JP2003246833A - Active hydrogen ingredient for preparing flexible polyurethane foam and process for preparing foam - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain an active hydrogen ingredient for preparing a flexible polyurethane foam which shows good moldability and yields a foam having high hardness. <P>SOLUTION: The active hydrogen ingredient for preparing a one-shot flexible polyurethane foam has a viscosity satisfying an inequality: y<SB>0</SB>≥0.000005x<SB>0</SB><SP>2</SP>+10 [wherein x<SB>0</SB>is the viscosity of the active oxygen ingredient used (mPas, measured at 25°C); and y<SB>0</SB>is the hardness [25% ILD] (kgf/314 cm<SP>2</SP>) of a molded foam having a core density of 42 kg/m<SP>3</SP>obtained through expansion by injecting an organic polyisocyanate having a ratio of TDI-80/crude MDI (average number of functional groups: 2.9) of 80/20 (mass ratio), an isocyanate index of 105 and a raw material solution temperature of 25°C and 3.3 pts.mass water (foaming agent) against 100 pts.mass active hydrogen ingredient into a mold with a size of 300 mm×300 mm×100 mm at 65°C]. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an active hydrogen component for producing a flexible polyurethane foam and a method for producing a foam using the same, and more specifically, a flexible polyurethane foam suitable for use as a cushion for vehicle seats. The present invention relates to an active hydrogen component for producing and a method for producing foam.

[0002]

2. Description of the Related Art Conventionally, flexible polyurethane foam has been widely used as a cushioning material for automobiles and the like, by taking advantage of its excellent cushioning property. Also, in recent years, for the purpose of improving the riding comfort of automobiles, a different hardness seat cushion using a urethane foam with a high foam hardness for the side support and a soft urethane foam for the central part has been used. There is. A method of using a polymer polyol in producing a urethane foam having a high foam hardness is widely known.

[0003]

When a large amount of polymer polyol is used to produce a cushion material having a high foam hardness, a poor appearance of the molded product occurs due to a decrease in the mixing property of the active hydrogen component and the isocyanate component. However, there is a problem that productivity of the cushioning material is reduced.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies to solve these problems, and have used an active hydrogen component whose viscosity and hardness of the foam obtained satisfy a specific relational expression. As a result, the active hydrogen component for a flexible polyurethane foam having good moldability was found, and the present invention was completed.

That is, the present invention is the following 5 inventions.
[First Invention] An active hydrogen component for producing a one-shot flexible polyurethane foam, which has a viscosity satisfying the relationship of the following formula [1]. y ₀ ≧ 0.000005x ₀ ² +10 [1] x ₀ : viscosity of the active hydrogen component used (JIS K-155
According to 7. (Unit: mPa · s, measurement temperature: 25 ° C.) y ₀ : hardness of a molding foam having a core density of 42 kg / m ³ obtained by the following foaming formulation [25% IL
D] (according to JIS K-6400. Compressive stress when compressing 25% of 10 cm-thick flexible polyurethane foam, unit: kgf / 314 cm ² ) [Foaming formulation] Organic polyisocyanate: TDI-80 /
Crude MDI (average number of functional groups: 2.9) = 80/20 (mass ratio), isocyanate index: 105, raw material liquid temperature: 25
° C, water (foaming agent): 3.3 parts by mass per 100 parts by mass of active hydrogen component, 300 mm x 300 mm x 10 at 65 ° C
Inject into a 0 mm mold.

[Second Invention] An active hydrogen component containing a polymer polyol (A) obtained by polymerizing a vinyl monomer (b) in a polyol (a1) and another active hydrogen compound (B), One-shot flexible polyurethane foam-producing activity containing the following addition-polymerizable active hydrogen compound (a2) in (B) and the following polyols (a11) and (a12) in (a1) and / or (B) Hydrogen component. Addition-polymerizable active hydrogen compound (a2): a compound having an active hydrogen-containing group and an addition-polymerizable functional group in the molecule and having an active hydrogen-containing group value of 100 to 1000 (mgKOH / g). Polyol (a11): The average number of functional groups is 2.5 to 4, the hydroxyl value is 20 to 40 (mgKOH / g),
The content of terminal oxyethylene units is 10 to 25% by mass, and the content of internal oxyethylene units is 0 to 5% by mass.
And the total content of oxyethylene units is 10 to 30
Polyoxyethylene polyoxypropylene polyol which is mass%. Polyol (a12): the average number of functional groups is 2 to 8,
A (polyoxyalkylene) polyol having an alkylene group having a hydroxyl value of 200 to 1850 (mgKOH / g) and having 2 and / or 3 carbon atoms.

[Third invention] A method for producing a flexible polyurethane foam from an active hydrogen component, a polyisocyanate component, a foaming agent, a catalyst and a foam stabilizer, wherein any one of the above active hydrogen components is used. Manufacturing method of flexible polyurethane foam. [Fourth Invention] An active hydrogen component and a polyisocyanate component are reacted in the presence of a foaming agent, a catalyst and a foam stabilizer by a one-shot method to obtain a foam hardness satisfying the relationship of the following formula [2]. A method for producing a foam, which comprises producing a flexible polyurethane foam having the same. y ≧ 0.000005x ² +10 [2] x: viscosity of active hydrogen component used (JIS K-1557)
by. Unit: mPa · s, measurement temperature: 25 ° C. y: hardness of foam [25% ILD] (JIS K-6
According to 400. Compressive stress when compressing 25% of 10 cm-thick flexible polyurethane foam, unit: kgf / 31
4 cm ² ) [Fifth Invention] A vehicle cushion made of a flexible polyurethane foam obtained by any one of the above production methods.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION In the first and fourth inventions,
The viscosity of the active hydrogen component and the hardness of the obtained foam satisfy the relationship of the above formula [1] or [2]. Preferably, the relationship of the following formula [1 ′] or [2 ′] is satisfied. 0.000005x ₀ ² +60 ≥ y ₀ ≥ 0.000005x ₀ ² +11 [1 '] 0.000005x ² +60 ≥ y ≥ 0.000005x ² +11 [2'] satisfy the relationship of the formula [1] or [2] As a result, the appearance defect of the molded product is prevented. The viscosity x or x _{0 at} 25 ° C. is 3000 mPa · s or less, particularly 100 to 2
It is preferably 500 mPa · s. x is 3000
When it is mPa · s or less, the mixing property of the active hydrogen component and the isocyanate component is improved, the moldability is improved, and the productivity of the cushion material is improved.

