JP2001316407A - Process for preparing polymer-dispersed polyol - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a process for preparing a polymer-dispersed polyol which is suitable for a raw material of a polyurethane foam having excellent flame retardancy and durability including wet-heat compression durable strain. SOLUTION: There is provided a process for preparing a polymer-dispersed polyol, wherein in the polymerization of 5-50 wt.% of an ethylenically unsaturated monomer, which comprises 5-80 wt.% of acrylamide, 5-70 wt.% of acrylonitrile and 5-60 wt.% of styrene, in 95-50 wt.% of a polyol, an initiator of a relatively low concentration is used in the first step to polymerize the monomer mixture of 1-10 wt.% concentration based on the polyol in 60-80 wt.% of the total polyol, while in the second step, an initiator of a relatively high concentration is used to polymerize the rest of the monomer mixture by adding the rest of the polyol and the rest of the monomer mixture to the reaction liquid of the first step.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

[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 dispersed has conventionally been 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, it is referred to as 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. But,
On the other hand, there is a disadvantage that durability such as wet heat compression set of the foam deteriorates with an increase in the polymer concentration 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 Publication No. 2527006 discloses an aldehyde condensation-based resin fine particle dispersion. However, the results of the additional tests by the present inventors show that, when the aldehyde condensation-based resin fine particle dispersion is made of polyurethane, the physical properties such as wet heat permanent set, which are particularly related to durability, are lower than our target level. Have been obtained.

[0005] It is an object to provide a polymer-dispersed polyol that imparts flame retardancy without deteriorating the physical properties of a polyurethane foam.
It 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 is obtained. However, when flame retardancy is further required depending on the application, maintenance of durability, that is, improvement of wet heat properties becomes an issue.

[0006]

SUMMARY OF THE INVENTION In view of the above problems, an object of the present invention is to provide a polymer-dispersed polyol having excellent water resistance even when foam properties are expected to deteriorate due to high hardness or flame retardancy. It is another object of the present invention to provide a polymer-dispersed polyol suitable for a raw material of a polyurethane foam having excellent flame retardancy and durability such as durable compression under wet heat.

[0007]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that the above object can be achieved by limiting the monomer concentration and the initiator concentration of the reaction solution at the beginning of polymerization and thereafter, respectively. The present invention has been reached.

[0008] That is, the present invention is to polymerize an ethylenically unsaturated monomer mixture in 95 to 50% by weight of a polyol in the presence of a radical polymerization initiator to form polymer fine particles of 5 to 50%.
In the method for producing a polymer-dispersed polyol in which a weight% is dispersed, (1) the ethylenically unsaturated monomer mixture is
5 to 80% by weight of an acrylamide compound (A), 5 to 70% by weight of at least one compound selected from acrylonitrile and methacrylonitrile (B), and 5 to 60% by weight of a styrene monomer (C); A) preparing a polyol diluent (a) in which the concentration of the ethylenically unsaturated monomer mixture is 1 to 10% by weight from 60 to 80% by weight of the total polyol and a part of the ethylenically unsaturated monomer mixture; A first step of adding 0.02 to 0.1 times the equivalent of a radical initiator to the liquid (a) to polymerize the mixture by adding a radical initiator to the liquid (a), and (3) 40 to 20% by weight of the total polyl, From the balance of the ethylenically unsaturated monomer mixture and the radical initiator, the concentration of the ethylenically unsaturated monomer mixture is from 10 to 85% by weight, Of over mixture 0.001 to 0.0
A polyol diluent (b) containing a 25-fold equivalent of a radical initiator, a diluent (b) is added to the reaction solution obtained in the first step, and polymerization is performed. This is a method for producing a polymer-dispersed polyol characterized by polymerizing.

