4 '-, 2, 4' -or 2, 2 '-diphenylmethane diisocyanate or a mixture thereof (MDI), 4' -toluidine diisocyanate (TODI), 4 '-diphenyl ether diisocyanate, 4' -diphenyl diisocyanate, and 1, 5-Naphthalene Diisocyanate (NDI).

Examples of the araliphatic polyisocyanate include araliphatic diisocyanates such as 1, 3-or 1, 4-xylylene diisocyanate or a mixture thereof (XDI), 1, 3-or 1, 4-tetramethylxylylene diisocyanate or a mixture Thereof (TMXDI), and omega, omega' -diisocyanato-1, 4-diethylbenzene.

These polyisocyanate monomers may be used alone or in combination of 2 or more.

Examples of the polyisocyanate derivative (excluding the derivative of the aliphatic polyisocyanate) include a polymer of the above-mentioned polyisocyanate monomer (for example, a dimer, a trimer, a pentamer, a heptamer, etc.), an allophanate derivative (for example, an allophanate derivative produced by a reaction of the above-mentioned polyisocyanate monomer with an alcohol), a biuret derivative (for example, a biuret derivative produced by a reaction of the above-mentioned polyisocyanate monomer with water or an amine), a urea derivative (for example, a urea derivative produced by a reaction of the above-mentioned polyisocyanate monomer with a diamine), an oxadiazinetrione derivative (for example, an oxadiazinetrione derivative produced by a reaction of the above-mentioned polyisocyanate monomer with carbon dioxide), a carbodiimide derivative (for example, a carbodiimide derivative produced by a decarboxylative condensation reaction of the above-mentioned polyisocyanate monomer), and the like, Polyol derivatives (for example, polyol derivatives (alcohol addition products) produced by the reaction of the above polyisocyanate monomers with known low molecular weight polyols (preferably low molecular weight triols), polyol derivatives (polyisocyanate-terminated prepolymers) produced by the reaction of the above polyisocyanate monomers with known low molecular weight polyols and/or known high molecular weight polyols (preferably high molecular weight polyols), and the like) and the like.

These polyisocyanate derivatives may be used alone or in combination of 2 or more.

These other polyisocyanates and/or derivatives thereof may be used alone or in combination of 2 or more.

The other polyisocyanate preferably includes a polyisocyanate monomer, more preferably an aliphatic polyisocyanate (monomer), and still more preferably an alicyclic polyisocyanate (monomer).

In other words, the polyisocyanate component preferably further contains an aliphatic polyisocyanate (monomer), and more preferably an alicyclic polyisocyanate (monomer).

Further, as the alicyclic polyisocyanate (monomer), 3-isocyanatomethyl-3, 5, 5-trimethylcyclohexyl isocyanate (isophorone diisocyanate; IPDI) is particularly preferable.

When the polyisocyanate component contains an alicyclic polyisocyanate (monomer), the elongation can be improved.

In the polyisocyanate component, the content of the component other than the derivative of the aliphatic polyisocyanate (other polyisocyanate and/or derivative thereof) is, for example, less than 50% by mass, preferably 30% by mass or less, more preferably 20% by mass or less, still more preferably 10% by mass or less, and still more preferably 5% by mass or less, relative to the total amount of the polyisocyanate component.

In addition, as the polyisocyanate component, a derivative containing an aliphatic polyisocyanate alone is preferably used. That is, as the polyisocyanate component, preferred are: the composition does not contain a component other than the derivative of the aliphatic polyisocyanate (other polyisocyanate and/or derivative thereof).

The isocyanate group equivalent of the polyisocyanate component prepared in the above manner is, for example, 150 or more, preferably 200 or more, and is, for example, 750 or less, preferably 500 or less.

The isocyanate group equivalent has the same meaning as the amine equivalent, and can be determined by the method a or the method B of JIS K1603-1 (2007) (the same applies hereinafter).

The average number of functional groups of the polyisocyanate component is, for example, 1.80 or more, preferably 2.00 or more, more preferably 2.10 or more, and is, for example, 2.90 or less, preferably 2.80 or less.

The isocyanate group concentration of the polyisocyanate component is, for example, 18 mass% or more, preferably 20 mass% or more, for example, 28 mass% or less, preferably 25 mass% or less, and more preferably 24 mass% or less.

The isocyanate group concentration can be determined in accordance with the examples described later (the same applies hereinafter).

The viscosity of the polyisocyanate component at 25 ℃ is, for example, 20 mPas or more, preferably 100 mPas or more, more preferably 150 mPas or more, further preferably 200 mPas or more, for example 5000 mPas, preferably 3000 mPas or less, more preferably 1500 mPas or less, further preferably 1000 mPas or less, further preferably 980 mPas or less, and particularly preferably 800 mPas or less.

When the viscosity of the isocyanate component is in the above range, workability in the production of a flexible polyurethane foam can be improved.

The viscosity can be determined in accordance with the examples described later (the same applies hereinafter).

The polyol component contains a polyoxyalkylene polyol as an essential component, and preferably contains the polyoxyalkylene polyol alone.

The polyoxyalkylene polyol is a polyether polyol having 2 or more oxyalkylene units and 2 or more hydroxyl groups in the molecule.

In the present invention, the polyoxyalkylene polyol has both oxyethylene units and oxypropylene units. That is, in the present invention, the polyoxyalkylene polyol is a polyoxyethylene-polyoxypropylene (random/block) copolymer.

The content ratio of the oxyethylene unit is 5 mol% or more, preferably 8 mol% or more, more preferably 10 mol% or more, further preferably 12 mol% or more, and 20 mol% or less, preferably 18 mol% or less, more preferably 15 mol% or less, relative to the polyoxyalkylene polyol.

The content of the oxypropylene unit is, for example, 80 mol% or more, preferably 82 mol% or more, more preferably 85 mol% or more, for example 95 mol% or less, preferably 92 mol% or less, more preferably 90 mol% or less, and still more preferably 88 mol% or less, relative to the polyoxyalkylene polyol.

When the content ratio of oxyethylene units and oxypropylene units is in the above range, a flexible polyurethane foam having both air permeability and mechanical properties can be obtained.

In addition, polyoxyalkylene polyol has a hydroxyl group at the molecular terminal, which can be classified as a primary hydroxyl group or a secondary hydroxyl group depending on the oxyalkylene unit (oxyethylene unit or oxypropylene unit) directly bonded thereto.