The active hydrogen components that can satisfy the relation of the formula [1] or [2] include (a2) and (a11).
The active hydrogen component of the second invention containing and (a12) is preferable.

In the second aspect of the present invention, the (polyoxyalkylene) polyol (a12) is a compound having no addition-polymerizable functional group, such as polyhydric alcohol and
For polyhydric alcohols, polyhydric phenols or amines,
Examples thereof include compounds having a structure in which an alkylene oxide having an alkylene group having 2 and / or 3 carbon atoms (hereinafter abbreviated as AO) is added. These (a12) may be used in combination of two or more kinds. Polyhydric alcohol has 2 carbon atoms
To 20 dihydric alcohols (aliphatic diols such as ethylene glycol, propylene glycol, 1,3- and 1,4-butanediol, 1,6-hexanediol, alkylene glycols such as neopentyl glycol; and cycloaliphatic groups). Diols such as cycloalkylene glycols such as cyclohexanediol and cyclohexanedimethanol), trihydric alcohols having 3 to 20 carbon atoms (aliphatic triols such as glycerin, trimethylolpropane, trimethylolethane and alkanetriols such as hexanetriol). ; 4 having 5 to 20 carbon atoms
~ Polyhydric alcohols with 8 or more hydric groups (aliphatic polyols such as pentaerythritol, sorbitol,
Alkane polyols such as mannitol, sorbitan, diglycerin and dipentaerythritol, and intramolecular or intermolecular dehydration products of the or alkanetriol; and saccharides such as sucrose, glucose, mannose, fructose and methylglucoside and derivatives thereof). To be

Examples of polyhydric (2 to 8 or higher) phenols include monocyclic polyhydric phenols such as pyrogallol, hydroquinone and phloroglucin; bisphenols such as bisphenol A, bisphenol F and bisphenol sulfone; condensation of phenol and formaldehyde. (Novolak); for example US Pat. No. 3,265.
Examples thereof include polyphenols described in Japanese Patent No. 641.

As the amines, the number of active hydrogen is 2 to 1
Ammonia; aliphatic amines such as alkanolamines having 2 to 20 carbon atoms (for example, monoethanolamine, diethanolamine and isopropanolamine), and 1 to 2 carbon atoms.
0 alkylamines (for example, n-butylamine and octylamine), alkylenediamines having 2 to 6 carbon atoms (for example, ethylenediamine, propylenediamine, and hexamethylenediamine), polyalkylenepolyamines having 4 to 20 carbon atoms (alkylene group) Has 2 to 2 carbon atoms
6 dialkylenetriamine to hexaalkyleneheptamine, such as diethylenetriamine and triethylenetetramine). Further, aromatic mono- or polyamines having 6 to 20 carbon atoms (for example, aniline,
(Phenylenediamine, tolylenediamine, xylylenediamine, diethyltoluenediamine, methylenedianiline and diphenyletherdiamine); carbon number 4 to 2
Alicyclic amines of 0 (isophoronediamine, cyclohexylenediamine and dicyclohexylmethanediamine); heterocyclic amines of 4 to 20 carbon atoms (for example, piperazine, aminoethylpiperazine and JP-B-55-
No. 21044) and the like. Two or more kinds of polyhydric alcohols, polyhydric phenols, and amines to which AO is added may be used in combination.

AO is propylene oxide (hereinafter abbreviated as PO) and / or ethylene oxide (hereinafter E).
It is abbreviated as O. ). AO is preferably composed of only these, but may be an adduct in which other AO is used in combination within the range of 10% by mass or less (particularly 5% by mass or less) in AO. As other AO, those having 4 to 8 carbon atoms are preferable, and 1,2-, 1,3-, 1,4-, or 2,3
-Butylene oxide, styrene oxide and the like. As a method of adding PO and / or EO,
PO alone, EO alone, or block addition of PO, EO, random addition, or combination thereof may be used. PO alone addition or EO alone addition [(poly) oxypropylene polyol or (poly) oxyethylene polyol] Is obtained] is preferred. The average number of functional groups per molecule of (a2) is 2 to 8, preferably 2 to 6, and the hydroxyl value is 200 to 1850 (mgKOH / g,
The same applies hereinafter), preferably the lower limit is 250 and the upper limit is 1810.
Is.

When the number of functional groups in the polyol (a12) is 2 or more, the compression set becomes good and the curing time can be shortened. If the average number of functional groups is 8 or less, no adverse effect is exerted on the elongation physical properties of the foam. If the hydroxyl value is 200 or more,
The foam hardness can be sufficiently expressed, and if it is 1850 or less, the foam elongation properties are not adversely affected.

Polyol (a11) used in the second invention
Is, for example, one of compounds having a structure in which AO is added to polyhydric alcohol, polyhydric phenol or amines.
Species, or a mixture of two or more species. Specific examples of the polyhydric alcohols, polyhydric phenols, and amines include the same as those in the above (a12),
It is used so that the average number of functional groups of (a11) is 2.5 to 4. Two or more of these may be used in combination.
AO is PO and EO. AO is preferably composed of only these, but may be an adduct in which other AO is used in combination within the range of 10% by mass or less (particularly 5% by mass or less) in AO. As the other AO, those having 4 to 8 carbon atoms are preferable, and examples thereof include those mentioned above. PO and E
The method of adding O may be block addition, random addition, or combination addition thereof, but block addition is preferable. (A11) is obtained by adding EO to the terminal and optionally inside so that the total mass of oxyethylene units is 10 to 30% by mass, preferably the lower limit is 12% by mass, the upper limit is 20% by mass, and the internal oxyethylene unit is contained. Amount is 0
˜5% by mass, preferably the lower limit is 0.1% by mass and the upper limit is 4
Mass%, content of terminal oxyethylene unit is 10 to 25
It is a polyoxyethylene polyoxypropylene polyol having a mass%, preferably a lower limit of 12% by mass and an upper limit of 20% by mass. The average number of functional groups per molecule of (a11) is 2.5 to 4, preferably 3 to 4, and the hydroxyl value is 20.
-40, preferably the lower limit is 22, and the upper limit is 38.

