JP2000297131A - Highly durable flexible polyurethane cold-cure molded foam and preparation thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a low-density flexible polyurethane cold cure molded foam which shows an excellent durability, especially the hardness change in repetitive compression test and the thickness change properties such as wet hot compression set, and a preparation process thereof. SOLUTION: This highly durable flexible polyurethane cold cure molded foam has a total density of from 35 to 45 kg/m3 and a wet hot compression set of 15% or smaller. Preferably, the hardness change in repetitive compression test is 15% or smaller. In a preparation process of the cold cure molded foam, the foam is obtained from a polymer and/or polymer polyol, water, a catalyst and a polyisocyanate, wherein the polymer polyol is obtained by dispersing in a polyol a polymer fine particle obtained by radical polymerizing a compound having an unsaturated bond in a polyol. Here, the polyol is prepared by using a catalyst containing either a compound having at least a nitrogen-phosphorus double bond, cesium hydroxide or rubidium hydroxide.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flexible polyurethane cold cure mold foam and a method for producing the same.
More specifically, a flexible polyurethane cold-cure mold foam suitable for use in vehicle interior materials, furniture cushion materials, bedding, sundries, etc., which is lightweight and has improved durability represented by wet heat compression set, and a method for producing the same. About.

[0002]

BACKGROUND OF THE INVENTION Flexible polyurethane cold-cured foam (hereinafter sometimes abbreviated as flexible foam) is used for vehicles, furniture, and the like due to its cushioning property.
Widely used for bedding, sundries, etc. This flexible foam is a polyol, or a polymer polyol in which polymer particles obtained by radical polymerization of acrylonitrile or styrene in the polyol are dispersed in the polyol, water as a foaming agent, and a silicone-based surfactant,
It is produced by mixing a catalyst such as an amine or a tin compound, if necessary, a crosslinking agent or the like, an additive such as a flame retardant or a pigment, and an aromatic polyisocyanate.

Water as a foaming agent functions as a foaming agent by a reaction in which aromatic polyisocyanate and water react with each other and desorbed carbon dioxide gas becomes a foaming gas, and at the same time, generates an aromatic polyurea. In recent years, CFC-11 (CCl ₃ F) has been approved by the Montreal Convention to protect the global environment.
Can no longer be used, and the amount of water used in the formulation is increased in proportion to the foaming effect of the foaming aid (physical foaming agent).

[0004] In recent years, there has been a strong demand for cost reduction of flexible foams, and there has been a demand for a reduction in density for weight reduction. In addition, for flexible foams for vehicles, a reduction in density for weight reduction in accordance with fuel efficiency regulations has also been required. Requested. In order to meet such a demand for low density, the amount of water used as a foaming agent is
There is a tendency to further increase.

[0005] However, increasing the amount of water is effective in reducing the density of the flexible foam because the amount of generated carbon dioxide gas is increased. However, when the aromatic polyurea formed increases, the compression of the flexible foam becomes permanent. It becomes difficult to maintain durability characteristics such as distortion characteristics. Further, the decrease in the density of the flexible foam itself causes deterioration of durability characteristics such as compression set characteristics of the flexible foam.

As described above, the deterioration of the compression set characteristic of the flexible foam means that the shape stability of the flexible foam is poor, which causes various problems. For example, the thickness of the bed cushion decreases with use, and the thickness and hardness of the vehicle cushion change with use.
Especially for vehicle cushions, etc., by driving for a long time,
The cushion thickness and hardness at the time of the initial design decrease, the driver's fixed position lowers, and the sitting comfort and riding comfort deteriorate. These problems are durability problems of the flexible foam, and can be evaluated by a change in hardness in a repeated compression test or a permanent set under wet heat compression.

Therefore, it is lightweight and has a small rate of change in hardness in a wet heat compression set and a repeated compression test.
That is, the appearance of a flexible polyurethane cold cure mold foam having excellent durability has been desired.

Accordingly, the present inventors have conducted various studies and found a flexible polyurethane cold-cure mold foam having excellent durability even at a low density, and completed the invention. Further, in the production of the flexible foam, polymer fine particles (vinyl polymer fine particles) obtained by radical polymerization of a polyol and / or a compound having an unsaturated bond such as acrylonitrile or styrene in the polyol to be used are dispersed in the polyol. In a polymer polyol, at least a compound having a nitrogen-phosphorus double bond, by using a polyol containing a polyol synthesized using a catalyst containing one of cesium hydroxide or rubidium hydroxide, durability Found that flexible foams with excellent properties can be produced efficiently,
The present invention has been completed.

[0009]

SUMMARY OF THE INVENTION The object of the present invention is to solve the problems associated with the prior art described above, and is excellent in durability, in particular, the rate of change in hardness in a repeated compression test and the change in thickness in wet heat compression set. It is another object of the present invention to provide a lower-density flexible polyurethane cold-cure mold foam and a method for producing the same.

In the method for producing a flexible polyurethane cold-cured mold foam according to the present invention, a highly durable flexible polyurethane cold-cured molded foam is economically produced by using a resin premix excellent in moldability and the like in the flexible foam production process. The purpose of the present invention is to provide a method that can be manufactured.

[0011]

SUMMARY OF THE INVENTION A flexible polyurethane cold-cured foam according to the present invention has a total density of 35 kg / m ³ or more and 45 kg / m ³ or less, and a wet heat compression set of 15 kg / m ³ or less.
% Or less.

The flexible polyurethane cold-cured mold foam according to the present invention preferably has a hardness change rate of not more than 15% in a repeated compression test. As described above, the flexible polyurethane cold-cure mold foam according to the present invention specifically includes, in the polyol, polymer fine particles obtained by radical polymerization of a polyol and / or a compound having an unsaturated bond in the polyol. A soft polyurethane cold-cure mold foam obtained from a dispersed polymer polyol, water, a catalyst, a polyisocyanate, and, if necessary, a crosslinking agent and / or a foam stabilizer, wherein the polyol is (1) ) Hydroxy value is more than 15mgKOH / g, 25mgK
A polyoxyalkylene polyol having an OH / g or less and a total degree of unsaturation of 0.060 meq / g or less, (2) a hydroxyl value of 2
A polyoxyalkylene polyol having a total unsaturation of not more than 5 mgKOH / g and not more than 35 mgKOH / g and not more than 0.050 meq / g, and (3) having a hydroxyl group of 35 mgKOH / g
Over 45 mgKOH / g and a total unsaturation of 0.0
Any polyoxyalkylene polyol selected from the group consisting of polyoxyalkylene polyols of 40 meq / g or less is preferably used.

The polyol is preferably a polyol synthesized using a catalyst containing at least one of a compound having a nitrogen-phosphorus double bond and one of cesium hydroxide and rubidium hydroxide.

[0014] The viscosity of the resin premix containing the polyol and / or polymer polyol, water, catalyst and, if necessary, a crosslinking agent and / or a foam stabilizer may be 2500 mPa · s or less. preferable.

The polyisocyanate includes toluylene diisocyanate, toluylene diisocyanate, and a compound represented by the general formula (1):

[0016]

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A mixture containing a polymethylene polyphenyl polyisocyanate represented by the formula (where n = 0 or an integer of 1 or more) in a weight ratio of 98: 2 to 50:50 is preferred. The compound having a nitrogen-phosphorus double bond is preferably a phosphazenium compound or a phosphine oxide compound.

The method for producing a flexible polyurethane cold-cure mold foam according to the present invention is directed to a polymer in which polymer fine particles obtained by radical polymerization of a polyol and / or a compound having an unsaturated bond in the polyol are dispersed in the polyol. A method for producing a flexible polyurethane cold-cure mold foam obtained from a polyol, water, a catalyst, a polyisocyanate and, if necessary, a crosslinking agent and / or a foam stabilizer, wherein the polyol is (1) Hydroxyl value is 15mgKOH / g or more,
25 mgKOH / g or less, total unsaturation is 0.060 meq
/ G or less, a polyoxyalkylene polyol having a hydroxyl value of more than 25 mgKOH / g, 35 mgKOH / g or less, and a total unsaturation of 0.050 meq / g or less, and (3) a hydroxyl group. 35m
It is any polyoxyalkylene polyol selected from the group consisting of polyoxyalkylene polyols having a gKOH / g of not more than 45 mgKOH / g and a total degree of unsaturation of not more than 0.040 meq / g.

