JP2001302892A - Polymer-dispersed polyol, method for producing the same, and polyurethane foam - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polymer-dispersed polyol excellent in water resistance and capable of providing a flexible polyurethane foam excellent in wet heat characteristics, to provide a method for producing the polymer-dispersed polyol, and to provide the polyurethane foam obtained from the polymer-dispersed polyol. SOLUTION: This polymer-dispersed polyol comprises 5-50 wt.% of polymer fine particles dispersed in 95-50 wt.% of a polyol, and the polymer comprises (A) 5-30 wt.% of an N-metylolacrylamide unit and (B) 70-95 wt.% of a monomer unit copolymerizable with the N-methylolacrylamide unit (A).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a polymer-dispersed polyol, a method for producing the same, and a polyurethane foam using the polymer-dispersed polyol.

[0002]

2. Description of the Related Art A polyol in which polymer fine particles obtained by polymerizing an ethylenically unsaturated monomer such as styrene or acrylonitrile in a polyol are conventionally dispersed is called a polymer polyol or a polymer-dispersed polyol.
It is used as a raw material for polyurethane foams and polyurethane elastomers. In the present invention, this is called a polymer-dispersed polyol.

[0003] In particular, when a polymer-dispersed polyol is used for a flexible polyurethane foam, effects such as promotion of cell communication and improvement of foam hardness are obtained. On the other hand, there is also a drawback that the durability such as the wet heat compression set of the foam deteriorates as the polymer concentration increases for the purpose of increasing the hardness. Speaking of flame retardancy, polymer-dispersed polyols have a problem that they not only have an effect on flame retardancy of polyurethane but also lower flame retardancy.

[0004] For the purpose of flame retardation of polyurethane, a method of adding a phosphorus-halogen flame retardant such as tris (2-chloroethyl) phosphate or tris (β-chloropropyl) phosphate is known. However, in any case, the physical properties of the polyurethane foam are significantly reduced.

As a polymer-dispersed polyol having an effect on flame retardation of polyurethane, Japanese Patent No. 2527006 discloses an aldehyde condensation type resin fine particle dispersion. However, as a result of the additional tests by the inventors,
When the aldehyde-condensed resin fine particle dispersion is used as a polyurethane, it has been found that physical properties such as wet heat permanent distortion, which are particularly related to durability, are lower than our target level.

[0006] It is an object in the art to provide a polymer-dispersed polyol that imparts flame retardancy without deteriorating the physical properties of the polyurethane foam. One such solution is described in JP-A-11-049829. That is, a polymer-dispersed polyol that provides a polyurethane foam satisfying flame retardancy and durability can be obtained by limiting the combination of the types of monomers and the composition ratio. According to this method, the desired polymer-dispersed polyol can be obtained, but depending on the use, a combination of monomers that is not limited may be required. Japanese Patent Application Laid-Open No. H11-049829 discloses N-methylolacrylamide used in the present invention as an acrylamide derivative, but the amount used when N-methylolacrylamide is selected and other combinations of monomers are specifically described. There is no description.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a polymer-dispersed polyol which is a polymer-dispersed polyol having excellent water resistance and which gives a flexible polyurethane foam having excellent wet heat properties, a method for producing the same, and a method for producing the same. It is to provide a polyurethane foam obtained from a polymer-dispersed polyol.

[0008]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that a polymer-dispersed polyol in which a polymer fine particle containing a specific amount of N-methylolacrylamide units is dispersed in a polyol is a polymer capable of solving the above-mentioned problems. The inventors have found that the polyol is a dispersed polyol, and have reached the present invention.

That is, the present invention relates to a polymer-dispersed polyol in which 5 to 50% by weight of polymer fine particles are dispersed in 95 to 50% by weight of a polyol, wherein the polymer comprises 5 to 30% by weight of an N-methylolacrylamide unit (A). %, And 70 to 95% by weight of a monomer unit (B) copolymerizable with (A).

In the present invention, the monomer unit (B) copolymerizable with the N-methylolacrylamide unit (A) is
It is preferably at least one compound unit selected from acrylamide units, methacrylamide units, acrylonitrile units, methacrylonitrile units, and styrene units.

In a preferred embodiment of the present invention, (1) the content of at least one kind of (B) selected from acrylamide units and methacrylamide units is 5 to 80 with respect to the total amount of the above (A) and (B). The content of at least one (B) selected from the above polymer-dispersed polyol, (2) acrylonitrile unit and methacrylonitrile unit is 5 to 70% by weight based on the total amount of (A) and (B). % By weight of the above polymer-dispersed polyol,
(3) The content of the above polymer-dispersed polyol in which the content of the styrene unit (B) is 5 to 60% by weight based on the total amount of the components (A) and (B), (4) the content of the acrylonitrile unit and the content of the styrene unit is as follows: The polymer-dispersed polyols are 5 to 70% by weight and 5 to 60% by weight, respectively, based on the total amount of the above (A) and (B).

The above-mentioned polymer-dispersed polyol according to the present invention is obtained by using 95 to 50% by weight of a polyol as a reaction medium.
When polymerizing 5 to 50% by weight of the ethylenically unsaturated monomer mixture, 5 to 30% by weight of N-methylolacrylamide (A) and 70% of monomer (B) copolymerizable with (A) are used as ethylenically unsaturated monomers. It is produced by a method using a monomer mixture containing ９５95% by weight.

The copolymerizable monomer (B) is preferably at least one compound selected from acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, and styrene.