When the total content of oxyethylene units of (a11) is 10% by mass or more, or the content of terminal oxyethylene units is 10% by mass or more, curing just before the completion of foaming is sufficient, and the total content of oxyethylene units is Is 30% by mass or less or the content of terminal oxyethylene units is 25% by mass or less, the air permeability of the foam is good and the foam does not shrink. When the content of the internal oxyethylene unit is 5% by mass or less, the hardness of the foam (stress during compression) can be sufficiently exhibited. When the average number of functional groups per molecule is 2.5 or more, the compression set becomes good and the curing time can be shortened. When the average number of functional groups per molecule is 4 or less, the foam has good air permeability, and the foam has good elongation properties. When the hydroxyl value is 20 or more, the compression set is good and the curing time can be shortened. If the hydroxyl value is 40 or less, the air permeability of the foam will be good.

In the second aspect of the present invention, the addition-polymerizable functional group contained in the addition-polymerizable active hydrogen compound (a2) is a terminal olefin type or internal olefin type radical polymerizable functional group, a cationic polymerizable functional group (vinyl ether group). , Propenyl ether groups, etc.) and anionic polymerizable functional groups (vinyl carboxyl groups, cyanoacryloyl groups, etc.)
One or more groups selected from Of these, radically polymerizable functional groups are preferable, and the following general formula (1)
The terminal olefin type radically polymerizable functional group represented by is more preferable. [In the formula, R represents hydrogen, an alkyl group having 1 to 15 carbon atoms or an aryl group having 6 to 21 carbon atoms. ]

In the formula (1), the alkyl group having 1 to 15 carbon atoms represented by R may be linear or branched, and may be methyl group, ethyl group, n- and i-propyl groups, and butyl group. , Hexyl group, octyl group and the like. Examples of the aryl group having 6 to 21 carbon atoms include phenyl group, benzyl group, toluyl group, xylyl group and butylphenyl group. Specific examples of the group having a group represented by the general formula (1) include an acryloyl group,
Examples thereof include a terminal unsaturated bond-containing group such as methacryloyl group, vinyl group, vinylbenzyl group, vinylphenyl group and allyl ether group. Among these groups, an acryloyl group, a methacryloyl group and an allyl ether group are particularly preferable. The number of addition-polymerizable functional groups in (a2) is preferably 1-10, more preferably 1-5.
The active hydrogen-containing group contained in (a2) is not particularly limited, and examples thereof include at least one active hydrogen-containing group selected from a hydroxyl group, a mercapto group, a carboxyl group, a primary amino group, a secondary amino group and the like. Can be mentioned. Preferred active hydrogen-containing groups are hydroxyl groups and mercapto groups, especially hydroxyl groups. The number of active hydrogen-containing groups in (a2) (excluding NH in G described later) is preferably 1 to 8, more preferably 1 to 5, and particularly preferably 2 to 4. Further, the proportion of the active hydrogen-containing groups in (a2) which is 2 or more is preferably 5% by mass or more.

As (a2), those represented by the following formula (2) are more preferable. [In the formula, R represents hydrogen, an alkyl group having 1 to 15 carbon atoms or an aryl group having 6 to 21 carbon atoms, and G represents O, S, or N.
H, u and v are positive integers, L is an active hydrogen-containing group, J
Represents a residue obtained by removing all active hydrogen-containing groups from a compound having u + v active hydrogen-containing groups. In the formula (2), R is the same as that in the formula (1). Examples of the active hydrogen-containing group of L include those exemplified as the active hydrogen-containing group of the above (a2). Examples of the active hydrogen compound forming J include the below-mentioned polyols, amines, polythiols and the like. R is preferably hydrogen or an alkyl group, particularly hydrogen or a methyl group, and G is preferably O. The value of u is preferably 1 to
7, more preferably 1 to 5, the value of v is preferably 1 to 7, more preferably 1 to 4, and particularly preferably 2 to
It is 4. The value of u + v is preferably 2-8, more preferably 3-8. Further, the active hydrogen-containing group of L is preferably a hydroxyl group.

Specific examples of the above (a2) include the following (a
21) to (a24), and two or more kinds may be used in combination. (A21) Polyols [polyhydric alcohols; polyhydric phenols; polyols having AO added thereto; polyols having AO added to amines; polyester polyols derived from polyhydric alcohols and polycarboxylic acids or lactones] Unsaturated Carboxylic Acid Partial Esters (a22) Unsaturated Carboxylic Acid (Partial) Amides of Amines, and Unsaturated Carboxylic Acid (Partial) Esters of Alkanolamines (a23) Unsaturated Carboxylic Acid Partial Thioesters of Polythiols (a24) Vinyl monomers having other hydroxyl groups

Among the polyols used in the production of (a21), examples of the polyhydric alcohol, polyhydric phenol and amine include those exemplified in the above (a12), and two or more kinds may be used in combination. The AO to be added is preferably one having 2 to 8 carbon atoms, such as EO and P
O, 1,2-, 1,3-, 1,4- or 2,3-butylene oxide, styrene oxide and a combination of two or more thereof (block and / or random addition) can be mentioned. Preferable ones are those containing PO and / or EO as main components and containing 20% by mass or less of other AO. The number of moles of AO added is preferably 1 to 70, more preferably 2 to 50.

