JP5407544B2 - Method for producing polymer-dispersed polyol - Google Patents

Description

  The present invention relates to a method for producing a polymer-dispersed polyol for rigid polyurethane foam.

A rigid foamed synthetic resin produced by reacting a polyol component and a polyisocyanate component in the presence of a foaming agent or the like (for example, rigid polyurethane foam or the like; hereinafter sometimes referred to as “rigid foam”) has closed cells. It is widely used as a heat insulating material.
As a foaming agent used for the rigid foam, water, a low-boiling point hydrofluorocarbon compound or a hydrocarbon compound is mainly used.

In rigid foams typified by boards and the like, further reduction in density of foams is desired in order to reduce costs and reduce weight by reducing the amount of raw materials used. However, as the density of the foam is reduced, there is a problem that the foam strength is reduced and the rigid foam is likely to shrink.
In addition, in the case of foaming agents, considering the burden on the environment, reducing low-boiling hydrofluorocarbon compounds and increasing water, or considering flammability, reducing hydrocarbon compounds and increasing water In addition, a technique of using only water without using a low-boiling point hydrofluorocarbon compound or hydrocarbon compound has been studied.
However, when the density of the foam is reduced by water foaming, such as by using a hydrofluorocarbon compound or hydrocarbon compound in combination with water to reduce the density of the foam or by foaming only with water, the foam is prominent. The dimensional stability of the foam deteriorates.

As measures for the dimensional stability of the foam, usually, the foam density is increased to increase the foam strength, or the foam bubbles are made to be open cells.
However, measures to increase the density of the foam increase the cost because the amount of raw material used increases. In addition, the measures for making the foam cells into continuous cells improve the dimensional stability of the foam, but cannot provide sufficient heat insulation performance.
That is, in a rigid foam, when water is frequently used as a foaming agent or foamed with only water, a foam having good foam dimensional stability and sufficient heat insulating performance is desired.

  Conventionally, a method using a fluorine-containing compound such as polytetrafluoroethylene (PTFE) has been proposed as a known technique for preventing shrinkage of rigid polyurethane foam and improving dimensional stability (see Patent Documents 1 and 2). . According to the methods described in Patent Documents 1 and 2, by adding PTFE having a small particle size, dimensional stability is improved by opening fine pores in the foam, and good heat insulating performance is also obtained.

Moreover, the method of mix | blending polymer-dispersed polyol with a polyol component is proposed (refer patent document 3, 4).
The “polymer-dispersed polyol” is a polyol in which polymer fine particles are dispersed in a polyol such as polyether polyol or polyester polyol.
The polymer-dispersed polyol is conventionally used for improving the hardness of a flexible foam or a semi-rigid foam.

  The following method is known as a typical example of a method for producing a polymer-dispersed polyol. That is, in a saturated polyol having no polymerizable unsaturated bond, in some cases, under the condition that an unsaturated polyol having a polymerizable unsaturated bond is also present, the monomer having a polymerizable unsaturated group is polymerized, and then This is a method for removing unreacted components. As the saturated polyol or the unsaturated polyol, various polyether polyols and polyester polyols are known.

European Patent Application No. 0224945 JP-T 8-503720 JP 57-25313 A JP-A-11-302340

However, for example, the fluorine-containing compounds used in the methods described in Patent Documents 1 and 2 generally have poor solubility in organic substances. Therefore, a fluorine-containing compound such as PTFE is added to the polyol compound for storage. In this case, it was found that the storage stability was insufficient such as separation of the fluorine-containing compound and the polyol compound.
In addition, the polymer-dispersed polyol used in the method described in Patent Document 3 has insufficient storage stability when mixed with a polyol for rigid polyurethane foam having a low molecular weight, and dimensional stability when formed into a rigid polyurethane foam. It has been found that it is difficult to achieve both compatibility and heat insulation performance.
The method described in Patent Document 4 aims to achieve both dimensional stability and heat insulation performance, and there remains a problem with respect to heat insulation performance, that is, thermal conductivity.

Therefore, the present invention provides a polymer-dispersed polyol that has high compatibility with polyols for rigid polyurethane foam, excellent storage stability, and excellent dimensional stability and good heat insulation performance when used as rigid polyurethane foam. Provide a method.
The “storage stability” in the present invention means a characteristic capable of maintaining the uniformity of the mixture when the mixture of the polymer-dispersed polyol and the polyol for rigid polyurethane foam is stored. When the storage stability is poor, it is difficult to obtain a rigid polyurethane foam of stable quality, such as polymer fine particles are separated from the polyol compound, or the polymer-dispersed polyol migrates in the mixture and the composition becomes non-uniform. Become.

In the method for producing a polymer-dispersed polyol for rigid polyurethane foam in which polymer fine particles are dispersed in a polyol by polymerizing a monomer having a polymerizable unsaturated group in the polyol (X), the polyol (X) is: The monomer containing the following polyether polyol (Y) and having the polymerizable unsaturated group contains a fluorine-containing acrylate or a fluorine-containing methacrylate, and is a method for producing a polymer-dispersed polyol.
The polyether polyol (Y) has an oxyethylene group content of 15% by mass or more, and the polyether polyol (Y) is a polyol Y1 having a hydroxyl value of 200 to 800 mgKOH / g and a polyol Y2 having a hydroxyl value of 5 to 84 mgKOH / g. only including, the blend ratio (Y1 / Y2) of the polyol Y1 and the polyol Y2 is a 5/95 to 70/30 (weight ratio).

  In the method for producing a polymer-dispersed polyol of the present invention, the fluorine-containing acrylate or fluorine-containing methacrylate is preferably a monomer represented by the following formula (1).

However, in Formula (1), ^Rf is a C1-C18 polyfluoroalkyl group, R is a hydrogen atom or a methyl group, Z is a bivalent coupling group which does not contain a fluorine atom, Z And R ^f are separated so that the carbon number of R ^f is small.

In the method for producing a polymer-dispersed polyol of the present invention, it is preferable that the monomer having a polymerizable unsaturated group further contains at least one selected from the group consisting of acrylonitrile, vinyl acetate and styrene.
In the method for producing a polymer-dispersed polyol of the present invention, the polyether polyol (Y) preferably has an oxyethylene group content of 20% by mass or more .
Also, in the method for producing a polymer-dispersed polyol of the present invention, the polyol Y2 is a polyhydric alcohol, is preferably a polyoxyalkylene polyol obtained by addition polymerization of propylene oxide and ethylene oxide.
Moreover, in the manufacturing method of the polymer dispersion | distribution polyol of this invention, it is preferable that the ratio of the monomer represented by the said Formula (1) in all the monomers which have the said polymerizable unsaturated group is 30-100 mass%.
In the method for producing a polymer-dispersed polyol according to the present invention, the monomer represented by the formula (1) is such that R ^f is a polyfluoroalkyl group having 3 to 8 carbon atoms, and Z is an alkylene group or an arylene group. Preferably there is.
Moreover, in the manufacturing method of the polymer dispersion | distribution polyol of this invention, the monomer represented by the said Formula (1) is either the monomer represented by the following Formula (1-1)-(1-3). Is preferred.