In the present invention, the acrylamide compound (A) is at least one compound selected from acrylamide and methacrylamide, and the polyol has an average number of functional groups of 1 to 8 and a hydroxyl value of 10 to 60.
It is preferably at least one polyol selected from a polyoxyalkylene polyol, a polyester polyol, and a polyester ether polyol, which is 0 mgKOH / g. The polymer-dispersed polyol obtained according to the present invention has excellent water resistance. Further, the polymer-dispersed polyol obtained according to the present invention is suitably used as a raw material for a polyurethane foam having excellent flame retardancy and durability such as wet heat compression durability distortion.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The polymer-dispersed polyol of the present invention is obtained by dispersing polymer fine particles obtained by polymerizing an ethylenically unsaturated monomer in a polyol. Hereinafter, the polymer fine particles comprising the ethylenically unsaturated monomer according to the present invention and the method for producing the polymer-dispersed polyol of the present invention in which this polymer is dispersed will be described in detail.

In the method for producing a polymer-dispersed polyol according to the present invention, the polyol is a hydrocarbon-based polyol such as a polyoxyalkylene polyol, a polyester polyol, a polyester ether polyol, a polycarbonate polyol, or a polybutadiene polyol which is generally used as a raw material for polyurethane. Etc. can be used.

Examples of the polyoxyalkylene polyol include those obtained by addition-polymerizing 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, a polyester polyol obtained by ring-opening addition of ε-caprolactone, γ-butyrolactone, or the like with a polyhydric alcohol such as glycerin as an initiator, diols such as ethylene glycol, propylene glycol, and pentanediol; Examples thereof include acids, dicarboxylic acids such as phthalic anhydride and acid anhydrides, 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. Examples of the polycarbonate polyol include those obtained by condensation of a divalent or trivalent low molecular polyol with a diester carbonate such as dimethyl carbonate or diethyl carbonate. Examples of the polybutadiene polyol include Poly-bd (trade name, manufactured by ARCO) and Nisso PB (trade name, manufactured by Nippon Soda Co., Ltd.). 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 method for producing a polymer-dispersed polyol according to 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 is a mixture containing an acrylamide compound (A), at least one compound (B) selected from acrylonitrile and methacrylonitrile, and a styrene monomer (C). .

Examples of the acrylamide compound (A) include acrylamide, methacrylamide, 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-diacryloylpiperazine, N, N-dioctyl Acryloylamide, methylenebisacrylamide, N, N-dimethylmethacryloylamide, 1-methacryloylimidazole, methacryloyl-L-valineme Glycol ester, methacryloyl -L
-Leucine methyl ester and the like. Preferred are acrylamide and methacrylamide. The preferred monomer mixture in the present invention is a mixture containing (A) acrylamide, (B) acrylonitrile, and (C) styrene.

In the present invention, other monomers can be used in addition to the acrylamide compound (A), at least one compound selected from acrylonitrile and methacrylonitrile (B), and the styrene monomer (C). .

Other monomers include α-methylstyrene, 2-methylstyrene, 3-methylstyrene,
-Methylstyrene, 2-vinylphenol, 3-vinylphenol, p-isopropenylphenol, 3-vinylbenzoic acid, 4-vinylbenzoic acid, 4-vinylthiophenol, 4-methoxystyrene, 4-ethoxystyrene, 4-vinylbiphenyl, p
Sodium styrene sulfonate, potassium p-styrene sulfonate, 4-aminostyrene, 5-aminostyrene, 4-dimethylaminostyrene, 4-vinylbenzyl alcohol, 4-phenoxystyrene, 4-vinylbenzoate, 4-acetoxystyrene, Aromatic monomers such as vinylphenylacetonitrile, 4-t-butylstyrene, p-octylstyrene, p-cyclohexylstyrene, p-dodecylstyrene, 4-isopropylstyrene, N- (4-vinylphenyl) maleimide and 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 esters such as vinyl n-hexanoate, vinyl n-octanoate, vinyl n-decanoate, vinyl laurate, vinyl palmitate and vinyl stearate are exemplified.