According to this method, the total density is 35 kg / m ^3.
45 kg / m ³ or less, and a wet heat compression set of 1
A flexible polyurethane cold-cured mold foam of 5% or less, and a total density of 35 kg / m ³ or more 4
A flexible polyurethane cold-cured foam having a compression set of 5 kg / m ³ or less, a permanent set of wet heat compression of 15% or less, and a rate of change in hardness in a repeated compression test of 15% or less is obtained.

The polyol is preferably synthesized using a compound containing at least a compound having a nitrogen-phosphorus double bond and one of cesium hydroxide and rubidium hydroxide.

The viscosity of the resin premix containing the above-mentioned polyol and / or polymer polyol, water, a catalyst and, if necessary, a crosslinking agent and / or a foam stabilizer is preferably 2500 mPa · s or less. .

As the polyisocyanate, toluylene diisocyanate, tolylene diisocyanate, and polymethylene polyphenyl polyisocyanate represented by the general formula (1) can be used in a ratio of 98: 2 to 50: 5.
Mixtures containing a weight ratio of 0 are preferred.

The compound having a nitrogen-phosphorus double bond is preferably a phosphazenium compound or a phosphine oxide compound. ADVANTAGE OF THE INVENTION According to this invention, the soft polyurethane cold cure mold foam which is lightweight, and has a small rate of change in hardness in wet heat compression set and a repeated compression test, ie, excellent durability, can be provided.

[0024]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the flexible polyurethane cold-cure mold foam according to the present invention and a method for producing the same will be specifically described.

Soft polyurethane cold cure mold
Form flexible polyurethane cold cure molded foam according to the present invention, the total density of 35 kg / m ³ or more 45 kg / m ³
Or less, and the wet heat compression set is 15% or less, and preferably, the total density is 35 kg / m ³ or more and 43 kg / m ³ or less,
In addition, the wet heat compression set is 15% or less and 8% or more.

The rate of change in hardness of the flexible polyurethane cold-cured mold foam of the present invention in a repeated compression test is preferably 15% or less.
% And more preferably 8% or more, and most preferably 12% or less and 8% or more.

Further, the elongation of the flexible polyurethane cold-cure mold foam according to the present invention is 50% or more and 5% or more.
00% or less, preferably 80% or more and 500% or less, more preferably 100% or more and 350% or less.

Soft polyurethane cold cure mold
The flexible polyurethane cold-cure mold foam according to the present invention as described above reacts a polyisocyanate, a foaming agent (water) and a catalyst with any of the following compounds (a) to (g) or a mixture. Manufactured by letting

In the present production, a foam stabilizer, a crosslinking agent, and other additives may be used alone or in combination of two or more, if necessary, as long as the object of the present invention is not impaired. At this time, a foam stabilizer, a crosslinking agent, and other additives may be added in advance to one or both of the following compounds (a) to (g) or the mixture and the polyisocyanate. It may be added in a mixer or a reactor for mixing the isocyanate, the blowing agent (water) and the catalyst with the compounds or mixtures of the following (a) to (g). (A) Polyol alone. (B) a mixture of a plurality of polyols (c) a polymer polyol alone (d) a mixture of a plurality of polymer polyols (e) a mixture of a polyol and a polymer polyol (f) a mixture of a plurality of polyols and a polymer polyol (g) A mixture of a polyol and a plurality of polymer polyols [polyol] In producing the flexible polyurethane cold-cured mold foam according to the present invention, examples of the polyol to be reacted with polyisocyanate include dihydric alcohols such as ethylene glycol and propylene glycol; 3 such as glycerin and trimethylolpropane
And polyhydric alcohols such as pentaerythritol and diglycerin; polyoxyalkylene polyols; and polyester polyols. Among them, it is preferable to use a polyoxyalkylene polyol or a polyester polyol, and it is more preferable to use a polyoxyalkylene polyol.

These polyols may be used alone or in combination of two or more. In the present invention, the hydroxyl value of the polyol is preferably 15 mg KOH
/ G or more and 45 mgKOH / g or less, more preferably 20 mgKOH / g or less.
It is not less than mgKOH / g and not more than 35 mgKOH / g.

In the present invention, when a polyoxyalkylene polyol is used as the polyol, the total amount of the structural units derived from ethylene oxide is 100% by weight based on the total amount of the structural units derived from the alkylene oxide constituting the polyoxyalkylene polyol. Content (ethylene oxide content) is 20 wt% or more, and
A polyoxyalkylene polyol having a hydroxyl value of 15 mgKOH / g or more and 100 mgKOH / g or less is blended at a ratio of 0.5 to 30 parts by weight based on 100 parts by weight of another polyoxyalkylene polyol having an ethylene oxide content of less than 20 wt%. Can be used.

(Polyoxyalkylene polyol) The polyoxyalkylene polyol preferably used in the present invention refers to an oligomer or a polymer obtained by subjecting an alkylene oxide to ring-opening polymerization, and usually in the presence of a catalyst.
It is obtained by subjecting an alkylene oxide to ring-opening polymerization using an active hydrogen compound as an initiator. The polyoxyalkylene polyol thus obtained may be used alone or in combination of two or more. Polyoxyalkylene polyols are sometimes referred to as "polyoxyalkylene polyether polyols."

In the production of the polyoxyalkylene polyol, the initiator and the alkylene oxide may be used alone or in combination. As the catalyst, a polyol synthesis catalyst containing at least one of a compound having a nitrogen-phosphorus double bond and one of cesium hydroxide and rubidium hydroxide is used.

The use of such a catalyst for synthesizing a polyol increases the molecular weight of the polyoxyalkylene polyol and increases the number of unsaturated groups at one end of the by-produced molecule, as compared with the case where a potassium hydroxide catalyst is used as the catalyst for synthesizing the polyol. And a polyoxyalkylene polyol having an extremely low monol content can be produced. Since the monol has a low molecular weight as compared with the polyoxyalkylene polyol produced by the main reaction, the monool may significantly broaden the molecular weight distribution of the polyoxyalkylene polyol and cause a decrease in the average number of functional groups. For this reason, the monool content in the polyoxyalkylene polyol is preferably smaller. The monol content in the polyoxyalkylene polyol is usually represented by the total degree of unsaturation, and a lower value indicates a lower monol content.

The polyoxyalkylene polyol used in the present invention includes (1) a hydroxyl value of 15 mgKOH /
g and 25 mgKOH / g or less, and the total unsaturation is 0.06
0 meq / g or less, preferably 0.040 meq / g or less, more preferably 0.025 meq / g or less, (2) a hydroxyl value of 25 m
It is more than gKOH / g, 35 mgKOH / g or less, and the total degree of unsaturation is 0.050 meq / g or less, preferably 0.030 mq / g or less.
eq / g or less, more preferably 0.020 meq / g
The following polyoxyalkylene polyol, or
(3) The hydroxyl group exceeds 35 mgKOH / g,
g and a total degree of unsaturation of 0.040 meq / g or less, preferably 0.020 meq / g or less, more preferably 0.015 meq / g or less.

These polyoxyalkylene polyols can be used alone or in combination of two or more. When a polyol synthesis catalyst containing at least one of a compound having a nitrogen-phosphorus double bond and one of cesium hydroxide and rubidium hydroxide is used in the production of a polyoxyalkylene polyol, the above-mentioned molecular terminal is not Since a polyoxyalkylene polyol having a low monool content having a saturated group or containing substantially no monool can be obtained,
It is preferable to produce a flexible polyurethane foam using the polyoxyalkylene polyol, since a flexible foam having excellent properties such as hysteresis, extensibility, and curing properties can be easily obtained.

It is needless to say that the above-mentioned monool or a polyoxyalkylene polyol containing a monool may be used without departing from the gist of the present invention.
Further, in the case of synthesizing a polyoxyalkylene polyol by ring-opening polymerization of propylene oxide, polymerization may be performed such that oxypropylene groups are bonded head-to-head, or head-to-tail. It is possible to polymerize. A high head-to-tail bond selectivity is preferred because the stability of the foamed foam is improved. Specifically, a polyoxypropylene polyol having a head-to-tail bond selectivity of 96% or more is preferable. Needless to say, the polyoxypropylene polyol may have a segment derived from an alkylene oxide other than propylene oxide such as ethylene oxide.