  Moreover, in the manufacturing method of the polymer dispersion | distribution polyol of this invention, it is preferable that the density | concentration of the said polymer fine particle is 1-50 mass%.

  According to the method for producing a polymer-dispersed polyol of the present invention, the compatibility with a polyol for a rigid polyurethane foam is high, and the storage stability is excellent. The resulting polymer-dispersed polyol can be produced.

≪Method for producing polymer-dispersed polyol≫
The method for producing a polymer-dispersed polyol of the present invention produces a polymer-dispersed polyol for a rigid polyurethane foam in which polymer fine particles are dispersed in a polyol by polymerizing a monomer having a polymerizable unsaturated group in the polyol (X). In the method, the polyol (X) contains a specific polyether polyol (Y), and the monomer having a polymerizable unsaturated group contains a fluorine-containing acrylate or a fluorine-containing methacrylate.

  In the present invention, “in the polyol (X)” may be in the polyol (X) alone, and the solvent exemplified in the description of the “method for producing a polymer-dispersed polyol” described later and the polyol (X )).

[Polyol (X)]
As the polyol (X) in the present invention, for example, a polyether polyol, a polyester polyol, or a hydrocarbon polymer having a hydroxyl group at the terminal can be used.
However, in the present invention, the polyol (X) contains at least a polyether polyol (Y) having an oxyethylene group content of 15% by mass or more. The polyether polyol (Y) contains a polyol Y1 having a hydroxyl value of 200 to 800 mgKOH / g and a polyol Y2 having a hydroxyl value of 5 to 84 mgKOH / g.

Examples of the polyether polyol include water; polyhydroxy compounds such as polyhydric alcohols and polyhydric phenols; and those obtained by addition polymerization of cyclic ethers such as alkylene oxides with initiators such as amines. .
Specific examples of the initiator include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, neopentyl glycol, 3-methyl-1,5-pentanediol, 1,4-butanediol, 1,6-hexanediol, water , Polyglycerols such as glycerin, trimethylolpropane, 1,2,6-hexanetriol, pentaerythritol, diglycerin, tetramethylolcyclohexane, methylglucoside, sorbitol, mannitol, dulcitol, sucrose, triethanolamine; bisphenol A, Polyhydric phenol such as phenol-formaldehyde initial condensate; piperazine, aniline, monoethanolamine, diethanolamine, isopropanolamine, aminoethylethanol Examples include amino compounds such as amine, ammonia, aminomethylpiperazine, aminoethylpiperazine, ethylenediamine, propylenediamine, hexamethylenediamine, tolylenediamine, xylylenediamine, diphenylmethanediamine, diethylenetriamine, triethylenetetramine, and their cyclic ether adducts. It is done.
The said initiator can be used individually by 1 type or in combination of 2 or more types.

As the cyclic ether, for example, a 3- to 6-membered cyclic ether compound having one oxygen atom in the ring can be used.
Specific examples of cyclic ethers include ethylene oxide, propylene oxide, isobutylene oxide, 1-butene oxide, 2-butene oxide, trimethylethylene oxide, tetramethylethylene oxide, butadiene monooxide, styrene oxide, α-methylstyrene oxide, epichlorohydrin. , Epifluorohydrin, epibromohydrin, glycidol, butyl glycidyl ether, hexyl glycidyl ether, phenyl glycidyl ether, 2-chloroethyl glycidyl ether, o-chlorophenyl glycidyl ether, ethylene glycol diglycidyl ether, bisphenol A diglycidyl ether, 3-membered cyclic esters such as cyclohexene oxide, dihydronaphthalene oxide, vinylcyclohexene monoxide Compounds having an ether group (monoepoxide); oxetane, tetrahydrofuran, a compound having a 4-6 membered cyclic ether group such as tetrahydrofuran and tetrahydropyran.
Among these, a compound having a three-membered cyclic ether group (monoepoxide) is preferable, an alkylene oxide having 2 to 4 carbon atoms is more preferable, and ethylene oxide, propylene oxide, isobutylene oxide, 1-butene oxide or 2-butene oxide is more preferable. Further preferred is ethylene oxide or propylene oxide.
The said cyclic ether can be used individually by 1 type or in combination of 2 or more types.
When using in combination of 2 or more types of cyclic ether, as a cyclic ether, a C2-C4 alkylene oxide is preferable and the combination of a propylene oxide and ethylene oxide is the most preferable. At that time, the initiator can be subjected to addition polymerization of a mixture of two or more kinds of cyclic ethers, or two or more kinds of cyclic ethers can be addition-polymerized sequentially.

In the present invention, the polyol (X) contains at least a specific polyether polyol (Y) among the polyether polyols.
By including the polyether polyol (Y), compatibility with a polyol for rigid polyurethane foam (described later) is increased, and a polymer-dispersed polyol having excellent storage stability can be obtained.

The polyether polyol (Y) has an oxyethylene group content in the polyether polyol (Y) of 15% by mass or more, preferably 20% by mass or more, and particularly preferably 30% by mass or more. . On the other hand, the oxyethylene group content is preferably 90% by mass or less.
When the oxyethylene group content is 15% by mass or more, polymer fine particles are stably dispersed, and a polymer-dispersed polyol having improved storage stability is easily obtained. In particular, when the oxyethylene group content is 30% by mass or more, a polymer-dispersed polyol having excellent long-term storage stability is easily obtained.
In the present invention, “oxyethylene group content” means the proportion of oxyethylene groups in the polyol compound. The ratio of oxyethylene groups in the polyol compound (oxyethylene group content) was determined by using JEOL's 300 MHz ¹ H-NMR (nuclear magnetic resonance) apparatus, deuterated chloroform as a solvent, and polyoxyalkylene polyol NMR. It can be measured by measuring the spectrum.

Moreover, polyether polyol (Y) contains polyol Y1 and polyol Y2.
The hydroxyl value of the polyol Y1 is 200 to 800 mgKOH / g, preferably 300 to 700 mgKOH / g, more preferably 400 to 700 mgKOH / g, and particularly preferably 500 to 700 mgKOH / g. When the hydroxyl value is 800 mgKOH / g or less, the viscosity is low and compatibility with Y2 is easily obtained, so that the storage stability can be improved. When it is 200 mgKOH / g or more, the effect of the dispersion polymer is easily obtained, and it is easy to achieve both dimensional stability and heat insulation performance.
Moreover, the hydroxyl value of polyol Y2 is 5-84 mgKOH / g, it is preferable that it is 10-67 mgKOH / g, and it is especially preferable that it is 10-60 mgKOH / g. When the hydroxyl value is 84 mgKOH / g or less, the storage stability can be improved while the viscosity is low, and when the hydroxyl value is 5 mgKOH / g or more, the storage stability is improved.

  The blending ratio (Y1 / Y2) of the polyol Y1 and the polyol Y2 is preferably 5/95 to 70/30 (mass ratio), more preferably 5/95 to 55/45 (mass ratio), It is particularly preferably 5/95 to 50/50 (mass ratio). When the mass ratio of the polyol Y1 is 70 or less, the storage stability can be improved while the viscosity is low. Since stability and heat insulation performance can be made compatible, it is preferable.