In the polymer-dispersed polyol obtained by the production method of the present invention, 5 to 50% by weight of polymer fine particles obtained by polymerizing a mixture of the above ethylenically unsaturated monomers is dispersed in 95 to 50% by weight of a polyol. Things. 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 a polymer-dispersed polyol, such as communication and high hardness, when formed into a polyurethane foam is small. If it exceeds 50% by weight, the dispersion stability of the polymer-dispersed polyol is lowered, the viscosity becomes high, and the handling becomes difficult.

The amount of the acrylamide compound (A) used in the present invention is 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 the acrylamide compound is used in an amount of 5% by weight or more based on the total amount of the ethylenically unsaturated monomer, the polyurethane using the obtained polymer-dispersed polyol has an excellent flame retardancy. 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.

The amount of at least one compound (B) selected from acrylonitrile and methacrylonitrile in the present invention is 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 to 60% by weight. Compound (B) is added to the total amount of ethylenically unsaturated monomers in an amount of 5%.
When it is used in an amount of not less than% by weight, the dispersion stability of the polymer-dispersed polyol is improved, and the effect of increasing the hardness of the polyurethane foam using the obtained polymer-dispersed polyol is obtained. If the amount is less than 5% by weight, the above-mentioned effects cannot be obtained.
Exceeding 0% by weight is not preferred because the wet heat permanent set of the polyurethane foam decreases.

The amount of the styrene monomer (C) used in the present invention is 5 to the total amount of the ethylenically unsaturated monomer.
６０60% by weight. Preferably it is 7 to 55% by weight, 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. If the amount is less than 5% by weight, the above-mentioned effects cannot be obtained. If the amount exceeds 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.

In the method for producing a polymer-dispersed polyol of the present invention, the polymerization is preferably carried out by a semi-batch method. In the first step, the concentration of the ethylenically unsaturated monomer mixture is from 1 to 10 using 60 to 80% by weight of the total polyol.
A polyol diluent (a) is prepared by weight%. In the polyol diluent (a), a radical initiator is added in an amount of 0.02 to 0.1 times equivalent of the ethylenically unsaturated monomer to perform polymerization.

In the second step, the concentration of the ethylenically unsaturated monomer mixture is from 10 to 85% by weight, based on 40 to 20% by weight of the total polyl, the balance of the ethylenically unsaturated monomer mixture, and the radical initiator. A polyol diluent (b) containing a radical initiator in an amount of 0.001 to 0.025 equivalents of the unsaturated monomer mixture is prepared. Then, the diluent (b) is added to the reaction solution obtained in the first step to carry out polymerization. In the present invention, the first step and the second step are sequentially performed to produce a polymer-dispersed polyol.

That is, in the first step, the equivalent of the initiator to the monomer is relatively large, and it can be expected that a graftmer which contributes to the stabilization of the polymer particles will be formed. Further, according to the findings of the present inventors, the amount of the styrene monomer reacted at this time is larger than that in the normal stage of polymerization, and it can be expected that the resulting graft mer is relatively hydrophobic.
In the second step, since the polymerization reaction proceeds in the presence of the hydrophobic graftmer, the obtained polymer particles are covered with the hydrophobic graftmer, and water resistance under wet heat conditions can be expected.

The polyol diluent (a) prepared in the first step has a total monomer concentration of 1 to 10% by weight, preferably 1 to 7% by weight, more preferably 1 to 5% by weight of the total amount of the diluent.
% By weight. If the amount is less than 1% by weight, the amount of the hydrophobic graftmer that becomes a seed is reduced, and the effect of improving the wet heat properties of a polyurethane foam cannot be obtained. On the other hand, if it exceeds 10% by weight, the viscosity increases at the beginning of polymerization, which is not preferable.

The polyol diluent (b) used in the second step has a total monomer concentration of 10 to 85% by weight, preferably 20 to 50% by weight, more preferably 25 to 35% by weight of the total amount of the diluent. . If the content is less than 10% by weight, the finally obtained polymer concentration is low, and effects such as high hardness of the polyurethane foam cannot be obtained. If it exceeds 85% by weight, dispersion stability cannot be maintained due to a sudden change in the monomer concentration in the system, which is not preferable.