As a preferred embodiment of the above-mentioned production method,
(1) The above production method, wherein the content of at least one (B) selected from acrylamide and methacrylamide is 5 to 80% by weight based on the total amount of (A) and (B), (2) acrylonitrile And (3) styrene (B), wherein the content of at least one (B) selected from methacrylonitrile is 5 to 70% by weight based on the total amount of (A) and (B). Wherein the content of (A) and (B) is 5 to 60% by weight based on the total amount of (A) and (B), and (4) the content of acrylonitrile and styrene is the same as the total amount of (A) and (B). On the other hand, the above-mentioned production method is 5 to 70% by weight and 5 to 60% by weight, respectively.

Another invention of the present invention is a polyurethane foam obtained by reacting an active hydrogen compound with a polyisocyanate in the presence of a catalyst, a foam stabilizer, and a foaming agent, wherein the active hydrogen compound is a polymer comprising the polymer Polyurethane foam containing at least 30% by weight of a dispersed polyol.

The polymer-dispersed polyol of the present invention has excellent water resistance. In addition, the flexible polyurethane foam obtained from the polymer-dispersed polyol of the present invention has excellent wet heat compression set resistance. Therefore, the polymer-dispersed polyol of the present invention is extremely useful as a raw material for a flexible polyurethane.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The method for producing the polymer-dispersed polyol of the present invention includes: (1) a method in which an ethylenically unsaturated monomer is polymerized in a polyol, and the obtained polymer fine particles are dispersed in the polyol; A method of dispersing polymer fine particles obtained by polymerizing a unsaturated monomer in a polyol, (3) the method (1) or (2),
And a method of mixing those obtained by the above method. The method (1) is preferred.

The polymer fine particles comprising an ethylenically unsaturated monomer according to the present invention and the polymer-dispersed polyol of the present invention in which this polymer is dispersed will be described in detail. In the polymer-dispersed polyol of the present invention, the polyol can be a hydrocarbon-based polyol such as a polyoxyalkylene polyol, a polyester polyol, a polyester ether polyol, a polycarbonate polyol, and a polybutadiene polyol, which are usually used as raw materials for polyurethane. .

Examples of the polyoxyalkylene polyol include those obtained by addition polymerization of an epoxide with an active hydrogen compound as an initiator in the presence of a catalyst. Examples of the active hydrogen compound include monools such as methanol, butanol, and allyl alcohol; water, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, and neopentyl. Diols such as glycol; glycerin, hexanetriol,
Polyols such as trimethylolpropane, pentaerythritol, sorbitol, and sucrose; aromatic compounds such as bisphenol A, bisphenol F, dihydroxybiphenyl, hydroquinone, resorcin, phloroglucin, naphthalene diol, aminophenol, aminonaphthol, and phenol formaldehyde condensate; methyl Diethanolamine, ethyldiisopronolamine, monoethanolamine, diethanolamine, triethanolamine, ethylenediamine, hexamethylenediamine, diethylenetriamine, bis (p-aminocyclohexyl) methane, aniline, toluidine, tolylenediamine, diphenylmethanediamine, naphthalenediamine, etc. Examples include compounds arbitrarily selected from the group consisting of amines.

As the catalyst, at least one of an alkali metal compound and an amine, a complex metal cyanide complex, a phosphazenium compound described in JP-A-11-106500, a phosphazene compound described in JP-A-10-36499, And phosphine oxide compounds described in JP-A-11-302371. Epoxides include ethylene oxide, propylene oxide, butylene oxide, styrene oxide and the like.

As the polyoxyalkylene polyol,
Polytetramethylene ether glycol or the like obtained by polymerizing tetrahydrofuran in the presence of an acidic catalyst such as a boron trifluoride ether complex can also be used.

As the polyester polyol, diols such as polyester polyol obtained by ring-opening addition of ε-caprolactone, γ-butyrolactone and the like with a polyhydric alcohol such as glycerin as an initiator, diols such as ethylene glycol, propylene glycol and pentanediol are used. And dicarboxylic acids and acid anhydrides such as terephthalic acid and phthalic anhydride, and polyester polyols obtained by condensation with carboxylic esters such as dimethyl terephthalate.

As the polyester ether polyol, a half ester produced by reacting a polyether polyol with a dicarboxylic anhydride such as phthalic anhydride is subjected to dehydration condensation, or an epoxide is added to the half ester in the presence of a basic catalyst or the like. Examples thereof include those obtained by addition.

As the polycarbonate polyol, 2
Examples include those obtained by condensation of a trivalent low molecular polyol with a diester carbonate such as dimethyl carbonate and diethyl carbonate. As the polybutadiene polyol, AR
CO-brand name: Poly-bd; Nippon Soda Co., Ltd. brand name: NissoPB. In the present invention, a mixture of two or more arbitrarily selected from the above-mentioned various polyols can also be used.

Preferred polyols among the above polyols are those having an average number of functional groups of 1 to 8 and a hydroxyl value of 10 to 600 mgK.
It is at least one polyol selected from polyoxyalkylene polyol, polyester polyol, and polyester ether polyol having an OH / g.
More preferred polyols are polyoxyalkylene polyols having an average functionality of 1 to 8 and a hydroxyl value of 10 to 600 mg KOH / g, and the most preferred polyols have an average functionality of 1 to 4 and a hydroxyl value of 10 to 100 mg KOH / g.
g, polyoxypropylene polyol and polyoxyethylene polyoxypropylene polyol.

In the polymer-dispersed polyol of the present invention, the ethylenically unsaturated monomers for obtaining polymer fine particles are as follows. That is, the ethylenically unsaturated monomer mixture used in the present invention contains N-methylolacrylamide (A) and a monomer (B) copolymerizable with (A).