Among the polyols used in the production of (a21), as the polyester polyol, the above-mentioned polyhydric alcohol and / or polyether [ethylene glycol, diethylene glycol, propylene glycol,
Dihydric alcohols such as 1,3- or 1,4-butanediol, 1,6-hexanediol and neopentyl glycol, or mixtures thereof with trihydric or higher alcohols such as glycerin and trimethylolpropane, and these AO low mole (1 to 10 mole) adduct of polyhydric alcohol] and polycarboxylic acid having 4 to 18 carbon atoms, or its anhydride, ester forming derivative such as lower ester (eg, adipic acid, sebacic acid, Condensation reaction product with maleic anhydride, phthalic anhydride, dimethyl terephthalate, etc .; Alkyleon oxide (EO, PO, etc.) addition reaction product; Obtained by ring-opening polymerization of lactone (ε-caprolactone, etc.) The thing etc. are mentioned. (A
The polyol used in the production of 21) has 2 to 8 (especially 2 to 6) hydroxyl groups and has an OH equivalent of 3
Those of 0 to 1200 (particularly 31 to 250) are preferable.

(A21) is obtained by partially esterifying the above-exemplified polyols with unsaturated carboxylic acids in an equivalent ratio such that at least one hydroxyl group remains unreacted in one molecule. To be The unsaturated carboxylic acids preferably have 3 to 18 carbon atoms,
(Meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, anicotic acid, cinnamic acid, vinylbenzoic acid, and the like, and combinations of two or more thereof [where (meth) Acrylic acid means acrylic acid and / or methacrylic acid, and the same description method is used below. ]; Ester-forming derivatives of these unsaturated carboxylic acids such as halides [(meth)]
Acrylic acid chloride, etc.], acid anhydrides [maleic acid anhydride, itaconic acid anhydride, citraconic acid anhydride, etc.]; and a combination of two or more thereof.

Specific compounds of (a21) include 2-
Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3-phenoxy-2-hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate, glycerin di (meth) Examples thereof include acrylate, diethylene glycol mono (meth) acrylate, pentaerythritol triacrylate, sorbitol di (meth) acrylate, and a combination of two or more thereof.

(A22) is a polyamine (including diamine) or alkanolamine among the above amines and the above unsaturated carboxylic acid, and at least one amino group or hydroxyl group (alkanolamine It is obtained by reacting in an equivalent ratio such that (in case) remains unreacted. Specific compounds include (meth) acrylamidoethylamine, (meth) acrylamidohexylamine, aminoethyl (meth) acrylate, and the like, and combinations of two or more thereof.

The polythiols used for the production of (a23) are preferably those having 2 to 4 thiol groups and 2 to 18 carbon atoms, such as ethanedithiol and 1,2-
Propanedithiol, 1,3-propanedithiol,
1,4-propanedithiol, 1,4-benzenedithiol, 1,2-benzenedithiol, bis (4-mercaptophenyl) sulfide, 4-t-butyl-1,2-
Examples thereof include benzenedithiol, ethylene glycol dithioglycolate, trimethylolpropane tris (thioglycolate) thiocyanuric acid, di (2-mercaptoethyl) sulfide, di (2-mercaptoethyl) ether, and combinations of two or more thereof. (A23) is
It can be obtained by reacting these polythiols with the above-mentioned unsaturated carboxylic acids in an equivalent ratio such that at least one thiol group remains unreacted in one molecule.
Specific compounds include acryloylthioethyl mercaptan, acryloylthiobutyl mercaptan, and the like.
And combinations of two or more of these.

Examples of (a24) include aromatic hydroxyl group-containing monomers having 8 to 24 carbon atoms (p-hydroxystyrene, etc.), unsaturated alcohols having 3 to 24 carbon atoms ((meth) allyl alcohol, cinnamyl alcohol). , Crotonyl alcohol, etc.], partially unsaturated alcohol (especially allyl) etherification product of the above polyhydric alcohol (having at least one hydroxyl group in one molecule such as pentaerythritol triallyl ether), and the above compounds AO adduct (preferably 2 to 20 mol adduct), and a combination of two or more thereof. The number of radically polymerizable functional groups of (a24) is preferably 1 to 5, the number of active hydrogen-containing groups is preferably 1 to 5, and the number average molecular weight is 1
000 or less is preferable.

Of these, preferred are (a21) and (a24) (particularly allyl ethers of polyhydric alcohols), because of their low viscosity and low viscosity when used as a polyurethane-forming composition. Preferred are unsaturated carboxylic acid partial esters of polyhydric alcohols or alkylene oxide adducts thereof.

The active hydrogen-containing group value of (a2) is usually 10
0 to 1000, preferably the lower limit is 150 and the upper limit is 800
Is. When the active hydrogen-containing group value is 100 or more, sufficient foam hardness can be exhibited, and when it is 1000 or less, good elongation property of the foam is exhibited. Here, the active hydrogen-containing group value is 56100 / active hydrogen-containing group equivalent, that is, 56.
100 / molecular weight per active hydrogen-containing group,
When the active hydrogen-containing group is a hydroxyl group, it corresponds to a hydroxyl value.

The polymer polyol (A) in the second aspect of the present invention can be produced by polymerizing the vinyl monomer (b) in the polyol (a1) by a usual method.
As a specific example, a method of polymerizing a vinyl-based monomer in a polyol in the presence of a polymerization initiator (for example, U.S. Pat. No. 3,383,351, Japanese Patent Publication No. 39-24737, Japanese Patent Publication No. 47-47999, and JP-A No. 47-47999). 50-
15894). The polymerization reaction can be carried out in the presence of a dispersant and / or a diluent, if necessary. As (A), for example, (a1
Examples thereof include those obtained by polymerizing the vinyl-based monomer (b) in the presence of a radical polymerization initiator in at least one polyol selected from 1) and (a12) and stably dispersing it. As (A), those obtained by polymerizing (b) in (a11) are preferable from the viewpoint of dispersion stability.

As (b), an aromatic vinyl monomer (b
1), unsaturated nitriles (b2), (meth) acrylic acid esters (b3) and mixtures of two or more of these are preferred. Examples of (b1) include styrene, α-methylstyrene, hydroxystyrene and chlorostyrene. Examples of (b2) include acrylonitrile and methacrylonitrile. As (b3), C,
Those consisting of H and O atoms, for example, (meth) acrylic acid alkyl esters (wherein the alkyl group has 1 to 2 carbon atoms)
4) [For example, methyl (meth) acrylate, butyl (meth) acrylate, nonyl (meth) acrylate,
Decyl (meth) acrylate, dodecyl (meth) acrylate, eicosyl (meth) acrylate, docosyl (meth) acrylate], hydroxyalkyl (C2-5) (meth) acrylate [eg hydroxyethyl (meth) acrylate], and Hydroxypolyoxyalkylene mono (meth) acrylates [eg,
The alkylene group has 2 to 4 carbon atoms and the polyoxyalkylene chain has a number average molecular weight of 200 to 1,000].