Examples of the primary hydroxyl group include-OCH₂CH₂-OH、-OCH(CH₃)CH₂-OH and the like. Further, as the secondary hydroxyl group, for example, -OCH₂CH(CH₃) -OH and the like. However, due to the selectivity of the primary hydroxyl group and the secondary hydroxyl group in the addition reaction, substantially no-OCH (CH) is formed₃)CH₂-OH. Thus, the terminal hydroxyl group of the oxyethylene unit is a primary hydroxyl group (-OCH)₂CH₂-OH), the terminal hydroxyl group of the oxypropylene unit is a secondary hydroxyl group (-OCH)₂CH(CH₃)-OH)。

In such a polyoxyalkylene polyol, the proportion of primary hydroxyl groups is, for example, 1 mol% or more, preferably 5 mol% or more, more preferably 10 mol% or more, further preferably 15 mol% or more, particularly preferably 20 mol% or more, and 50 mol% or less, preferably less than 50 mol%, more preferably 45 mol% or less, further preferably 40 mol% or less, further preferably 35 mol% or less, and particularly preferably 30 mol% or less, relative to the total number of moles of terminal hydroxyl groups of the polyoxyalkylene polyol.

When the proportion of primary hydroxyl groups is in the above range, a flexible polyurethane foam having both air permeability and mechanical properties can be obtained.

The content ratio of oxyethylene units in the polyoxyalkylene polyol and the proportion of primary hydroxyl groups to the total amount of terminal hydroxyl groups may be, for example, in¹The proton integral value was calculated by a method using deuterated chloroform added with trifluoroacetic anhydride as a solvent in an H-NMR (nuclear magnetic resonance) apparatus.

The content of oxyethylene units in the polyoxyalkylene polyol can also be calculated from the raw material components (charged amount) of the polyoxyalkylene polyol.

Such a polyoxyalkylene polyol can be obtained, for example, by addition polymerization of an alkylene oxide to an initiator such as water, a low molecular weight alcohol, a low molecular weight amine, or ammonia in the presence of a polymerization catalyst.

The low molecular weight alcohol is a polyol having a molecular weight of 30 or more and less than 400, and specific examples thereof include a dihydric aliphatic alcohol such as ethylene glycol, propylene glycol, and dipropylene glycol, a trihydric aliphatic alcohol such as glycerin and trimethylolpropane, a tetrahydric aliphatic alcohol such as pentaerythritol and diglycerin, a hexahydric aliphatic alcohol such as sorbitol, and a dihydric to octahydric aliphatic alcohol such as an octahydric aliphatic alcohol such as sucrose.

The low-molecular-weight amine is a polyvalent amine compound having a molecular weight of 30 or more and less than 400, and specific examples thereof include a divalent aliphatic amine (an aliphatic amine having 2 active hydrogens) such as methylamine and ethylamine, a trivalent aliphatic amine (an aliphatic amine having 3 active hydrogens) (specifically, an alkanolamine) such as monoethanolamine, diethanolamine, and triethanolamine, a quarternary aliphatic amine (an aliphatic amine having 4 active hydrogens) such as ethylenediamine, 1, 3-and/or 1, 4-bis (aminomethyl) cyclohexane, and isophoronediamine, and a di-to pentavalent aliphatic amine (an aliphatic amine having 1 or more active hydrogens) such as a pentavalent aliphatic amine (an aliphatic amine having 5 active hydrogens) such as diethylenetriamine. Examples of the low molecular weight amine include polyvalent aromatic amines (aromatic amines having a plurality of active hydrogens) such as aromatic diamines such as 2, 4-or 2, 6-Tolylenediamine (TDA).

These initiators may be used alone or in combination of 2 or more.

The initiator is preferably an alcohol, more preferably a polyhydric aliphatic alcohol, still more preferably a dihydric to hexahydric aliphatic alcohol, yet more preferably a dihydric to tetrahydric aliphatic alcohol, and particularly preferably a trihydric aliphatic alcohol.

Examples of the polymerization catalyst include alkali metal catalysts such as potassium hydroxide, sodium hydroxide and cesium hydroxide, composite metal catalysts such as cyano complexes of zinc and cobalt (for example, composite metal cyanide complexes described in USP4,477,589), and phosphazenium catalysts such as phosphazene and phosphazenium having a nitrogen-phosphorus double bond.

These polymerization catalysts may be used alone or in combination of 2 or more.

The alkylene oxide contains ethylene oxide and propylene oxide.

The alkylene oxide preferably consists of ethylene oxide and propylene oxide. The addition form of ethylene oxide and propylene oxide is not particularly limited, and may be either block or random.

The ratio of ethylene oxide and propylene oxide used in combination can be appropriately set so that the ratio of oxyethylene units to oxypropylene units in the resulting polyoxyalkylene polyol falls within the above range and the ratio of primary hydroxyl groups to the total amount of terminal hydroxyl groups falls within the above range.

The method for addition polymerization of an alkylene oxide to an initiator is not particularly limited, and a known method can be employed. In addition polymerization, the initiator may be charged together with the alkylene oxide, or the alkylene oxide may be added to the initiator in sequence.

More specifically, for example, propylene oxide may be first addition-polymerized with an initiator, and ethylene oxide may be subsequently addition-polymerized with an initiator. Further, propylene oxide may be further addition-polymerized to a part or all of the molecular terminals of the obtained polymer.

For example, ethylene oxide may be first addition-polymerized with an initiator, and then propylene oxide may be addition-polymerized with an initiator. Further, ethylene oxide may be further subjected to addition polymerization to a part or all of the molecular terminals of the obtained polymer.

Preferably, propylene oxide is first addition-polymerized, and then ethylene oxide is addition-polymerized.

This makes it possible to easily adjust the ratio of oxyethylene units to oxypropylene units and the ratio of primary hydroxyl groups.

Further, as the polyol component, a single type of polyoxyalkylene polyol may be used, or 2 or more types of polyoxyalkylene polyols may be used in combination.

That is, as the polyol component, 2 or more kinds of polyoxyalkylene polyols having different content ratios of oxyethylene units and oxypropylene units, for example, the ratio of primary hydroxyl groups to terminal hydroxyl groups, and the like can be used in combination.

In addition, a polyoxyalkylene polyol having both an oxyethylene unit and an oxypropylene unit, and, for example, a polyoxyethylene polyol (a polyoxyalkylene polyol containing only oxyethylene units) and/or a polyoxypropylene polyol (a polyoxyalkylene polyol containing only oxypropylene units) may be mixed and used.

Further, as the polyoxyalkylene polyol, for example, a polyoxyethylene polyol (a polyoxyalkylene polyol containing only oxyethylene units) and a polyoxypropylene polyol (a polyoxyalkylene polyol containing only oxypropylene units) may be mixed and used.

In this case, the ratio of 2 or more polyoxyalkylene polyols to be used in combination can be appropriately set so that the content ratio of oxyethylene units based on the total amount of polyoxyalkylene polyols (total amount of mixture) is within the above range and the ratio of primary hydroxyl groups based on the total amount of terminal hydroxyl groups is within the above range.

Further, the polyol component may contain other polyols (polyols other than the polyoxyalkylene polyol described above) as necessary.