As the monomer (B), an acrylamide compound such as acrylamide and methacrylamide, a nitrile compound such as acrylonitrile and methacrylonitrile, and an ethylenically unsaturated monomer generally used for producing a polymer-dispersed polyol such as styrene are used. can do.

Specifically, N, N-dimethylacrylamide, N, N-dimethylaminomethylacrylamide,
N, N-dimethylaminopropylacrylamide, N-
Isopropylacrylamide, N, N-dimethylolacrylamide, N, N-diethylacrylamide, diacetoneacrylamide, acryloylmorpholine, acryloyl-L-glutamic acid dimethyl ester, acryloyl-L-proline methyl ester, acryloylpyrrolidine, 1,4-diacryloyl Piperazine, N, N
Acrylamides such as dioctylacryloylamide, methylenebisacrylamide;

N, N-dimethylmethacryloylamide,
1-methacryloylimidazole, methacryloyl-L
Methacrylamides such as -valine methyl ester and methacryloyl-L-leucine methyl ester; α-methylstyrene, 2-methylstyrene, 3-methylstyrene,
4-methylstyrene, 2-vinylphenol, 3-vinylphenol, p-isopropenylphenol, 3-vinylbenzoic acid, 4-vinylbenzoic acid, 4-vinylthiophenol, 4-methoxystyrene, 4-ethoxystyrene , 4-vinylbiphenyl,
Sodium p-styrenesulfonate, potassium p-styrenesulfonate, 4-aminostyrene, 5-aminostyrene, 4-dimethylaminostyrene, 4-vinylbenzyl alcohol, 4-phenoxystyrene, 4-vinylbenzoate, 4-acetoxystyrene , Vinylphenylacetonitrile, 4-t-butylstyrene, p-octylstyrene, p-cyclohexylstyrene, p-dodecylstyrene, 4-isopropylstyrene, N- (4-vinylphenyl) maleimide, and aromatic monomers such as divinylbenzene ;

Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n
-Butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, 3-dimethylaminoneo (Meth) acrylates such as pentyl (meth) acrylate, 3- (dimethylamino) propyl (meth) acrylate, glycidyl methacrylate, hydroxyethyl methacrylate, and hydroxypropyl methacrylate;

Vinyl acetate, vinyl propionate, vinyl butyrate, vinyl crotonate, vinyl n-hexanoate, n-
Vinyl esters such as vinyl octanoate, vinyl n-decanoate, vinyl laurate, vinyl palmitate, and vinyl stearate.

Preferably, acrylamide compounds such as acrylamide and methacrylamide, acrylonitrile,
One or a mixture of two or more selected from a nitrile compound such as methacrylonitrile and styrene. More preferably, it is a two-component system of acrylamide and acrylonitrile, acrylonitrile and styrene, or a three-component system of acrylamide, acrylonitrile and styrene.

The polymer-dispersed polyol of the present invention comprises 5 to 50% by weight of polymer fine particles obtained by polymerizing a mixture of the above-mentioned ethylenically unsaturated monomers, and a polyol of 95 to 95%.
It is dispersed in 50% by weight. Preferably, 10 to 45% by weight of polymer fine particles are dispersed in 90 to 55% by weight of a polyol. When the concentration of the polymer fine particles is less than 5% by weight, the effect of using the polymer-dispersed polyol such as communication and high hardness when the polyurethane foam is formed is small, and when the concentration exceeds 50% by weight, the dispersion stability of the polymer-dispersed polyol decreases. Or high viscosity,
It is not preferable because handling becomes difficult.

In the present invention, the amount of N-methylolacrylamide used is 5 to 30% by weight based on the total amount of the ethylenically unsaturated monomer. Preferably it is 7 to 25% by weight, more preferably 10 to 20% by weight. When the amount of N-methylolacrylamide used is less than 5% by weight,
It is difficult to obtain the effect of improving the wet heat compression set, 30% by weight
Exceeding the viscosity is not preferred because the viscosity during production is so high that a polymer-dispersed polyol cannot be obtained.

In the present invention, as the monomer (B),
At least one acrylamide compound selected from acrylamide and methacrylamide may or may not be used depending on the purpose. When used, it can be used in an amount of 5 to 80% by weight based on the total amount of the ethylenically unsaturated monomer. Preferably it is 7 to 50% by weight, more preferably 10 to 30% by weight. When these acrylamide compounds are used in an amount of 5% by weight or more based on the total amount of the ethylenically unsaturated monomer (the above (A) and (B), the same applies hereinafter), the polyurethane using the obtained polymer-dispersed polyol becomes flame-retardant. Has excellent effects. If the amount is less than 5% by weight, no effect is exerted on the flame retardancy of the polyurethane. It is not preferable because it becomes a gel and storage stability deteriorates.

In the present invention, as the monomer (B),
At least one kind of nitrile compound selected from acrylonitrile and methacrylonitrile may or may not be used according to the purpose. When used, it can be used in an amount of 5 to 70% by weight based on the total amount of the ethylenically unsaturated monomer. Preferably, it is 7 to 65% by weight, more preferably 10% by weight.
６０60% by weight. When the above nitrile compound is used in an amount of 5% by weight or more based on the total amount of the ethylenically unsaturated monomer,
The dispersion stability of the polymer-dispersed polyol is improved, and
It is effective in increasing the hardness of a polyurethane foam using the obtained polymer-dispersed polyol. If the amount is less than 5% by weight, the above-mentioned effects cannot be obtained. If the amount exceeds 70% by weight, the wet heat permanent set of the polyurethane foam is undesirably reduced. When it is desired to reduce the yellowness of the polymer-dispersed polyol or to significantly improve the wet heat compression set of the polyurethane foam, the above nitrile compound may not be used.