(For the production of polyoxyalkylene polyol
Catalyst) In the present invention, in producing the polyoxyalkylene polyol, a catalyst for producing a polyoxyalkylene polyol containing at least one of a compound having a nitrogen-phosphorus double bond and one of cesium hydroxide and rubidium hydroxide is used.

(Compound Having a Nitrogen-Phosphorus Double Bond) The compound having a nitrogen-phosphorus double bond as a catalyst for producing the polyoxyalkylene polyol used in the present invention is not particularly limited, but may be a phosphazenium compound or a phosphine compound. Oxide compounds are preferred.

<Phospazenium compound> The phosphazenium compound used in the present invention is represented by the general formula (2)

[0041]

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[In the formula, a, b and c are each 0 or a positive integer of 3 or less, but not all 0 at the same time. R is the same or different hydrocarbon group having 1 to 10 carbon atoms, and two Rs on the same nitrogen atom may combine with each other to form a ring structure. x represents the number of phosphazenium cations, and Z ^x- represents the x-valent anion of the active hydrogen compound. Or general formula (3)

[0043]

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[In the formula, d, e, f and g are each 0 or a positive integer of 3 or less, but not all 0 at the same time. R is the same or different and has 1 to 10 carbon atoms.
And two Rs on the same nitrogen atom may combine with each other to form a ring structure. x represents the number of phosphazenium cations, and Z ^x- represents the x-valent anion of the active hydrogen compound. Is a salt of a phosphazenium cation having the structure represented by the following formula: and an active hydrogen compound anion, and the phosphazenium cation is represented by an extreme structural formula whose charge is localized on a central phosphorus atom. In addition, innumerable limit structural formulas are drawn, and the charges are actually non-polarized as a whole.

In the general formula (2) representing a phosphazenium compound, a, b and c are each a positive integer of 0 or 3 or less. Preferably it is 0 or a positive integer of 2 or less. More preferably, irrespective of the order of a, b and c, in the combination of (2,1,1), (1,1,1), (0,1,1) or (0,0,1) Is the number of

In the general formula (3) representing a phosphazenium compound, d, e, f and g are each 0 or 3
It is the following positive integer: Preferably it is 0 or a positive integer of 2 or less. More preferably, regardless of the order of d, e, f and g, (2,1,1,1), (1,1,1,1),
(0,1,1,1), (0,0,1,1) or (0,0,0,1)
Is the number in the combination. More preferably,
It is a number in the combination of (1, 1, 1, 1), (0, 1, 1, 1), (0, 0, 1, 1) or (0, 0, 0, 1).

R in the general formula (2) or (3) representing the phosphazenium compound is the same or different and is an aliphatic or aromatic hydrocarbon group having 1 to 10 carbon atoms.

As such R, specifically, methyl, ethyl, n-propyl, isopropyl, allyl, n-butyl, sec-butyl, tert-butyl, 2-butenyl, 1-pentyl, 2-pentyl , 3-pentyl, 2-methyl-1-butyl,
Isopentyl, tert-pentyl, 3-methyl-2-butyl,
Neopentyl, n-hexyl, 4-methyl-2-pentyl, cyclopentyl, cyclohexyl, 1-heptyl, 3-heptyl, 1-octyl, 2-octyl, 2-ethyl-1-hexyl,
Aliphatic or aromatic carbons such as 1,1-dimethyl-3,3-dimethylbutyl (commonly called tert-octyl), nonyl, decyl, phenyl, 4-toluyl, benzyl, 1-phenylethyl or 2-phenylethyl Selected from hydrogen groups. Of these, methyl, ethyl, n-propyl, isoperopyr, te
rt-butyl, tert-pentyl or 1,1-dimethyl-3,3-
Aliphatic hydrocarbon groups such as dimethylbutyl are preferred.

Further, in the general formula (2) or (3), which represents a phosphazenium compound,
When two Rs combine with each other to form a ring structure, the divalent group (RR) on the nitrogen atom is a divalent hydrocarbon group having a main chain having 4 to 6 carbon atoms. (The ring is a 5- to 7-membered ring containing a nitrogen atom), for example, tetramethylene, pentamethylene, hexamethylene and the like, and those in which the main chain is substituted by an alkyl group such as methyl or ethyl are exemplified. Among them, tetramethylene or pentamethylene is preferable. In the phosphazenium cation, such a ring structure may be formed for all possible nitrogen atoms, or a ring structure may be formed for some nitrogen atoms.

X in the general formula (2) or (3) representing the phosphazenium compound is not uniform depending on the type of the active hydrogen compound, but is usually 1 to 8, preferably 1
It is.

<Phosphine oxide compound> The phosphine oxide compound used in the present invention has the general formula (4)

[0052]

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Wherein R ′ is the same or different and is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. x
Represents the amount of water molecules contained in a molar ratio, from 0 to 5.
0. ] The phosphine oxide compound represented by these.

R ′ in the general formula (4) representing a phosphine oxide compound is the same or different and is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. Specific examples of the hydrocarbon group having 1 to 10 carbon atoms for R ′ include methyl, ethyl, n-propyl, isopropyl, allyl, n-butyl, sec-butyl, tert-butyl, 2-butenyl, -Pentyl, 2-pentyl, 3-pentyl, 2-methyl-1-butyl,
Isopentyl, tert-pentyl, 3-methyl-2-butyl,
Neopentyl, n-hexyl, 4-methyl-2-pentyl, cyclopentyl, cyclohexyl, 1-heptyl, 3-heptyl, 1-octyl, 2-octyl, 2-ethyl-1-hexyl,
Aliphatic or aromatic carbons such as 1,1-dimethyl-3,3-dimethylbutyl (commonly called tert-octyl), nonyl, decyl, phenyl, 4-toluyl, benzyl, 1-phenylethyl or 2-phenylethyl Selected from hydrogen groups. Of these, methyl, ethyl, n-propyl, isopropyl, te
rt-butyl, tert-pentyl or 1,1-dimethyl-3,3-
An aliphatic hydrocarbon group having 1 to 8 carbon atoms such as dimethylbutyl is preferable, and a methyl group or an ethyl group is more preferable.

The phosphine oxide compound represented by the above general formula (4) can be obtained from N. Koidan (G.N.K.
oidan) et al., Journal of General Chemistry of the USS (USS)
R), vol. 55, p. 1453, 1985 or a similar method.

Usually, the phosphine oxide compound represented by the above general formula (4) has a hygroscopic property, and easily becomes a hydrate or a hydrate thereof. X representing the amount of water molecules contained is 0 to 5.0, preferably 0 to 2.0, in a molar ratio to the phosphine oxide.
It is. The amount of water is at most about several times the amount of the catalyst, and even if hydrolysis of the reaction raw material and the oxyalkylene derivative occurs due to the amount of water, the amount is extremely small and does not inhibit the object of the present invention. .

(For the production of polyoxyalkylene polyol
Active hydrogen compound) Examples of the active hydrogen compound used as an initiator in the production of a polyoxyalkylene polyol include an active hydrogen compound having an active hydrogen atom on an oxygen atom and an active hydrogen compound having an active hydrogen atom on a nitrogen atom. Can be

Specific examples of the active hydrogen compound having an active hydrogen atom on the oxygen atom include water; formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, lauric acid, stearic acid, oleic acid, phenylacetic acid, dihydrocinnamate Acid or cyclohexanecarboxylic acid, benzoic acid, p-methylbenzoic acid or 2-carboxynaphthalene such as 1 to 1 carbon atoms
20 carboxylic acids; carbon such as oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, adipic acid, itaconic acid, butanetetracarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid or pyromellitic acid Polyvalent carboxylic acids having 2 to 6 carboxyl groups having 2 to 20 atoms; n, n-diethylcarbamic acid, n-carboxypyrrolidone, n-carboxyaniline or n, n'-dicarboxy-2,4 -Carbamic acids such as toluenediamine;
Methanol, ethanol, n-propanol, isopropanol, n-butyl alcohol, sec-butyl alcohol,
tert-butyl alcohol, isopentyl alcohol, te
rt-pentyl alcohol, n-octyl alcohol, lauryl alcohol, cetyl alcohol, cyclopentanol, cyclohexanol, allyl alcohol, crotyl alcohol, methyl vinyl carbinol, benzyl alcohol, 1-phenylethyl alcohol, triphenyl carbinol or cinna C1-C20 alcohols such as mill alcohol; ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,6 -Hexanediol, 1,4-
2 to 20 carbon atoms such as cyclohexanediol, trimethylolpropane, glycerin, diglycerin, pentaerythritol or dipentaerythritol;
Polyhydric alcohols having -8 hydroxyl groups; sugars such as glucose, sorbitol, dextrose, fructose or sucrose or derivatives thereof; phenol, 2-naphthol, 2,6-dihydroxynaphthalene or bisphenol A or the like having 6 carbon atoms Aromatic compounds having 1 to 3 hydroxyl groups, such as polyethylene oxide, polypropylene oxide or copolymers thereof, having 2 to 8 terminals and having 1 to 8
And polyalkylene oxides having two hydroxyl groups.