In addition to the above, other monomers (b
4) can also be used. Examples of (b4) include ethylenically unsaturated carboxylic acids and their derivatives, specifically (meth) acrylic acid, (meth) acrylamide, etc .; aliphatic hydrocarbon monomers, specifically alkenes (ethylene,
Propylene, etc.), alkadienes (butadiene, etc.), etc .;
Fluorine-based vinyl monomers, specifically, fluorine-containing (meth) acrylates (perfluorooctylethyl methacrylate, perfluorooctylethyl acrylate, etc.); chlorine-based vinyl monomers, specifically vinylidene chloride, etc .; Other nitrogen-containing vinyl monomers, specifically nitrogen-containing (meth) acrylates (diaminoethyl methacrylate, morpholinoethyl methacrylate, etc.); and vinyl-modified silicone. Preferred among these (b) are (b1) and (b2).
And especially styrene and / or acrylonitrile.

(B1) and (b) in the vinyl monomer (b)
The mass ratio of 2), (b3) and (b4) can be changed according to the required physical properties of polyurethane and the like, and is not particularly limited, but an example is as follows.
(B1) and / or (b2) is preferably 50-
It is 100% by mass, more preferably 80 to 100% by mass. The mass ratio of (b1) and (b2) is not particularly limited, but is preferably 0/100 to 80/20. (B
3) is preferably 0 to 50% by mass, more preferably 0 to 20% by mass. (B4) is preferably 0 to 1.
It is 0% by mass, more preferably 0 to 5% by mass.

A small amount (preferably 0.0) is added to (b).
5 to 1% by mass) bifunctional or more (preferably 2 to 8 functional)
By using the polyfunctional vinyl monomer (b5)
The dispersion stability of (A) can be further improved.
Examples of (b5) include divinylbenzene, ethylene di (meth) acrylate, polyalkylene (alkylene group having 2 to 8 carbon atoms, and polymerization degree: 2 to 10) glycol di (meth) acrylate, pentaerythritol triallyl ether, and triethyl ether. Methylolpropane tri (meth) acrylate and the like can be mentioned. The content of the polymer composed of (b) in (A) is preferably 5 to 50% by mass, more preferably 15 to 40% by mass, based on the mass of (A). When the content of the polymer is 5% by mass or more, sufficient foam hardness can be exhibited, and when it is 50% by mass or less, the viscosity of the polymer polyol is low and the handling is easy.

In the second aspect of the present invention, as the active hydrogen component, an active hydrogen compound (B) other than (A) is used together with the polymer polyol (A). (B) consists of (a2) and optionally one or more polyols selected from (a11) and (a12). (A12) is preferably contained in (B).

If necessary, one or more other polyols such as polyether polyols and polyester polyols other than the above may be used in combination in the active hydrogen component. As the other polyol, a polyether polyol is preferable, and examples thereof include polyhydric alcohols, polyhydric phenols, or AO adducts of amines, and (a11) and (a)
Other than 12) are mentioned. As the polyhydric alcohol, the polyhydric phenol, the amines and the AO to be added, the same ones as those in the above (a12) can be mentioned.
The average number of functional groups per molecule of the other polyol is preferably 2 to 8, more preferably 3 to 6, and the hydroxyl value is preferably 20 to 1850.

In the second invention, the content of (A) is 30 to 7 based on the total mass of (A) and (B).
It is preferably 0% by mass. More preferably,
The upper limit of the content of (A) is 40% by mass, and the lower limit is 60% by mass. When the content of (A) is 30% by mass or more, sufficient foam hardness can be exhibited, and when it is 70% by mass or less, the mixing property of the active hydrogen component and the polyisocyanate component is improved, and a defective appearance of the molded product occurs. Without, the productivity of the cushioning material is improved. Further, based on the total mass of the active hydrogen components [(A) and (B)], (a2) is 1 to 8% by mass, (a1)
It is preferable that 1) is 70 to 90 mass% and (a12) is 1 to 8 mass%. More preferably, the lower limit of (a2) is 1.5% by mass, the upper limit is 5.5% by mass, the lower limit of (a11) is 75% by mass, the upper limit is 85% by mass, and the lower limit of (a12) is 2% by mass, The upper limit is 7% by mass. When (a2) and (a12) are 1% by mass or more, the hardness of the foam does not become insufficient, and when 8% by mass or less, the elongation properties do not deteriorate. When (a11) is 70% by mass or more, the elongation property of the foam is good, and when it is 90% by mass or less, the hardness of the foam is not insufficient. The content of other polyols other than these is preferably 20% by mass or less, more preferably 10% by mass or less.

The content of the polymer (b) is preferably 5 to 20% by mass based on the total mass of active hydrogen components. More preferably, the lower limit is 7% by mass or more and the upper limit is 18%.
It is not more than mass%. If it is 5% by mass or more, the hardness of the foam will not be insufficient, and if it is 20% by mass or less, the compression set will be good.

In the method for producing a flexible polyurethane foam of the present invention, as the polyisocyanate component, all organic polyisocyanates usually used in polyurethane foam can be used, and aromatic polyisocyanates, aliphatic polyisocyanates, alicyclic polyisocyanates can be used. Isocyanate,
Aromatic aliphatic polyisocyanates, modified products thereof (for example, carbodiimide group, allophanate group, urea group,
Buret group, isocyanurate group, or oxazolidone group-containing modified product), and a mixture of two or more thereof.

