WO2018181151A1

WO2018181151A1 - Soft polyurethane foam, clothing material, pad of brassiere, cup of brassiere, and production method for soft polyurethane foam

Info

Publication number: WO2018181151A1
Application number: PCT/JP2018/012092
Authority: WO
Inventors: 宏金山; 実渡邉; 俊彦中川; 森田　広一; 山崎　聡
Original assignee: 三井化学株式会社
Priority date: 2017-03-31
Filing date: 2018-03-26
Publication date: 2018-10-04
Also published as: CN110114383A; JPWO2018181151A1; JP6793249B2; TWI732112B; CN110114383B; TW201841965A

Abstract

This soft polyurethane foam is obtained by reaction and foaming of a polyisocyanate component containing a derivative of an aliphatic polyisocyanate and a polyol component containing a polyoxyalkylene polyol, wherein the derivative includes an allophanate derivative of an aliphatic polyisocyanate, the content ratio of the allophanate derivative of the aliphatic polyisocyanate is 70 mol% or more with respect to the total amount of the derivatives of the aliphatic polyisocyanate, the polyoxyalkylene polyol contains a combination of an oxyethylene unit and an oxypropylene unit, the oxyethylene unit accounts for 5-20 mol% with respect to the polyoxyalkylene polyol, and the primary hydroxy group accounts for 50 mol% or less with respect to the total number of moles of the terminal hydroxy groups of the polyoxyalkylene polyol.

Description

Flexible polyurethane foam, clothing material, brassiere pad, brassiere cup, and method for producing flexible polyurethane foam

TECHNICAL FIELD The present invention relates to a flexible polyurethane foam, a clothing material, a brassiere pad, a brassiere cup, and a method for producing a flexible polyurethane foam, and more specifically, a flexible polyurethane foam, a clothing material containing the flexible polyurethane foam, and a molding of the clothing material. The present invention relates to a brassiere pad, a brassiere cup provided with the brassiere pad, and a method for producing a flexible polyurethane foam.

A flexible polyurethane foam is obtained by reacting a polyisocyanate component and a polyol component in the presence of a urethanization catalyst and a foaming agent, and is used in a wide range of fields.

As such a polyisocyanate component, it is known that an aromatic polyisocyanate is used. An aromatic flexible polyurethane foam obtained by using an aromatic polyisocyanate contains ultraviolet light or oxygen gas (for example, nitrogen oxide gas). (NO _x ) and the like) may cause discoloration.

Therefore, the use of aliphatic polyisocyanates and / or derivatives thereof as polyisocyanate components has been studied.

For example, in a flexible polyurethane foam obtained by reaction foaming and curing of a mixed liquid of organic polyisocyanate (A), polyol (B), catalyst (C), foaming agent (D), and foam stabilizer (E), an isocyanate component As (A), an allophanate-modified organic polyisocyanate composition (A1) comprising a monool and an aliphatic and / or alicyclic diisocyanate, an alcohol containing two or more hydroxyl groups, an aliphatic and / or alicyclic An allophanate-modified organic polyisocyanate composition (A2) comprising an aliphatic diisocyanate, an organic polyisocyanate compound (A3) obtained by reacting an aliphatic and / or alicyclic diisocyanate with a polyol component (a1), It has been proposed to use a mixture of In such a flexible polyurethane foam, it has been proposed to use polypropylene glycol (PPG) as the polyol (B). Specifically, PPG having 2 to 3 functional groups and an OH number of 56 to 560 is proposed. It has been proposed to use (see, for example, Patent Document 1 (Preparation Examples 44 to 47)).

JP 2012-224712 A

On the other hand, the flexible polyurethane foam has recently been required to have air permeability, and the flexible polyurethane foam obtained by using the polyisocyanate composition and polypropylene glycol (PPG) described in Patent Document 1 does not have sufficient air permeability. Have the problem.

In addition to the breathability, the flexible polyurethane foam may require mechanical properties (deformation resistance (strain resistance), tear strength, elongation, etc.).

The present invention relates to a flexible polyurethane foam having breathability and mechanical properties, a clothing material including the flexible polyurethane foam, a brassiere pad which is a molded product of the clothing material, a brassiere cup including the brassiere pad, and a flexible polyurethane. It is a manufacturing method of a foam.

The present invention [1] is a flexible polyurethane foam obtained by reacting and foaming a polyisocyanate component containing a derivative of an aliphatic polyisocyanate and a polyol component containing a polyoxyalkylene polyol. The derivative comprises an allophanate derivative of an aliphatic polyisocyanate, the content ratio 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, and the polyoxy The alkylene polyol has both an oxyethylene unit and an oxypropylene unit, and the polyoxyalkylene polyol contains 5 mol% to 20 mol% of the oxyethylene unit, Relative to the total number of moles of terminal hydroxyl groups of Lumpur, the primary hydroxyl group is less than 50 mol%, contains a flexible polyurethane foam.

The present invention [2] is the above [1], wherein the content ratio of the allophanate derivative of the aliphatic polyisocyanate is 75 mol% or more and 99 mol% or less with respect to the total amount of the derivative of the aliphatic polyisocyanate. Contains flexible polyurethane foam.

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

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

The invention [5] is any one of the above [1] to [4], wherein the derivative includes an allophanate derivative modified with alcohol, and the alcohol contains a monohydric alcohol and a dihydric alcohol. The flexible polyurethane foam described in 1. is included.

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

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

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

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

The present invention [10] comprises a step of preparing a polyisocyanate component containing a derivative of an aliphatic polyisocyanate and a polyol component containing a polyoxyalkylene polyol; reacting the polyisocyanate component with the polyol component; Foaming and producing a flexible polyurethane foam, wherein the aliphatic polyisocyanate derivative includes an allophanate derivative of the aliphatic polyisocyanate, and the content ratio of the allophanate derivative of the aliphatic polyisocyanate is the aliphatic polyisocyanate derivative. The polyoxyalkylene polyol has both an oxyethylene unit and an oxypropylene unit, based on the total amount of isocyanate derivatives. Including a method for producing a flexible polyurethane foam, wherein the ethylene unit is 5 mol% or more and 20 mol% or less, and the primary hydroxyl group is 50 mol% or less with respect to the total number of terminal hydroxyl groups of the polyoxyalkylene polyol. Yes.

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

Also, a clothing material containing the flexible polyurethane foam of the present invention, and a brassiere pad and a brassiere cup as a molded article of the clothing material have both air permeability and mechanical properties.

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 is obtained by reacting and foaming a polyisocyanate component and a polyol component in the presence of a urethanization 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 a linear (straight or branched chain: acyclic) aliphatic polyisocyanate, and specific examples include ethylene diisocyanate, trimethylene diisocyanate, 1,2- Propylene diisocyanate, butylene diisocyanate (tetramethylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate), 1,5-pentamethylene diisocyanate (PDI), 1,6-hexamethylene diisocyanate (HDI), chain aliphatic diisocyanates such as 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanate methylcapate, dodecamethylene diisocyanate Etc. can be mentioned, preferably, 1,5-pentamethylene diisocyanate (PDI), 1,6-hexamethylene diisocyanate (HDI) and the like.

In addition, examples of the aliphatic polyisocyanate include alicyclic polyisocyanates.

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

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

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

If the aliphatic polyisocyanate contains a chain aliphatic polyisocyanate (preferably a chain aliphatic diisocyanate), it is possible to improve air permeability and mechanical properties. Moreover, if the aliphatic polyisocyanate contains pentamethylene diisocyanate and / or hexamethylene diisocyanate, the reactivity can be improved.

Particularly preferred as the aliphatic polyisocyanate is pentamethylene diisocyanate.

If 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.

An allophanate derivative of an aliphatic polyisocyanate can be obtained, for example, by reacting the above-described aliphatic polyisocyanate with an alcohol and then reacting the allophanate in the presence of an allophanate catalyst.

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

Examples of monohydric alcohols include linear monohydric alcohols and branched monohydric alcohols.

Examples of the linear monohydric alcohol include 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 -Linear monohydric alcohol having 1 to 20 carbon atoms (carbon number, the same shall apply hereinafter) such as nonadecanol and eicosanol.

Examples of branched monohydric alcohols include isopropanol, isobutanol (isobutyl alcohol), sec-butanol, tert-butanol, isopentanol, isohexanol, isoheptanol, isooctanol, and 2-ethylhexane-1-ol. , Isononanol, isodecanol, 5-ethyl-2-nonanol, trimethylnonyl alcohol, 2-hexyldecanol, 3,9-diethyl-6-tridecanol, 2-isoheptylisoundecanol, 2-octyldodecanol, other branched And C3-20 branched monohydric alcohols such as alkanol (C5-20).

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

From the viewpoint of reducing the viscosity of the aliphatic polyisocyanate derivative, the monohydric alcohol is preferably a branched monohydric alcohol, more preferably a C3-20 branched monohydric alcohol. More preferred are isopropanol and isobutanol, and particularly preferred is isobutanol.