Specific examples of the active hydrogen compound having an active hydrogen atom on the nitrogen atom include methylamine, ethylamine, n-propylamine, isopropylamine, n-
Butylamine, isobutylamine, sec-butylamine,
aliphatic or aromatic primary amines having 1 to 20 carbon atoms such as tert-butylamine, cyclohexylamine, benzylamine, β-phenylethylamine, aniline, o-toluidine, m-toluidine or p-toluidine; dimethylamine, methyl Ethylamine, diethylamine, di-n
-Propylamine, ethyl-n-butylamine, methyl-s
aliphatic or aromatic secondary amines having 2 to 20 carbon atoms such as ec-butylamine, dipentylamine, dicyclohexylamine, n-methylaniline or diphenylamine; ethylenediamine, di (2-aminoethyl) amine,
Carbon atoms such as hexamethylenediamine, 4,4'-diaminodiphenylmethane, tri (2-aminoethyl) amine, n, n'-dimethylethylenediamine, n, n'-diethylethylenediamine or di (2-methylaminoethyl) amine Polyvalent amines having 2 to 3 primary or secondary amino groups of 2 to 20; saturated with 4 to 20 carbon atoms such as pyrrolidine, piperidine, morpholine or 1,2,3,4-tetrahydroquinoline Cyclic secondary amines; unsaturated cyclic secondary amines having 4 to 20 carbon atoms such as 3-pyrroline, pyrrole, indole, carbazole, imidazole, pyrazole or purine; piperazine, pyrazine or 1,4,7-triaza Cyclic polyamines having 2 to 3 secondary amino groups having 4 to 20 carbon atoms, such as cyclononane; acetamide, propionamide, n-methyl Propionamide, n-
Unsubstituted or n-monosubstituted acid amides having 2 to 20 carbon atoms, such as methylbenzoic acid amide or n-ethylstearic acid amide; 5- to 7-membered cyclic amides such as 2-pyrrolidone or ε-caprolactam Imides of dicarboxylic acids having 4 to 10 carbon atoms, such as succinimide, maleic imide or phthalimide.

Among these active hydrogen compounds, preferred active hydrogen compounds are water; methanol, ethanol, n-propanol, isopropanol, n-butyl alcohol,
sec-butyl alcohol, tert-butyl alcohol, isopentyl alcohol, tert-pentyl alcohol, n-octyl alcohol, lauryl alcohol, cetyl alcohol, cyclopentanol, cyclohexanol, allyl alcohol, crotyl alcohol, methylvinylcarbinol, benzyl Alcohols having 1 to 20 carbon atoms such as alcohol, 1-phenylethyl alcohol, triphenylcarbinol or cinnamyl alcohol; ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,3-propanediol, 1,3 -Butanediol, 1,4-butanediol, 1,6-
Polyhydric alcohols having 2 to 8 hydroxyl groups having 2 to 20 carbon atoms, such as hexanediol, 1,4-cyclohexanediol, trimethylolpropane, glycerin, diglycerin, pentaerythritol or dipentaerythritol; glucose, Saccharides or derivatives thereof such as sorbitol, dextrose, fructose or sucrose; polyethylene oxide, polypropylene oxide or copolymers thereof, having 2 to 8 terminals and having 1 to 8 hydroxyl groups at the terminals Polyalkylene oxides having a molecular weight of 100 to 50,000;
Ethylenediamine, di (2-aminoethyl) amine, hexamethylenediamine, 4,4'-diaminodiphenylmethane, tri (2-aminoethyl) amine, n, n'-dimethylethylenediamine, n, n'-diethylethylenediamine or di ( 2 carbon atoms such as 2-methylaminoethyl) amine
Polyamines having from 2 to 3 primary or secondary amino groups, such as pyrrolidine, piperidine, morpholine or 1,2,3,4-tetrahydroquinoline;
Saturated cyclic secondary amines having a carbon number of 4 to 20, such as piperazine, pyrazine or 1,4,7-triazacyclononane;
20 cyclic polyamines containing two or three secondary amino groups.

More preferred active hydrogen compounds are water; methanol, ethanol, n-propanol, isopropanol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol.
-Butyl alcohol, isopentyl alcohol, tert-
Alcohols having 1 to 10 carbon atoms such as pentyl alcohol or n-octyl alcohol; carbon atoms such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, trimethylolpropane, glycerin or pentaerythritol Polyhydric alcohols having 2 to 4 hydroxyl groups of 2 to 10, such as polyethylene oxide, polypropylene oxide or copolymers thereof, having 2 to 6 terminals and 2 to 6 terminals at the terminals Hydroxyl-containing polyalkylene oxides having a molecular weight of 100 to 10,000; n, n'-dimethylethylenediamine, n, n '
-Polyvalent amines having 2 to 3 carbon atoms and having 2 to 3 secondary amino groups such as diethylethylenediamine or di (2-methylaminoethyl) amine; pyrrolidine, piperidine, morpholine or 1,2,3 Saturated cyclic secondary amines having 4 to 10 carbon atoms such as 1,4-tetrahydroquinoline; 2 to 3 carbon atoms having 4 to 10 carbon atoms such as piperazine, pyrazine or 1,4,7-triazacyclononane; Cyclic polyamines containing secondary amino groups.

(Alkylene Oxide Compound) Specific examples of the alkylene oxide compound used for producing the polyoxyalkylene polyol used in the present invention include ethylene oxide, propylene oxide, 1,2-
Butylene oxide, 2,3-butylene oxide, styrene oxide, cyclohexene oxide, epichlorohydrin, epibromohydrin, methyl glycidyl ether,
Epoxy compounds such as allyl glycidyl ether and phenyl glycidyl ether are exemplified. Among these alkylene oxide compounds, ethylene oxide, propylene oxide, 1,2-butylene oxide and styrene oxide are preferred, and ethylene oxide and propylene oxide are more preferred.

These compounds may be used alone or in a combination of two or more. When these compounds are used in combination, a method in which a plurality of alkylene oxide compounds are used simultaneously, a method in which the compounds are used sequentially, or a method in which the steps are repeated repeatedly can be used. When used in combination, it is particularly preferable that the ratio of ethylene oxide in the alkylene oxide is 5 to 30% by weight.

[Polymer polyol] In the present invention,
Polymer polyol (hereinafter sometimes referred to as “polymer-dispersed polyol”) is a dispersion polymerization in a polyol using a radical initiator such as azobisisobutyronitrile on a compound having an unsaturated bond such as acrylonitrile or styrene. The vinyl polymer particles obtained by the
Simply referred to as “polymer fine particles”).

This vinyl polymer particle may be a vinyl polymer particle composed of a homopolymer of a compound having an unsaturated bond. In the present invention, at least a part of the compound having an unsaturated bond such as acrylonitrile during dispersion polymerization is used. It is preferable to graft onto a polyol which is a dispersion medium. Thus, in the present invention, the polyol may be used as a non-reaction solvent or as a reaction solvent.

The polyol used here may be any of the above-mentioned polyols, but it is more preferable to use a polyoxyalkylene polyol. In the polymer-dispersed polyol used in the present invention, the proportion of the polymer fine particles in the polyoxyalkylene polyol,
Usually, it is 2 to 50% by weight, preferably 10 to 40% by weight.

(Compound Having an Unsaturated Bond) The compound having an unsaturated bond is a compound having an unsaturated bond in a molecule, and examples thereof include acrylonitrile and styrene.

These compounds can be used alone or in combination of two or more. In the present invention, it is preferable to use a mixture of two or more compounds having an unsaturated bond.

In producing the polymer-dispersed polyol, a dispersion stabilizer, a chain transfer agent and the like may be used in addition to the compound having an unsaturated bond. [Blowing agent] Water can be used as a blowing agent in the present invention because water can foam a polyurethane resin by carbon dioxide gas generated by reacting with polyisocyanate.