As the aromatic polyisocyanate, aromatic diisocyanates having 6 to 16 carbon atoms (excluding carbon in NCO group; the same applies to the following polyisocyanates), aromatic triisocyanates having 6 to 20 carbon atoms, and these isocyanates are also included. Crude products of the above. Specific examples include 1,3- and 1,4-phenylene diisocyanate, 2,4- and 2,6-tolylene diisocyanate (TDI), crude TDI, 2,4'- and 4,4'-.
Diphenylmethane diisocyanate (MDI), polymethylene polyphenylene polyisocyanate (crude MD
I), naphthylene-1,5-diisocyanate, triphenylmethane-4,4 ′, 4 ″ -triisocyanate and the like. Examples of the aliphatic polyisocyanate include aliphatic diisocyanates having 6 to 10 carbon atoms. Specific examples include 1,6-hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate and lysine diisocyanate.

Examples of the alicyclic polyisocyanate include alicyclic diisocyanates having 6 to 16 carbon atoms. Specific examples include isophorone diisocyanate,
4,4'-dicyclohexylmethane diisocyanate,
1,4-cyclohexane diisocyanate, norbornane diisocyanate and the like can be mentioned. Examples of the araliphatic isocyanate include araliphatic diisocyanates having 8 to 12 carbon atoms. Specific examples include xylylene diisocyanate, α, α, α ′, α′-tetramethylxylylene diisocyanate, and the like.
Specific examples of the modified polyisocyanate include carbodiimide modified MDI.

Of these, aromatic polyisocyanates are preferable, and TDI and crude T are more preferable.
One or more selected from DI, MDI, crude MDI, and modified products of these isocyanates, and particularly preferably MDI and crude MDI for reasons such as improvement in productivity.
The total content of DI and / or modified products thereof is 1
0 mass% or more (especially 15 to 25 mass%), other polyisocyanate (especially TDI) content is 90 mass%
The following (especially 75 to 85 mass%) is used. Isocyanate group content as polyisocyanate component (N
The CO%) is preferably 35 to 45% by mass.

Water is preferably used as the foaming agent in the production method of the present invention. In addition, hydrogen atom-containing halogenated hydrocarbons, low boiling point hydrocarbons, liquefied carbon dioxide gas and the like may be used, or two or more kinds may be used in combination. The amount of water used when water alone is used as the foaming agent is preferably 0.1 to 30 parts by mass, per 100 parts by mass of the active hydrogen component,
It is more preferably 0.5 to 20 parts by mass, and particularly preferably 2 to 5 parts by mass. When used in combination with another foaming agent, the amount of water used is preferably 0.1 to 10 parts by mass, more preferably 2 to 5 parts by mass.

Specific examples of the hydrogen atom-containing halogenated hydrocarbon include HCFC (hydrochlorofluorocarbon) type ones (for example, HCFC-123, HCFC).
-141b, HCFC-22 and HCFC-142
b); HFC (hydrofluorocarbon) type (for example, HFC-134a, HFC-152a, HF
C-356mff, HFC-236ea, HFC-24
5ca, HFC-245fa and HFC-365mf
c) etc. are mentioned. Of these, the preferred one is
HCFC-141b, HFC-134a, HFC-35
6mff, HFC-236ea, HFC-245ca,
HFC-245fa, HFC-365mfc and mixtures of two or more thereof. The amount of the hydrogen atom-containing halogenated hydrocarbon used is 100% of the active hydrogen component.
It is preferably 50 parts by mass or less, and more preferably 5 to 45 parts by mass per mass part.

The low boiling point hydrocarbon usually has a boiling point of -5 to 70.
It is a hydrocarbon at ° C, and specific examples thereof include butane, pentane, cyclopentane, and a mixture thereof. When a low boiling point hydrocarbon is used, the amount used is preferably 40 parts by mass or less, more preferably 5 to 30 parts by mass, per 100 parts by mass of the active hydrogen component. When using liquefied carbon dioxide, the amount of active hydrogen component is 10
It is preferably 30 parts by mass or less, more preferably 25 parts by mass or less, per 0 parts by mass.

As the catalyst in the production method of the present invention, usually, two kinds of catalysts, a urethanization catalyst and a polymerization catalyst, are used. As the urethanization catalyst, all usual catalysts that accelerate the urethanization reaction can be used, and examples thereof include triethylenediamine, bis (N, N-dimethylamino-2-ethyl) ether, N, N, N ′, N ′. And tertiary amines such as tetramethylhexamethylenediamine and carboxylic acid salts thereof; carboxylic acid metal salts such as potassium acetate, potassium octylate and stannas octoate; organometallic compounds such as dibutyltin dilaurate. The amount of the urethanization catalyst used is preferably 0.01 to 5 parts by mass, more preferably 0.2 to 2 parts by mass based on 100 parts by mass of the active hydrogen component.
Parts by mass.

As the polymerization catalyst, a polymerization initiator usually used as an initiator for radical polymerization can be used. Examples thereof include 2,2'-azobisisobutyronitrile and 2,2'-azobis (2,4-dimethyl). Valeronitrile), 2,2 '
-Azobis (2-methylbutyronitrile), 1,1'-
Azobis (cyclohexane-1-carbonitrile),
2,2'-azobis (2,4,4-trimethylpentane), dimethyl 2,2'-azobis (2-methylpropionate), 2,2'-azobis [2- (hydroxymethyl) propionitrile] And 1,1′-azobis (1
-Acetoxy-1-phenylethane) and other azo compounds;
Dibenzoyl peroxide, dicumyl peroxide, t-butyl hydroperoxide, bis (4-t
-Butylcyclohexyl) peroxydicarbonate,
Examples thereof include organic peroxides such as benzoyl peroxide, lauroyl peroxide and persuccinic acid; inorganic peroxides such as persulfate salts and perborate salts; and the like. In addition, these can use 2 or more types together. The amount of the polymerization catalyst used is preferably 0. 0, based on 100 parts by mass of the active hydrogen component.
The amount is 01 to 10 parts by mass, more preferably 0.1 to 2 parts by mass.