Examples of dihydric alcohols include linear dihydric alcohols and branched dihydric alcohols.

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

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

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

From the viewpoint of reducing the viscosity of the aliphatic polyisocyanate derivative, the dihydric alcohol is preferably a branched dihydric alcohol, more preferably a C3-20 branched dihydric alcohol. More preferred are 1,3-butanediol and 3-methyl-1,5-pentanediol, and particularly preferred is 3-methyl-1,5-pentanediol.

Examples of the trivalent or higher alcohol include trivalent alcohols such as glycerin, trimethylolpropane, and triisopropanolamine, for example, tetravalent alcohols such as tetramethylolmethane (pentaerythritol), diglycerin, and pentavalent such as xylitol. Alcohols, for example, hexavalent alcohols such as sorbitol, mannitol, allitol, iditol, dulcitol, altritol, inositol, dipentaerythritol, for example, 7-valent alcohols such as perseitol, for example, 8-valent alcohols such as sucrose, etc. .

These trivalent or higher alcohols can be used alone or in combination of two or more.

Alcohols preferably include monohydric alcohols and dihydric alcohols, and from the viewpoint of air permeability and mechanical properties, more preferred are branched monohydric alcohols and branched dihydric alcohols.

In the production of the allophanate derivative of aliphatic polyisocyanate, the blending ratio in the reaction of aliphatic polyisocyanate and alcohol is, for example, 3 parts by mass or more, preferably 3 parts by mass with respect to 100 parts by mass of aliphatic polyisocyanate. More than 3.2 parts by mass, more preferably at least 3.5 parts by mass, for example, 50 parts by mass or less, preferably 20 parts by mass or less, more preferably 10 parts by mass. It is below mass parts.

In this reaction, as long as the excellent effects of the present invention are not inhibited, the above-described alcohol and active hydrogen such as thiols, oximes, lactams, phenols, β diketones, etc. A group-containing compound can be used in combination.

As reaction conditions in the reaction between the aliphatic polyisocyanate and the alcohol, for example, under an inert gas atmosphere such as nitrogen gas, under normal pressure (atmospheric pressure), the reaction temperature is, for example, room temperature (for example, 25 ° C.) or more, Preferably, it is 40 ° C. or higher, for example, 100 ° C. or lower, preferably 90 ° C. 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.

This causes the urethanization reaction of aliphatic polyisocyanate and alcohol.

In the urethanization reaction, a known urethanization catalyst (for example, amines (described later), organometallic compounds (described later), etc.) may be blended as necessary. In addition, the compounding ratio of a urethanization catalyst is not restrict | limited in particular, According to the objective and a use, it sets suitably.

In this method, an allophanatization catalyst is added to the resulting reaction solution, and a reaction product of aliphatic polyisocyanate and alcohol is allophanated.

Examples of the allophanatization catalyst include organic carboxylic acid bismuth salts such as bismuth octylate and bismuth tris (2-ethylhexanoate), and organic carboxylic acid lead salts such as lead octylate.

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

The allophanatization catalyst is preferably an organic carboxylic acid bismuth salt, and more preferably tris (2-ethylhexanoic acid) bismuth.

The addition ratio of the allophanatization catalyst 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 100 parts by mass of the aliphatic polyisocyanate. Is 0.05 parts by mass or less, more preferably 0.03 parts by mass or less.

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

In the above allophanatization reaction, when a predetermined reaction rate (isocyanate group conversion rate) is reached, for example, phosphoric acid, monochloroacetic acid, benzoyl chloride, dodecylbenzenesulfonic acid, toluenesulfonic acid (o- or p-) A reaction terminator such as toluene sulfonic acid) and derivatives thereof (eg, methyl o- or p-toluene sulfonate), toluene sulfonamide (o- or p-toluene sulfonamide) is added to the reaction solution, Inactivate to stop the allophanatization reaction. In this case, an allophanatization reaction can be stopped by adding an adsorbent that adsorbs a catalyst, such as a chelate resin or an ion exchange resin.

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

In addition, the conversion rate of the isocyanate group can be determined according to the examples described later.

Thereby, the aliphatic polyisocyanate can be allophanatized.

In the above urethanization reaction and / or allophanatization reaction, for example, a known organic phosphite can be blended as a co-catalyst in order to adjust urethanization and allophanation. The organic phosphites can be used alone or in combination of two or more. The organic phosphite is preferably monophosphites, more preferably tris (tridecyl) phosphite.

The addition ratio of the organic phosphite is, for example, 0.01 parts by mass or more, preferably 0.02 parts by mass or more, more preferably 0.03 parts by mass or more with respect to 100 parts by mass of the aliphatic polyisocyanate. For example, it is 0.2 parts by mass or less, preferably 0.15 parts by mass or less, and more preferably 0.1 parts by mass or less.

In the above urethanization reaction and / or allophanatization reaction, a hindered phenol antioxidant such as 2,6-di (tert-butyl) -4-methylphenol (BHT), Irganox 1010 is optionally used. Reaction stabilizers such as Irganox 1076, Irganox 1135, Irganox 245 (manufactured by BASF Japan Ltd., trade name) can also be blended.

The blending 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 100 parts by mass of the aliphatic polyisocyanate. Is 0.10 parts by mass or less.

In the urethanization reaction and / or allophanatization reaction, a known reaction solvent may be blended in an appropriate ratio as necessary.

And after completion | finish of reaction, when mix | blending unreacted aliphatic polyisocyanate (a catalyst, a reaction solvent, and / or a catalyst deactivator from a reaction liquid mixture obtained, a catalyst, a reaction solvent, and / or a catalyst deactivator Is removed by a known method such as distillation such as thin film distillation (Smith distillation) or extraction, for example, to obtain an allophanate derivative of an aliphatic polyisocyanate. Moreover, after removal of the unreacted aliphatic polyisocyanate, a reaction terminator can be added to the allophanate derivative of the resulting aliphatic polyisocyanate as a stabilizer at an arbitrary addition ratio.

By such a method, an allophanate derivative of an aliphatic polyisocyanate can be obtained, and more specifically, an allophanate derivative modified with alcohol can be obtained.

In the allophanate derivative modified with alcohol, as described above, the alcohol is preferably a monohydric alcohol or a dihydric alcohol, more preferably a branched monohydric alcohol or a branched dihydric alcohol. Can be mentioned.

Further, the alcohol is more 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.

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

The combination form of monohydric alcohol and dihydric alcohol is not particularly limited, and for example, a mixed alcohol of monohydric alcohol and dihydric alcohol can be used for the production of the above allophanate derivative.

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

Further, for example, allophanate derivatives obtained using only monohydric alcohols, allophanate derivatives obtained using only dihydric alcohols, and allophanates obtained using mixed alcohols of monohydric alcohols and dihydric alcohols. Each of the derivatives may be prepared and mixed.

The ratio of monohydric alcohol to dihydric alcohol (raw material basis) is, for example, 10 mass parts or more, preferably 50 masses of monohydric alcohol with respect to 100 mass parts of the total amount of monohydric alcohol and dihydric alcohol Part or more, for example, 90 parts by mass or less, preferably 80 parts by mass or less. Moreover, a dihydric alcohol is 10 mass parts or more, for example, Preferably, it is 20 mass parts or more, for example, is 90 mass parts or less, Preferably, it is 50 mass parts or less.

In addition, the derivative of the aliphatic polyisocyanate can contain a derivative other than the above-described allophanate derivative of the aliphatic polyisocyanate (hereinafter referred to as other derivatives) in an appropriate ratio.

Other derivatives include, for example, aliphatic polyisocyanate multimers (for example, dimers, trimers, pentamers, heptamers, etc.), biuret derivatives (for example, the above-described aliphatic polyisocyanates, Biuret derivatives produced by reaction with water and amines, etc.), urea derivatives (eg urea derivatives produced by reaction of the above-mentioned aliphatic polyisocyanates with diamines), oxadiazine trione derivatives (eg, above) Oxadiazine trione derivatives produced by the reaction of the aliphatic polyisocyanate and carbon dioxide, etc.), carbodiimide derivatives (carbodiimide derivatives produced by the decarboxylation condensation reaction of the aliphatic polyisocyanates described above), polyol derivatives (for example, , Known aliphatic polyisocyanates and known A polyol derivative (alcohol adduct) produced from a reaction with a molecular weight polyol (preferably a low molecular weight triol), a reaction between the above-mentioned aliphatic polyisocyanate and a known low molecular weight polyol and / or a known high molecular weight polyol. Polyol derivatives) and the like.

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

Other derivatives are preferably trimers of aliphatic polyisocyanates.