In the present invention, styrene may or may not be used as the monomer (B) according to the purpose. When used, it can be used in an amount of 5 to 60% by weight based on the total amount of the ethylenically unsaturated monomer. Preferably 7 to 55
%, More preferably 10 to 50% by weight. When styrene is used in an amount of 5% by weight or more based on the total amount of the ethylenically unsaturated monomers, the color of the polymer-dispersed polyol and the polyurethane using the same can be improved, and the wet-heat compression set of the polyurethane foam can be improved. 5
If the amount is less than 60% by weight, the above effects cannot be obtained. If the amount is more than 60% by weight, the dispersion stability of the polymer-dispersed polyol tends to decrease, and the flame retardancy of the obtained polyurethane tends to decrease.

The polymer obtained from the above ethylenically unsaturated monomers can be used as a copolymer,
It can also serve the purpose in a blend system of the respective polymers. It is particularly preferable to use it as a copolymer.

The polymer-dispersed polyol of the present invention may contain a polymer formed by polymerizing the above-mentioned ethylenically unsaturated monomer in a polyol, or may be obtained by polymerizing an ethylenically unsaturated monomer in a medium other than the polyol. The obtained polymer particles may be isolated and dispersed in a predetermined amount of a polyol, or the reaction mixture containing the produced polymer may be added to the polyol without isolation, and the reaction solvent may be distilled off. . In particular, a polymer-dispersed polyol obtained by polymerizing an ethylenically unsaturated monomer in a polyol is preferable.

As a polymerization initiator for polymerizing the ethylenically unsaturated monomer, a radical initiator which generates a radical to start polymerization is usually used. Specifically, 2,
2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), 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], 1,1'-azobis (1-acetoxy-1-phenylethane) Azo compounds such as
t-butyl peroxide, benzoyl peroxide, dibenzo peroxide, dicumyl peroxide, bis (4
(T-butylcyclohexyl) peroxydicarbonate, peroxides such as lauroyl peroxide, persulfates such as sodium persulfate, potassium persulfate and ammonium persulfate, perborates, persuccinates and the like. Two or more of these initiators may be used in combination. The amount of the polymerization initiator used is usually, based on the ethylenically unsaturated monomer,
It is 0.1 to 10.0% by weight, preferably 0.5 to 5.0% by weight.

The polymerization reaction is carried out by the above polyol, ethylenically unsaturated monomer, polymerization initiator, chain transfer agent if necessary,
A polymerization reaction is carried out using a dispersion stabilizer, a solvent, an acid catalyst and the like to produce a polymer-dispersed polyol. The production method can be carried out by either a batch type or a continuous type polymerization reaction. The polymerization temperature is determined according to the type of the polymerization initiator. Usually, it is carried out at a temperature higher than the decomposition temperature of the initiator.
Preferably from 60 to 200 ° C, more preferably from 80 to 16 ° C.
Perform at 0 ° C. The polymerization reaction can be carried out either under pressure or under atmospheric pressure. Usually, a polyol, an ethylenically unsaturated monomer, a polymerization initiator, a chain transfer agent used if necessary,
A mixture comprising a dispersion stabilizer, a solvent, an acid catalyst and the like is charged into the reactor at a rate as uniform as possible, and polymerization is carried out.

In the polymerization reaction, a chain transfer agent can be used if necessary. Specifically, methanol, ethanol, propanol, isopropanol, 1-butanol, 2-butanol, 2-methyl-1-propanol,
2-methyl-2-propanol, 1-pentanol, 2
-Pentanol, 3-pentanol, 2-methyl-1-
Aliphatic alcohols such as butanol, 3-methyl-1-butanol, 3-methyl-2-butanol, hexyl alcohol, ethylene glycol and propylene glycol, mercaptans such as dodecyl mercaptan and mercaptoethanol, carbon tetrachloride, and tetrabromide Carbon, halogen hydrocarbons such as chloroform, aliphatic tertiary amines such as triethylamine, tripropylamine, tributylamine, N, N-diethylethanolamine, N-methylmorpholine and N-ethylmorpholine, sodium methallylsulfonate; Sodium allyl sulfonate, toluene, xylene, acetonitrile, hexane, heptane, dioxane, ethylene glycol dimethyl ether, N, N-
Dimethylformamide and the like. When the chain transfer agent is used, it is used in an amount of 0.01 to 30% by weight, preferably 0.05 to 20% by weight, more preferably 0.1 to 30% by weight, based on the total amount of the polyol and the ethylenically unsaturated monomer.
-10% by weight are used.

Further, for the purpose of stably dispersing the polymer particles, it is possible to carry out the polymerization in the presence of a dispersion stabilizer. Such a dispersion stabilizer is disclosed in Japanese Patent Publication No. Sho 49-4.
Examples thereof include a polyester ether polyol having a carbon-carbon unsaturated bond as described in JP-A-6556, a modified polyol having an acryl group, a methacryl group, an allyl group, or the like at the terminal. Further, a high molecular weight polyoxyalkylene polyol or a polyester ether polyol substantially containing no carbon-carbon unsaturated bond can also be used.