As the other polyol, known polyols usable in flexible polyurethane foams are exemplified, and specifically, high molecular weight polyols, low molecular weight polyols and the like are exemplified, and high molecular weight polyols are preferably exemplified.

The high molecular weight polyol is a polyol having a number average molecular weight (Mn) of 400 to 10000, and examples thereof include polyester polyol, polyether polyester polyol, polyester polyurethane polyol and the like. These may be used alone or in combination of 2 or more.

These other polyols may be used alone or in combination of 2 or more.

It is preferable that the polyol component contains the polyoxyalkylene polyol described above alone and no other polyol.

The polyol component has a hydroxyl value and an average number of functional groups for obtaining a flexible polyurethane foam.

Specifically, the hydroxyl value (OH value) of the polyol component is, for example, 5mgKOH/g or more, preferably 50mgKOH/g or more and 100mgKOH/g or more, for example, 500mgKOH/g or less, preferably 300mgKOH/g or less, more preferably 250mgKOH/g or less, and still more preferably 200mgKOH/g or less.

The average number of functional groups of the polyol component is, for example, 1.5 or more, preferably 2.0 or more, for example, 8.0 or less, preferably 4.0 or less, and more preferably 3.0 or less.

The hydroxyl value of the polyol component can be measured according to the description of JIS K1557-1 (2007), and the average number of functional groups of the polyol component can be calculated from the charged compounding formula.

Further, the flexible polyurethane foam can be obtained by: the polyisocyanate component and the polyol component are prepared as described above, and reacted in the presence of a urethane-forming catalyst and a blowing agent.

Examples of the urethane-forming catalyst include amines and organic metal compounds.

Examples of the amines include tertiary amines such as triethylamine, triethylenediamine, bis (2-dimethylaminoethyl) ether, and N-methylmorpholine, quaternary ammonium salts such as tetraethylammonium hydroxide, and imidazoles such as imidazole and 2-ethyl-4-methylimidazole. These amines may be used alone or in combination of 2 or more.

Further, these amines are commercially available, and examples thereof include KAOLIZER No.31 (manufactured by Kao corporation), KAOLIZER No.120 (manufactured by Kao corporation), KAOLIZER No.12 (manufactured by Kao corporation), KAOLIZER No.25 (manufactured by Kao corporation), DABCO 33LV (a 33 mass% diethylene glycol solution of triethylene diamine, manufactured by Air Products Japan K.K.), Niax A-1 (manufactured by Momentive Performance Materials Inc. (hereinafter, referred to as "Momentive corporation")), TOYOCAT-NCE (manufactured by Tosoh corporation), and the like.

Examples of the organic metal compound include organic tin compounds such as tin acetate, tin octylate, tin oleate, tin laurate, dibutyltin diacetate, dimethyltin dilaurate, dibutyltin dithiolate, dibutyltin maleate, dibutyltin dineodecanoate, dioctyltin dithiolate, dioctyltin dilaurate and dibutyltin dichloride, organic lead compounds such as lead octylate and lead naphthenate, organic nickel compounds such as nickel naphthenate, organic cobalt compounds such as cobalt naphthenate, organic copper compounds such as copper octylate, and organic bismuth compounds such as bismuth octylate and bismuth neodecanoate. These organometallic compounds may be used alone or in combination of 2 or more.

The organometallic compound is commercially available, and examples thereof include NEOSTANN U-100 (organotin compound, manufactured by NIDDM corporation), Formate TK-1 (organotin compound, manufactured by Mitsui chemical Co., Ltd.), Formrez UL-28 (organotin compound, manufactured by Momentive Co., Ltd.), Stanoct (organotin compound, manufactured by Mitsubishi chemical Co., Ltd.).

These urethane-forming catalysts (amines and organometallic compounds) may be used alone or in combination of 2 or more, preferably in combination of amines and organometallic compounds.

The blending ratio of the urethane-forming catalyst (in terms of 100% of the amount of the active ingredient) is, for example, 0.1 part by mass or more, preferably 0.3 part by mass or more, more preferably 1.0 part by mass or more, and is, for example, 5 parts by mass or less, preferably 3 parts by mass or less, relative to 100 parts by mass of the polyol component.

When the blending ratio of the urethane-forming catalyst is in the above range, the yellowing resistance of the flexible polyurethane foam obtained can be improved.

In the case where the amine and the organometallic compound are used in combination as the urethane-forming catalyst, the ratio of the blending ratio of the amine to the organometallic compound (the blending ratio of the amine/the blending ratio of the organometallic compound in terms of 100% of the amount of the active ingredient) is, for example, 0.1 or more, preferably 0.3 or more, and, for example, 1 or less, preferably 0.7 or less.

The foaming agent is not particularly limited, and known foaming agents may be mentioned, and water is preferably mentioned.

Further, as the blowing agent, water and a physical blowing agent (for example, halogenated hydrocarbons (for example, methylene chloride and the like), hydrocarbons (for example, cyclopentane and the like), carbon dioxide, liquid carbon dioxide and the like) may be used in combination at an appropriate ratio. As the physical blowing agent, carbon dioxide and liquid carbon dioxide are preferably used from the viewpoint of reducing the environmental load.

These physical blowing agents may be used alone or in combination of 2 or more.

The mixing ratio of the foaming agent is, for example, 0.5 parts by mass or more, preferably 1 part by mass or more, for example, 10 parts by mass or less, preferably 7 parts by mass or less, relative to 100 parts by mass of the polyol component.

When the content ratio of the foaming agent is in the above range, excellent foamability can be obtained.

In order to produce the flexible polyurethane foam of the present invention, first, the urethane-forming catalyst and the blowing agent are mixed in the polyol component in the above-mentioned mixing ratio to prepare a premix (resin premix).

In addition, in the preparation of the premix, additives such as a foam stabilizer, a stabilizer and the like may be added as necessary, and the premix is preferably prepared from the above polyol component, the above urethane-forming catalyst, the above blowing agent, the foam stabilizer and the stabilizer.

The foam stabilizer is not particularly limited, and known foam stabilizers, for example, silicone foam stabilizers, can be mentioned.

The foam stabilizer is commercially available, and examples thereof include DC-6070, DC-2525 (trade name, manufactured by Air Products Japan K.K., supra), SZ-1966, SRX-274C, SF-2969, SF-2961, SF-2962, SZ-1325, SZ-1328 (trade name, manufactured by Dow Corning Toray Co., Ltd., supra), L-5309, L-3601, L-5307, L-3600, L-5366, Y-10366 (trade name, manufactured by Momentive Co., Ltd., supra), B-8002, B-8545, and B-8715LF2 (trade name, manufactured by Evanic Corporation, supra).

These foam stabilizers may be used alone or in combination of 2 or more.

The mixing ratio of the foam stabilizer is, for example, 0.1 part by mass or more, preferably 0.5 part by mass or more, for example, 10 parts by mass or less, preferably 5 parts by mass or less, with respect to 100 parts by mass of the polyol component.