The trimer of the aliphatic polyisocyanate contains a symmetric / asymmetric isocyanurate group (hereinafter, the trimer of the aliphatic polyisocyanate may be 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 symmetric isocyanurate group is an isocyanurate group and is contained in a symmetric trimer (trimer) of an aliphatic polyisocyanate.

The asymmetric isocyanurate group is an iminooxadiazinedione group and is contained in an asymmetric trimer (trimer) of aliphatic polyisocyanate.

The form in which the other derivative is contained is not particularly limited. For example, in the production of the allophanate derivative of the aliphatic polyisocyanate described above, other by-products in each reaction (urethane reaction, allophanate reaction, etc.) Derivatives (for example, isocyanurate derivatives of aliphatic polyisocyanates) are produced, and other derivatives may be contained in the aliphatic polyisocyanate derivatives.

Also, for example, other separately prepared derivatives (for example, isocyanurate derivatives of aliphatic polyisocyanates) may be mixed with the above-described allophanate derivatives of aliphatic polyisocyanates and contained in the polyisocyanate derivatives.

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

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, based on the total amount of the aliphatic polyisocyanate derivative. Is 85 mol% or more, more preferably 90 mol% or more, particularly preferably 95 mol% or more, and usually less than 100 mol%, preferably 99 mol% or less, more preferably 98 mol% or less. It is.

The content ratio 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, for example, 30 mol% or less, Preferably, it is at most 25 mol%, more preferably at most 20 mol%, further preferably at most 15 mol%, further preferably at most 10 mol%, particularly preferably at most 5 mol%.

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

In addition, the derivative of the aliphatic polyisocyanate preferably does not contain a dimer of the aliphatic polyisocyanate as the other derivative, or the content thereof is very small.

The dimer of the aliphatic polyisocyanate contains a uretdione group (hereinafter, the dimer of the aliphatic polyisocyanate may be referred to as an uretdione derivative of the aliphatic polyisocyanate).

The content ratio 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, even more preferably, based on the total amount of the aliphatic polyisocyanate derivative. Is 1 mol% or less, particularly preferably 0 mol%.

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

As the derivative of the aliphatic polyisocyanate, particularly preferably, only the allophanate derivative of the aliphatic polyisocyanate and the isocyanurate derivative of the aliphatic polyisocyanate are contained.

The content ratios of allophanate derivatives, isocyanurate derivatives and uretdione derivatives in the aliphatic polyisocyanate derivatives are allophanate groups obtained from an NMR chart measured by a ¹ H-NMR method in accordance with Examples described later. And a symmetric / asymmetric isocyanurate group and a molar ratio between a uretdione group and a symmetric / asymmetric isocyanurate group obtained from an NMR chart measured by a ¹³ C-NMR method.

More specifically, in this method, first, in accordance with an example described later, an allophanate group obtained from an NMR chart of an aliphatic polyisocyanate derivative measured by ¹ H-NMR method, and asymmetric / asymmetric The molar ratio with the isocyanurate group is calculated.

For example, in a ¹ H-NMR measurement (400 MHz, solvent: D ⁶ -DMSO (solute: 5% by mass), reference substance: tetramethylsilane) of a derivative of an aliphatic polyisocyanate, a peak of 8.3 to 8.7 ppm was obtained. The proton assignment peak of the allophanate group of the aliphatic polyisocyanate (NH group in the allophanate group) is used, and the peak of 3.8 ppm is directly applied to the symmetric / asymmetric isocyanurate group (symmetric / asymmetric isocyanurate group of the aliphatic polyisocyanate). The assigned peak of the proton of the methylene group (CH ₂ group) to be bonded is used. Then, the peak area ratio (integration ratio) is calculated as the content ratio of the allophanate group to the symmetric / asymmetric isocyanurate group by the following formula.

Content ratio of allophanate group to symmetric / asymmetric isocyanurate group = integrated value of proton assigned peak of allophanate group / (integrated value of assigned peak of proton of symmetric / asymmetric isocyanurate group / 6)
In this method, the molarity of the uretdione group obtained from the NMR chart measured by the ¹³ C-NMR method of the derivative of the aliphatic polyisocyanate and the symmetric / asymmetric isocyanurate group in accordance with the examples described later. Calculate the ratio.

For example, ¹³ C-NMR measurement of a derivative of an aliphatic polyisocyanate (100 MHz, solvent: CDCL ₃ (solute: 50% by mass), reference material: tetramethylsilane) shows a peak of 157.8 ppm of uretdione of the aliphatic polyisocyanate. And the peak of 149.1 ppm of the symmetric / asymmetric isocyanurate group of the aliphatic polyisocyanate (CO group in the symmetric / asymmetric isocyanurate group). Assigned peak. Then, the peak area ratio (integration ratio) is calculated as the content ratio of the uretdione group to the symmetric / asymmetric isocyanurate group by the following formula.

Mole ratio of uretdione group / symmetric / asymmetric isocyanurate group = (integral value of carbon attribute peak of uretdione group / 2) / (integral value of carbon attribute peak of symmetric / asymmetric isocyanurate group / 3)
Thereafter, the number of moles of allophanate groups and the number of moles of uretdione groups with respect to 100 moles of symmetric / asymmetric isocyanurate groups are calculated. Then, the molar ratio of each group to the total amount of symmetric / asymmetric isocyanurate group, allophanate group and uretdione group is calculated.

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

The molar ratio of symmetric / asymmetric isocyanurate groups to the total amount of symmetric / asymmetric isocyanurate groups, allophanate groups and uretdione groups is the content ratio of the isocyanurate derivatives of aliphatic polyisocyanates in the derivatives of aliphatic polyisocyanates. .

Also, the molar ratio of uretdione groups to the total amount of symmetric / asymmetric isocyanurate groups, allophanate groups and uretdione groups is the content ratio of the uretdione derivative of the aliphatic polyisocyanate in the derivative of the aliphatic polyisocyanate.

Further, the polyisocyanate component may contain other polyisocyanates and / or derivatives thereof in addition to the above-described derivatives of aliphatic polyisocyanates (that is, allophanate derivatives of aliphatic polyisocyanates (and other derivatives that are blended as necessary)). Can also be contained.

Examples of other polyisocyanates and / or derivatives thereof include polyisocyanate monomers and polyisocyanate derivatives (excluding aliphatic polyisocyanate derivatives).

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

Examples of the aromatic polyisocyanate include m- or p-phenylene diisocyanate or a mixture thereof, 2,4- or 2,6-tolylene diisocyanate or a mixture thereof (TDI), 4,4'-, 2,4'- Or 2,2′-diphenylmethane diisocyanate or a mixture thereof (MDI), 4,4′-toluidine diisocyanate (TODI), 4,4′-diphenyl ether diisocyanate, 4,4′-diphenyl diisocyanate, 1,5-naphthalene diisocyanate (NDI) And aromatic diisocyanates.

Examples of the araliphatic polyisocyanate include 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 araliphatic diisocyanates such as ω, ω′-diisocyanate-1,4-diethylbenzene.

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

Examples of polyisocyanate derivatives (excluding aliphatic polyisocyanate derivatives) include multimers (for example, dimers, trimers, pentamers, and heptamers) of the above-described polyisocyanate monomers. ), Allophanate derivatives (for example, allophanate derivatives produced from the reaction of the above-mentioned polyisocyanate monomer and alcohol), biuret derivatives (for example, reaction of the above-mentioned polyisocyanate monomer with water and amines) Biuret derivatives produced by the above), urea derivatives (eg urea derivatives produced by the reaction of the above polyisocyanate monomers and diamines), oxadiazine trione derivatives (eg the above polyisocyanate monomers). Oxadiazinetrione Derivatives Formed by Reaction of Carbon Dioxide with Carbon Dioxide ), Carbodiimide derivatives (such as carbodiimide derivatives produced by the decarboxylation condensation reaction of the above polyisocyanate monomers), polyol derivatives (for example, the above polyisocyanate monomers and known low molecular weight polyols (preferably, Reaction of polyol derivative (alcohol adduct) produced by reaction with low molecular weight triol), polyisocyanate monomer and known low molecular weight polyol and / or known high molecular weight polyol (preferably high molecular weight polyol) Polyol derivatives (polyisocyanate group-terminated prepolymers, etc.) produced from

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

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

The other polyisocyanate is preferably a polyisocyanate monomer, more preferably an aliphatic polyisocyanate (monomer), and still more preferably an alicyclic polyisocyanate (monomer). Can be mentioned.

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

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

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

In the polyisocyanate component, the content of components other than aliphatic polyisocyanate derivatives (other polyisocyanates and / or derivatives thereof) is, for example, less than 50% by mass, preferably 30%, based on the total amount of polyisocyanate components. It is 20 mass% or less, More preferably, it is 20 mass% or less, More preferably, it is 10 mass% or less, More preferably, it is 5 mass% or less.