  The polyol Y1 contained in the polyether polyol (Y) is obtained by addition polymerization of propylene oxide or ethylene oxide, or propylene oxide or ethylene oxide and one or more of the other cyclic ethers to the initiators listed above. Are preferred. The polyol (Y1) is more preferably obtained by addition polymerization of propylene oxide or ethylene oxide using a polyhydric alcohol as an initiator, and most preferably propylene oxide is used alone.

  Polyol Y1 is more preferably obtained by using one or more of glycerin, trimethylolpropane and 1,2,6-hexanetriol as an initiator, and addition polymerization of propylene oxide alone, and using glycerin as an initiator. Particularly preferred are those obtained by addition polymerization of propylene oxide alone.

  Polyol Y2 contained in the polyether polyol (Y) is preferably obtained by addition polymerization of propylene oxide, ethylene oxide or one or more of the other cyclic ethers using a polyhydric alcohol as an initiator. The polyol (Y2) is more preferably a polyoxyalkylene polyol obtained by addition polymerization of propylene oxide and ethylene oxide to a polyhydric alcohol as an initiator.

Polyol Y2 is more preferably one obtained by addition polymerization of propylene oxide and ethylene oxide using one or more of glycerin, trimethylolpropane and 1,2,6-hexanetriol as an initiator, and only glycerin as an initiator. Those obtained by addition polymerization of propylene oxide and ethylene oxide are more preferred, and those obtained by addition polymerization of a mixture of propylene oxide and ethylene oxide using only glycerin as an initiator are particularly preferred. The proportion of ethylene oxide as the cyclic ether used for addition polymerization is preferably 10% by mass to 90% by mass, more preferably 20% by mass to 90% by mass, and more preferably 20% by mass to 80% by mass, based on 100% by mass of the entire polyol Y2. Mass% is particularly preferred.
When the polyoxyalkylene polyol is used, when a rigid urethane foam is produced, it is possible to achieve both heat insulation performance and dimensional stability by adding a smaller amount of the polymer-dispersed polyol. Moreover, since performance is expressed with a small amount of addition, when mixed in a polyol for rigid urethane foam, the polymer fine particles are stably dispersed, and the storage stability can be improved.

  It is preferable that 50% by mass or more of the total amount of oxyethylene groups contained in the polyether polyol (Y) is contained in the polyol Y2. 70 mass% or more is more preferable, and 100 mass% is the most preferable.

  As the polyester polyol as the polyol (X), for example, a polyester polyol obtained by polycondensation of a polyhydric alcohol and a polycarboxylic acid can be used. Other examples include polycondensation of hydroxycarboxylic acids, polymerization of cyclic esters (lactones), polyaddition of cyclic ethers to polycarboxylic anhydrides, polyester polyols obtained by transesterification of waste polyethylene terephthalate, and the like.

  As the hydrocarbon polymer having a hydroxyl group at the terminal as the polyol (X), for example, polytetramethylene glycol (PTMG) or polybutadiene polyol can be used.

In the present invention, as the polyol (X), at least the polyether polyol (Y), a polyether polyol other than the polyether polyol (Y), a polyester polyol, and a hydrocarbon polymer having a hydroxyl group at the terminal are used in combination. May be.
The content of the polyether polyol (Y) in the polyol (X) is preferably 50% by mass or more, more preferably 80% by mass or more, and most preferably 100% by mass. When the content is 50% by mass or more, and most preferably 100% by mass, polymer fine particles are stably dispersed, and a polymer-dispersed polyol having improved storage stability is easily obtained.

[Monomer having a polymerizable unsaturated group]
The monomer having a polymerizable unsaturated group in the present invention includes fluorine-containing acrylate or fluorine-containing methacrylate (hereinafter sometimes referred to as “fluorine-containing monomer”).
By including the fluorine-containing monomer, compatibility with a polyol for rigid polyurethane foam (described later) is increased, and a polymer-dispersed polyol having excellent storage stability can be obtained. Moreover, when it is set as a rigid polyurethane foam, favorable heat insulation performance is obtained. Further, the dispersion stability of the polymer fine particles in the polyol (X) is improved, and the dimensional stability is improved when a rigid polyurethane foam is obtained.

In the present invention, the preferred fluorine-containing monomer includes a monomer represented by the formula (1) because it has high compatibility with the polyol (X).
In said formula (1), ^Rf is a C1-C18 polyfluoroalkyl group. In ^Rf , the number of carbon atoms is 1 to 18, preferably 1 to 10, and more preferably 3 to 8.
R ^f is preferably such that the proportion of fluorine atoms in the alkyl group (the proportion of the number of hydrogen atoms in the alkyl group substituted by fluorine atoms) is 80% or more, and all the hydrogen atoms are fluorine atoms. It is preferably substituted. When the number of carbon atoms is 18 or less, the foam stability is good when foaming in the production of rigid polyurethane foam, which is preferable.
R is a hydrogen atom or a methyl group. That is, the monomer represented by the formula (1) becomes an acrylate when R is a hydrogen atom, and becomes a methacrylate when R is a methyl group.
Z is a divalent linking group containing no fluorine atom, preferably a hydrocarbon group, such as an alkylene group or an arylene group, and more preferably an alkylene group. The alkylene group is preferably an alkylene group having 1 to 10 carbon atoms, particularly preferably an alkylene group having 1 to 5 carbon atoms, and may be linear or branched. In Formula (1), Z and R ^f are separated so that the number of carbon atoms in R ^f is small.
Specific examples of the monomer represented by the formula (1) are shown below.

The said fluorine-containing monomer can be used individually by 1 type or in combination of 2 or more types.
The amount of the fluorine-containing monomer used is preferably 10 to 100% by mass, and more preferably 30 to 100% by mass, based on the total monomer having the polymerizable unsaturated group.
In particular, the proportion of the monomer represented by the formula (1) in the total monomer having a polymerizable unsaturated group is preferably 20 to 100% by mass, and more preferably 30 to 100% by mass. 40% by mass or more is most preferable.
When the proportion of the monomer represented by the formula (1) is 20% by mass or more, particularly 30% by mass or more, good heat insulation performance can be obtained when a rigid polyurethane foam is obtained.
From the above, the polymer fine particles in the present invention may be a polymer composed solely of a fluorine-containing monomer, or may be a copolymer of a fluorine-containing monomer and another monomer having a polymerizable unsaturated group. Especially, since the dispersion stability of the polymer fine particle in the said polyol (X) is favorable, it is preferable that a polymer fine particle is a copolymer.