Examples of the stabilizer include an antioxidant, an ultraviolet absorber, a heat stabilizer, and a light stabilizer, and preferably include an antioxidant and a light stabilizer.

Examples of the antioxidant include hindered phenol antioxidants (e.g., 4-methyl-2, 6-di-t-Butylphenol (BHT), triethylene glycol bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate ], pentaerythritol tetrakis [3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ], and the like), other antioxidants (for example, phosphorus antioxidants such as bis (2, 4-di-t-butylphenyl) pentaerythritol diphosphite, tridecyl phosphite, and tris (2-ethylhexyl) phosphite, and thiophene antioxidants such as 2, 5-thiophenediylbis (5-t-butyl-1, 3-benzoxazole) other than hindered phenol antioxidants).

Among these antioxidants, a phosphorus-based antioxidant is preferable, and tris (2-ethylhexyl) phosphite is more preferable. As tris (2-ethylhexyl) phosphite, a commercially available product can be used, and JP-308E (product name, manufactured by North City chemical Co., Ltd.) is exemplified.

These antioxidants may be used alone or in combination of 2 or more.

Examples of the ultraviolet absorber include benzophenone-based, benzotriazole-based, triazine-based, and cyanoacrylate-based ultraviolet absorbers.

These ultraviolet absorbers may be used alone or in combination of 2 or more.

Examples of the heat stabilizer include compounds containing a sulfonamide group.

Examples of the sulfonamide group-containing compound include aromatic sulfonamides and aliphatic sulfonamides, and preferable examples include o-toluenesulfonamide.

These heat stabilizers may be used alone or in combination of 2 or more.

Examples of the light stabilizer include hindered amine-based light stabilizers and blend-based light stabilizers, and preferred examples thereof include hindered amine-based light stabilizers. Examples of the hindered amine-based light stabilizer include ADK STAB LA62, ADK STAB LA67 (trade name, manufactured by Adeka Argus Chemical co.ltd.), TINUVIN 765, TINUVIN 144, TINUVIN 770, and TINUVIN 622 (trade name, manufactured by BASF Japan).

These light stabilizers may be used alone or in combination of 2 or more.

The blending ratio of the stabilizer is, for example, 0.1 part by mass or more, preferably 0.5 part by mass or more, for example, 10 parts by mass or less, preferably 5 parts by mass or less, with respect to 100 parts by mass of the polyol component.

In addition to the above-mentioned additives, if necessary, other known additives such as a crosslinking agent, a linking agent, a pigment (coloring pigment), a dye, a curing accelerator, a matting agent, an adhesion imparting agent, and a silane coupling agent may be further added to the premix in an appropriate ratio within a range not to impair the excellent effects of the present invention.

In addition, other known additives such as a chain extender, a defoaming agent, a plasticizer, an antiblocking agent, a mold release agent, a lubricant, a filler, a hydrolysis preventing agent, and the like may be further blended in an appropriate ratio within a range not to impair the excellent effects of the present invention.

The flexible polyurethane foam of the present invention can be obtained by mixing and reacting the premix obtained as described above and the polyisocyanate component and simultaneously foaming the mixture by a known foaming method such as a flat foam method, a mold foam method, a spray foam method, or the like.

The reaction conditions (for example, reaction temperature and the like) of the premix and the polyisocyanate component can be appropriately set according to the purpose and use thereof.

The mixing ratio of the polyisocyanate component is, for example, 60 or more, preferably 70 or more, for example 500 or less, preferably 130 or less in terms of an isocyanate index (a ratio of isocyanate groups to 100 total of active hydrogen such as hydroxyl groups in the polyol component and water as a blowing agent).

The reaction time (cream time (CT)) of the premix and the polyisocyanate component can be measured in the examples described later, and is, for example, 40 seconds or more, for example, 200 seconds or less, preferably 100 seconds or less, more preferably 60 seconds or less, and further preferably 50 seconds or less.

When the reaction time (cream time (CT)) of the premix and the polyisocyanate component is in the above range, the workability can be improved.

Thus, the flexible polyurethane foam of the present invention is obtained as a reaction product of the polyisocyanate component and the polyol component.

In the flexible polyurethane foam of the present invention obtained as described above, the polyisocyanate component contains an allophanate derivative of an aliphatic polyisocyanate in a predetermined ratio with respect to the derivative of the aliphatic polyisocyanate, and the polyol component contains a polyoxyalkylene polyol in which the ratio of oxyethylene units and the ratio of primary hydroxyl groups are in a predetermined ratio. Therefore, the flexible polyurethane foam of the present invention has both air permeability and mechanical properties.

In the flexible polyurethane foam of the present invention, the term "flexible" is defined as: the hardness (25% CLD, measured in examples described later) of the polyurethane foam is, for example, 40.0N/100cm²Hereinafter, it is preferably 30.0N/100cm²Hereinafter, more preferably 20.0N/100cm²Hereinafter, it is more preferably 15.0N/100cm²The concentration is more preferably 10.0N/100cm²Hereinafter, more preferably 7.0N/100cm²Hereinafter, more preferably 5.0N/100cm²The following.

The density of the flexible polyurethane foam of the present invention (measured in examples described later) is, for example, 10.0kg/m³Above, preferably 15.0kg/m³Above, and in addition, for example, 50.0kg/m³Hereinafter, it is preferably 45.0kg/m³Hereinafter, more preferably 40.0kg/m³Hereinafter, more preferably 37.0kg/m³The amount of the surfactant is preferably 35.0kg/m³The following.

The air permeability of the flexible polyurethane foam of the present invention (measured in examples described later) is, for exampleIs 10cc/cm²At least sec, preferably 100cc/cm²Sec or more, more preferably 200cc/cm²At least sec, for example, 500cc/cm²A/sec or less, preferably 400cc/cm²And/sec or less.

The tear strength (measured in examples described later) of the flexible polyurethane foam of the present invention is, for example, 1N/cm or more, preferably 1.5N/cm or more, and more preferably 2N/cm or more.

The flexible polyurethane foam of the present invention has an elongation at tensile break (measured in examples described later) of, for example, 35% or more, preferably 100% or more, more preferably 150% or more, further preferably 185% or more, further preferably 190% or more, particularly preferably 200% or more, for example, 500% or less, and preferably 400% or less.

The flexible polyurethane foam of the present invention has a Wet heat compression Set (Wet Set (measured in examples described later)) of, for example, 10% or less, preferably 6% or less, more preferably 5% or less, still more preferably 4% or less, still more preferably 3% or less, and particularly preferably 2% or less.

The flexible polyurethane foam of the present invention is excellent in discoloration resistance. In other words, the polyurethane foam of the present invention is a non-yellowing foam.