In addition, the polyisocyanate component preferably includes an aliphatic polyisocyanate derivative alone. That is, the polyisocyanate component preferably contains no components other than aliphatic polyisocyanate derivatives (other polyisocyanates and / or derivatives thereof).

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

The isocyanate group equivalent is synonymous with the amine equivalent and can be determined by the method A or method B of JIS K 1603-1 (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 for example, 2.90 or less, preferably 2 .80 or less.

Further, the isocyanate group concentration of the polyisocyanate component is, for example, 18% by mass or more, preferably 20% by mass or more, for example, 28% by mass or less, preferably 25% by mass or less, more preferably 24% by mass. It is as follows.

The isocyanate group concentration can be determined according to the examples described later (the same applies hereinafter).

The viscosity of the polyisocyanate component at 25 ° C. is, for example, 20 mPa · s or more, preferably 100 mPa · s or more, more preferably 150 mPa · s or more, and further preferably 200 mPa · s or more, for example, 5000 mPa · s. · S, preferably 3000 mPa · s or less, more preferably 1500 mPa · s or less, further preferably 1000 mPa · s or less, further preferably 980 mPa · s or less, and particularly preferably 800 mPa · s or less.

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

The viscosity can be determined according to the examples described later (the same applies hereinafter).

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

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

In the present invention, the polyoxyalkylene polyol has both an oxyethylene unit and an oxypropylene unit. 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, still more preferably 12 mol% or more, relative to the polyoxyalkylene polyol. The mol% or less, preferably 18 mol% or less, more preferably 15 mol% or less.

The content ratio 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, relative to the polyoxyalkylene polyol. Preferably, it is 92 mol% or less, More preferably, it is 90 mol% or less, More preferably, it is 88 mol% or less.

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

The polyoxyalkylene polyol has a hydroxyl group at the molecular end, and the hydroxyl group is classified as a primary hydroxyl group or a secondary hydroxyl group depending on the oxyalkylene unit (oxyethylene unit or oxypropylene unit) directly bonded. Is done.

Examples of the primary hydroxyl group include —OCH ₂ CH ₂ —OH, —OCH (CH ₃ ) CH ₂ —OH, and the like. Examples of the secondary hydroxyl group include —OCH ₂ CH (CH ₃ ) —OH. However, due to the selectivity of the primary hydroxyl group and the secondary hydroxyl group in the addition reaction, —OCH (CH ₃ ) CH ₂ —OH is not substantially formed. Therefore, the terminal hydroxyl group of the oxyethylene unit is a primary hydroxyl group (—OCH ₂ CH ₂ —OH), and the terminal hydroxyl group of the oxypropylene unit is a secondary hydroxyl group (—OCH ₂ CH (CH ₃ ) —OH). .

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

If the ratio of the primary hydroxyl group is within the above range, a flexible polyurethane foam having both air permeability and mechanical properties can be obtained.

Note that the content ratio of the oxyethylene unit in the polyoxyalkylene polyol and the ratio of the primary hydroxyl group to the total amount of terminal hydroxyl groups are, for example, those obtained by adding heavy trifluoroacetic acid to ¹ H-NMR (nuclear magnetic resonance) apparatus. It can be calculated as a proton integral value by a method using hydrogenated chloroform as a solvent.

Also, the content ratio of the oxyethylene unit in the polyoxyalkylene polyol can be calculated from the raw material component (preparation amount) of the polyoxyalkylene polyol.

Such a polyoxyalkylene polyol can be obtained, for example, by addition polymerization of an alkylene oxide in 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 polyhydric alcohol having a molecular weight of 30 or more and less than 400, and specifically, for example, a divalent aliphatic alcohol such as ethylene glycol, propylene glycol, dipropylene glycol, such as glycerin, trimethylol. 2 to 3 such as trivalent aliphatic alcohols such as propane, tetravalent aliphatic alcohols such as pentaerythritol and diglycerin, hexavalent aliphatic alcohols such as sorbitol, and octavalent aliphatic alcohols such as sucrose An octavalent aliphatic alcohol is mentioned.

The low molecular weight amine is a polyvalent amine compound having a molecular weight of 30 or more and less than 400. Specifically, for example, a divalent aliphatic amine such as methylamine or ethylamine (aliphatic amine having two active hydrogens). For example, trivalent aliphatic amines (aliphatic amines having three active hydrogens) such as monoethanolamine, diethanolamine, and triethanolamine (specifically, alkanolamines) such as ethylenediamine, 1,3- and / or Alternatively, tetravalent aliphatic amines (aliphatic amines having 4 active hydrogens) such as 1,4-bis (aminomethyl) cyclohexane and isophoronediamine, for example, pentavalent aliphatic amines such as diethylenetriamine (5 active hydrogens) Divalent to pentavalent aliphatic amines (fats having one or more active hydrogens) such as aliphatic amines having Amine) and the like. 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 can be used alone or in combination of two or more.

The initiator is preferably an alcohol, more preferably a polyhydric aliphatic alcohol, more preferably a 2 to 6 valent aliphatic alcohol, still more preferably a 2 to 4 valent fatty acid. A trivalent aliphatic alcohol is particularly preferable.

Examples of the polymerization catalyst include alkali metal catalysts such as potassium hydroxide, sodium hydroxide and cesium hydroxide, and composite metal catalysts such as cyano complexes of zinc and cobalt (for example, described in US Pat. No. 4,477,589). And a phosphazenium catalyst such as phosphazene or phosphazenium having a nitrogen-phosphorus double bond.

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

Alkylene oxide contains ethylene oxide and propylene oxide.

The alkylene oxide is preferably composed 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.

As for the combined proportion of ethylene oxide and propylene oxide, the proportion of oxyethylene units and oxypropylene units in the obtained polyoxyalkylene polyol is in the above range, and the proportion of primary hydroxyl groups relative to the total amount of terminal hydroxyl groups is in the above range. Thus, it is set as appropriate.

The method for addition polymerization of alkylene oxide to the initiator is not particularly limited, and a known method is employed. In addition, in addition polymerization, an initiator and an alkylene oxide may be charged all at once, and an alkylene oxide may be sequentially added to the initiator.

More specifically, for example, propylene oxide can be first addition-polymerized to the initiator, and then ethylene oxide can be addition-polymerized. In addition, propylene oxide can be further subjected to addition polymerization with respect to part or all of the molecular terminals of the obtained polymer.

Also, for example, ethylene oxide can be addition-polymerized first with respect to the initiator, and then propylene oxide can be addition-polymerized. In addition, ethylene oxide can be further subjected to addition polymerization with respect to a part or all of the molecular terminals of the obtained polymer.

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

Thereby, the ratio of the oxyethylene unit and the oxypropylene unit and the ratio of the primary hydroxyl group can be easily adjusted.

In addition, as the polyol component, a single type of polyoxyalkylene polyol can be used, but two or more types of polyoxyalkylene polyol can be used in combination.

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

Also, polyoxyalkylene polyols having both oxyethylene units and oxypropylene units, for example, polyoxyethylene polyols (polyoxyalkylene polyols containing only oxyethylene units) and / or polyoxypropylene polyols (only oxypropylene units) And a polyoxyalkylene polyol contained).

Furthermore, as polyoxyalkylene polyol, for example, polyoxyethylene polyol (polyoxyalkylene polyol containing only oxyethylene units) and polyoxypropylene polyol (polyoxyalkylene polyol containing only oxypropylene units) are mixed. Can also be used.

In such a case, the combined ratio of two or more types of polyoxyalkylene polyols is such that the content ratio of the oxyethylene unit relative to the total amount of polyoxyalkylene polyol (total amount of the mixture) is in the above range, and the primary class relative to the total amount of terminal hydroxyl groups It is appropriately set so that the ratio of the hydroxyl group falls within the above range.

The polyol component can also contain other polyols (polyols other than the above polyoxyalkylene polyols) as necessary.

Other polyols include known polyols used for flexible polyurethane foams, specifically, high molecular weight polyols and low molecular weight polyols, and preferably high molecular weight polyols.

The high molecular weight polyol is a polyol having a number average molecular weight (Mn) of 400 or more and 10,000 or less, and examples thereof include polyester polyol, polyether polyester polyol, and polyester polyurethane polyol. These can be used alone or in combination of two or more.

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

In addition, Preferably, a polyol component does not contain other polyols but contains said polyoxyalkylene polyol independently.

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

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

The average functional group number 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. It is.

The hydroxyl value of the polyol component is measured according to the description of JIS K 1557-1 (2007), and the average functional group number of the polyol component is calculated from the blended recipe.

A flexible polyurethane foam can be obtained by preparing the polyisocyanate component and the polyol component as described above and reacting them in the presence of a urethanization catalyst and a foaming agent.

Examples of the urethanization catalyst include amines and organometallic compounds.