In the first step, the total amount of the polyol is 6
0-80% by weight is used. Preferably 60-70% by weight, more preferably 60-65% by weight is used. Therefore, the polyol used in the second step is the balance, and is 40 to 20% by weight. Preferably it is 40 to 30% by weight, more preferably 40 to 35% by weight. If the amount of the polyol used in the first step is less than 60% by weight, it is difficult to obtain a monomer concentration sufficiently diluted to suppress viscosity increase at the beginning of polymerization. Further, even if the polymerization is started at a dilute monomer concentration, the amount of the hydrophobic graft mer expected to improve the wet heat property of the polyurethane is insufficient, which is not preferable. If the amount of the polyol used in the first step exceeds 80% by weight, it exceeds the limit monomer concentration required for maintaining the dispersion stability in the second step, which is not preferable.

As the polymerization initiator for polymerizing the ethylenically unsaturated monomer, usually, a radical initiator which generates a radical to start polymerization is 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 in the first step is as follows:
0.02 to 0.1 with respect to the ethylenically unsaturated monomer
Double equivalent. The equivalent is preferably 0.025 to 0.050 equivalent, more preferably 0.025 to 0.040 equivalent. If the equivalent is less than 0.02 equivalent, the amount of generated radicals is small, and a hydrophobic graftmer required for improving the wet heat property of the polyurethane foam is not formed, which is not preferable. On the other hand, if it exceeds 0.1 equivalent, the molecular weight of the hydrophobic graftmer becomes short, and it becomes impossible to cover the surface of the polymer particles, which is not preferable.

The amount of the polymerization initiator used in the second step is as follows:
0.001 to 0. 0 to the ethylenically unsaturated monomer.
It is 025 times equivalent. Preferably 0.010 to 0.02
It is 5 equivalents, more preferably 0.015 to 0.025 equivalents. If the equivalent weight is less than 0.001 equivalent, the radical concentration is low and the polymerization becomes difficult, and the molecular weight of the polymer is too long to increase the viscosity. Exceeding 0.025 equivalents is undesirable because the initiator efficiency is reduced and waste is caused, and the polymer has a low molecular weight and affects physical properties such as hardness of the polyurethane foam.

In the polymerization reaction of the present invention, a polymerization reaction is carried out using the above-mentioned polyol, ethylenically unsaturated monomer, polymerization initiator, and if necessary, a chain transfer agent, a dispersion stabilizer, a solvent and the like, to produce a polymer-dispersed polyol. . The polymerization temperature is determined according to the type of the polymerization initiator. Usually, the reaction is carried out at a temperature not lower than the decomposition temperature of the initiator, preferably 60 to 200 ° C, more preferably 80 to 160 ° C. Further, the polymerization reaction can be carried out under a pressure system or under atmospheric pressure.

In the polymerization reaction of the present invention, 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-
Aliphatic alcohols such as methyl-1-butanol, 3-methyl-1-butanol, 3-methyl-2-butanol, hexyl alcohol, ethylene glycol and propylene glycol, mercaptans such as dodecyl mercaptan and mercaptoethanol, and carbon tetrachloride , Carbon tetrabromide, halogen hydrocarbons such as chloroform, triethylamine, tripropylamine, tributylamine, N, N
-Diethylethanolamine, N-methylmorpholine,
Aliphatic tertiary amines such as N-ethylmorpholine, sodium methallylsulfonate, sodium allylsulfonate, toluene, xylene, acetonitrile, hexane,
Heptane, dioxane, ethylene glycol dimethyl ether, N, N-dimethylformamide and the like. When the chain transfer agent is used, the amount used is 0.01 to the total amount of the polyol and the ethylenically unsaturated monomer.
３０30% by weight. Preferably 0.05 to 20% by weight, more preferably 0.1 to 10% by weight is 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
Examples thereof include a polyester ether polyol having a carbon-carbon unsaturated bond as described in No. 46556, 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. However, by carrying out the polymerization in the presence of a suitable solvent, it is possible to suppress an increase in the particle diameter due to aggregation of the polymer particles. 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,
One or more of alkyl ethers of aliphatic alcohols such as 1,2-dimethoxypropane, 1,2-diethoxypropane, 1,2-dimethoxyethane, 1,2-diethoxyethane, and the like, alone or in combination. It is. Preferably, it is at least one selected from water, 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. After completion of the polymerization, the obtained polymer-dispersed polyol can be used as a raw material for polyurethane as it is. It is preferable that unreacted monomers, decomposition products of initiators, catalysts, chain transfer agents, solvents and the like are distilled off under reduced pressure before use.