"non-yellowing" means that: the light resistance Δ b of the flexible polyurethane foam is, for example, 15.0 or less, preferably 12.0 or less.

Therefore, the obtained flexible polyurethane foam can be effectively used as an elastic material such as a pressure-resistant dispersion material, a shape-retaining material, a sound-absorbing material, an impact-absorbing material, a vibration-absorbing material, and an optical material in the fields of automobiles, furniture, bedding, electronic materials, medical care, clothing, sanitary materials, and the like.

More specifically, the flexible polyurethane foam is used for, for example, bedding such as seats, headrests, armrests, chairs, pillows, and mattresses, sofas, nursing cushions, leisure pads (leisureshets), protectors, hairpieces, filters, covers for microphones, covers for earphones, covers for headphones, floor materials for cushion pads, cosmetic powder puffs, eye shadow sticks, medical materials, coating rollers, OA rollers, ink absorbing sheets, electronic components (e.g., tablet computers, smart phones, and the like), polishing pads, sanitary goods, and diapers.

In particular, since the polyurethane foam has a soft touch and excellent yellowing resistance, it can be preferably used for a pressure-resistant cushion material for clothing, shoes, and robots, specifically, shoulder pads, knee pads, elbow pads, swimming pads, tongue portions, shoe insoles, medical materials, clothing materials, robot skins, manipulators, and the like, and is particularly suitable for bra pads, bra cups, and the like which are molded products of clothing materials.

The material for clothing comprising the flexible polyurethane foam of the present invention, and the bra pad and the bra cup which are molded articles of the material for clothing have both air permeability and mechanical properties.

Examples

Specific numerical values of the blending ratio (content ratio), physical property value, parameter, and the like used in the following description may be replaced with upper limit values (numerical values defined as "lower" and "lower") or lower limit values (numerical values defined as "upper" and "higher" respectively) described in association with the corresponding blending ratio (content ratio), physical property value, parameter, and the like described in the above-mentioned "embodiment".

In addition, the measurement methods used in the respective production examples, the respective synthesis examples, the respective examples, and the respective comparative examples are described below.

1. Measurement method

< isocyanate group concentration (unit: mass%), conversion of isocyanate group (unit: mass%) >

The isocyanate group concentration (isocyanate group content) was measured by a toluene/dibutylamine hydrochloride method according to JIS K-1603-1 (2007) using a potential differential titration apparatus (manufactured by Kyoto electronics industries, model: AT-510), and the conversion of the isocyanate group of the measurement sample was calculated by the following formula.

Conversion of isocyanate group is 100 — (isocyanate group concentration of the reaction mixture after completion of the reaction/isocyanate group concentration of the reaction mixture before completion of the reaction × 100)

< isocyanate monomer concentration (unit: mass%) >

The concentration of unreacted pentamethylene diisocyanate monomer or hexamethylene diisocyanate monomer was calculated from a calibration curve prepared from the area value of the chromatogram obtained under the following HPLC measurement conditions, using pentamethylene diisocyanate produced in the same manner as in example 1 in the specification of the international publication No. 2012/121291 or commercially available hexamethylene diisocyanate as a standard substance, and labeling with dibenzylamine.

The device comprises the following steps: prominine (manufactured by Shimadzu corporation)

Pump LC-20AT

Degasser DGU-20A3

Autosampler SIL-20A

Column thermostatic bath COT-20A

Detector SPD-20A

Column: SHISEIDO SILICA SG-120

Column temperature: 40 deg.C

Eluent: n-hexane/methanol/1, 2-dichloroethane (volume ratio) 90/5/5

Flow rate: 0.2mL/min

The detection method comprises the following steps: UV 225nm

< viscosity (unit: mPas) >

The viscosity of the measurement sample was measured at 25 ℃ by the cone and plate viscometer method according to JIS K5600-2-3 (2014) using an E-type viscometer TV-30 (rotor angle: 1 ℃ 34', rotor radius: 24cm) manufactured by Toyobo industries, Inc. The rotational speed of the conical plate during measurement was changed in sequence between 100rpm and 2.5rpm in accordance with the increase in viscosity.

Under the following apparatus and conditions¹H-NMR measurement of allophanate in the derivative of aliphatic polyisocyanate was calculated by the following formula based on 1 mole of isocyanurate groupThe content ratio of ester groups (molar ratio of allophanate groups/isocyanurate groups). In addition, D was used as a reference for chemical shift ppm⁶Tetramethylsilane (0ppm) in DMSO solvent.

The device comprises the following steps: JNM-AL400 (manufactured by JEOL)

Conditions are as follows: measuring frequency: 400MHz, solvent: d⁶-DMSO, solute concentration: 5% by mass

Peak assignment of proton of allophanate group (NH group in allophanate group) (1H): 8.3 to 8.7ppm

Isocyanurate group (methylene (CH) directly bonded to isocyanurate group₂Basal)) of proton, peak (6H): 3.8ppm of

The molar ratio of allophanate groups to isocyanurate groups (integral of peak ascribed to proton of allophanate group/(integral of peak ascribed to proton of isocyanurate group)/6)

Under the following apparatus and conditions¹³In the C-NMR measurement, the content ratio of the uretdione groups (molar ratio of uretdione groups/isocyanurate groups) in the polyisocyanate derivative relative to 1 mole of isocyanurate groups was calculated by the following formula. CDCL was used as a reference for chemical shift ppm₃Tetramethylsilane (0ppm) in solvent.

The device comprises the following steps: JNM-AL400 (manufactured by JEOL)

Conditions are as follows: measuring frequency: 100MHz, solvent: CDCL₃The solute concentration: 50% by mass

Peak assignment of carbon to uretdione group (CO group in uretdione group) (2H): 157.8ppm

Peak ascribed to carbon of isocyanurate group (CO group in isocyanurate group) (3H): 149.1ppm

Molar ratio of uretdione group/isocyanurate group (integrated value of peak ascribed to carbon of uretdione group/2)/(integrated value of peak ascribed to carbon of isocyanurate group/3)

< method for measuring hydroxyl value of polyol >

The hydroxyl value is defined as the number of mg of potassium hydroxide corresponding to the hydroxyl group in 1g of the polyoxyalkylene polyol. The hydroxyl value was measured in accordance with JIS K1557 (2007) under the term "hydroxyl value" of 6.4.

< method for measuring concentration of primary hydroxyl groups relative to all terminal hydroxyl groups of polyol >

About 30mg of a measurement sample to a 5mm diameter sample tube for NMR was weighed and dissolved by adding about 0.5ml of a deuterated solvent. Then, about 0.1ml of trifluoroacetic anhydride was added as a sample for analysis. Then, proceed with¹H-NMR measurement (device: JNM-AL400(JEOL Ltd.), measurement frequency: 400 MHz).