In the present invention, examples of the monomer having a polymerizable unsaturated group that may be used in combination with the fluorine-containing monomer include cyano group-containing monomers such as acrylonitrile, methacrylonitrile, 2,4-dicyanobutene-1, styrene, α- Styrene monomers such as methyl styrene and halogenated styrene; acrylic monomers such as acrylic acid, methacrylic acid or their alkyl esters, acrylamide and methacrylamide; vinyl ester monomers such as vinyl acetate and vinyl propionate; isoprene, butadiene and others Diene-based monomers; unsaturated fatty acid esters such as maleic acid diester and itaconic acid diester; vinyl halides such as vinyl chloride, vinyl bromide and vinyl fluoride; halo such as vinylidene chloride, vinylidene bromide and vinylidene fluoride Lanka vinylidene; methyl vinyl ether, ethyl vinyl ether, vinyl ether monomer such as isopropyl vinyl ether; or than those olefins, halogenated olefins, macromonomers, and the like.
The “macromonomer” refers to a low molecular weight polymer or oligomer having a radical polymerizable unsaturated group at one end.
Among these, acrylonitrile, vinyl acetate or styrene is preferable, and vinyl acetate is particularly preferable because storage stability for a longer period (for example, about one month) is improved.
One or two or more monomers other than the fluorine-containing monomer can be used.

When the fluorine-containing monomer and acrylonitrile are used in combination, the mixing ratio of the fluorine-containing monomer and acrylonitrile is preferably 10:90 to 90:10, and preferably 30:70 to 70:30. Is more preferable. Within this range, long-term storage stability is improved. Moreover, especially when it is set as a rigid polyurethane foam, heat insulation performance improves.
Preferably, the fluorine-containing monomer and acrylonitrile are used in combination, and further, polyether polyol (Y) having an oxyethylene group content of 60% by mass or more is used as polyol (X). As a result, it is possible to obtain a polymer-dispersed polyol that is particularly excellent in storage stability and exhibits good heat insulation performance when made into a rigid polyurethane foam.

  Moreover, when using together the said fluorine-containing monomer and styrene, it is preferable that the mixing ratio of the said fluorine-containing monomer and styrene is 1: 99-99: 1 by mass ratio, and is 30: 70-70: 30. More preferably. In the mixing ratio, when the ratio of styrene is not less than the lower limit value, the dimensional stability is further improved when a rigid polyurethane foam is obtained. On the other hand, when the proportion of styrene is not more than the upper limit value, the heat insulation performance is further improved when a rigid polyurethane foam is obtained.

Furthermore, when using together the said fluorine-containing monomer, acrylonitrile, and styrene, it is preferable that the mixing ratio of the said fluorine-containing monomer and other monomers is 10: 90-90: 10 by mass ratio, 30: More preferably, it is 70-70: 30.
Further, the mixing ratio of acrylonitrile and styrene is preferably 0: 100 to 100: 0, more preferably 90:10 to 10:90, in terms of mass ratio.
With this mixing ratio, the storage stability when the mixture of the polymer-dispersed polyol and the polyol for rigid polyurethane foam according to the present invention is stored, and the dimensional stability and the heat insulation performance when the mixture is made into a rigid polyurethane foam are both improved. And these characteristics can be obtained in a well-balanced manner.

Furthermore, when using together the said fluorine-containing monomer and vinyl acetate monomer, the mixing ratio (fluorine-containing monomer: vinyl acetate monomer) of the said fluorine-containing monomer and vinyl acetate monomer is 30: 70-70: 30 by mass ratio. It is preferable that it is 40:60 to 70:30.
When it is the mixing ratio, it is excellent in storage stability when the mixture of the polymer-dispersed polyol and the polyol for rigid polyurethane foam according to the present invention is stored, excellent in dimensional stability when used as a rigid polyurethane foam, and in heat insulation performance. It is excellent and these properties are well balanced.

<Method for producing polymer-dispersed polyol>
The method for producing a polymer-dispersed polyol according to the present invention includes a polymer for a rigid polyurethane foam in which a polymer having a polymerizable unsaturated group is polymerized in the polyol (X) to disperse polymer fine particles polymerized in the monomer in the polyol. The method is not particularly limited as long as it is a method for producing a dispersed polyol. For example, since the dispersion stability of the polymer fine particles in the polyol (X) is good, a monomer having a polymerizable unsaturated group is polymerized in the polyol (X) in the presence of a solvent as necessary to directly polymerize the polymer. A suitable method is a production method in which fine particles are precipitated to obtain a polymer-dispersed polyol.

Specific examples of the method for producing the polymer-dispersed polyol include the following production methods (1) and (2).
(1) A part of the polyol (X) is charged into the reactor, and while stirring, a mixture of the remaining polyol (X), a monomer having a polymerizable unsaturated group, a polymerization initiator and the like is gradually added to the reactor. A batch method in which polymerization is carried out by feeding to a catalyst.
(2) A mixture of polyol (X), a monomer having a polymerizable unsaturated group, a polymerization initiator, etc. is continuously fed into the reactor under stirring to conduct polymerization, and at the same time, the produced polymer-dispersed polyol is Continuous process that continuously discharges from the reactor.
In the present invention, any of the production methods (1) and (2) can be used.

  In the present invention, the amount of the total monomer having a polymerizable unsaturated group is not particularly limited, but the entire polymer-dispersed polyol obtained by polymerizing the monomer having a polymerizable unsaturated group in the polyol (X) is used. When the amount is 100% by mass, the polymer fine particle concentration is preferably 50% by mass or less, more preferably 1 to 50% by mass, and more preferably 2 to 45% by mass. Particularly preferred is an amount of 5 to 30% by mass. When the concentration of the polymer fine particles is 50% by mass or less, the polymer fine particles are stably dispersed in the polyol (X), and the storage stability is further improved. Moreover, a moderate viscosity is obtained and the liquid stability of the polymer-dispersed polyol is improved.

In the method for producing a polymer-dispersed polyol, as the polymerization initiator, one that generates a free radical and starts polymerization of a monomer having a polymerizable unsaturated group is usually used.
Specifically, for example, 2,2-azobis-isobutyronitrile (hereinafter abbreviated as “AIBN”), 2,2-azobis-2-methylbutyronitrile (hereinafter abbreviated as “AMBN”), 2 , 2-azobis-2,4-dimethylvaleronitrile, benzoyl peroxide, diisopropyl peroxydicarbonate, acetyl peroxide, di-tert-butyl peroxide, persulfate and the like. Of these, AIBN and AMBN are preferable.
These polymerization initiators can be used singly or in combination of two or more.
The amount of the polymerization initiator used is a total of 100 masses of the polyol (X), all monomers having a polymerizable unsaturated group including a fluorine-containing monomer, and a stabilizer or grafting agent (described later) used as necessary. It is preferable that it is 0.01-10 mass parts with respect to a part.