As the foam stabilizer in the production method of the present invention, all those used in the production of ordinary polyurethane foams can be used. For example, a dimethylsiloxane foam stabilizer [eg, manufactured by Toray Dow Corning Silicone Co., Ltd. "SRX-253" and the like], a polyether-modified dimethylsiloxane-based foam stabilizer [for example, "L-5309", "SZ-1311", and "L-360 manufactured by Nippon Unicar Co., Ltd.].
1 "," S "manufactured by Toray Dow Corning Silicone Co., Ltd.
F-2969 "," SRX-274C ", etc.] and the like. The amount of the foam stabilizer used is preferably 0.5 to 3 parts by mass, and more preferably 1 to 2 parts by mass with respect to 100 parts by mass of the active hydrogen component.

In the production method of the present invention, if necessary, other additives as described below are further used,
You may make it react in the presence. For example, colorants (dye, pigment), flame retardants (phosphoric acid esters, halogenated phosphoric acid esters, etc.), antiaging agents (triazole-based,
The reaction can be carried out in the presence of a known auxiliary component such as a benzophenone type) and an antioxidant (hindered phenol type, hindered amine type, etc.). Active hydrogen component 1
With respect to the amount of these auxiliary components used relative to 00 parts by weight, the colorant is preferably 1 part by weight or less. The flame retardant is preferably 5 parts by mass or less, more preferably 2 parts by mass or less. The amount of the antioxidant is preferably 1 part by mass or less, more preferably 0.5 part by mass or less. The antioxidant is preferably 1 part by mass or less, and more preferably 0.
It is from 01 to 0.5 parts by mass.

In the production method of the present invention, the isocyanate index (index) [(equivalent ratio of NCO group / active hydrogen atom-containing group) in the production of polyurethane foam]
X100] is preferably 70 to 125, more preferably 75 to 120, and particularly preferably 80 to 115.

An example of the method for producing a polyurethane foam according to the method of the present invention is shown below, but the method is not limited to this method. First, an active hydrogen component, a foaming agent, a catalyst, a foam stabilizer and, if necessary, other additives are mixed in predetermined amounts. Then, using a polyurethane foaming machine or a stirrer, this mixture is rapidly mixed with the organic polyisocyanate (preferably each liquid temperature is 20 to 30 ° C.). The obtained mixed liquid is 40 to 80 ° C. (especially 55
~ 70 ℃) in a closed mold at atmospheric pressure, pack rate 1
It is injected at a rate of 05-115%, and is injected for a predetermined time (for example, 3-15
Min) and then demolding to obtain a flexible polyurethane foam.

According to the method of the present invention, it is possible to obtain a polyurethane foam in which the viscosity of the active hydrogen component used in the reaction and the foam hardness of the obtained foam satisfy the relation of the above formula [2], especially [2 ']. it can. The total density of the obtained foam is preferably 30 to 65 kg / m ³ , and more preferably 35 to 60 kg / m ³ . The hardness of the foam (25% ILD) is preferably 10 to 45.
kgf / 314 cm ² , more preferably 15-40 k
It is gf / 314 cm ² . According to the method for producing a flexible polyurethane foam of the present invention using the active hydrogen component of the present invention, a flexible polyurethane foam having good moldability and high hardness can be obtained as compared with the conventional method.
Therefore, the flexible polyurethane foam obtained by the present invention is suitably used, for example, as a cushion material, particularly as a cushion for a vehicle seat (particularly an automobile).

[0053]

The present invention will be further described below with reference to examples, but the present invention is not limited thereto. In the examples and comparative examples, parts and% are parts by mass and% by mass, respectively, unless otherwise specified.
Indicates.

Raw materials for polyurethane foam in Examples and Comparative Examples are as follows. (1) Polyol a11-1: PO-EO-PO-EO block adduct of pentaerythritol, hydroxyl value 2
8. Content of terminal oxyethylene unit (hereinafter referred to as EO unit) = 14%, content of internal EO unit = 2%. (2) Polyol a11-2: PO / EO of glycerin
・ PO / EO block adduct, hydroxyl value 28, terminal EO
Unit content = 14%, internal EO unit content = 2%. (3) Polyol a11-3: PO / EO of glycerin
Block addition product, hydroxyl value 28, content of terminal EO unit = 16%, content of internal EO unit = 0%. (4) Polyol a12-1: Diethanolamine (hydroxyl value 1070). (5) Polyol a12-2: glycerin EO adduct, hydroxyl value 280. (6) Polyol a12-3: PO adduct of sorbitol, hydroxyl value 449. (7) Polyol a12-4: EO adduct of glycerin, hydroxyl value 842. (8) Polyol a12-5: sorbitol EO adduct, hydroxyl value 1250.

(9) Addition-polymerizable active hydrogen compound a2-
1: Monoacrylate of diethylene glycol (hydroxyl value 351). (10) Addition-polymerizable active hydrogen compound a2-2: diacrylate of sorbitol (hydroxyl value 774). (11) Polymer polyol A1: polyol a11-1
Among them, styrene and acrylonitrile were copolymerized with styrene / acrylonitrile = 30/70 (mass ratio) (polymer content 30%). (12) Polymer polyol A2: polyol a11-2
Polymerized acrylonitrile in (polymer content 2
0%).

(13) Urethane-forming catalyst A: 70% dipropylene glycol solution of bis (dimethylaminoethyl) ether [TOYOCAT ET manufactured by Tosoh Corporation] (14) Urethane-forming catalyst B: Ethylene glycol solution of triethylenediamine [Sankyo] TEDA manufactured by Airpro Co., Ltd.
-L33] (15) Polymerization catalyst C: t-butyl hydroperoxide ("Perbutyl H-69" manufactured by NOF CORPORATION) (16) Foaming agent A "SZ-13 manufactured by Nippon Unicar Co., Ltd."
11 "(17) Foaming agent B" L-360 "manufactured by Nippon Unicar Co., Ltd.
1 ”(18) Isocyanate A: TDI-80 (ratio of 2,4- and 2,6-TDI, 2,4-form is 80%) / crude MDI (average number of functional groups: 2.9) = 80/20 (Mass ratio) (NCO% 44.6%)

Examples 1 and 2 and Comparative Examples 3 to 5 To the active hydrogen components shown in Table 1, a predetermined amount of isocyanate A was added so that the NCO index was 105, and the mixture was stirred with a homodisper (agitator manufactured by Tokushu Kika Co., Ltd.). After stirring at 4000 rpm for 10 seconds, the temperature was adjusted to 65 ° C. 300 mm (length) × 30
It was poured into an aluminum mold of 0 mm (width) × 100 mm (height), and was molded at a curing time of 7 minutes. Table 1 shows the measurement results of the physical property values of each foam. The viscosity of the active hydrogen component is according to JIS K-1557 (1970). The evaluation of the moldability was made as follows: the foam had no stickiness and the appearance was good, and the foam had stickiness. Other measurement methods were based on JIS K 6400 (1997). The total density is the apparent density of the entire molded foam, and the core density is 50 m from the center of the foam.
It is the density measured by cutting into a size of m × 50 mm × 30 mm.