In this method, the terminal hydroxyl group of the polyoxyalkylene polyol reacts with trifluoroacetic anhydride to form trifluoroacetate, and therefore, a signal derived from a methylene group to which a primary hydroxyl group is bonded can be observed in the vicinity of 4.3 ppm. In addition, a signal derived from a methine group to which a secondary hydroxyl group is bonded was observed at around 5.2 ppm. Therefore, the primary hydroxylation ratio of the terminal hydroxyl group is calculated by the following calculation formula.

Primary hydroxylation ratio (%) of terminal hydroxyl group, ([ a/(a +2 xb) ] × 100

(wherein a is an integrated value of a signal derived from a methylene group bonded to a primary hydroxyl group in the vicinity of 4.3ppm, and b is an integrated value of a signal derived from a methine group bonded to a secondary hydroxyl group in the vicinity of 5.2 ppm.)

2. Raw materials

(1) Polyisocyanate component (a)

Preparation example 1 (allophanate derivative of aliphatic polyisocyanate (a-1) (iBA-modified allophanate derivative of PDI))

A reactor equipped with a thermometer, a stirrer, a nitrogen inlet tube and a condenser was charged with 500 parts by mass of pentamethylene diisocyanate, 24 parts by mass of isobutanol, 0.3 part by mass of 2, 6-di-t-butyl-4-methylphenol and 0.3 part by mass of tridecyl phosphite, which were produced in the same manner as in example 1 in the specification of the pamphlet of International publication No. 2012/121291, in a nitrogen atmosphere, and urethanization was carried out at 85 ℃ for 3 hours.

Next, 0.02 part by mass of bismuth tris (2-ethylhexanoate) as an allophanatization catalyst was added, a reaction was conducted until the isocyanate group concentration reached the calculated value (46.7 mass%, that is, the conversion rate was 10 mass%), and then 0.02 part by mass of o-toluenesulfonamide was added.

Then, the obtained reaction solution was passed through a thin film distillation apparatus (degree of vacuum of 0.093KPa, temperature of 150 ℃ C.), unreacted pentamethylene diisocyanate was removed, and 0.02 part by mass of o-toluenesulfonamide was added to 100 parts by mass of the obtained filtrate, to obtain isocyanate (a-1).

The obtained allophanate derivative (a-1) of aliphatic polyisocyanate had an isocyanate group concentration of 20.4% by mass, a viscosity at 25 ℃ of 200 mPas, and an isocyanate monomer concentration of 0.2% by mass.

In addition, use of¹The molar ratio of allophanate groups to isocyanurate groups determined by H-NMR was 100/3.

In addition, use of¹³The molar ratio of uretdione groups to isocyanurate groups determined by C-NMR was 0/3.

From this, the isocyanurate derivative content, allophanate derivative content and uretdione derivative content were determined for the total amount of the derivatives. The results are shown in table 1.

Preparation example 2 (allophanate derivative of aliphatic polyisocyanate (a-2) (iPA-modified allophanate derivative of PDI))

Allophanate derivative (a-2) of an aliphatic polyisocyanate was obtained in the same manner as in preparation example 1, except that 24 parts by mass of isopropyl alcohol was used instead of isobutyl alcohol.

The obtained allophanate derivative (a-2) of aliphatic polyisocyanate had an isocyanate group concentration of 21.2% by mass, a viscosity at 25 ℃ of 180 mPas, and an isocyanate monomer concentration of 0.2% by mass.

Preparation example 3 (allophanate derivative of aliphatic polyisocyanate (a-3) (nBA-modified allophanate derivative of PDI))

Allophanate derivative (a-3) of an aliphatic polyisocyanate was obtained in the same manner as in preparation example 1, except that 24 parts by mass of n-butanol was used instead of isobutanol.

The obtained allophanate derivative (a-3) of aliphatic polyisocyanate had an isocyanate group concentration of 20.5% by mass, a viscosity at 25 ℃ of 320 mPas, and an isocyanate monomer concentration of 0.2% by mass.

Preparation example 4 (allophanate derivative of aliphatic polyisocyanate (a-4) (3 MPD-modified allophanate derivative of PDI))

Allophanate derivative (a-4) of an aliphatic polyisocyanate was obtained in the same manner as in preparation example 1, except that 14.6 parts by mass of 3-methyl-pentanediol was used instead of isobutanol.

The obtained allophanate derivative (a-4) of aliphatic polyisocyanate had an isocyanate group concentration of 21.3% by mass, a viscosity at 25 ℃ of 1800 mPas, and an isocyanate monomer concentration of 0.2% by mass.

Preparation example 5 (allophanate derivative of aliphatic polyisocyanate (a-5) (1, 4-BG-modified allophanate derivative of PDI))

Allophanate derivative (a-5) of aliphatic polyisocyanate was obtained in the same manner as in preparation example 1, except that 14.6 parts by mass of 1, 4-butanediol was used instead of isobutanol.

The obtained allophanate derivative (a-5) of an aliphatic polyisocyanate had an isocyanate group concentration of 22.1% by mass, a viscosity at 25 ℃ of 2400 mPas, and an isocyanate monomer concentration of 0.2% by mass.

Preparation example 6 (allophanate derivative of aliphatic polyisocyanate (a-6): iBA-modified allophanate derivative of HDI)

Allophanate derivatives (a-6) of aliphatic polyisocyanates were obtained in the same manner as in preparation example 1, except that pentamethylene diisocyanate was changed to hexamethylene diisocyanate (product name: Takenate 700, manufactured by Mitsui chemical Co., Ltd.).

The obtained allophanate derivative (a-6) of aliphatic polyisocyanate had an isocyanate group concentration of 19.3%, a viscosity at 25 ℃ of 300 mPas and an isocyanate monomer concentration of 0.4% by mass.

Preparation example 7 (isocyanurate derivative of aliphatic polyisocyanate (a-7): iBA-modified isocyanurate derivative of PDI)

500 parts by mass of pentamethylene diisocyanate, 0.5 part by mass of isobutyl alcohol, 0.3 part by mass of 2, 6-di-t-butyl-4-methylphenol, and 0.3 part by mass of tridecyl phosphite, which were produced in the same manner as in example 1 in the specification of the pamphlet of International publication No. 2012/121291, were placed in a four-necked flask equipped with a thermometer, a stirrer, a reflux tube, and a nitrogen introduction tube, and reacted at 80 ℃ for 2 hours.

Next, 0.05 part by mass of N- (2-hydroxypropyl) -N, N, N-trimethylammonium 2-ethylhexanoate as an isocyanuric acid esterification catalyst was added. The isocyanate group concentration was measured, and the reaction was continued until the concentration thereof reached 48.9 mass% (i.e., conversion rate was 10 mass%). After 50 minutes, when a predetermined conversion (conversion: 10% by mass) was obtained, 0.12 parts by mass of o-toluenesulfonamide was added. The obtained reaction mixture was passed through a thin film distillation apparatus (temperature: 150 ℃ C., vacuum degree: 0.093kPa) to remove unreacted pentamethylene diisocyanate monomer, and 0.02 part by mass of o-toluenesulfonamide and 0.003 part by mass of benzoyl chloride were added to 100 parts by mass of the obtained filtrate to obtain an isocyanurate derivative (a-7) of an aliphatic polyisocyanate.