The amount of water usually used is preferably 2 to 7 parts by weight, more preferably 2.5 parts by weight, based on 100 parts by weight of the total amount of the polyol and / or the polymer polyol.
６6 parts by weight.

Along with water, chlorofluorocarbons, hydroxychlorofluorocarbons (such as HCFC-134a), and hydrocarbons (such as cyclopentane, etc.) developed for the purpose of protecting the global environment, as long as the gist of the present invention is not impaired. ) And other foaming agents may be used in combination as foaming aids. Moreover, you may foam only with a foaming agent other than water.

[0072] As the [catalytic] catalyst used in the production of flexible polyurethane cold cure molded foam according to the present invention, conventionally known catalysts can be used is not particularly limited, for example triethylenediamine, bis (n,
aliphatic amines such as n-dimethylaminoethyl ether) and morpholines; and organic tin compounds such as tin octoate and dibutyltin dilaurate.

These catalysts can be used alone or in combination of two or more. The amount of the catalyst used is preferably 0.005 to 10 parts by weight based on 100 parts by weight of the total amount of the polyol and / or the polymer polyol.

[Other Additives] In the present invention, other additives such as a crosslinking agent and a foam stabilizer can be used as long as the object of the present invention is not impaired.

(Crosslinking Agent) In the present invention, a crosslinking agent may not be particularly used, but when used, a compound having a hydroxyl value of 200 to 1800 mgKOH / g is used.

For example, aliphatic polyhydric alcohols such as glycerin; alkanolamines such as diethanolamine and triethanolamine are used. Further, a polyoxyalkylene polyol having a hydroxyl value of 200 to 1800 mgKOH / g is used as a crosslinking agent, and a conventionally known crosslinking agent may be used in an amount of 0.5 to 0.5 parts by weight based on 100 parts by weight of the total amount of polyol and / or polymer polyol. 10
Any amount between parts by weight can be used.

(Foam stabilizer) As the foam stabilizer used as required in the present invention, a commonly used organosilicon surfactant can be used.

For example, SRX-274C, SF-2969, SF-2 manufactured by Dow Corning Toray Silicone Co., Ltd.
961, SF-2962 (above, trade names) and L-5309, L-3601, L-530 manufactured by Nippon Unicar Co., Ltd.
7, L-3600 and the like can be used.

The amount of the foam stabilizer used is based on 100 parts by weight of the total amount of the polyol and / or the polymer polyol.
0.2 to 3 parts by weight. (Resin premix) A mixture of the above-mentioned polyol and / or polymer polyol and, if necessary, a crosslinking agent, a surfactant, water and a catalyst is referred to as a “resin premix”.

Further, a flame retardant, a pigment, an ultraviolet absorber, an antioxidant, and the like can be added to the resin premix as needed. [Polyisocyanate] The polyisocyanate to be reacted with the resin premix is not particularly limited, but the conventionally known toluylene diisocyanate (the isomer ratio such as 2,4-form and 2,6-form is not particularly limited). However, those having a ratio of 2,4-form / 2,6-form of 80/20 are preferably used.)
Or tolylene diisocyanate and polymethylene polyphenyl polyisocyanate represented by the following general formula (1) (for example, Cosmonate M-20 manufactured by Mitsui Chemicals, Inc.)
0 (trade name) or the like is preferably used.

[0081]

Embedded image

In the general formula (1), n is 0 or an integer of 1 or more. The isomers of the component of n = 0 in the above formula (1) representing polymethylene polyphenyl polyisocyanate are 2,4′-form, 4,4′-form and 2,2′-form. Although the ratio of the isomers is not particularly limited, the 2,2'-form is usually a trace amount, and the 2,4'-form is less than 10%. The ratio of the component of n = 0 in the formula (1) is not particularly limited, but polymethylene polyphenyl polyisocyanate containing the component of n = 0 in an amount of less than 50% is generally used. I have.

When the polyisocyanate is a mixture of toluylene diisocyanate and polymethylene polyphenyl polyisocyanate, the mixing ratio is 98: 2 to 5 by weight.
A ratio of 0:50 is particularly suitable for the production of flexible polyurethane cold cured mold foam.

The polyisocyanate can be preferably used even if it is a composition comprising polymethylene polyphenyl polyisocyanate having different degrees of polymerization. A mixture of polyisocyanate which is such a polymethylene polyphenyl polyisocyanate composition or a urethane modified product thereof and toluylene diisocyanate can also be preferably used.

The amount of organic polyisocyanate containing isocyanate groups stoichiometrically equal to the total amount of functional groups that react with isocyanate groups, such as hydroxyl groups and amino groups, in the resin premix was determined using a soft polyurethane cold cure. When NCO index is defined as 1.00 when used in the manufacture of mold foam,
The index is preferably 0.70 or more and 1.40 or less.

[Soft Polyurethane Cold Cure Mall
Method for producing foam] The method for producing a flexible polyurethane foam is not particularly limited, but a method in which a resin premix and a polyisocyanate are usually mixed using a high-pressure foaming machine or a low-pressure foaming machine is used.

In the case of a low-pressure foaming machine, it is possible to mix more than two kinds of components, and it is also possible to divide and mix into polyol type, aqueous type, organotin catalyst type, flame retardant type, isocyanate type and the like. . The mixed liquid obtained by such mixing is discharged into a mold, foamed, filled, and cured to obtain a target having a uniform shape. The curing time is usually 30 seconds to 30 minutes, the mold temperature is from room temperature to about 80 ° C, and the curing temperature is from room temperature to 80 ° C. The production of the flexible polyurethane foam according to the present invention is performed under such curing conditions (usually called a cold cure method). After curing, the temperature may be up to 80 to 180 ° C. within a range that does not impair the objects and effects of the present invention.

The resin premix is usually mixed with the polyisocyanate in a high or low pressure foamer,
When using a compound showing hydrolyzability as a catalyst such as an organotin catalyst, it is preferable to separate the water component and the organotin catalyst component from each other in order to avoid contact with water, and to mix them with a mixing head of a foaming machine. .

The viscosity of the resin premix used is 2,500 from the viewpoint of the mixing property in a foaming machine and the foam moldability.
It is preferably at most mPa · s.

[0090]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

"Parts" and "%" in the examples represent "parts by weight" and "% by weight", respectively. In addition, the synthetic examples, the total density measured in the examples and the like, foam hardness, wet heat compression set, hardness change rate in repeated compression test,
Elongation, hydroxyl value, total unsaturation, and head-to-tail bond selectivity were measured according to the following methods.

(Measurement Method) (1) Total Density The total density was measured according to the method described in JIS K-6400. The total density refers to "apparent density" defined by JIS standards. In the present invention, the total density was measured using a rectangular foam sample having a skin skin. (2) Foam hardness The foam hardness (25% ILD) was measured by the method A described in JIS K-6400. A foam having a thickness of 94 to 100 mm was used as a sample. (3) Wet heat compression set The wet heat compression set was measured by the method of measuring the residual compression strain described in JIS K-6400. However,
When measuring, the core of the molded flexible foam was
A 50 × 25 mm cutout was used as a test piece. The test piece was compressed to a thickness of 50%, sandwiched between parallel flat plates, and allowed to stand at 50 ° C. and a relative humidity of 95% for 22 hours. After leaving for 22 hours, the test piece was taken out and 30 minutes later, its thickness was measured and compared with the thickness value before the test, the strain rate was measured, and this strain rate was defined as the wet heat compression permanent strain. In Tables 4 to 9, the wet heat compression set was represented by wet heat durability (Wet set [%]). (4) Hardness Change Rate in Repeated Compression Test The hardness change rate in the repeated compression test was measured by the measuring method (A method) of the residual compression residual strain described in JIS K-6400. At the time of measurement, the core portion of the molded flexible foam was cut out 100 × 100 × 50 mm and used as a test piece. The test piece was sandwiched between parallel flat plates, and was repeatedly compressed at room temperature at a rate of 60 times per minute and 50% of its thickness continuously for 80,000 times. Take out the test piece and 3
After 0 minutes, the hardness was measured and compared with the value of the hardness before the test, and the rate of change in hardness was measured. In Tables 4 to 9, this rate of change in hardness is represented by hardness loss [%].