The polymerization reaction can be carried out without a solvent, but by carrying out the reaction in the presence of a suitable solvent, it is possible to suppress an increase in the particle size due to aggregation of the polymer particles. When the monomer (B) does not dissolve N-methylolacrylamide or when the ethylenically unsaturated monomer is solid, it can be used for the purpose of dissolving it. Some that can be used as a solvent have an effect as a chain transfer agent. Preferred solvents include hydrocarbons such as toluene and xylene, polar compounds such as water, dimethylformamide and dimethylsulfoxide, and aliphatic compounds having 1 to 4 carbon atoms such as methanol, ethanol, isopropanol, butanol, ethylene glycol and propylene glycol. Alcohols, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1,2-dimethoxypropane,
1,2-diethoxypropane, 1,2-dimethoxyethane, one or more selected from alkyl ethers of aliphatic alcohols such as 1,2-diethoxyethane and the like, or a mixture thereof, preferably water, It is at least one selected from aliphatic alcohols having 1 to 4 carbon atoms and alkyl ethers of aliphatic alcohols.

The amount of the solvent to be used is not limited, but is preferably as small as possible in order to remove the solvent after the polymerization. In the present invention, it is preferable to use 0.1 to 100 parts by weight based on 100 parts by weight of the obtained polymer-dispersed polyol.

In the polymerization reaction, if necessary, an acid catalyst can be used as a reaction regulator for N-methylolacrylamide. Acid catalysts include carboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, octanoic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, and stearic acid, oxalic acid, malonic acid, and succinic acid , Glutaric acid, dicarboxylic acids such as adipic acid, benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, salicylic acid, aromatic carboxylic acids such as p-toluenesulfonic acid, sulfuric acid, phosphoric acid, hydrochloric acid, and inorganic acids such as nitric acid. No. Two or more of these acid catalysts may be used in combination. When the acid catalyst is used, the amount is 0.5 to 5.0% by weight based on the total amount of the polyol and the ethylenically unsaturated monomer.
Preferably 0.8 to 4.0% by weight, more preferably 1.0 to 3.0% by weight is used.

After completion of the polymerization, the obtained polymer-dispersed polyol can be used as a raw material for polyurethane as it is, but unreacted monomers, decomposition products of the initiator, catalyst, chain transfer agent, solvent and the like were distilled off under reduced pressure. It is preferred to use it later.

The average particle size of the polymer particles contained in the polymer-dispersed polyol of the present invention is 0.01 to 0.01 from the viewpoint of the dispersion stability of the polymer and the effect on the physical properties of the polyurethane.
It is preferably from 10 to 10 μm. Such a particle size can be achieved by appropriately adjusting the types and amounts of the chain transfer agent and the dispersion stabilizer, the weight composition ratio of the monomers, and the like.

The polymer-dispersed polyol of the present invention produced by the above method is a polymer-dispersed polyol in which fine particles of a polymer are dispersed in 5 to 50% by weight in 95 to 50% by weight of a polyol, and the polymer is an N-methylolacrylamide unit. It is a polymer-dispersed polyol containing 5 to 30% by weight of (A) and 70 to 95% by weight of a monomer unit (B) copolymerizable with (A). In the present invention, the above (B)
Is preferably at least one compound unit selected from acrylamide units, methacrylamide units, acrylonitrile units, methacrylonitrile units, and styrene units.

As a preferred polymer-dispersed polyol of the present invention, (1) the content of at least one (B) selected from acrylamide units and methacrylamide units is 5 to the total amount of the above (A) and (B). ~ 80% by weight
Wherein the content of at least one (B) selected from the above polymer-dispersed polyol, (2) acrylonitrile unit and methacrylonitrile unit is 5 to 70% by weight based on the total amount of (A) and (B). Wherein the content of the styrene unit (B) is 5 to 60% by weight based on the total amount of the components (A) and (B).
The content of the above polymer-dispersed polyol, (4) acrylonitrile units and styrene units is 5 to 70% by weight and 5 to 70% by weight, respectively, based on the total amount of (A) and (B).
And 60% by weight of the above-mentioned polymer-dispersed polyol.

The main characteristic of the polymer-dispersed polyol of the present invention having the above composition is that the viscosity is 1000 to 7000 mP.
a · s, water absorption is 0 to 6%. In particular, it is characterized by low water absorption and excellent water resistance. On the other hand, the water absorption of a conventional polymer-dispersed polyol shows a considerably high value of 6 to 10% depending on the polymer composition.

When the polymer-dispersed polyol of the present invention is used as a raw material for polyurethane, it may be mixed with polymer-dispersed polyols, mixed with a conventionally known polymer-dispersed polyol, or diluted with the above-mentioned polyol. Can be used. In that case, the polymer-dispersed polyol according to the present invention has at least 30
It is preferred that the content be contained by weight.

The polyurethane foam of the present invention is prepared by reacting an active hydrogen compound containing the above-mentioned polymer-dispersed polyol or a mixture of the polymer-dispersed polyol and polyol with a polyisocyanate in the presence of a catalyst, a foam stabilizer and a foaming agent. can get.

The average hydroxyl value of the polyol used as a raw material can be selected depending on the use and the molding method of the polyurethane foam. For flexible polyurethane foam,
A polyol having an average hydroxyl value of 10 to 100 mgKOH / g is preferred. 100 ~ for rigid polyurethane foam
A 600 mg KOH / g polyol is preferred. Further, for a flexible polyurethane foam, 10 to 50 mgKOH / g for a high elastic mold foam (cold cure foam) depending on the molding temperature at which the mold is molded.
Are preferred. For hot cure molds, 30-80 mg KOH / g polyol is preferred. For slab foam, 20 ~ 100mgKO
H / g polyols are preferred. The polymer-dispersed polyol of the present invention can be used for any of the above polyurethane foams.