The isocyanurate derivative of an aliphatic polyisocyanate (a-7) had an isocyanate monomer concentration of 0.5% by mass, an isocyanate group concentration of 24.7% by mass, and a viscosity at 25 ℃ of 2000 mPas.

In addition, use of¹The molar ratio of allophanate groups to isocyanurate groups determined by H-NMR was 7.4/100.

In addition, use of¹³The molar ratio of uretdione groups to isocyanurate groups determined by C-NMR was 1/100.

Preparation example 8 (alicyclic polyisocyanate (a-8))

Isophorone diisocyanate (product name: VESTANATIPDI, manufactured by EVONIK corporation, isocyanate group concentration 37.8 mass%, viscosity at 25 ℃ 5 mPas) was used as the alicyclic polyisocyanate (a-8).

(2) Polyol component (b)

Preparation example 1 (polyol (b-1))

As the polyol (b-1), a polyoxyalkylene polyol (a polyether polyol obtained by addition polymerization of propylene oxide to glycerin and then addition polymerization of ethylene oxide, the number average molecular weight (Mn) 940, the number of functional groups f 3, the OH value 180mgKOH/g, the ethylene oxide concentration in all alkylene oxides 20 mass% (25 mol%), and the primary hydroxyl group concentration in all terminal hydroxyl groups 45.5%) was used.

Preparation example 2 (polyol (b-2))

A polyoxyalkylene polyol (a polyether polyol obtained by addition polymerization of propylene oxide to pentaerythritol followed by addition polymerization of ethylene oxide, the number average molecular weight (Mn) being 1250, the functional group number f being 4, the OH value being 180mgKOH/g, the ethylene oxide concentration in all alkylene oxides being 20 mass% (25 mol%), and the primary hydroxyl group concentration in all terminal hydroxyl groups being 46.6%) was used as the polyol (b-2).

Preparation example 3 (polyol (b-3))

As the polyol (b-3), a polyoxyalkylene polyol (a polyether polyol obtained by addition polymerization of propylene oxide to propylene glycol and then addition polymerization of ethylene oxide, the number average molecular weight (Mn) of 620, the number of functional groups f of 2, the OH value of 180mgKOH/g, the ethylene oxide concentration in all alkylene oxides of 20 mass% (25 mol%), and the primary hydroxyl group concentration in all terminal hydroxyl groups of 45.7%) was used.

Preparation example 4 (polyol (b-4))

A polyoxyalkylene polyol (a polyether polyol obtained by addition polymerization of propylene oxide to triethanolamine followed by addition polymerization of ethylene oxide, the number average molecular weight (Mn) 940, the number of functional groups f 3, the OH value 180mgKOH/g, the ethylene oxide concentration in all alkylene oxides 20 mass% (25 mol%), and the primary hydroxyl group concentration in all terminal hydroxyl groups 46.8%) was used as the polyol (b-4).

Preparation example 5 (polyol (b-5))

As the polyol (b-5), a polyoxyalkylene polyol (a polyether polyol obtained by addition polymerization of propylene oxide to glycerin and then addition polymerization of ethylene oxide, the number average molecular weight (Mn) of 5000, the number of functional groups f of 3, the OH value of 34mgKOH/g, the ethylene oxide concentration of all alkylene oxides of 15 mass% (19 mol%), and the primary hydroxyl group concentration of all terminal hydroxyl groups of 90.0%) was used.

Preparation example 6 (polyol (b-6))

As the polyol (b-6), a polyoxyalkylene polyol (a polyether polyol obtained by addition polymerization of propylene oxide to glycerin and then addition polymerization of ethylene oxide, the number average molecular weight (Mn) of 6000, the number of functional groups f of 3, the OH value of 28mgKOH/g, the ethylene oxide concentration of all alkylene oxides of 40 mass% (47 mol%), and the primary hydroxyl group concentration of all terminal hydroxyl groups of 92.0%) was used.

Preparation example 7 (polyol (b-7))

As the polyol (b-7), a polyoxyalkylene polyol (a polyether polyol obtained by addition polymerization of propylene oxide to glycerin, the number average molecular weight (Mn) of 5000, the number of functional groups f of 3, the OH value of 34mgKOH/g, and the primary hydroxyl group concentration of all terminal hydroxyl groups of 3.3%) was used.

Preparation example 8 (polyol (b-8))

As the polyol (b-8), a polyoxyalkylene polyol (a polyether polyol obtained by addition polymerization of propylene oxide to glycerin and then addition polymerization of ethylene oxide, the number average molecular weight (Mn) of 700, the number f of functional groups of 3, the OH value of 240mgKOH/g, and the concentration of primary hydroxyl groups in all terminal hydroxyl groups of 3.5%) was used.

(3) Catalyst (c)

(catalyst (c-1))

A33 mass% dipropylene glycol solution of triethylenediamine (product K.K., trade name: Dabco-33LV)

(catalyst (c-2))

Organotin compound (product name: Formrez UL-28, manufactured by Momentive Co., Ltd.)

(4) Foaming agent (d)

(blowing agent (d-1))

Pure water (H)₂O)

(5) Foam stabilizer (e)

(foam stabilizer (e-1))

Polysiloxane foam stabilizer (product name: B-8002, manufactured by Evonic Corporation)

(6) Stabilizer (f)

(stabilizer (f-1))

Hindered amine compound (light stabilizer, product name: TINUVIN 765 from BASF Japan)

(stabilizer (f-2))

Organic phosphorus compound (antioxidant, product name: JP-308E, manufactured by Tokyo chemical Co., Ltd.)

3. Examples 1 to 20 and comparative examples 1 to 5 (production of Flexible polyurethane foam)

(1) Example 1

In the components (raw materials) shown in the following table 1, components other than the polyisocyanate component were weighed, and mixed in accordance with the formulation shown in table 1 in a laboratory at a temperature of 23 ℃ and a relative humidity of 55%, and stirred and mixed so as to be uniform, thereby preparing a premix.

Separately prepared polyisocyanate components were weighed according to the formulation shown in tables 3 to 6, and the temperature was adjusted to 23 ℃.

Then, the polyisocyanate components were added to the premix, they were stirred for 15 seconds using a hand-held mixer (rotation speed 5000rpm), and immediately and rapidly put into a wooden box to be foamed. Thus, a flexible polyurethane foam was obtained.

(2) Examples 2 to 20 and comparative examples 1 to 5

Flexible polyurethane foams were obtained in the same manner as in example 1, except that the components were weighed according to the formulation shown in tables 3 to 6 below.