Note that the 25% CLD change rate is used as the hardness change rate. The measurement of 25% CLD was performed under the following conditions using the same apparatus as that for 25% ILD. -At a compression speed of 50 mm / min, 7
Compress 5% (pre-compression). -Release the compression and let stand for 1 minute. -Compress 25% at a compression speed of 50 mm / min. -After holding for 20 seconds while compressing, read the resistance (this resistance is hardness / 25% CLD).・ Sample shape is 100 × 100 × 50mm as described
(50 mm thickness). (5) Elongation Tensile elongation was measured by the method described in JIS K-6400. (6) Hydroxyl value The hydroxyl value was measured by the method described in JIS K-1557. (7) Total Unsaturation The total unsaturation was measured by the method described in JIS K-1557. (8) Head-to-tail bond selectivity Using a 400 MHz, C ¹³ -nuclear magnetic resonance (NMR) device manufactured by JEOL Ltd., using heavy chloroform as a solvent, the C ^{13 of} this polyoxyalkylene polyol was -N
Take the MR spectrum and use the head-to-tail
Tail) The signal of the methyl group of the oxypropylene segment of the bond (16.9 to 17.4 ppm) and the head-to-head (H
ead-to-Head) from the ratio of the methyl group signal (17.7 to 18.5 ppm) of the oxypropylene segment of the head-
The to-tail bond selectivity was determined.

The assignment of each signal is based on the values described in the reports of Macromolecules, 19.1337-1343 (1986), F, Shi, Schering (FCSchiling), A, Y, Tonel (AETonelli). Performed on the basis of (Synthesis of polyoxyalkylene polyol)

[0095]

[Synthesis Example 1] (Synthesis of polyoxyalkylene polyol A) 0.01 mol of tetrakis [tris (dimethylamino) phosphoranylideneamino] phosphonium hydroxide is added to 1 mol of glycerin, and the mixture is added at 100 ° C for 6 hours. After dehydration under reduced pressure, propylene oxide was reacted at a reaction temperature of 80
C. and a maximum reaction pressure of 3.8 kg / cm ² , followed by addition polymerization of ethylene oxide at a reaction temperature of 100 ° C. to obtain a polyoxyalkylene polyol A having a hydroxyl value of 28 mgKOH / g.

The obtained polyoxyalkylene polyol A had a terminal oxyethylene group content of 15% by weight, a total unsaturation of 0.015 meq / g, and a head-to-tail bond selectivity of 96.7%.

[0097]

Synthesis Examples 2 to 4 (Synthesis of Polyoxyalkylene Polyols B, C and D) In Synthesis Example 1, the active hydrogen compound as an initiator and the hydroxyl value of the obtained polyoxyalkylene polyol are shown in Table 1. Except as described above, polyoxyalkylene polyols B, C, and D were synthesized in the same manner as in Synthesis Example 1.

Table 1 shows polyoxyalkylene polyol A
1 shows the structures and analytical values of D. In Table 1, glycerin was used as the active hydrogen compound for 3 hydroxyl groups and pentaerythritol for 4 hydroxyl groups as the active hydrogen compound.

[0099]

[Table 1]

[0100]

Synthesis Example 5 (Synthesis of polyoxyalkylene polyol E) Potassium hydroxide 0.37 per mole of glycerin
After dehydration under reduced pressure at 100 ° C. for 6 hours, propylene oxide was subjected to a reaction temperature of 115 ° C. and a maximum reaction pressure of 5.
Addition polymerization was carried out at 0 kg / cm ² and then ethylene oxide was subjected to addition polymerization at a reaction temperature of 115 ° C. to give a hydroxyl value of 28 m
gKOH / g of polyoxyalkylene polyol E was obtained.

The obtained polyoxyalkylene polyol E had a terminal oxyethylene group content of 15% by weight, a total unsaturation of 0.065 meq / g, and a head-to-tail bond selectivity of 96.2%.

[0102]

Synthesis Examples 6 and 7 (Synthesis of Polyoxyalkylene Polyols F and G) In Synthesis Example 5, the active hydrogen compound as an initiator and the hydroxyl value of the obtained polyoxyalkylene polyol were as shown in Table 2. Except having been described, polyoxyalkylene polyols F and G were synthesized in the same manner as in Synthesis Example 5.

Table 2 shows polyoxyalkylene polyol E
1 shows the structures and analytical values of G. In Table 2, glycerin was used as the active hydrogen compound with 3 hydroxyl groups, and pentaerythritol was used as the active hydrogen compound with 4 hydroxyl groups.

[0104]

[Table 2]

[0105]

Synthesis Example 8 (Synthesis of polyoxyalkylene polyol H) Cesium hydroxide 0.23 per mole of glycerin
After dehydration under reduced pressure at 100 ° C for 6 hours, propylene oxide was reacted at a reaction temperature of 80 ° C and a maximum reaction pressure of 3.5 kg / cm ^2.
And then ethylene oxide is reacted at a reaction temperature of 1
Polyoxyalkylene polyol H having a hydroxyl value of 28 mgKOH / g was obtained by addition polymerization at 00 ° C.

The resulting polyoxyalkylene polyol H had a terminal oxyethylene group content of 15% by weight, a total unsaturation of 0.016 meq / g, and a head-to-tail bond selectivity of 97.1%.

[0107]

Synthesis Examples 9 to 11 (Synthesis of Polyoxyalkylene Polyols I, J and K) In Synthesis Example 8, the active hydrogen compound as an initiator and the hydroxyl value of the obtained polyol are shown in Table 3.
Except that it was as described in Synthesis Example 8,
Polyoxyalkylene polyols I, J and K were synthesized.

Table 3 shows polyoxyalkylene polyol H
The structures and analytical values of ~ K are shown. In Table 3, glycerin was used as the active hydrogen compound with 3 hydroxyl groups, and pentaerythritol was used as the active hydrogen compound with 4 hydroxyl groups.

[0109]

[Table 3]

(Synthesis of Polymer Polyol)

[0111]

Synthesis Example 21 (Synthesis of Polymer Polyol a) In the polyoxyalkylene polyol B having a hydroxyl value of 34 mgKOH / g obtained in Synthesis Example 2, acrylonitrile and styrene were graft-polymerized to give a hydroxyl value of 28 mgKOH.
/ G of polymer polyol a. The vinyl polymer content was 20% by weight (the total amount of acrylonitrile and styrene used was polyoxyalkylene polyol B,
20% by weight based on 100% by weight of the total amount of acrylonitrile and styrene). Specifically, polymer polyol a was synthesized as follows.

The properties of the raw materials used are as follows. Radical polymerization initiator: 2,2′-azobis (2-isobutyronitrile). Dispersion stabilizing agent: a hydroxyl value (OHV) obtained by addition polymerization of glycerin to propylene oxide and then ethylene oxide using KOH as a catalyst is 34 mg KOH /
g, terminal ethylene oxide (EO) content is 14% by weight
The hydroxyl value (OHV) obtained by reacting maleic anhydride and ethylene oxide with the polyol of the formula is 29 mg KOH
/ G of polyetherester polyol.

In a 1-liter pressure-resistant autoclave equipped with a thermometer, a stirrer, a pressure gauge, and a liquid feeder,
The polyoxyalkylene polyol B was charged until the liquid state was reached, and the temperature was raised to 120 ° C. while stirring. A mixture of polyoxyalkylene polyol B, a radical polymerization initiator, acrylonitrile, styrene and a dispersion stabilizer was continuously charged into the autoclave, and a polymer polyol a was continuously obtained from the outlet except for the first distillation. At a reaction temperature of 120 ° C. and a reaction pressure of 440 kPa, the residence time was 50 minutes. The obtained reaction solution was added to 120
Under a condition of not more than 655 Pa and a temperature of 655 Pa or less, a heating and depressurizing treatment was performed for 3 hours to remove unreacted acrylonitrile, styrene, decomposed products of the radical polymerization initiator and the like. The charged amounts of the raw materials were as follows.

Polyoxyalkylene polyol B 7500 g Radical polymerization initiator 50 g Acrylonitrile 1500 g Styrene 500 g Dispersion stabilizer 500 g

[0115]

Synthesis Example 22 (Synthesis of Polymer Polyol b) Acrylonitrile and styrene were graft-polymerized in polyoxyalkylene polyol F having a hydroxyl value of 34 mgKOH / g obtained in Synthesis Example 6 to obtain a hydroxyl value of 28 mgKOH / g.
g of polymer polyol b was obtained. The vinyl polymer content was 20% by weight. Specifically, polymer polyol b was synthesized as follows.