Examples of the solvent include alcohols such as methanol, ethanol, isopropanol, butanol, cyclohexanol and benzyl alcohol; aliphatic hydrocarbons such as pentane, hexane, cyclohexane and hexene; aromatic hydrocarbons such as benzene, toluene and xylene; acetone Ketones such as methyl ethyl ketone and acetophenone; esters such as ethyl acetate and butyl acetate; ethers such as isopropyl ether, tetrahydrofuran, benzyl ethyl ether, acetal, anisole and methyl tert-butyl ether; chlorobenzene, chloroform, dichloroethane, 1, Halogenated hydrocarbons such as 1,2-trichlorotrifluoroethane; nitro compounds such as nitrobenzene; nitriles such as acetonitrile and benzonitrile; Trimethylamine, triethylamine, tributylamine, amines such as dimethylaniline; N, N- dimethylformamide, amides such as N- methyl pyrrolidone; dimethyl sulfoxide, sulfur compounds such as sulfolane.
The said solvent can be used individually by 1 type or in combination of 2 or more type.
In the production of the polymer-dispersed polyol, when a solvent is used, the mixing ratio of the solvent and the polyol (X) is preferably 0: 100 to 60:40 by mass ratio, and 0: 100 to 40:60. It is more preferable that When the mixing ratio is within the range, aggregation of polymer particles is suppressed, and a polymer-dispersed polyol in which polymer fine particles are stably dispersed is easily obtained.
After the polymerization of the monomer having a polymerizable unsaturated group is completed, the solvent is removed. The method for removing the solvent is usually performed by heating under reduced pressure. It can also be carried out under normal pressure heating or reduced pressure at room temperature. At this time, unreacted monomers are also removed together with the solvent.

  The polymerization reaction of the monomer having a polymerizable unsaturated group in the polyol (X) is carried out at a temperature equal to or higher than the decomposition temperature of the polymerization initiator, usually 80 to 160 ° C., preferably 90 to 150 ° C., More preferably, it is performed at -130 degreeC, 105-125 degreeC is further more preferable, and 110-120 degreeC is especially preferable.

In the present invention, a stabilizer or a grafting agent can be used to improve the dispersion stability of the polymer fine particles in the polymer-dispersed polyol.
Preferable examples of the stabilizer or grafting agent include compounds having an unsaturated bond in the molecule. Specifically, a high molecular weight polyol or monool obtained by reacting an alkylene oxide with an active hydrogen compound having an unsaturated bond-containing group such as a vinyl group, an allyl group, or an isopropyl group as an initiator; After reacting with an unsaturated carboxylic acid such as maleic anhydride, itaconic anhydride, maleic acid, fumaric acid, acrylic acid, methacrylic acid, or its anhydride, an alkylene oxide such as propylene oxide or ethylene oxide is added as necessary. High-molecular-weight polyols or monools obtained as above; reaction products of unsaturated alcohols such as 2-hydroxyethyl acrylate and butenediol with other polyols and polyisocyanates; unsaturated epoxy compounds such as allyl glycidyl ether and polyols And the like.
These stabilizers or grafting agents may have a hydroxyl group or may not have a hydroxyl group, but preferably have a hydroxyl group.
The stabilizer or grafting agent can be mixed and blended with the polyol (X), a monomer having a polymerizable unsaturated group, a polymerization initiator, and the like.

  After completion of the polymerization reaction, the obtained polymer-dispersed polyol may be used as it is as a raw material for rigid polyurethane foam, or may be used after removing the unreacted monomer by subjecting the obtained polymer-dispersed polyol to reduced pressure. Of these, the latter is preferred.

[Polyol for rigid polyurethane foam]
The polymer-dispersed polyol produced according to the present invention is highly compatible with the polyol for rigid polyurethane foam and has excellent storage stability.
Examples of the polyol for rigid polyurethane foam include polyols usually used for producing rigid polyurethane foam, such as polyether polyol, polyester polyol, and hydrocarbon-based polymer having a hydroxyl group at the terminal.
The polyol for rigid polyurethane foam preferably has an average functional group number of 2 to 8.
The number of functional groups means the number of functional groups (hydroxyl groups) of a polyol that reacts with a polyisocyanate component when producing a rigid polyurethane foam. For example, in the case of a polyether polyol, when producing the polyether polyol Equal to the number of active hydrogens used in the initiator.
Specific examples of the polyol for rigid polyurethane foam include the same as those exemplified for the polyol (X).

When a mixture of a polyol for rigid polyurethane foam and a polymer-dispersed polyol according to the present invention (hereinafter referred to as “polyol component”) is used for producing a rigid polyurethane foam, the average hydroxyl value of the polyol component is 200 to 800 mgKOH / g is preferable, 200 to 700 mgKOH / g is more preferable, and 200 to 600 mgKOH / g is more preferable.
It is preferable that the average hydroxyl value is 200 mgKOH / g or more because the strength of the resulting rigid polyurethane foam is easily obtained. When the average hydroxyl value is 800 mgKOH / g or less, the resulting rigid polyurethane foam is difficult to be brittle, which is preferable.
In this invention, an average hydroxyl value means the average value of the hydroxyl value of all the polyol compounds which comprise a polyol component.

In the preparation of the polyol component, the mixing ratio of the polymer-dispersed polyol and the polyol for rigid polyurethane foam is preferably such that the ratio of the polymer-dispersed polyol in the polyol component is 0.01% by mass or more, and 0.1% by mass or more. It is more preferable that it is 0.9 mass% or more. On the other hand, the ratio of the polymer-dispersed polyol is preferably 10% by mass or less, and more preferably 7% by mass or less.
Further, the ratio of the polymer fine particles in the polyol component is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, and further preferably 0.01% by mass or more. On the other hand, the ratio of the polymer fine particles is preferably 5% by mass or less, and more preferably 1% by mass or less.
When the ratio of the polymer-dispersed polyol and polymer fine particles in the polyol component is at least the lower limit value, both the dimensional stability and the heat insulation performance are improved when a rigid polyurethane foam is obtained. On the other hand, when it is at most the upper limit value, the compatibility between the two is further increased, the storage stability is improved, and the rigid polyurethane foam can be stably produced. Moreover, an appropriate viscosity is easily obtained as a polyol component, and the liquid stability is improved.

The production of the rigid polyurethane foam includes, for example, a method in which the polyol component and the polyisocyanate component are reacted in the presence of a foaming agent, a foam stabilizer and a catalyst.
In production, a polyol component is prepared in advance by mixing a polyol for rigid polyurethane foam and the polymer-dispersed polyol according to the present invention, and a mixture (polyol) of the polyol component and a part or all of the components other than the polyisocyanate component. It is preferable to prepare a system liquid).
The blowing agent may be blended in advance in the polyol system liquid, or may be blended after mixing the polyisocyanate component in the polyol system liquid, and in particular, it is preferably blended in advance in the polyol system liquid. .

  According to the method for producing a polymer-dispersed polyol of the present invention, the compatibility with a polyol for a rigid polyurethane foam is high, and the storage stability is excellent. The resulting polymer-dispersed polyol can be produced.

EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited at all by these examples. [Table 1] [Table 2] Production Examples 1 to 7 and Production Examples 9 to 17 are examples, and Production Examples 8, 18, and 19 are comparative examples. [Table 3] to [Table 8] Test Examples 1 to 7, Test Examples 9 to 17, and Test Examples 19 to 25, Test Examples 27 to 35, Test Examples 37 to 43, Test Examples 45 to 53 are examples. It is an evaluation result of the storage stability of the produced polymer-dispersed polyol, and Test Example 18, Test Example 36, and Test Example 54 are the evaluation results of the storage stability when PTFE powder is used instead of the polymer-dispersed polyol of the present invention. It is. [Table 9] to [Table 14] Production Examples 20 to 37, 42 to 47 and 51 to 52, 56 to 57, 61 to 62 produced rigid urethane foams using the polymer-dispersed polyols produced in Examples. The production examples 38 to 41, 48 to 50, 53 to 55, 58 to 60, and 63 to 65 were produced by producing a rigid urethane foam without using the polymer-dispersed polyol of the present invention. It is the result of evaluating.
In the following examples, the hydroxyl value was measured according to JIS K1557 (1970 edition). The viscosity was measured according to JIS K1557 (1970 edition). The concentration of polymer fine particles (solid content) was defined as the concentration of monomers having a polymerizable unsaturated group as the fine particle concentration (solid content).

≪Evaluation of polymer-dispersed polyol≫
According to the blending ratios shown in Tables 1 and 2, polymer-dispersed polyols F1 to F19 were produced by the following Production Examples 1 to 19.
Formulation composition during production of polymer-dispersed polyol, hydroxyl value (mgKOH / g), viscosity (mPa · s) of polymer-dispersed polyols F1 to F19 obtained, concentration of polymer fine particles (solid content: mass%), polyol Y2 and polyol The ratio of Y1 (Y2 / Y1, mass%) and the oxyethylene group (%) in the polyol (Y) are shown in Table 1 and Table 2, respectively.
The oxyethylene group (%) in the polyol (Y) indicated the content (%) when the entire polyol (Y) was 100% by mass.
In the blending compositions of Tables 1 and 2, polyols D, E, F, G, N, macromonomers M1 and M2 and monomers having polymerizable unsaturated groups are “g”; the polymerization initiator is polyols D, E, It is a value of “parts by mass” relative to 100 parts by mass in total of F, G, N and all monomers having a polymerizable unsaturated group.

(Raw materials used).
・ Polyether polyol (Y)
The following polyols E, F and G correspond to the polyol Y1, and the polyols D and N correspond to the polyol Y2.
Polyol D: Glycerol was used as an initiator, and ethylene oxide was added to the glycerin, and then a mixture of propylene oxide (PO) and ethylene oxide (EO) [PO / EO = 46.2 / 53.8 (mass ratio). ], Polyoxyalkylene polyol having an oxyethylene group content of 65% by mass and a hydroxyl value of 48 mgKOH / g in polyol D.
Polyol E: A polyoxyalkylene polyol having a hydroxyl value of 400 mgKOH / g obtained by addition polymerization of propylene oxide (PO) to glycerin using glycerin as an initiator.
Polyol N: glycerin was used as an initiator, and propylene oxide was added to the glycerin, and then a mixture of propylene oxide (PO) and ethylene oxide (EO) [PO / EO = 88.2 / 11.8 (mass ratio) )] Is a polyoxyalkylene polyol having an oxyethylene group content of 7% by mass and a hydroxyl value of 56 mgKOH / g in the polyol N.

Polyol F: A polyoxyalkylene polyol having an oxyethylene group content of 0% by mass and a hydroxyl value of 760 mgKOH / g in polyol F, in which ethylenediamine was used as an initiator and only PO was added to the ethylenediamine.
Polyol G: Polyoxyalkylene polyol having an oxyethylene group content of 0% by mass and a hydroxyl value of 650 mgKOH / g in polyol G, in which glycerin is used as an initiator and only PO is added to the glycerin.
Polyol S: Using glycerin as an initiator, ethylene oxide was added to the glycerin, and then a mixture of propylene oxide (PO) and ethylene oxide (EO) [PO / EO = 48.0 / 52.0 (mass ratio) ] Is a polyoxyalkylene polyol having an oxyethylene group content of 60% by mass and a hydroxyl value of 28 mgKOH / g in the polyol S.

Fluorine-containing monomer Fluorine-containing monomer (f): A monomer (manufactured by Asahi Glass Co., Ltd.) represented by the following chemical formula (1-1) was used.

・ Monomer acrylonitrile (manufactured by Junsei Chemical Co., Ltd.) having other polymerizable unsaturated groups.
Styrene (manufactured by Gordo Solvent).
Vinyl acetate (made by Junsei Co., Ltd.).
Polymerization initiator 2,2-azobis-2-methylbutyronitrile (trade name: ABN-E, manufactured by Nippon Hydrazine Kogyo Co., Ltd .; hereinafter abbreviated as “AMBN”).

Macromonomer Macromonomer M1: Polyol D, toluene diphenyl diisocyanate (trade name: T-80, manufactured by Nippon Polyurethane Industry Co., Ltd.) and 2-hydroxyethyl methacrylate (manufactured by Junsei Chemical Co., Ltd.), polyol D / toluene diphenyl diisocyanate / 2-hydroxy Polymerization unsaturation with a hydroxyl value of 40 mgKOH / g was obtained by charging to a molar ratio of ethyl methacrylate = 1/1/1, reacting at 60 ° C. for 1 hour, and further reacting at 80 ° C. for 6 hours. Macromonomer having a group.
Macromonomer M2: polyol S, toluene diphenyl diisocyanate (trade name: T-80, manufactured by Nippon Polyurethane Industry Co., Ltd.) and 2-hydroxyethyl methacrylate (manufactured by Junsei Chemical Co., Ltd.), polyol E / toluene diphenyl diisocyanate / 2-hydroxyethyl methacrylate = 1/1/1 The molar ratio of 21 mgKOH / g of the polymerizable unsaturated group obtained by charging at a molar ratio of 1/1/1, reacting at 60 ° C for 1 hour, and further reacting at 80 ° C for 6 hours was obtained. Having macromonomer.

<Production of polymer-dispersed polyol>
Production Example 1: Production of polymer-dispersed polyol F1 In a 5 L pressurized reaction vessel, the total amount is 100 mass%, 75 mass% of polyol D, 4 mass% of polyol G and 1 mass% of macromonomer M1 are charged. The mixture of the remaining 20% by mass of vinyl acetate, the fluorinated monomer (f) and the polymerization initiator (AMBN) was fed over 2 hours while stirring, and after the completion of all the feeds, the same temperature was maintained. Stirring was continued for about 0.5 hours. Then, the polymer-dispersed polyol F1 was manufactured by removing unreacted monomers at 120 ° C. under reduced pressure for 3 hours. The results are shown in Table 1.

Production Examples 2 to 8: Production of polymer-dispersed polyols F2 to 8 Polymer-dispersed polyols F2 to 8 were produced in the same manner as in Example 1 except that the amounts of polyol D and polyol G used were changed as follows. The results are shown in Table 1.
Production Example 2: 71.1% by mass of polyol D and 7.9% by mass of polyol G.
Production Example 3: 63.2% by mass of polyol D and 15.8% by mass of polyol G.
Production Example 4: 55.3 mass% of polyol D and 23.7 mass% of polyol G.
Production Example 5: 47.4% by mass of polyol D and 31.6% by mass of polyol G.
Production Example 6: 39.5% by mass of polyol D and 39.5% by mass of polyol G.
Production Example 7: 23.7% by mass of polyol D and 55.3% by mass of polyol G.
Production Example 8: 15.8% by mass of polyol D and 63.2% by mass of polyol G.