As the polyisocyanate, any known polyisocyanate that is usually used in the production of polyurethane can be used. For example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 80/20 weight ratio of these organic polyisocyanates (TDI-80 /
20), 65/35 by weight (TDI-65 / 35) isomer mixture, crude tolylene diisocyanate containing polyfunctional tar, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane Diisocyanate, 2,2′-diphenylmethane diisocyanate,
Crude MDI containing any mixture of isomers of diphenylmethane diisocyanate, tri- or higher polyfunctional tar
(Polymeric MDI), toluidine diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, and carbodiimide-modified or burette-modified organic polyisocyanates, or polyols or monools alone or in combination. And a modified prepolymer. The above polyisocyanates can be used by mixing at an arbitrary ratio.

The equivalent ratio between the polyisocyanate and the active hydrogen compound is not particularly limited, but is based on the NCO in the polyisocyanate and the active hydrogen such as a polyol containing a polymer-dispersed polyol, water and a crosslinking agent. And then N
CO / H (active hydrogen) is preferably in the range of 0.50 to 3.0.

Examples of the foaming agent include water, low-boiling hydrocarbons such as carbon dioxide, cyclopentane, n-pentane and isopentane, hydrofluorocarbons such as HFC-245fa, fluorinated ethers, perfluorocarbons and the like. Blowing agents commonly used for polyurethane foam production can be used. Preferably it is water.

As the catalyst, all those usually used in the production of polyurethane can be used. For example, amine catalysts include triethylamine, tripropylamine, tributylamine, N, N, N ', N'-tetramethylhexamethylenediamine, N-methylmorpholine,
N-ethylmorpholine, dimethylcyclohexylamine, bis [2- (dimethylamino) ethyl] ether,
Triethylenediamine, salts of triethylenediamine, etc.
Organometallic catalysts include tin acetate, tin octylate, tin oleate, tin laurate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dichloride, lead octanoate, lead naphthenate, nickel naphthenate, cobalt naphthenate And the like. These catalysts can be arbitrarily mixed and used, and the used amount is 0.0001 to 10.0 parts by weight based on 100 parts by weight of the active hydrogen compound.

The foam stabilizer is a conventionally known organic silicon-based surfactant, for example, trade name: L-5 manufactured by Nippon Unicar Co., Ltd.
20, L-532, L-540, L-544, L-55
0, L-3600, L-3601, L-5305, L-
5307, L-5309, etc., manufactured by Dow Corning Toray Co., Ltd .: SRX-253, SRX-274C, SF-
2961, SF-2962, etc., brand names manufactured by Shin-Etsu Silicone Co .: F-114, F-121, F-122, F-22
0, F-230, F-258, F-260B, F-31
7, F-341, F-601, F-606, etc., trade names: TFA-4200, TFA-42 manufactured by Toshiba Silicone Co., Ltd.
02 and the like. These foam stabilizers can be arbitrarily mixed and used.
0.1 to 10 parts by weight with respect to 0 parts by weight.

Examples of the crosslinking agent include polyols such as ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, 1,3-butanediol and 1,4-butanediol, triethanolamine,
Alkanolamines such as diethanolamine, aliphatic polyamines such as ethylenediamine, diethylenetriamine, and triethylenetetramine; aromatic polyamines such as aniline, 2,4-tolylenediamine and 2,6-tolylenediamine; , A compound having a hydroxyl value of 200 mgKOH / g or more obtained by adding propylene oxide or the like. In addition, a compound having a hydroxyl value of 200 mgKOH / g or more obtained by adding ethylene oxide, propylene oxide, or the like to hydroquinone, resorcin, aniline, or the like can also be used.

The polymer-dispersed polyol described above, or the polymer-dispersed polyol diluted with the polyol, a foaming agent,
A resin solution is prepared by mixing a predetermined amount of an auxiliary agent such as a catalyst, a foam stabilizer, and a crosslinking agent, and the temperature is adjusted to a predetermined temperature, for example, 20 to 30 ° C. The polyisocyanate is weighed in accordance with a predetermined NCO and an equivalent ratio of active hydrogen in the resin solution, and adjusted to a predetermined temperature, for example, 20 to 30 ° C. Thereafter, the resin solution and the polyisocyanate are rapidly mixed and free-foamed, or poured into a mold adjusted to a predetermined temperature, for example, 30 to 70 ° C. After the reaction solution is sufficiently foamed, or after foam filling, if necessary, a predetermined temperature, for example,
A predetermined time in an oven at 60 to 200 ° C., for example, 1 to 2
After curing for 0 minutes, the polyurethane foam is released from the mold and, if necessary, the foam is crushed to open the cells to obtain a desired polyurethane foam.

A flexible polyurethane foam obtained by using as a raw material an active hydrogen compound such as a polyol containing at least 30% by weight of the polymer-dispersed polyol according to the present invention has excellent wet heat compression set resistance. For example, when the foam density (overall) is 40 to 50 kg / m ³ , the wet heat compression set is less than 16%. When the foam density (overall) is 25 to 40 kg / m ³ , the wet heat compression set is 25% or less. Therefore, the polymer-dispersed polyol of the present invention is particularly suitable as a raw material for a flexible polyurethane foam having excellent resistance to wet heat compression set.

[0063]

The present invention will be described below with reference to examples. The numbers in the examples represent parts by weight in principle.