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

Also, these amines can be obtained as commercial products, for example, Kaorizer No. 31 (manufactured by Kao Corporation), Kao Riser No. 120 (manufactured by Kao Corporation), Kao Riser No. 12 (manufactured by Kao Corporation), Kaoriza No. 25 (manufactured by Kao Corporation), DABCO 33LV (33% by weight diethylene glycol solution of triethylenediamine, manufactured by Air Products Japan), Niax A-1 (manufactured by Momentive Performance Materials Japan G.K. And TOYOCAT-NCE (manufactured by Tosoh Corporation).

Examples of organometallic compounds include tin acetate, tin octylate, tin oleate, tin laurate, dibutyltin diacetate, dimethyltin dilaurate, dibutyltin dilaurate, dibutyltin dimercaptide, dibutyltin maleate, dibutyltin dineodecano Organic tin compounds, such as lead, dioctyltin dimercaptide, dioctyltin dilaurate, dibutyltin dichloride, for example, organic lead compounds such as lead octoate and lead naphthenate, for example, organic nickel compounds such as nickel naphthenate, for example, cobalt naphthenate Organic cobalt compounds such as, for example, organic copper compounds such as copper octenoate, for example, organic bismuth compounds such as bismuth octylate and bismuth neodecanoate, and the like. These organometallic compounds can be used alone or in combination of two or more.

These organometallic compounds can be obtained as commercial products, for example, Neostan U-100 (organotin compound, manufactured by Nitto Kasei Co., Ltd.), Formate TK-1 (organotin compound, manufactured by Mitsui Chemicals), Examples include Formrez UL-28 (organotin compound, manufactured by Momentive), Stanoct (organotin compound, manufactured by Mitsubishi Chemical Corporation), and the like.

These urethanization catalysts (amines and organometallic compounds) can be used alone or in combination of two or more. Preferably, amines and organometallic compounds are used in combination.

The blending ratio of the urethanization catalyst (converted to 100% of the active ingredient) is, for example, 0.1 parts by mass or more, preferably 0.3 parts by mass or more, more preferably 1. For example, it is 5 parts by mass or less, preferably 3 parts by mass or less.

If the blending ratio of the urethanization catalyst is within the above range, non-yellowing of the resulting flexible polyurethane foam can be improved.

Moreover, when using together amines and an organometallic compound as a urethanization catalyst, the ratio of the blending ratio of amines and an organometallic compound (the blending ratio of amines / the blending ratio of an organometallic compound, the amount of active ingredients is 100). % Conversion) 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 may be a known foaming agent, preferably water.

Examples of the foaming agent include water and physical foaming agents (eg, halogenated hydrocarbons (eg, methylene chloride), hydrocarbons (eg, cyclopentane), carbon dioxide gas, liquefied carbon dioxide gas, etc.). , And can be used in appropriate proportions. The physical foaming agent is preferably carbon dioxide gas or liquefied carbon dioxide gas from the viewpoint of reducing environmental burden.

These physical foaming agents can be used alone or in combination of two or more.

The blending 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 with respect to 100 parts by mass of the polyol component. is there.

If the content of the foaming agent is within the above range, excellent foamability can be obtained.

In order to produce the flexible polyurethane foam of the present invention, first, a premix (resin premix) is prepared by blending the above-mentioned urethanization catalyst and the above-mentioned foaming agent in the above-mentioned blending ratio to the above-described polyol component. Prepare.

Moreover, in preparation of a premix, additives, such as a foam stabilizer and a stabilizer, can be mix | blended as needed, Preferably, a premix is an above-described polyol component, an above-mentioned urethanization catalyst, and an above-mentioned foaming agent. Prepared from foam stabilizers and stabilizers.

The foam stabilizer is not particularly limited, and may be a known foam stabilizer, for example, a silicone foam stabilizer.

Further, the foam stabilizer can be obtained as a commercial product, for example, DC-6070, DC-2525 (above, manufactured by Air Products Japan, trade name), SZ-1966, SRX-274C, SF-2969. SF-2961, SF-2962, SZ-1325, SZ-1328 (above, manufactured by Toray Dow Corning Co., Ltd., trade name), L-5309, L-3601, L-5307, L-3600, L-5366, Y-10366 (above, trade name, manufactured by Momentive), B-8002, B-8545, B-8715LF2 (above, trade name, manufactured by Evonik).

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

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

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 (for example, 4-methyl-2,6-di-tert-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]), other antioxidants (for example, bis (2 , 4-di-t-butylphenyl) pentaerythritol diphosphite, tridecyl phosphite, tris (2-ethylhexyl) phosphite, for example, 2,5-thiophenediylbis (5-t- Hindered thiophene antioxidants such as butyl-1,3-benzoxazole) Antioxidants except Lumpur antioxidants) and the like.

Of these antioxidants, phosphorus-based antioxidants are preferable, and tris (2-ethylhexyl) phosphite is more preferable. As the tris (2-ethylhexyl) phosphite, a commercially available product can be used, for example, JP-308E (trade name, manufactured by Johoku Chemical Co., Ltd.).

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

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

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

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

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

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

Examples of light stabilizers include hindered amine light resistance stabilizers and blend light resistance stabilizers, and preferably hindered amine light resistance stabilizers. Examples of the hindered amine light resistance stabilizer include ADK STAB LA62, ADK STAB LA67 (above, manufactured by Adeka Argus Chemical Co., Ltd., trade name), Tinuvin 765, Tinuvin 144, Tinuvin 770, Tinuvin 622 (above, manufactured by BASF Japan Ltd., product) Name).

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

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

In addition to the above-mentioned additives, the premix may further include, for example, a crosslinking agent, a communication agent, a pigment (color pigment), a dye, a curing accelerator, a matting agent, an adhesion imparting agent, and a silane cup. Other known additives such as a ring agent can be blended at an appropriate ratio as long as the excellent effects of the present invention are not impaired.

Furthermore, as other known additives, for example, chain extenders, antifoaming agents, plasticizers, antiblocking agents, mold release agents, lubricants, fillers, hydrolysis inhibitors, and the like are excellent effects of the present invention. As long as the above is not impaired, the composition can be blended at an appropriate ratio.

And while mixing the premix obtained in this way and a polyisocyanate component and making it react, it is made to foam by well-known foaming methods, such as a slab system, a mold system, a spray system, etc. of the present invention, for example. A flexible polyurethane foam is obtained.

The reaction conditions (for example, reaction temperature) between the premix and the polyisocyanate component are appropriately set according to the purpose and application.

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

The reaction time (cream time (CT)) between the premix and the polyisocyanate component is measured according to the examples described later, and is, for example, 40 seconds or longer, for example, 200 seconds or shorter, preferably 100 seconds or shorter. More preferably, it is 60 seconds or less, and more preferably 50 seconds or less.

If the reaction time (cream time (CT)) between the premix and the polyisocyanate component is within the above range, workability can be improved.

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

In the flexible polyurethane foam of the present invention thus obtained, the polyisocyanate component contains an allophanate derivative of an aliphatic polyisocyanate, and the allophanate derivative is a predetermined ratio with respect to the derivative of the aliphatic polyisocyanate, And the polyol component contains polyoxyalkylene polyol, and the ratio of the oxyethylene unit and the ratio of the primary hydroxyl group in the polyoxyalkylene polyol are the 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, “soft” means, for example, 40.0 N / 100 cm ² or less, preferably 30 as the hardness of the polyurethane foam (25% CLD, measured in accordance with examples described later). .0N / 100cm ² or less, more preferably, 20.0N / 100cm ² or less, more preferably, 15.0 N / 100 cm ² or less, more preferably, 10.0 N / 100 cm ² or less, more preferably, 7.0 N / 100 cm ² or less, more preferably 5.0 N / 100 cm ² or less.

The density of the flexible polyurethane foam of the present invention (measured in accordance with examples described later) is, for example, 10.0 kg / m ³ or more, preferably 15.0 kg / m ³ or more. 50.0 kg / m ³ or less, preferably 45.0 kg / m ³ or less, more preferably 40.0 kg / m ³ or less, still more preferably 37.0 kg / m ³ or less, particularly preferably 35.0 kg / M ³ or less.

The air permeability (measured in accordance with Examples described later) of the flexible polyurethane foam of the present invention is, for example, 10 cc / cm ² / sec or more, preferably 100 cc / cm ² / sec or more, more preferably 200 cc / cm. ² / sec or more, for example, 500 cc / cm ² / sec or less, preferably 400 cc / cm ² / sec or less.

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

Further, the elongation at break (measured in accordance with Examples described later) of the flexible polyurethane foam of the present invention is, for example, 35% or more, preferably 100% or more, more preferably 150% or more, and still more preferably. 185% or more, more preferably 190% or more, particularly preferably 200% or more, for example, 500% or less, preferably 400% or less.

Moreover, the wet heat compression set (Wet Set (measured in accordance with Examples described later)) of the flexible polyurethane foam of the present invention is, for example, 10% or less, preferably 6% or less, more preferably 5% or less. More preferably, it is 4% or less, more preferably 3% or less, and particularly preferably 2% or less.