Production Example 9: Production of polymer-dispersed polyol F9 In a 5 L pressurized reaction vessel, the total amount is 100 mass%, polyol D is 39.5 mass%, polyol G is 39.5 mass%, and macromonomer M2 is 1 mass. The remaining 20% by mass of a mixture of vinyl acetate, fluorine-containing monomer (f) and polymerization initiator (AMBN) was fed over 2 hours with stirring while maintaining at 120 ° C. Thereafter, stirring was continued for about 0.5 hours at the same temperature. Thereafter, unreacted monomer was removed under reduced pressure at 120 ° C. for 3 hours to produce a polymer-dispersed polyol F9. The results are shown in Table 2.

Production Example 10: Production of polymer-dispersed polyol F10 Polymer dispersion was carried out in the same manner as in Production Example 9, except that the amount of polyol D used was changed to 23.7% by mass and the amount of polyol G used was changed to 55.3% by mass. Polyol F10 was produced. The results are shown in Table 2.

Production Examples 11 to 13: Production of polymer-dispersed polyols F11 to F13 Polymer-dispersed polyols F11 to F13 were produced in the same manner as in Production Example 5 except that the ratio of the monomer composition having a polymerizable unsaturated group in Table 2 was used. did. The results are shown in Table 2.

Production Example 14 Production of Polymer-Dispersed Polyol F14 In a 5 L pressurized reaction vessel, the total amount is 100 mass%, 47.4 mass% of polyol D, 31.6 mass% of polyol G, and 1 mass of macromonomer M1 %, And while maintaining the temperature at 120 ° C., the remaining 20% by mass of the mixture of acrylonitrile, fluorine-containing monomer (f) and polymerization initiator (AMBN) was fed over 2 hours with stirring, and after all feeds were completed The stirring was continued for about 0.5 hours at the same temperature. Thereafter, unreacted monomer was removed under reduced pressure at 120 ° C. for 3 hours to produce polymer-dispersed polyol F14. The results are shown in Table 2.

Production Example 15: Production of polymer-dispersed polyol F15 Polymer-dispersed polyol F15 was produced in the same manner as in Production Example 14 except that the ratio of the monomer composition having a polymerizable unsaturated group shown in Table 2 was used. The results are shown in Table 2.

Production Example 16: Production of polymer-dispersed polyol F16 In a 5 L pressurized reaction vessel, the total amount is 100 mass%, polyol D is 84.6 mass%, polyol F is 4.4 mass%, and macromonomer M1 is 1 mass. The remaining 10% by mass of vinyl acetate, the fluorine-containing monomer (f) and the polymerization initiator (AMBN) are fed over 2 hours with stirring while the temperature is kept at 120 ° C. Thereafter, stirring was continued for about 0.5 hours at the same temperature. Thereafter, unreacted monomer was removed under reduced pressure at 120 ° C. for 3 hours to produce a polymer-dispersed polyol F16. The results are shown in Table 2.

Production Example 17: Production of polymer-dispersed polyol F17 In a 5 L pressurized reaction vessel, the total amount is 100 mass%, polyol D is 47.4 mass%, polyol E is 31.6 mass%, and macromonomer M1 is 1 mass. The remaining 20% by mass of a mixture of vinyl acetate, fluorine-containing monomer (f) and polymerization initiator (AMBN) was fed over 2 hours with stirring while maintaining at 120 ° C. Thereafter, stirring was continued for about 0.5 hours at the same temperature. Thereafter, unreacted monomer was removed under reduced pressure at 120 ° C. for 3 hours to produce polymer-dispersed polyol F17. The results are shown in Table 2.

Production Example 18: Production of polymer-dispersed polyol F18 In a 5 L pressurized reaction vessel, the total amount is 100 mass%, polyol D is 47.4 mass%, polyol N is 31.6 mass%, and macromonomer M1 is 1 mass. The remaining 20% by mass of a mixture of vinyl acetate, fluorine-containing monomer (f) and polymerization initiator (AMBN) was fed over 2 hours with stirring while maintaining at 120 ° C. Thereafter, stirring was continued for about 0.5 hours at the same temperature. Thereafter, unreacted monomer was removed under reduced pressure at 120 ° C. for 3 hours to produce polymer-dispersed polyol F18. The results are shown in Table 2.

Production Example 19: Production of polymer-dispersed polyol F19 In a 5 L pressure reaction tank, the total amount was 100% by mass, and 79% by mass of polyol D and 1% by mass of macromonomer M1 were charged and kept at 120 ° C. A mixture of 20% by mass of vinyl acetate, a fluorine-containing monomer (f) and a polymerization initiator (AMBN) is fed over 2 hours with stirring. After the completion of all the feeding, stirring is performed for about 0.5 hours at the same temperature. Continued. Thereafter, unreacted monomer was removed under reduced pressure at 120 ° C. for 3 hours to produce polymer-dispersed polyol F19. The results are shown in Table 2.

<Evaluation of storage stability>
According to the blending ratios of Test Examples 1 to 54 shown in Tables 3 to 8, the polymer-dispersed polyols F1 to F17 or the following polytetrafluoroethylene (PTFE) powders produced in Production Examples 1 to 19 were added to the following polyols A to C and A sample for evaluating storage stability was prepared by adding H and I to the mixed polyol.
Then, the evaluation sample is stored at 23 ° C. for 2 months, and the appearance (separated state) of the evaluation sample when stored for 1 week, 1 month, 6 weeks, 2 months is visually observed, according to the following evaluation criteria The storage stability was evaluated.
Evaluation criteria ○: It was a uniform dispersion solution.
X: The polymer fine particles or PTFE powder and the polyol were separated.

(Raw materials used)
Polytetrafluoroethylene (PTFE) powder (trade name: polytetrafluoroethylene resin powder fluon L-173, manufactured by Asahi Glass Co., Ltd.).

Polyol for rigid polyurethane foam Polyol A: Tolylenediamine is used as an initiator, and EO, PO, and EO are added and polymerized in this order to the tolylenediamine, the hydroxyl value is 350 mgKOH / g, and EO A polyether polyol in which the ratio of EO to the total of PO and PO is 33% by mass.
Polyol B: A polyether polyol having a hydroxyl value of 350 mgKOH / g, in which N- (2-aminoethyl) piperazine is used as an initiator and only EO is addition-polymerized to the N- (2-aminoethyl) piperazine.
Polyol C: A polyether polyol having a hydroxyl value of 380 mg KOH / g, in which a mixture of sucrose and glycerin (mass ratio of 5: 4) is used as an initiator, and only PO is subjected to addition polymerization.
Polyol H: Polyester polyol having a hydroxyl value of 200 mgKOH / g, obtained by polycondensation of diethylene glycol and terephthalic acid.
Polyol I: A hydroxyl value obtained by adding PO and EO in this order to a Mannich condensation product obtained by reacting nonylphenol, formaldehyde and diethanolamine in a molar ratio of 1 to 1.4 to 2.1 was 300 mgKOH / g. A polyol in which the ratio of EO to the total amount of PO and EO added is 60% by mass.