(1) Production of polymer-dispersed polyol The following raw materials were used. Polyol A: polyoxyethylene polyoxypropylene triol (EO content 1) having a hydroxyl value of 33 mgKOH / g obtained by adding propylene oxide to glycerin and then adding ethylene oxide in the presence of a KOH catalyst.
4% by weight). -Dispersion stabilizer A: a hydroxyl value of 29 mgK obtained by reacting polyol A with succinic anhydride and then ethylene oxide.
OH / g polyester ether polyol. Ethylenically unsaturated monomer: AN; acrylonitrile, St; styrene, AAM; acrylamide, NMA
M: N-methylolacrylamide Solvent: MeOH: methanol, MPrOH: 1-methoxy-2-propanol Initiator: V-59: 2,2'-azobis (2-methylbutyronitrile) manufactured by Wako Pure Chemical Industries, Ltd. .

Of the compositions shown in Tables 1 and 2, 23 parts of polyol A or polyol B were charged into a polymerization tank equipped with a condenser, and an irrigated stirring blade was used at 400 rpm.
The temperature was raised to 100 ° C. while stirring at m. Polyol A
, The uniform mixture of the monomer, the solvent, the initiator, and the dispersion stabilizer was charged into the polymerization tank over 2 hours at a uniform rate, and stirring was continued for another 1 hour. 1.33 kP of unreacted monomer and initiator, decomposition product of initiator and solvent
a (10 mmHg) under reduced pressure at 120 ° C. to obtain a polymer-dispersed polyol shown in [Table 1] or [Table 2].

Physical properties were measured in the following manner. 1) Viscosity of polymer-dispersed polyol (mPa · s) Measured with a B-type viscometer according to the polyether test method for polyurethane specified in JIS K-1557. 2) Water absorption of polymer-dispersed polyol (% by weight) The polymer-dispersed polyol is weighed into a wide-mouthed container, and the container is left in a constant-temperature and constant-humidity oven adjusted to 50 ° C. and 95% RH to measure the moisture after 7 days I do. 3) Degree of swelling of polymer particles The polymer particles obtained by washing away the polyol component from the polymer-dispersed polyol using a MeOH solvent are subjected to solid-state NMR measurement in heavy water. Under the measurement conditions of 25 ° C. and 50 ° C., the hard,
mid. , Soft into three components, 25 ° C har
The difference between the ratio of the component d and the ratio of the hard component at 50 ° C. is defined as the degree of swelling of the particles.

(2) Production of polyurethane foam In addition to the polymer-dispersed polyol, the following raw materials were used. Polyol B: Polyoxyethylene polyoxypropylene triol having a hydroxyl value of 24 mgKOH / g (EO content: 15% by weight) obtained by adding propylene oxide to glycerin and then adding ethylene oxide in the presence of a CsOH catalyst.・ Polyisocyanate TM-20: manufactured by Mitsui Chemicals, Inc.
80:20 weight ratio mixture of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate) 80
And polyisocyanate (NCO% = 44.8) consisting of 20 parts by mass and Polymeric MDI (trade name; M-200, manufactured by Mitsui Chemicals, Inc.). -Crosslinking agent: KL-210; an amine-based crosslinking agent having a hydroxyl value of 830 mgKOH / g, manufactured by Mitsui Chemicals, Inc. -Catalyst: Minico L-1020; manufactured by Active Materials Chemical Co., Ltd., amine catalyst, Minico TMDA; manufactured by Active Materials Chemical Co., Ltd., amine catalyst. -Foam stabilizer: L-3601; a silicone surfactant manufactured by Nippon Unicar Co., Ltd.

The following components were mixed to prepare a resin solution. (Formulation 1) Polyol B: 50 parts, polymer dispersed polyol: 50 parts, KL-210: 3.0 parts, water: 3.4
Part, L-1020: 0.4 part, MDA: 0.1 part, L-
3601: 1.0 part. (Formulation 2) Polyol A: 50 parts, polymer-dispersed polyol: 50 parts, KL-210: 3.0 parts, water: 3.4
Part, L-1020: 0.4 part, TMDA: 0.1 part, L
-3601: 1.0 part.

Next, a polyisocyanate (TM-2)
0) was weighed so that the molar ratio of NCO / H (active hydrogen in the resin solution) became 1.05, and the temperature was adjusted to 23 ° C.

The above resin solution and polyisocyanate were mixed with 6
After stirring and mixing for 2 seconds, the mixture was poured into an aluminum mold having an internal dimension (length: width: depth) of 400 × 400 × 100 mm whose temperature was previously adjusted to 60 ° C., and the lid was closed to foam. 10
After heat curing in a hot air oven at 0 ° C. for 5 minutes, the foam was removed from the mold and crushed. 24
After the time, the physical properties of the foam were measured.

The foam properties were measured according to the following criteria. 1) Density (kg / m ³ ) Measurement is performed according to the method described in JIS K 6400. Refers to the apparent density according to JIS standards. The overall density is measured using a rectangular foam sample having a skin skin, and the core density is measured using a rectangular foam sample without a skin skin. 2) Hardness (N / 314 cm ² , kgf / 314 cm ² ) Measured by the method of method A specified in JIS K-6400. A foam having a thickness of 94 mm to 100 mm is used. 3) Tensile strength (kPa, kgf / cm ² ), elongation (%), rebound resilience (%) Measured by the method specified in JIS K-6400. 4) Permanent set under wet heat compression (%) Measured according to the method described in JIS K-6400. At the time of measurement, the core of the molded flexible foam was
Cut out to m, width 50 mm and thickness 25 mm. The test piece is compressed to a thickness of 50%, sandwiched between parallel flat plates, and left for 22 hours at a temperature of 50 ° C. and a relative humidity of 95%. 30 minutes after removing the test piece, its thickness was measured,
The strain rate is measured in comparison with the value before the test, and the measured value is defined as the wet heat compression set.