The average particle size of the polymer particles contained in the polymer-dispersed polyol produced according to the present invention is preferably from 0.01 to 10 μm from the viewpoint of the influence on the dispersion stability of the polymer and the physical properties of the polyurethane. 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 produced according to the present invention can be used as a raw material for polyurethane. In this case, the polymer-dispersed polyols may be mixed with each other, mixed with a conventionally known polymer-dispersed polyol, or diluted with the above-mentioned polyol.

The polymer-dispersed polyol produced according to the present invention is used as a raw material for a polyurethane foam. In that case, the above-mentioned polymer-dispersed polyol may be used alone. Further, it may be used as another polymer-dispersed polyol and / or a mixture with the polyol. When used in combination with another polymer-dispersed polyol and / or the polyol, it is preferable that the polymer-dispersed polyol according to the present invention is contained at least 30% by weight. These are collectively called active hydrogen compounds.

Usually, a polyurethane foam is obtained by reacting an active hydrogen compound with a polyisocyanate in the presence of a catalyst, a foam stabilizer and a foaming agent. The average hydroxyl value of the polyol in the active hydrogen compound used as a raw material can be selected depending on the use and the molding method of the polyurethane foam.

For a flexible polyurethane foam, a polyol having an average hydroxyl value of 10 to 100 mgKOH / g is preferable, and for a rigid polyurethane foam, a polyol having an average hydroxyl value of 100 to 600 mgKOH / g is preferable.
mg KOH / g polyol is preferred. Further, as the flexible polyurethane foam, a polyol of 10 to 50 mgKOH / g is preferable for a high elasticity mold foam (cold cure foam), and a polyol of 30 to 50 mgKOH / g is preferable for a hot cure mold.
80 mg KOH / g polyol is preferred. For slab foam, a polyol of 20 to 100 mgKOH / g is preferable.

Polymer-dispersed poly produced according to the present invention
Oars are used for any of the above polyurethane foams.
Can be used. In particular, as a raw material for flexible polyurethane foam
It is preferable to use it. Foam density (over
40-50 kg / m ^Three, 16
% Flexible polyurethane foam, foam density
(Overall) is 25-40kg / m^ThreeWith wet heat compression
Of a flexible polyurethane foam having a permanent set of 25% or less
It is preferably used as a raw material for production.

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 NCO in the polyisocyanate and 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 of 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. The amount of use 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. The amount of active hydrogen compound 1
0.1 to 10 parts by weight with respect to 00 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.

Active hydrogen compound (the polymer-dispersed polyol according to the present invention, the polymer-dispersed polyol diluted with a polyol, or a mixture of the polymer-dispersed polyol and another polymer-dispersed polyol according to the present invention or a polymerol diluent thereof) , Blowing agent, catalyst,
A resin solution is prepared by mixing a predetermined amount of an auxiliary agent such as 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 filled with foam, if necessary, at a predetermined temperature, for example, 60 to 20
The polyurethane foam is cured in an oven at 0 ° C. for a predetermined time, for example, 1 to 20 minutes, the polyurethane foam is released, and the foam is crushed, if necessary, to connect the cells to obtain a desired polyurethane foam.