In a 1-liter pressure-resistant autoclave equipped with a thermometer, a stirrer, a pressure gauge, and a liquid feeder,
The polyoxyalkylene polyol F was charged until the liquid state was reached, and the temperature was raised to 120 ° C. while stirring. A mixture of polyoxyalkylene polyol F, a radical polymerization initiator, acrylonitrile, styrene and a dispersion stabilizer was continuously charged into the autoclave, and a polymer polyol b was continuously obtained from the outlet except for the first distillation. At a reaction temperature of 120 ° C. and a reaction pressure of 440 kPa, the residence time was 50 minutes. The obtained reaction solution was added to 120
Under a condition of not more than 655 Pa and a temperature of 655 Pa or less, a heating and depressurizing treatment was performed for 3 hours to remove unreacted acrylonitrile, styrene, decomposed products of the radical polymerization initiator and the like. The charged amounts of the raw materials were as follows.

Polyoxyalkylene polyol F 7500 g Radical polymerization initiator 50 g Acrylonitrile 1500 g Styrene 500 g Dispersion stabilizer 500 g

[0118]

Synthesis Example 23 (Synthesis of Polymer Polyol c) Acrylonitrile and styrene were graft-polymerized in the polyoxyalkylene polyol I having a hydroxyl value of 34 mgKOH / g obtained in Synthesis Example 9 to obtain a hydroxyl value of 28 mgKOH / g.
g of polymer polyol c was obtained. The vinyl polymer content was 20% by weight. Specifically, polymer polyol c was synthesized as follows.

In a 1-liter pressure-resistant autoclave equipped with a thermometer, a stirrer, a pressure gauge, and a liquid feeder,
The polyoxyalkylene polyol I was charged until the liquid was full, and the temperature was raised to 120 ° C. while stirring. A mixture of polyoxyalkylene polyol I, a radical polymerization initiator, acrylonitrile, styrene, and a dispersion stabilizer was continuously charged into the autoclave, and a polymer polyol c was continuously obtained from the outlet except for the initial distillation. At a reaction temperature of 120 ° C. and a reaction pressure of 440 kPa, the residence time was 50 minutes. The obtained reaction solution was added to 120
Under a condition of not more than 655 Pa and a temperature of 655 Pa or less, a heating and depressurizing treatment was performed for 3 hours to remove unreacted acrylonitrile, styrene, decomposed products of the radical polymerization initiator and the like. The charged amounts of the raw materials were as follows.

Polyoxyalkylene polyol I 7500 g Radical polymerization initiator 50 g Acrylonitrile 1500 g Styrene 500 g Dispersion stabilizer 500 g (Production of flexible polyurethane cold-cured mold foam) As polyisocyanate, the following raw materials were used.

Polyisocyanate-1 Cosmonate TM-20 (trade name) manufactured by Mitsui Chemicals, Inc . ;
Mixture 8 comprising 4-toluylene diisocyanate and 2,6-toluylene diisocyanate in a weight ratio of 80:20
A mixture consisting of 0 parts by weight and 20 parts by weight of polymethylene polyphenyl polyisocyanate.

Polyisocyanate-2 Cosmonate T-80 (trade name) manufactured by Mitsui Chemicals, Inc . ; 2,4-
A mixture comprising toluylene diisocyanate and 2,6-toluylene diisocyanate in a weight ratio of 80:20.

In addition to the above-mentioned polyoxyalkylene polyol, polymer polyol and polyisocyanate, the following raw materials were used. Catalyst-1 Minico L-1020 (trade name); an amine catalyst (33% diethylene glycol solution of triethylenediamine) manufactured by Active Materials Chemical Co., Ltd.

Catalyst-2 Minico TMDA (trade name); an amine catalyst manufactured by Active Materials Chemical Company.

Crosslinking agent-1 KL-210 (trade name); manufactured by Mitsui Chemicals, Inc., hydroxyl value 83
0 mg KOH / g crosslinker.

Foam stabilizer- 1 SRX-274C (trade name); a silicone foam stabilizer manufactured by Dow Corning Toray Silicone Co., Ltd.

The density in Examples and Comparative Examples is as follows.
Shows the total density (overall density). (Comparison between polyoxyalkylene polyol using compound having nitrogen-phosphorus double bond as polyol synthesis catalyst and polyoxyalkylene polyol using potassium hydroxide)

[0128]

Example 1 A resin solution (resin premix) was prepared by mixing the following seven components. Polyoxyalkylene polyol A 50 parts Polymer polyol a 50 parts Crosslinking agent-1 3.0 parts Water 4.2 parts Catalyst-1 0.4 parts Catalyst-2 0.1 parts Foam stabilizer-1 1.0 parts Polyoxy Using polyoxyalkylene polyol A as the alkylene polyol and polymer polyol a as the polymer polyol, 58.7 parts of isocyanate-1 was mixed with 108.7 parts of the above resin solution, and the resulting mixture was immediately heated to 65 ° C. Adjusted inner size 400 × 400
The mixture was poured into a mold having a size of 100 mm, and the lid was closed to foam.

Next, the mold is kept at a set temperature of 1
Place in a hot air oven at 00 ° C and remove the foam in the mold to 7
After heating and curing for minutes, the flexible foam was taken out of the mold. Table 4 shows the physical properties of the obtained flexible foam.

The equivalent ratio of the polyisocyanate-1 to the active hydrogen of the resin solution (resin premix) (NCO /
H) (NCO index) was set to 1.05.

[0131]

Example 2 In Example 1, the total density (apparent density) of the obtained flexible foam was changed from 35.1 kg / m ³ to 42.7.
Except for controlling to kg / m ³ ,
A flexible foam was obtained. Table 4 shows the physical properties of the obtained flexible foam.

[0132]

Examples 3 to 7 In Example 1, the polyoxyalkylene polyol A was replaced with the polyoxyalkylene polyol B
To D, and a flexible foam was obtained in the same manner as in Example 1 except that the total density (apparent density) of the obtained flexible foam was controlled according to Table 4. Table 4 shows the physical properties of the obtained flexible foam.

[0133]

[Table 4]

[0134]

Comparative Examples 1 to 6 In Example 1, the polyoxyalkylene polyol A was replaced with the polyoxyalkylene polyol E
To G, the polymer polyol a was changed to the polymer polyol b, and the total density (apparent density) of the obtained flexible foam was controlled in accordance with Table 5 to obtain a flexible foam in the same manner as in Example 1. Was. Table 5 shows the physical properties of the obtained flexible foam.

The equivalent ratio of polyisocyanate-1 to active hydrogen in the resin solution (resin premix) (NCO /
H) (NCO index) was set to 1.05.

[0136]

[Table 5]

The following is understood from Tables 4 and 5. That is, the flexible foams of Examples 1 to 7 show good wet heat compression strain and change in hardness in a repeated compression test. On the other hand, the flexible foams of Comparative Examples 1 to 6 show that the polyol used is out of the range of the present invention, and the physical properties of the flexible foams are inferior. In addition, the viscosity of the resin premix used in the production of the flexible foams of Examples 1 to 6 was lower than that of Example 7 and showed good mixing properties and liquid elongation (fluidity). Therefore, it is more preferable.

[0138]

Examples 8 to 12 In Example 1, the polyoxyalkylene polyol A was changed to polyoxyalkylene polyols B to D, and the polyisocyanate-1 was changed to polyisocyanate-2. Except that the total density (apparent density) was controlled according to Table 6,
In the same manner as in Example 1, a flexible foam was obtained. Table 6 shows the physical properties of the obtained flexible foam.

The equivalent ratio of polyisocyanate-2 to active hydrogen in the resin solution (resin premix) (NCO /
H) (NCO index) was set to 1.05.

[0140]

[Table 6]

[0141]

Comparative Examples 7 to 10 In Example 1, polyoxyalkylene polyol A was changed to polyoxyalkylene polyols F and G, polymer polyol a was changed to polymer polyol b, and polyisocyanate-1 was changed to polyisocyanate-2. , The total density of the resulting flexible foam (apparent density)
Was controlled in accordance with Table 7, and a flexible foam was obtained in the same manner as in Example 1. Table 7 shows the physical properties of the obtained flexible foam.

The equivalent ratio of polyisocyanate-2 to active hydrogen in the resin solution (resin premix) (NCO /
H) (NCO index) was set to 1.05.