[0072]

[Table 1]

[0073]

[Table 2]

<Consideration of Examples> In Examples 1 to 3 and Examples 4 to 6, the water absorption of the polymer-dispersed polyol was lower than those of Comparative Examples 1 to 2 and Comparative Example 3, respectively, Has a low degree of swelling in water. Further, the polyurethane foam produced by using the polymer-dispersed polyol obtained in the example had improved wet heat compression set.

[0075]

Industrial Applicability The polymer-dispersed polyol of the present invention is water-resistant, and the wet heat properties of a polyurethane foam produced using the same are improved.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification FI FI Theme Court ゛ (Reference) C08G 101: 00) C08G 101: 00) (72) Inventor Shinsuke Matsumoto 2-chome Tango-dori, Minami-ku, Nagoya-shi, Aichi Prefecture. No. 1 Mitsui Chemicals Co., Ltd. (72) Saku Izugawa 2-1-1 Tango-dori, Minami-ku, Nagoya-shi, Aichi Prefecture Inside Mitsui Chemicals Co., Ltd. (72) Masahiro Isobe 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Chemicals (72) Inventor Kazuhiko Okubo 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Prefecture F-term (reference) 4J002 BC022 BG102 BG132 CH021 FA082 4J011 PA90 PC02 PC08 4J034 BA07 DA01 DB03 DB05 DC02 DC50 DF01 DF02 DF12 DF16 DF22 DG02 DG03 DG04 DG05 DG18 DH10 DQ02 DQ04 DQ05 DQ09 DQ13 DQ16 DQ18 HA06 HA07 HC03 HC12 HC61 HC64 HC67 HC71 KA01 KC17 KC18 KC35 KD02 KD12 NA02 NA03 NA06 QC01 QD03

Claims (15)

[Claims] 1. A polymer-dispersed polyol in which 5 to 50% by weight of polymer fine particles are dispersed in 95 to 50% by weight of a polyol, wherein the polymer comprises 5 to 30% by weight of an N-methylolacrylamide unit (A), and A polymer-dispersed polyol containing 70 to 95% by weight of a monomer unit (B) copolymerizable with A). 2. The polymer-dispersed polyol according to claim 1, wherein (B) is at least one compound unit selected from acrylamide units, methacrylamide units, acrylonitrile units, methacrylonitrile units, and styrene units. 3. The content of at least one kind of (B) selected from acrylamide units and methacrylamide units is from 5 to 80% by weight based on the total amount of (A) and (B).
The polymer-dispersed polyol according to claim 1, which is: 4. The content of at least one kind of (B) selected from acrylonitrile units and methacrylonitrile units is 5 to 70% by weight based on the total amount of (A) and (B). The polymer-dispersed polyol according to the above. 5. The polymer-dispersed polyol according to claim 1, wherein the content of the styrene unit (B) is 5 to 60% by weight based on the total amount of the components (A) and (B). 6. The content of acrylonitrile unit and styrene unit is 5 to 70% by weight and 5 to 60% by weight, respectively, based on the total amount of (A) and (B).
The polymer-dispersed polyol according to the above. 7. The polyol according to claim 1, wherein the polyol is at least one selected from polyoxyalkylene polyols, polyester polyols and polyester ether polyols having an average number of functional groups of 1 to 8 and a hydroxyl value of 10 to 600 mg KOH / g. The polymer-dispersed polyol according to the above. 8. A method for producing a polymer-dispersed polyol in which 95 to 50% by weight of a polyol is used as a reaction medium and 5 to 50% by weight of an ethylenically unsaturated monomer mixture is polymerized. A method for producing a polymer-dispersed polyol, comprising 5 to 30% by weight of methylol acrylamide (A) and 70 to 95% by weight of a monomer (B) copolymerizable with (A). 9. The method according to claim 9, wherein (B) is acrylamide, methacrylamide, acrylonitrile, methacrylonitrile,
The method for producing a polymer-dispersed polyol according to claim 8, which is at least one compound selected from styrene and styrene. 10. The polymer according to claim 8, wherein the content of at least one kind of (B) selected from acrylamide and methacrylamide is 5 to 80% by weight based on the total amount of (A) and (B). A method for producing a dispersed polyol. 11. The content of at least one (B) selected from acrylonitrile and methacrylonitrile is as follows:
The method for producing a polymer-dispersed polyol according to claim 8, wherein the amount is 5 to 70% by weight based on the total amount of (A) and (B). 12. The method for producing a polymer-dispersed polyol according to claim 8, wherein the content of styrene (B) is 5 to 60% by weight based on the total amount of (A) and (B). 13. The content of acrylonitrile and styrene is 5 to the total amount of (A) and (B), respectively.
The method for producing a polymer-dispersed polyol according to claim 8, wherein the amount is from 70 to 70% by weight and from 5 to 60% by weight. 14. The polyol has an average number of functional groups of 1 to 8,
The method for producing a polymer-dispersed polyol according to claim 8, wherein the polyol is at least one polyol selected from a polyoxyalkylene polyol, a polyester polyol, and a polyester ether polyol having a hydroxyl value of 10 to 600 mgKOH / g. 15. A polyurethane foam obtained by reacting an active hydrogen compound with a polyisocyanate in the presence of a catalyst, a foam stabilizer, and a foaming agent, wherein the active hydrogen compound is any one of claims 1 to 7. Polyurethane foam containing at least 30% by weight of the polymer-dispersed polyol according to 1.