[0058]

[Table 1]

From the above results, Examples 1 and 2 obtained by the method of the present invention were compared when foams of similar density were compared.
It can be seen that the foam No. 1 has better moldability and higher hardness than the foams of Comparative Examples 3 to 5.

[0060]

EFFECTS OF THE INVENTION According to the method for producing a flexible polyurethane foam of the present invention using the active hydrogen component of the present invention, it is possible to obtain a flexible polyurethane foam having good moldability and high hardness as compared with the conventional method. it can. Because of the above effects, the polyurethane foam obtained by the present invention is useful as a cushion material. In particular, it is extremely useful as a cushion for vehicle seats.

Continued front page    F-term (reference) 4J034 BA08 BA09 CA03 CA11 CA21                       CA31 CB02 CB07 CB08 CC01                       CC12 CC30 CC35 CC45 CC52                       CC61 CC62 CC65 DA01 DA03                       DA05 DA07 DB03 DB07 DB08                       DC02 DC17 DC23 DC35 DC37                       DC42 DC43 DF01 DF14 DF29                       DF32 DF33 DG02 DG03 DG04                       DG08 DG09 DG10 DG12 DG14                       DG15 DG16 DG23 DH02 DH06                       FA02 FA04 FB01 FB03 FB04                       FB06 FC01 FC02 FD01 FD02                       FD03 FD07 FD09 FE01 FE02                       GA54 GA74 HA01 HA06 HC01                       HC12 HC13 HC17 HC22 HC46                       HC52 HC54 HC61 HC64 HC67                       HC71 KA01 KC17 KD12 MA22                       NA01 NA02 NA03 NA08 QC01                       RA12 SA02 SB03 SB04 SB05                       SC01 SC04 SD02 SD03 SD07                       SD08

Claims (7)

[Claims] 1. An active hydrogen component for producing a one-shot flexible polyurethane foam, which has a viscosity satisfying the relationship of the following formula [1]. y ₀ ≧ 0.000005x ₀ ² +10 [1] x ₀ : viscosity of the active hydrogen component used (JIS K-155
According to 7. (Unit: mPa · s, measurement temperature: 25 ° C.) y ₀ : hardness of a molding foam having a core density of 42 kg / m ³ obtained by the following foaming formulation [25% IL
D] (according to JIS K-6400. Compressive stress when compressing 25% of 10 cm-thick flexible polyurethane foam, unit: kgf / 314 cm ² ) [Foaming formulation] Organic polyisocyanate: TDI-80 /
Crude MDI (average number of functional groups: 2.9) = 80/20 (mass ratio), isocyanate index: 105, raw material liquid temperature: 25
° C, water (foaming agent): 3.3 parts by mass per 100 parts by mass of active hydrogen component, 300 mm x 300 mm x 10 at 65 ° C
Inject into a 0 mm mold. 2. A polymer polyol (A) obtained by polymerizing a vinyl monomer (b) in the polyol (a1).
And an other active hydrogen compound (B), the following addition-polymerizable active hydrogen compound (a
An active hydrogen component for producing a one-shot flexible polyurethane foam containing 2) and containing the following polyols (a11) and (a12) in (a1) and / or (B). Addition-polymerizable active hydrogen compound (a2): a compound having an active hydrogen-containing group and an addition-polymerizable functional group in the molecule and having an active hydrogen-containing group value of 100 to 1000 (mgKOH / g). Polyol (a11): The average number of functional groups is 2.5 to 4, the hydroxyl value is 20 to 40 (mgKOH / g),
The content of terminal oxyethylene units is 10 to 25% by mass, and the content of internal oxyethylene units is 0 to 5% by mass.
And the total content of oxyethylene units is 10 to 30
Polyoxyethylene polyoxypropylene polyol which is mass%. Polyol (a12): the average number of functional groups is 2 to 8,
A (polyoxyalkylene) polyol having an alkylene group having a hydroxyl value of 200 to 1850 (mgKOH / g) and having 2 and / or 3 carbon atoms. 3. The active hydrogen component according to claim 2, wherein (a2) is a compound having a terminal olefin type group represented by the following general formula (1). _{R | CH 2 = C- (1} ) [ wherein R represents hydrogen, an alkyl group or an aryl group having a carbon number of 6 to 21 from 1 to 15 carbon atoms. ] 4. The content of (a2) is 1 to 8% by mass,
The content of the polymer (b) is 5 to 20% by mass.
Or the active hydrogen component described in 3. 5. A method for producing a flexible polyurethane foam from an active hydrogen component, a polyisocyanate component, a foaming agent, a catalyst and a foam stabilizer, wherein the active hydrogen component according to any one of claims 1 to 4 is used. One-shot flexible polyurethane foam manufacturing method. 6. An active hydrogen component and a polyisocyanate component are reacted by a one-shot method in the presence of a foaming agent, a catalyst and a foam stabilizer to adjust the hardness of the foam satisfying the relationship of the following formula [2]. A method for producing a foam, which comprises producing a flexible polyurethane foam having the same. y ≧ 0.000005x ² +10 [2] x: viscosity of active hydrogen component used (JIS K-1557)
by. Unit: mPa · s, measurement temperature: 25 ° C. y: hardness of foam [25% ILD] (JIS K-6
According to 400. Compressive stress when compressing 25% of 10 cm-thick flexible polyurethane foam, unit: kgf / 31
4 cm ² ) 7. A vehicle cushion made of a flexible polyurethane foam obtained by the method according to claim 5.