[0143]

[Table 7]

The following are understood from Tables 6 and 7. That is, the flexible foams of Examples 8 to 12 show good wet heat compression strain and change in hardness in a repeated compression test. On the other hand, the flexible foams of Comparative Examples 7 to 10 show that the polyol used is out of the range of the present invention and the foam properties are inferior. Further, the flexible foams of Examples 8 to 11 are more preferable because they have a lower resin premix viscosity than that of Example 12 and show good mixing properties and liquid elongation. (Comparison between polyoxyalkylene polyol using cesium hydroxide as polyol synthesis catalyst and polyoxyalkylene polyol using potassium hydroxide)

[0145]

Examples 13 to 19 In Example 1, the polyoxyalkylene polyol A was changed to polyoxyalkylene polyols HK and the polymer polyol a was changed to polymer polyol c, and the total density (apparent density) of the obtained flexible foam was changed. A flexible foam was obtained in the same manner as in Example 1 except that control was performed according to Table 8. Table 8 shows the physical properties of the obtained flexible foam.

[0146]

[Table 8]

The following is understood from Tables 8 and 5. That is, the flexible foams of Examples 13 to 19 show good wet heat compression strain and change in hardness in a repeated compression test. On the other hand, the flexible foams of Comparative Examples 1 to 6 show that the polyol used is out of the range of the present invention and the foam properties are inferior. Further, the flexible foams of Examples 13 to 18 are more preferable because they have a lower resin premix viscosity than that of Example 19 and exhibit good mixing properties and liquid elongation.

[0148]

Examples 20 to 24 In Example 1, polyoxyalkylene polyol A was used as polyoxyalkylene polyols I to K, polymer polyol a was used as polymer polyol c, and polyisocyanate-1 was used as polyisocyanate-2.
And a flexible foam was obtained in the same manner as in Example 1 except that the total density (apparent density) of the obtained flexible foam was controlled according to Table 9. Table 9 shows the physical properties of the obtained flexible foam.

The equivalent ratio of polyisocyanate-2 to active hydrogen in the resin solution (resin premix) (NCO /
H) (NCO index) was set to 1.05.

[0150]

[Table 9]

The following can be understood from Tables 9 and 7. That is, the flexible foams of Examples 20 to 24 show good wet heat compression strain and change in hardness in a repeated compression test. On the other hand, the flexible foams of Comparative Examples 7 to 10 show that the polyol used is out of the range of the present invention and the foam properties are inferior. Further, the flexible foams of Examples 20 to 23 are more preferable because they have a lower resin premix viscosity and better mixing properties and liquid elongation than those of Example 24.

[0152]

The flexible polyurethane cold-cure mold foam according to the present invention has a low density and excellent durability, especially a hardness change rate in a repeated compression test and a wet heat compression set.

The flexible polyurethane cold-cure mold foam according to the present invention has a total density of 35 kg / m ³ or more and 45 kg / m ³ or less, and a wet heat compression set of 15%.
The hardness change rate in the repeated compression test was 1
Since it can be 5% or less, it is lightweight, has excellent durability characteristics such as distortion characteristics, and is an excellent cushion for beds and vehicles.

According to the method for producing a flexible polyurethane cold-cure mold foam according to the present invention, a flexible polyurethane cold-cure mold foam having the above effects can be provided.

In the present invention, the viscosity of the resin premix is controlled by using a polyol synthesized using a catalyst containing at least a compound having a nitrogen-phosphorus double bond and one of cesium hydroxide and rubidium hydroxide. Can be 2500 mPa · s or less, facilitating handling during the production of polyurethane foam,
Flexible foams can be manufactured with inexpensive equipment. As a result, it is possible to easily produce a flexible foam having a small wet heat compression set and a small rate of change in hardness in a repeated compression test, that is, excellent durability.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 75:08

Claims (14)

[Claims] 1. A total density of 35 kg / m ³ or more 45 kg / m ³
A flexible polyurethane cold-cure mold foam having a wet heat compression set of 15% or less. 2. The hardness change rate in a repeated compression test is 1
The flexible polyurethane cold-cure mold foam according to claim 1, wherein the content is 5% or less. 3. A polymer polyol in which said flexible polyurethane cold-cure mold foam is obtained by radically polymerizing a polyol and / or a compound having an unsaturated bond in the polyol, wherein polymer polyol is dispersed in said polyol; And a catalyst and a polyisocyanate, wherein the polyol is (1) a hydroxyl value of 15 mgKOH / g or more and 25 mgKOH / g or less and a total degree of unsaturation of 0.060 m
eq / g or less polyoxyalkylene polyol,
(2) The hydroxyl value exceeds 25 mgKOH / g, and the
/ G or less and a polyoxyalkylene polyol having a total degree of unsaturation of 0.050 meq / g or less, and (3) a hydroxyl group exceeding 35 mgKOH / g and 45 mgKOH / g or less and a total degree of unsaturation of 0.040 meq / g The flexible polyurethane cold-cure mold foam according to claim 1 or 2, which is any polyoxyalkylene polyol selected from the group consisting of the following polyoxyalkylene polyols. 4. The polyol is synthesized using a compound containing at least one of a compound having a nitrogen-phosphorus double bond and one of cesium hydroxide and rubidium hydroxide. The flexible polyurethane cold-cure mold foam according to claim 3. 5. The flexible polyurethane cold according to claim 3, wherein the viscosity of the resin premix containing at least a polyol and / or a polymer polyol, water and a catalyst is 2500 mPa · s or less. Cure mold foam. 6. The flexible polyurethane cold-cured foam according to claim 3, wherein the polyisocyanate is toluylene diisocyanate. 7. The polyisocyanate is toluylene diisocyanate and a compound represented by the general formula (1): ## STR1 ## With polymethylene polyphenyl polyisocyanate represented by the formula: wherein n = 0 or an integer of 1 or more.
The flexible polyurethane cold-cure mold foam according to any one of claims 3 to 5, which is a mixture containing the mixture in a weight ratio of 50 to 50. 8. The flexible polyurethane cold-cure mold foam according to claim 3, wherein the compound having a nitrogen-phosphorus double bond is a phosphazenium compound or a phosphine oxide compound. 9. A polymer polyol in which fine particles of a polymer obtained by radical polymerization of a polyol and / or a compound having an unsaturated bond in the polyol are dispersed in the polyol; water; a catalyst; and a polyisocyanate. A method for producing a flexible polyurethane cold-cure mold foam obtained from the above, wherein the polyol has (1) a hydroxyl value of 15 mgKOH / g or more and 25 mgKOH / g or less, and a total degree of unsaturation of 0.060 m
eq / g or less polyoxyalkylene polyol,
(2) The hydroxyl value exceeds 25 mgKOH / g, and the
/ G or less and a polyoxyalkylene polyol having a total degree of unsaturation of 0.050 meq / g or less, and (3) a hydroxyl group exceeding 35 mgKOH / g and 45 mgKOH / g or less and a total degree of unsaturation of 0.040 meq / g The method for producing a flexible polyurethane cold-cure mold foam according to claim 1 or 2, wherein the polyoxyalkylene polyol is any polyoxyalkylene polyol selected from the group consisting of the following polyoxyalkylene polyols. 10. The polyol is synthesized using a catalyst containing at least one of a compound having a nitrogen-phosphorus double bond and one of cesium hydroxide and rubidium hydroxide. A method for producing the flexible polyurethane cold-cure mold foam according to claim 9. 11. The flexible polyurethane cold according to claim 9, wherein a viscosity of the resin premix containing at least a polyol and / or a polymer polyol, water and a catalyst is 2500 mPa · s or less. Manufacturing method of cure mold foam. 12. The method according to claim 9, wherein said polyisocyanate is toluylene diisocyanate.
The method for producing a flexible polyurethane cold-cured foam according to any one of the above. 13. The polyisocyanate according to claim 1, wherein the toluylene diisocyanate is represented by the general formula (1): ## STR2 ## With polymethylene polyphenyl polyisocyanate represented by the formula: wherein n = 0 or an integer of 1 or more.
The method for producing a flexible polyurethane cold-cure mold foam according to any one of claims 9 to 11, wherein the mixture is a mixture containing the mixture in a weight ratio of 50 to 50. 14. The method for producing a flexible polyurethane cold-cure mold foam according to claim 9, wherein the compound having a nitrogen-phosphorus double bond is a phosphazenium compound or a phosphine oxide compound.