The compounding formulations and the properties of the polyisocyanate components in the examples and comparative examples are shown in tables 3 to 6.

4. Evaluation of Flexible polyurethane foam

A rectangular parallelepiped having a size of 10 × 10 × 5cm was cut out from the center (core) of the flexible polyurethane foam of each example and each comparative example to prepare a measurement sample, and the apparent density of the measurement sample was measured according to JIS K7222 (2005).

A rectangular parallelepiped having a size of 10 × 10 × 5cm was cut out from the center (core) of the flexible polyurethane foam of each example and each comparative example to prepare a measurement sample, and then the hardness (25% CLD) of the measurement sample was measured according to JIS K-6400 (2012).

A measurement sample was prepared by cutting a flexible polyurethane foam of each example and each comparative example to a size of 10mm in thickness from the center thereof, crushing (crushing conditions: the flexible polyurethane foam passed through 2 rolls (at intervals of 0.2 mm)) and measuring air permeability according to JIS K-6400 (2012) B method using an air permeability measuring apparatus (manufactured by Toyo Seiki Seisaku-Sho Ltd.).

< tear Strength (Unit: N/cm)

A dimension of 10mm in thickness was cut out from the center of each of the flexible polyurethane foams of examples and comparative examples, and the samples were punched out into an angular test piece shape to prepare measurement samples, and a tear test was performed according to JIS K-6400 (2012) B using a tensile compression tester (INTESCO co., ltd., Model205N), and the stress at break was calculated.

< elongation at tensile Break (unit:%) >)

A dimension of 10mm in thickness was cut out from the center of each of the flexible polyurethane foams of examples and comparative examples, and the sample was punched out into a shape of test piece No.1 to prepare a measurement sample, and a tensile test was performed using a tensile compression tester (intasco co., ltd., model 1205N) in accordance with JIS K-6400 (2012) to calculate an elongation at break.

< Wet Heat compression Set Wet Set (unit:%) >)

A rectangular parallelepiped having a dimension of 50 mm. times.50 mm. times.25 mm was cut out from the center (core) of the flexible polyurethane foams of examples and comparative examples to prepare a measurement sample, and then the wet heat compression set (%) was measured according to the method described in JIS K6400-4. The test piece was compressed to a thickness of 50%, held between parallel flat plates, and left at 50 ℃ and a relative humidity of 95% for 22 hours. The test piece was taken out, and after 30 minutes, the thickness was measured, and the deformation ratio (%) was measured in comparison with the thickness before the test.

The evaluation of the flexible polyurethane foams of examples 1 to 20 and comparative examples 1 to 4 is shown in tables 3 to 6.

[ Table 1]

TABLE 1

[ Table 2]

TABLE 2

[ Table 3]

TABLE 3

[ Table 4]

TABLE 4

[ Table 5]

TABLE 5

[ Table 6]

TABLE 6

The detailed meanings of the abbreviations used in the tables are as follows.

PDI: pentamethylene diisocyanate

HDI: hexamethylene diisocyanate

IPDI: isophorone diisocyanate

iBA: isobutyl alcohol (isobutyl alcohol)

nBA: n-butanol

3 MPD: 3-methyl-pentanediol

1, 4-BG: 1, 4-butanediol

AO: alkylene oxide

EO: ethylene oxide

PO: propylene oxide

Gly: glycerol

PE: pentaerythritol

PG: propylene glycol

TEOA: triethanolamine

Dabco 33 LV: a33 mass% dipropylene glycol solution of triethylenediamine (manufactured by Air Products K.K.)

Formrez UL-28: organotin compound (manufactured by Momentive Co., Ltd.)

B-8002: silicone foam stabilizer (Evonic Corporation)

Tin, 765: hindered amine compound (light stabilizer, BASF Japan Co., Ltd.)

JP-308E: organic phosphorus compound (antioxidant, made by Tokyo chemical Co., Ltd.)

The above-described invention is provided as an embodiment of the present invention, and is merely an example and is not to be construed as a limitation. Variations of the invention as understood by those skilled in the art are intended to be encompassed by the following claims.

Industrial applicability

The flexible polyurethane foam of the present invention can be used for shoulder pads, knee pads, elbow pads, swimming pads, tongue shoes, shoe insoles, medical materials, clothing materials, robot skins, manipulators, and the like, and is particularly suitable for bra pads, bra cups, and the like which are molded articles of clothing materials.

Claims

1. A flexible polyurethane foam which is obtained by reacting and foaming a polyisocyanate component containing a derivative of an aliphatic polyisocyanate with a polyol component containing a polyoxyalkylene polyol,

the aliphatic polyisocyanate contains pentamethylene diisocyanate,

the derivative of an aliphatic polyisocyanate comprises an allophanate derivative of an aliphatic polyisocyanate,

the content ratio of the allophanate derivative of the aliphatic polyisocyanate is 70 mol% or more relative to the total amount of the derivatives of the aliphatic polyisocyanate,

the polyoxyalkylene polyol has both oxyethylene units and oxypropylene units,

the oxyethylene unit accounts for 5 mol% or more and 20 mol% or less relative to the polyoxyalkylene polyol,

the primary hydroxyl group is 50 mol% or less based on the total number of moles of the terminal hydroxyl groups of the polyoxyalkylene polyol.

2. The flexible polyurethane foam according to claim 1, wherein the content of the allophanate derivative of the aliphatic polyisocyanate is 75 mol% or more and 99 mol% or less based on the total amount of the derivatives of the aliphatic polyisocyanate.

3. The flexible polyurethane foam according to claim 1, wherein the aliphatic polyisocyanate further comprises hexamethylene diisocyanate.

4. The flexible polyurethane foam according to claim 3, wherein the polyisocyanate component further comprises a cycloaliphatic polyisocyanate.

5. The flexible polyurethane foam according to claim 1, wherein the derivative comprises an alcohol-modified allophanate derivative,

the alcohol comprises monohydric alcohol and dihydric alcohol.

6. The flexible polyurethane foam according to claim 5, wherein the alcohol comprises a branched chain monohydric alcohol and a branched chain dihydric alcohol.

7. A clothing material comprising the flexible polyurethane foam according to claim 1.

8. A bra pad which is a molded article of the clothing material according to claim 7.

9. A bra cup comprising the bra pad of claim 8.

10. A method for producing a flexible polyurethane foam, comprising the steps of:

a step for preparing a polyisocyanate component containing a derivative of an aliphatic polyisocyanate and a polyol component containing a polyoxyalkylene polyol; and

a step of producing a flexible polyurethane foam by reacting and foaming the polyisocyanate component and the polyol component,

the aliphatic polyisocyanate contains pentamethylene diisocyanate,

the polyoxyalkylene polyol has both oxyethylene units and oxypropylene units,