Further, 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” can be defined as, for example, 15.0 or less, preferably 12.0 or less, as the light resistance Δb of the flexible polyurethane foam.

Therefore, the use of the obtained flexible polyurethane foam includes, for example, pressure-resistant dispersion materials, shape-retaining materials, sound-absorbing materials, shock-absorbing materials in the fields of automobiles, furniture, bedding, electronic materials, medical care, clothing, hygiene materials, etc. It can be effectively used as an elastic material such as a vibration absorbing material and an optical material.

More specifically, flexible polyurethane foams include, for example, seat sheets, headrests, armrests, chairs, bedding and sofas such as pillows and mattresses, nursing cushion materials, leisure seats, supporters, wig shape retainers, filters, and microphones. Cover, earphone cover, headphone cover, cushion flooring, cosmetic puff, eye shadow chip, medical material, coating roll, OA roll, ink absorbing sheet, electronic member (eg, electronic tablet, smartphone, etc.) Can be used for polishing pads, sanitary products, and diapers.

In particular, since polyurethane foam has a soft touch and excellent non-yellowing property, it is preferably used as a pressure-resistant cushioning material for clothing or shoes, and further for robots, specifically, a shoulder pad. Can be used for knee pads, elbow pads, swimwear pads, shoe tongues, shoe inner soles, medical materials, clothing materials, robotic skins, robot hands, etc., especially as molded articles of clothing materials, Suitable for brassiere pads, brassiere cups and the like.

The clothing material containing the flexible polyurethane foam of the present invention, and the brassiere pad and the brassiere cup as a molded product of the clothing material have both air permeability and mechanical properties.

Specific numerical values such as blending ratio (content ratio), physical property values, and parameters used in the following description are described in the above-mentioned “Mode for Carrying Out the Invention”, and the corresponding blending ratio (content ratio) ), Physical property values, parameters, etc. may be replaced with the upper limit values (numerical values defined as “less than” or “less than”) or lower limit values (numbers defined as “greater than” or “exceeded”). it can.

In addition, measurement methods employed in each of the preparation examples, the synthesis examples, the examples, and the comparative examples are described below.

1. Measuring method <Isocyanate group concentration (unit: mass%), conversion rate of isocyanate group (unit: mass%)>
Isocyanate group concentration (isocyanate group content) by a toluene / dibutylamine / hydrochloric acid method in accordance with JIS K-1603-1 (2007) using a potentiometric titrator (manufactured by Kyoto Electronics Co., Ltd., model number: AT-510) Was measured, and the conversion rate of the isocyanate group of the measurement sample was calculated by the following formula.

Conversion rate of isocyanate group = 100− (isocyanate group concentration in reaction mixture after completion of reaction / isocyanate group concentration in reaction solution before reaction × 100)
<Isocyanate monomer concentration (unit: mass%)>
Using pentamethylene diisocyanate or commercially available hexamethylene diisocyanate prepared in the same manner as in Example 1 in the specification of WO 2012/121291 as a standard substance, labeling with dibenzylamine, and the following HPLC measurement conditions The concentration of unreacted pentamethylene diisocyanate monomer or hexamethylene diisocyanate monomer was calculated from a calibration curve created from the area values of the chromatogram obtained below.

Equipment; Prominence (manufactured by Shimadzu Corporation)
Pump LC-20AT
Degasser DGU-20A3
Autosampler SIL-20A
Column thermostat COT-20A
Detector SPD-20A
Column; SHISEIDO SILICA SG-120
Column temperature: 40 ° C
Eluent: n-hexane / methanol / 1,2-dichloroethane = 90/5/5 (volume ratio)
Flow rate: 0.2 mL / min
Detection method: UV 225 nm
<Viscosity (unit: mPa · s)>
In accordance with the cone plate viscometer method of JIS K5600-2-3 (2014), using an E-type viscometer TV-30 (rotor angle: 1 ° 34 ', rotor radius: 24 cm) manufactured by Toki Sangyo Co., Ltd. The viscosity of the measurement sample was measured at 25 ° C. The rotation speed of the cone plate at the time of measurement was sequentially changed between 100 rpm and 2.5 rpm as the viscosity increased.

<Calculation of molar ratio of allophanate group and isocyanurate group by ¹ H-NMR>
¹ H-NMR was measured using the following apparatus and conditions, and the content of allophanate groups (allophanate group / isocyanurate group molar ratio) with respect to 1 mole of isocyanurate groups in an aliphatic polyisocyanate derivative was Calculated. Note that tetramethylsilane (0 ppm) in a D ⁶ -DMSO solvent was used as a standard for chemical shift ppm.
Equipment; JNM-AL400 (manufactured by JEOL)
Conditions; Measurement frequency: 400 MHz, solvent: D ⁶ -DMSO, solute concentration: 5% by mass
Proton attribution peak (1H) of allophanate group (NH group in allophanate group): 8.3 to 8.7 ppm
Proton attribution peak (6H) of isocyanurate group (methylene group (CH2 group) directly bonded to isocyanurate group): 3.8 ppm
Molar ratio of allophanate group to isocyanurate group = integrated value of proton assigned peak of allophanate group / (integrated value of assigned peak of proton of isocyanurate group / 6)
<Calculation of molar ratio of uretdione group and isocyanurate group by ¹³ C-NMR>
¹³ C-NMR was measured using the following apparatus and conditions, and the content ratio of uretdione groups (uretodione group / isocyanurate group molar ratio) to 1 mol of isocyanurate groups in the polyisocyanate derivative was calculated by the following formula. In addition, tetramethylsilane (0 ppm) in CDCL ₃ solvent was used as a reference for chemical shift ppm.
Equipment; JNM-AL400 (manufactured by JEOL)
Conditions; Measurement frequency: 100 MHz, solvent: CDCL ₃ , solute concentration: 50% by mass
Assignment peak of carbon of uretdione group (CO group in uretdione group) (2H): 157.8 ppm
Carbon peak of isocyanurate group (CO group in isocyanurate group) (3H): 149.1 ppm
Mole ratio of uretdione group / isocyanurate group = (integrated value of carbon assigned peak of uretdione group / 2) / (integrated value of carbon assigned peak of isocyanurate group / 3)
<Measurement method of hydroxyl value of polyol>
The hydroxyl value was defined as the number of mg of potassium hydroxide corresponding to the hydroxyl group in 1 g of polyoxyalkylene polyol. Then, the hydroxyl value was measured according to 6.4 “Hydroxyl value” of JIS K1557 (2007).

<Method for measuring the concentration of primary hydroxyl groups with respect to all terminal hydroxyl groups of polyol>
About 30 mg of a measurement sample was weighed into an NMR sample tube having a diameter of 5 mm, and about 0.5 ml of deuterated solvent was added and dissolved. Thereafter, about 0.1 ml of trifluoroacetic anhydride was added to prepare a sample for analysis. Thereafter, ¹ H-NMR measurement (apparatus; JNM-AL400 (manufactured by JEOL), measurement frequency: 400 MHz) was performed.

In this method, since the terminal hydroxyl group of the polyoxyalkylene polyol reacts with trifluoroacetic anhydride to become a trifluoroacetic acid ester, a signal derived from a methylene group to which a primary hydroxyl group is bonded is observed around 4.3 ppm. Further, a signal derived from a methine group to which a secondary hydroxyl group is bonded is observed at around 5.2 ppm. Therefore, the primary hydroxylation rate of the terminal hydroxyl group was calculated by the following formula.

Terminal hydroxyl group primary ratio (%) = [a / (a + 2 × b)] × 100
(In the formula, a is an integral value of a signal derived from a methylene group to which a primary hydroxyl group is bonded in the vicinity of 4.3 ppm, and b is an integrated value of a signal derived from a methine group to which a secondary hydroxyl group is bonded in the vicinity of 5.2 ppm. is there.)
2. Raw material (1) Polyisocyanate component (a)
Preparation Example 1 (Allophanate derivative of aliphatic polyisocyanate (a-1) (iBA-modified allophanate derivative of PDI))
In a reactor equipped with a thermometer, a stirrer, a nitrogen introducing tube and a cooling tube, pentamethylene diisocyanate produced in the same manner as in Example 1 in the specification of WO 2012/121291 under a nitrogen atmosphere 500 parts by mass, 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 tris (tridecyl) phosphite were charged, 85 The urethanization reaction was carried out at 3 ° C. for 3 hours.

Next, 0.02 parts by mass of tris (2-ethylhexanoic acid) bismuth is added as an allophanatization catalyst, and the reaction is continued until the isocyanate group concentration reaches the calculated value (46.7% by mass, that is, the conversion rate is 10% by mass). Thereafter, 0.02 parts by mass of o-toluenesulfonamide was added.