[0053]

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

(Production of polymer-dispersed polyol) The following raw materials were used. Polyol A: Polyoxyethylene polyoxypropylene triol (EO content: 14 mg / g) 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.
weight%). 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. -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. -Solvent: MeOH; methanol. -Initiator: V-59; manufactured by Wako Pure Chemical Industries, Ltd., 2,2'-azobis (2-methylbutyronitrile).

Examples 1 to 3 10% by weight of a mixture of AN, St and AAM consisting of 5.00 parts of MeOH and 5.00 parts of MeOH was dissolved in 47 parts of polyol A (or B). The mixture was charged into a polymerization tank equipped with a condenser, and heated to 117 ° C. while stirring the squid type stirring blade at 400 rpm. 0.075 part of V-59 dissolved in 0.15 part of MeOH was charged into the polymerization tank, and stirring was continued for 30 minutes. Next, the monomer and Me
The remaining 90% by weight of the mixture of OH, the total amount of the dispersion stabilizer and 0.425 part of V-59 dissolved in the rest of the polyol A (or B) were mixed at a uniform rate over 3 hours. , And the mixture was further stirred for 1 hour. Unreacted monomers, initiators, decomposition products of the initiators, and solvents were removed at 120 ° C. under a reduced pressure of 1.33 kPa (10 mmHg) to obtain polymer-dispersed polyols shown in Table 1.

Comparative Examples 1 and 2 Among the compositions shown in Table 2, 23 parts of polyol A (or B) were charged into a polymerization tank equipped with a condenser, and the mixture was heated to 100 ° C. while stirring the squirrel-type stirring blade at 400 rpm. The temperature rose. The remainder of polyol A (or B), monomer,
A uniform mixture of the solvent, the initiator, and the dispersion stabilizer was charged into the polymerization tank at a uniform rate over 2 hours, and the mixture was further added for 1 hour.
Stirring was continued for hours. Unreacted monomers, initiators, decomposition products of the initiators, and solvents were removed at 120 ° C. under a reduced pressure of 1.33 kPa (10 mmHg) to obtain polymer-dispersed polyols shown in Table 2.

The physical properties were measured in the following manner. (1) Viscosity of polymer-dispersed polyol (mPa · s / 2)
5 ° C.) 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 The polymer-dispersed polyol was weighed in a wide-mouthed container, and the entire container was allowed to stand in a constant temperature and humidity oven adjusted to 50 ° C. and 95% RH. Measure the moisture.

(3) Swelling degree 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.

(Production Example of Polyurethane Foam) In addition to the polymer-dispersed polyol, the following raw materials were used.・ Polyisocyanate TM-20: manufactured by Mitsui Chemicals, Inc.
80 parts of a mixture of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate in a weight ratio of 80:20, and Polymeric MDI M-200 (Mitsui Chemicals, Inc.)
Polyisocyanate (NCO% = 4)
4.8). -Crosslinking agent KL-210: manufactured by Mitsui Chemicals, Inc., hydroxyl value 8
30 mg KOH / g amine-based crosslinking agent. -Catalyst: Minico L-1020; manufactured by Active Materials Chemical Co., Ltd., amine catalyst. Minico TMDA; Amine-based catalyst manufactured by Active Materials Chemical Co., Ltd. -Foam stabilizer L-3601: manufactured by Nippon Unicar Co., Ltd., a silicone surfactant.

The following components were mixed to prepare a resin solution. Polyol A: 50 parts, polymer dispersed polyol 50
Parts, KL-210: 3.0 parts, water: 3.4 parts, L-10
20: 0.4 part, TMDA: 0.1 part, L-3601:
1.0 parts.

Next, polyisocyanate (TM-20)
Has a molar ratio of NCO / H (active hydrogen in the resin solution) of 1.
The amount which became 05 was weighed, 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 physical properties of the foam are measured according to the following criteria. 1) Density (kg / m ³ ) Measured according to the method described in JIS K 6400. J
Refers to the apparent density in the IS standard. 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 / 3
14 cm ² ) Measured by the method described in Method A of JIS K 6400. A foam having a thickness of 94 mm to 100 mm is used. 3) Tensile strength (kPa), elongation (%), rebound resilience (%) Measured by the method specified in JIS K-6400.