Thereafter, the obtained reaction solution was passed through a thin-film distillation apparatus (vacuum degree 0.093 KPa, temperature 150 ° C.) to remove unreacted pentamethylene diisocyanate. Furthermore, 100 parts by mass of the obtained filtrate was subjected to o -Toluenesulfonamide was added in an amount of 0.02 parts by mass to obtain isocyanate (a-1).

The isocyanate group concentration of the obtained aliphatic polyisocyanate allophanate derivative (a-1) is 20.4 mass%, the viscosity at 25 ° C. is 200 mPa · s, and the isocyanate monomer concentration is 0.2 mass. %Met.

The molar ratio of allophanate group to isocyanurate group by ¹ H-NMR measurement was allophanate group / isocyanurate group = 100/3.

The molar ratio of uretdione group to isocyanurate group by ¹³ C-NMR measurement was uretdione group / isocyanurate group = 0/3.

From these, the isocyanurate derivative content, allophanate derivative content, and uretdione derivative content with respect to the total amount of the derivatives were determined. The results are shown in Table 1.

Preparation Example 2 (Allophanate derivative of aliphatic polyisocyanate (a-2) (iPA-modified allophanate derivative of PDI))
An 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 isopropanol was used instead of isobutanol.

The isocyanate group concentration of the obtained aliphatic polyisocyanate allophanate derivative (a-2) is 21.2% by mass, the viscosity at 25 ° C. is 180 mPa · s, and the isocyanate monomer concentration is 0.2% by mass. %Met.

Preparation Example 3 (Allophanate derivative of aliphatic polyisocyanate (a-3) (PBA nBA-modified allophanate derivative))
An aliphatic polyisocyanate allophanate derivative (a-3) was obtained in the same manner as in Preparation Example 1, except that 24 parts by mass of n-butanol was used in place of isobutanol.

The isocyanate group concentration of the obtained aliphatic polyisocyanate allophanate derivative (a-3) is 20.5% by mass, the viscosity at 25 ° C. is 320 mPa · s, and the isocyanate monomer concentration is 0.2% by mass. %Met.

Preparation Example 4 (Allophanate derivative of aliphatic polyisocyanate (a-4) (3MPD-modified allophanate derivative of PDI))
An 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 isocyanate group concentration of the obtained aliphatic polyisocyanate allophanate derivative (a-4) is 21.3% by mass, the viscosity at 25 ° C. is 1800 mPa · s, and the isocyanate monomer concentration is 0.2 mass. %Met.

Preparation Example 5 (Allophanate derivative of aliphatic polyisocyanate (a-5) (1,4-BG-modified allophanate derivative of PDI))
An allophanate derivative of an aliphatic polyisocyanate (a-5) was obtained in the same manner as in Preparation Example 1, except that 14.6 parts by mass of 1,4-butanediol was used in place of isobutanol.

The isocyanate group concentration of the aliphatic polyisocyanate allophanate derivative (a-5) obtained was 22.1% by mass, the viscosity at 25 ° C. was 2400 mPa · s, and the isocyanate monomer concentration was 0.2% by mass. %Met.

Preparation Example 6 (Allophanate derivative of aliphatic polyisocyanate (a-6): iBA-modified allophanate derivative of HDI))
An allophanate derivative (a-6) of an aliphatic polyisocyanate was obtained in the same manner as in Preparation Example 1, except that pentamethylene diisocyanate was changed to hexamethylene diisocyanate (trade name: Takenate 700, manufactured by Mitsui Chemicals, Inc.).

The obtained aliphatic polyisocyanate allophanate derivative (a-6) had an isocyanate group concentration of 19.3%, a viscosity at 25 ° C. of 300 mPa · s, and an isocyanate monomer concentration of 0.4% by mass. It was.

Preparation Example 7 (Isocyanurate derivative of aliphatic polyisocyanate (a-7): iBA-modified isocyanurate derivative of PDI))
Into a four-necked flask equipped with a thermometer, a stirrer, a reflux tube, and a nitrogen introduction tube, 500 m of pentamethylene diisocyanate produced in the same manner as in Example 1 in the specification of WO 2012/121291 is provided. Parts by weight, 0.5 parts by weight of isobutyl alcohol, 0.3 parts by weight of 2,6-di (tert-butyl) -4-methylphenol, and 0.3 parts by weight of tris (tridecyl) phosphite, And reacted at 80 ° C. for 2 hours.

Next, 0.05 parts by mass of N- (2-hydroxypropyl) -N, N, N-trimethylammonium-2-ethylhexanoate was blended as an isocyanuration catalyst. The isocyanate group concentration was measured, and the reaction was continued until the concentration reached 48.9% by mass (that is, the conversion rate was 10% by mass). When a predetermined conversion rate (conversion rate: 10% by mass) was reached after 50 minutes, 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: 0.093 kPa) to remove unreacted pentamethylene diisocyanate monomer, and further to 100 parts by mass of the obtained filtrate. Then, 0.02 parts by mass of o-toluenesulfonamide and 0.003 parts by mass of benzoyl chloride were added to obtain an isocyanurate derivative (a-7) of an aliphatic polyisocyanate.

The isocyanate monomer concentration of the aliphatic polyisocyanate isocyanurate derivative (a-7) was 0.5% by mass, the isocyanate group concentration was 24.7% by mass, and the viscosity at 25 ° C. was 2000 mPa · s.

The molar ratio of allophanate group to isocyanurate group by ¹ H-NMR measurement was allophanate group / isocyanurate group = 7.4 / 100.

The molar ratio of uretdione group to isocyanurate group as determined by ¹³ C-NMR was uretdione group / isocyanurate group = 1/100.

Preparation Example 8 (alicyclic polyisocyanate (a-8))
Isophorone diisocyanate (manufactured by EVONIK, trade name: VESTANAT IPDI, isocyanate group concentration was 37.8% by mass, viscosity at 25 ° C. was 5 mPa · s) was designated as alicyclic polyisocyanate (a-8).

(2) Polyol component (b)
Preparation Example 1 (Polyol (b-1))
Polyoxyalkylene polyol (polyether polyol obtained by addition polymerization of propylene oxide to glycerin and then addition polymerization of ethylene oxide, number average molecular weight (Mn) = 940, functional group number f = 3, OH value = 180 mgKOH / g, total oxy Ethylene oxide concentration in alkylene = 20% by mass (25 mol%) and primary hydroxyl group concentration in all terminal hydroxyl groups = 45.5% were designated as polyol (b-1).

Preparation Example 2 (Polyol (b-2))
Polyoxyalkylene polyol (polyether polyol obtained by addition polymerization of propylene oxide to pentaerythritol and then addition polymerization of ethylene oxide, number average molecular weight (Mn) = 1250, number of functional groups f = 4, OH value = 180 mgKOH / g, total The ethylene oxide concentration in oxyalkylene = 20% by mass (25 mol%) and the primary hydroxyl group concentration in all terminal hydroxyl groups = 46.6% were designated as polyol (b-2).

Preparation Example 3 (Polyol (b-3))
Polyoxyalkylene polyol (polypropylene polyol obtained by addition polymerization of propylene oxide to propylene glycol and then addition polymerization of ethylene oxide, number average molecular weight (Mn) = 620, number of functional groups f = 2, OH value = 180 mgKOH / g, total The polyol (b-3) was an ethylene oxide concentration in oxyalkylene = 20% by mass (25 mol%) and a primary hydroxyl group concentration in all terminal hydroxyl groups = 45.7%.

Preparation Example 4 (Polyol (b-4))
Polyoxyalkylene polyol (polyether polyol obtained by addition polymerization of propylene oxide to triethanolamine and then addition polymerization of ethylene oxide, number average molecular weight (Mn) = 940, number of functional groups f = 3, OH value = 180 mgKOH / g, The ethylene oxide concentration in all oxyalkylenes = 20% by mass (25 mol%) and the primary hydroxyl group concentration in all terminal hydroxyl groups = 46.8% were designated as polyol (b-4).

Preparation Example 5 (Polyol (b-5))
Polyoxyalkylene polyol (polyether polyol obtained by addition polymerization of propylene oxide to glycerin and then addition polymerization of ethylene oxide, number average molecular weight (Mn) = 5000, functional group number f = 3, OH value = 34 mgKOH / g, total oxy Ethylene oxide concentration in alkylene = 15 mass% (19 mol%) and primary hydroxyl group concentration in all terminal hydroxyl groups = 90.0% were designated as polyol (b-5).

Preparation Example 6 (Polyol (b-6))
Polyoxyalkylene polyol (polyether polyol obtained by addition polymerization of propylene oxide to glycerin and then addition polymerization of ethylene oxide, number average molecular weight (Mn) = 6000, number of functional groups f = 3, OH value = 28 mgKOH / g, total oxy Ethylene oxide concentration in alkylene = 40 mass% (47 mol%) and primary hydroxyl group concentration in all terminal hydroxyl groups = 92.0% were designated as polyol (b-6).