3) Wet heat compression set (%) Measured according to the method described in JIS K-6400. The core part of the flexible foam molded at the time of measurement is 50 mm long,
Cut out to a width of 50 mm and a thickness of 25 mm. The specimen was compressed to a thickness of 50%, sandwiched between parallel flat plates,
It is left for 22 hours under the conditions of 0 ° C. and 95% relative humidity. Thirty minutes after the test piece was taken out, its thickness was measured and compared with the value before the test to calculate the strain rate. 4) Burning rate (mm / min) The burning rate is measured according to the United States automobile safety standard FMVSS-302. 5) Oxygen index 23 ± according to the method for measuring the flame retardancy index of JIS D-1201
Measure the minimum oxygen concentration required for combustion at 2 ° C.

[0067]

[Table 1]

[0068]

[Table 2]

<Consideration of the Examples> The polymer-dispersed polyol obtained in the examples has low water absorption and a small degree of swelling of the polymer particles. The polyurethane foams produced using these were all flame retardant, and the wet heat compression set was improved as compared with the polyurethane foam produced using the polymer-dispersed polyol obtained in Comparative Example 1. . Further, the same foam properties as the polyurethane foam produced using the general-purpose polymer-dispersed polyol obtained in Comparative Example 2 are maintained.

[0070]

The polymer-dispersed polyol produced according to the present invention has excellent water resistance. In addition, the wet heat properties of the polyurethane foam produced using the same are improved.

 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Shinsuke Matsumoto 2-1-1 Tango-dori, Minami-ku, Nagoya, Aichi Prefecture Inside Mitsui Chemicals, Inc. (72) Inventor Saku Izugawa 2-1-1 Tango-dori, Minami-ku, Nagoya-shi, Aichi No. Mitsui Chemicals Co., Ltd. (72) Inventor Masahiro Isobe 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Prefecture Inside Mitsui Chemicals Co., Ltd. (72) Kazuhiko Okubo 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa F-term in Mitsui Chemicals Co., Ltd. (Reference) 4J011 PA25 PA88 PA90 PC02 4J026 AB07 AB19 AC36 BA05 BA31 BA32 DB03 DB12 DB13

Claims (3)

[Claims] 1. A method for producing a polymer-dispersed polyol, comprising polymerizing an ethylenically unsaturated monomer mixture in 95 to 50% by weight of a polyol in the presence of a radical polymerization initiator to disperse 5 to 50% by weight of polymer fine particles.
(1) An ethylenically unsaturated monomer mixture is 5 to 80% by weight of an acrylamide compound (A), 5 to 70% by weight of at least one compound (B) selected from acrylonitrile and methacrylonitrile, and a styrene monomer (C (2) 60 to 80% by weight of the total polyol, and from a part of the ethylenically unsaturated monomer mixture, the concentration of the ethylenically unsaturated monomer mixture is 1 to 10% by weight. A first step of preparing a polyol diluent (a), adding 0.02 to 0.1 times equivalent of a radical initiator of the ethylenically unsaturated monomer mixture to the diluent (a), and polymerizing; ) 40 of all the polyles
-20% by weight, from the remainder of the ethylenically unsaturated monomer mixture, and from the radical initiator, the concentration of the ethylenically unsaturated monomer mixture was 10-85% by weight, and 0.001-0. A polyol diluent (b) containing 025 equivalents of a radical initiator, a diluent (b) is added to the reaction liquid obtained in the first step, and polymerization is performed. A method for producing a polymer-dispersed polyol, which comprises polymerizing. 2. The method for producing a polymer-dispersed polyol according to claim 1, wherein the acrylamide compound (A) is at least one compound selected from acrylamide and methacrylamide. 3. The polyol is at least one polyol 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. 2. A method for producing the polymer-dispersed polyol according to 1.