Preparation Example 7 (Polyol (b-7))
Polyoxyalkylene polyol (polyether polyol obtained by addition polymerization of propylene oxide to glycerin, number average molecular weight (Mn) = 5000, number of functional groups f = 3, OH value = 34 mgKOH / g, primary hydroxyl group concentration in all terminal hydroxyl groups = 3. 3%) was designated as polyol (b-7).

Preparation Example 8 (Polyol (b-8))
Polyoxyalkylene polyol (polyether polyol obtained by addition polymerization of propylene oxide to glycerin and then addition polymerization of ethylene oxide, number average molecular weight (Mn) = 700, number of functional groups f = 3, OH value = 240 mgKOH / g, all terminals The polyol (b-8) was defined as a primary hydroxyl group concentration in the hydroxyl group = 3.5%.

(3) Catalyst (c)
(Catalyst (c-1))
33% by weight dipropylene glycol solution of triethylenediamine (manufactured by Air Products, trade name: Dabco-33LV)
(Catalyst (c-2))
Organotin compound (Momotiv Co., Ltd., trade name: Formrez UL-28)
(4) Foaming agent (d)
(Foaming agent (d-1))
Pure water (H ₂ O)
(5) Foam stabilizer (e)
(Foam stabilizer (e-1))
Silicone foam stabilizer (product name: B-8002, manufactured by Evonik)
(6) Stabilizer (f)
(Stabilizer (f-1))
Hindered amine compound (light stabilizer, manufactured by BASF Japan, trade name: Tinuvin 765)
(Stabilizer (f-2))
Organophosphorus compound (Antioxidant, manufactured by Johoku Chemical Co., Ltd., trade name: JP-308E)
3. Examples 1 to 20 and Comparative Examples 1 to 5 (Production of flexible polyurethane foam)
(1) Example 1
Among the components (raw materials) shown in Table 1 below, each component other than the polyisocyanate component is weighed and blended according to the formulation of Table 1 in a laboratory at a temperature of 23 ° C. and a relative humidity of 55%. The mixture was stirred and mixed so that they were uniform.

A separately prepared polyisocyanate component was weighed according to the formulation of Tables 3 to 6, and the temperature was adjusted to 23 ° C.

After that, polyisocyanate components were added to the premix, and after stirring them for 15 seconds with a hand mixer (rotation speed 5000 rpm), they were immediately put into a wooden box and foamed. As a result, a flexible polyurethane foam was obtained.

(2) Examples 2 to 20 and Comparative Examples 1 to 5
A flexible polyurethane foam was obtained in the same manner as in Example 1 except that it was weighed according to the formulation of Tables 3 to 6 below.

Tables 3 to 6 show the formulation and the properties of the polyisocyanate component in each Example and each Comparative Example.

4). Evaluation of flexible polyurethane foam <Density (unit: kg / m ³ )>
A rectangular parallelepiped having a size of 10 × 10 × 5 cm is 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 apparent density of the measurement sample is set to JIS K7222 (2005). ).

<Hardness (25% CLD) (unit: N / 100 cm ² )>
A rectangular parallelepiped having a size of 10 × 10 × 5 cm is cut out from the central portion (core) of the flexible polyurethane foam of each example and each comparative example to prepare a measurement sample, and then conforms to JIS K-6400 (2012). Then, the hardness (25% CLD) of the measurement sample was measured.

<Breathable ^{(unit: cc / cm 2 / sec)} >
Crushing (crushing condition: soft polyurethane foam passes between two rollers (interval 0.2 mm)) by cutting out to a size of 10 mm thickness from the center of the flexible polyurethane foam of each example and each comparative example Then, a measurement sample was prepared, and air permeability was measured according to JIS K-6400 (2012) B method using an air flow measuring device (manufactured by Toyo Seiki Co., Ltd.).

<Tear strength (unit: N / cm)
A flexible polyurethane foam of each example and each comparative example was cut out to a size of 10 mm in thickness and punched into an angular test piece shape to prepare a measurement sample. A tensile / compression tester (Model 205N, manufactured by Intesco) ) And a tear test according to JIS K-6400 (2012) B method, and the stress at break was calculated.

<Elongation at tensile break (unit:%)>
Cut out into a size of 10 mm thickness from the center of the flexible polyurethane foam of each example and each comparative example, punch a sample into the shape of No. 1 test piece, and prepare a measurement sample. Tensile compression tester (manufactured by Intesco, Using model 205N), a tensile test was performed according to JIS K-6400 (2012), and the elongation at break was calculated.

<Wet heat compression set Wet Set (unit:%)>
A rectangular parallelepiped having a size of 50 mm × 50 mm × 25 mm is cut out from the central part (core) of the flexible polyurethane foam of each example and each comparative example to prepare a measurement sample. Thereafter, according to the method described in JIS K 6400-4 The wet heat compression set (%) was measured. This test piece was compressed to a thickness of 50%, sandwiched between parallel flat plates, and allowed to stand for 22 hours at 50 ° C. and a relative humidity of 95%. 30 minutes after taking out a test piece, the thickness was measured and the distortion rate (%) was measured compared with the thickness before a test.

Tables 3 to 6 show the evaluations of the flexible polyurethane foams of Examples 1 to 20 and Comparative Examples 1 to 4.

The details of the abbreviations used in the table are shown below.
PDI: pentamethylene diisocyanate HDI: hexamethylene diisocyanate IPDI: isophorone diisocyanate iBA: isobutyl alcohol (isobutanol)
nBA: n-butanol 3MPD: 3-methyl-pentanediol 1,4-BG: 1,4-butanediol AO: alkylene oxide EO: ethylene oxide PO: propylene oxide Gly: glycerin PE: pentaerythritol PG: propylene glycol TEOA: Triethanolamine Dabco 33LV: 33% dipropylene glycol solution of triethylenediamine (manufactured by Air Products)
Formrez UL-28: Organotin compound (made by Momentive)
B-8002: Silicone foam stabilizer (manufactured by Evonik)
Tin. 765: hindered amine compound (light stabilizer, manufactured by BASF Japan)
JP-308E: Organophosphorus compound (Antioxidant, manufactured by Johoku Chemical Co., Ltd.)
In addition, although the said invention was provided as exemplary embodiment of this invention, this is only a mere illustration and should not be interpreted limitedly. Variations of the present invention that are apparent to one of ordinary skill in the art are within the scope of the following claims.

The flexible polyurethane foam of the present invention can be used for shoulder pads, knee pads, elbow pads, swimwear pads, shoe tongues, shoe inner soles, medical materials, clothing materials, robot skins, robot hands, etc. Particularly, it is suitable for brassiere pads, brassiere cups and the like as molded articles of clothing materials.

Claims

A flexible polyurethane foam obtained by reacting and foaming a polyisocyanate component containing a derivative of an aliphatic polyisocyanate and a polyol component containing a polyoxyalkylene polyol,
The derivative of the aliphatic polyisocyanate includes an allophanate derivative of the aliphatic polyisocyanate,
The content ratio 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 with respect to the polyoxyalkylene polyol,
A flexible polyurethane foam, wherein the primary hydroxyl group is 50 mol% or less based on the total number of moles of terminal hydroxyl groups of the polyoxyalkylene polyol.
2. The flexible polyurethane 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 with respect to the total amount of the derivative of the aliphatic polyisocyanate. Form.
The flexible polyurethane foam according to claim 1, wherein the aliphatic polyisocyanate contains pentamethylene diisocyanate and / or hexamethylene diisocyanate.
The flexible polyurethane foam according to claim 3, wherein the polyisocyanate component further contains an alicyclic polyisocyanate.
The derivative comprises an allophanate derivative modified with alcohol,
The flexible polyurethane foam according to claim 1, wherein the alcohol contains a monohydric alcohol and a dihydric alcohol.
6. The flexible polyurethane foam according to claim 5, wherein the alcohol contains a branched monohydric alcohol and a branched dihydric alcohol.
A clothing material comprising the flexible polyurethane foam according to claim 1.
A brassiere pad, which is a molded article of the clothing material according to claim 7.
A brassiere cup, comprising the brassiere pad according to claim 8.
Preparing a polyisocyanate component containing a derivative of an aliphatic polyisocyanate and a polyol component containing a polyoxyalkylene polyol;
Reacting and foaming the polyisocyanate component and the polyol component to produce a flexible polyurethane foam,
The derivative of the aliphatic polyisocyanate includes an allophanate derivative of the aliphatic polyisocyanate,
The content ratio 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 with respect to the polyoxyalkylene polyol,
The method for producing a flexible polyurethane foam, wherein the primary hydroxyl group is 50 mol% or less based on the total number of moles of terminal hydroxyl groups of the polyoxyalkylene polyol.