From the results shown in Tables 3 to 8, Test Examples 1 to 7, Test Examples 9 to 17, Test Examples 19 to 25, Test Examples 27 to 35, Test Examples using the polymer-dispersed polyols F1 to F7 and F9 to F17 It was confirmed that 37 to 43 and Test Examples 45 to 53 had good storage stability for 6 weeks. In Test Examples 1-6, Test Examples 9, 11, 12, 14, Test Examples 19-24, Test Examples 27, 29, 30, 32, Test Examples 37-42, Test Examples 45, 47, 48, 50 It was confirmed that the storage stability for 2 months was good.
On the other hand, it was confirmed that Test Examples 18, 36, and 54 and Test Example 54 using PTFE powder had poor storage stability.
Therefore, it can be confirmed that the polymer-dispersed polyols F1 to F7 and F9 to F17 produced by the method for producing a polymer-dispersed polyol of the present invention are highly compatible with the polyol for rigid polyurethane foam and excellent in storage stability. It was.

≪Evaluation of rigid polyurethane foam≫
According to the blending ratios of Production Examples 20 to 65 shown in Tables 9 to 14, rigid polyurethane foams were produced by the following production method.
In the blend compositions of Tables 9 to 14, the unit of the amount of each raw material used is “part by mass”.

(Raw materials used).
-Polyol component The polyols A to D and polyols H, I and F and the following polyols J, L, M, O, P, Q, R, PTFE powder, polymer-dispersed polyols F2, F5, F6 to F7 and F9 to F19.
Polyol J: Mannich compound was obtained by reacting aniline (1 mol), phenol (0.99 mol), paraformaldehyde (0.64 mol) and diethanolamine (2.2 mol). A polyether polyol having a hydroxyl value of 540 mgKOH / g, obtained by addition polymerization of only PO to the Mannich compound.
Polyol L: A polyether polyol having a hydroxyl value of 400 mgKOH / g, in which glycerin is used as an initiator and only PO is added to the glycerin.
Polyol M: A polyether polyol having a hydroxyl value of 300 mgKOH / g, in which ethylenediamine is used as an initiator and only PO is added to the ethylenediamine.
Polyol O: A polyether polyol having a hydroxyl value of 500 mgKOH / g, in which sorbitol is used as an initiator and only PO is subjected to addition polymerization with sorbitol.
Polyol P: 2,2-bis (4′hydroxyphenyl) propane was used as an initiator, and only EO was added and polymerized to 2,2-bis (4′hydroxyphenyl) propane. The hydroxyl value was 280 mgKOH / g. Polyether polyol.
Polyol Q: A polyether polyol having a hydroxyl value of 350 mgKOH / g, in which monoethanolamine is used as an initiator and only PO is added to the monoethanolamine for polymerization.
Polyol R: A polyether polyol having a hydroxyl value of 400 mgKOH / g, in which pentaerythritol is used as an initiator and only PO is added to the pentaerythritol.

Flame retardant: Tris (2-chloropropyl) phosphate (trade name: TMCPP, manufactured by Daihachi Chemical Co., Ltd.).
-Foaming agent A: water.
Blowing agent B: cyclopentane (trade name: Marcazole FH, manufactured by Maruzen Petrochemical Co., Ltd.).
Foaming agent C: 1,1,1,3,3-pentafluoropropane (HFC-245fa: manufactured by Honeywell).
-Foam stabilizer: Silicone foam stabilizer (trade name: SZ-1671, manufactured by Toray Dow Corning).
Catalyst A: N, N, N ′, N′-tetramethylhexamethylenediamine (trade name: TOYOCAT-MR, manufactured by Tosoh Corporation).
Catalyst B: Triethylenediamine (trade name: TEDA-L33, manufactured by Tosoh Corporation).
Catalyst C: N, N′N ″ -tris (dimethylaminopropyl) hexahydro-S-triazine (trade name: POLYCAT 41, manufactured by AIR PRODUCTS).
Catalyst D: Diethylene glycol solution of potassium 2-ethylhexanoate (potassium concentration 15%, trade name: DABCO K-15, manufactured by AIR PRODUCTS).
Catalyst E: A mixture of amino alcohols (trade name: TOYOCAT-RX7, manufactured by Tosoh Corporation).
Catalyst F: N, N-dimethylcyclohexylamine (trade name: Kao Riser No. 10, manufactured by Kao Corporation)
Catalyst G: Polyethylene polyamine (trade name: TOYOCAT-TT, manufactured by Tosoh Corporation).
Catalyst H: A mixture of 70% 1,2-dimethylimidazole and 30% ethylene glycol (trade name: TOYOCAT-DM70, manufactured by Tosoh Corporation).
Catalyst I: A mixture of a quaternary ammonium salt and ethylene glycol (trade name: TOYOCAT-TRX, manufactured by Tosoh Corporation).
Polyisocyanate: Polymethylene polyphenyl polyisocyanate (crude MDI) (trade name: MR-200, manufactured by Nippon Polyurethane Industry Co., Ltd.).

<Manufacture of rigid polyurethane foam>
[Tables 9-14]
In accordance with the blending ratio shown in Table 9 to Table 14, 100 parts by mass of a polyol component, a foaming agent, a foam stabilizer, a flame retardant and a catalyst are respectively added to a 1 L poly beaker, and these are mixed well with a stirrer to obtain a polyol system solution. Got.
The amount of polyisocyanate used is 110, 130, or 164 in terms of the isocyanate index (INDEX) when the foaming agent is only water, and the system using a hydrocarbon compound as the foaming agent is 105 in the isocyanate index. The system using a hydrofluorocarbon compound was set to 110 with an isocyanate index, and each was compared. The isocyanate index (INDEX) is a value expressed by multiplying the ratio of the number of isocyanate groups to 100 times the total equivalent of active hydrogen in the polyol composition and other active hydrogen compounds.

[Tables 9-14]
After keeping the liquid temperature of both the polyol system liquid and the raw material of the polyisocyanate component at 20 ° C., the mixture was stirred and mixed at a rotational speed of 3000 rpm for 5 seconds. Immediately after that, it was put into a wooden box of length 200 × width 200 × height 200 mm and subjected to free foaming to produce a rigid polyurethane foam by box-free foaming.

[Table 14]
About the example of Table 14, the heat insulation panel which bonded the metal surface material used for a freezer car or a freezer warehouse on both surfaces was assumed, and length (X) 400mm x width (Y) 400mm x thickness (T) 50mm A rigid polyurethane foam by panel foaming was manufactured using an aluminum mold.
That is, the liquid temperature of both the polyol system liquid and the raw material of the polyisocyanate component is maintained at 20 ° C., and the liquid which is stirred and mixed at a rotational speed of 3000 rpm for 5 seconds is vertical in the vertical (X) direction and horizontal in the horizontal (Y) direction. It inject | poured into the said metal mold | die installed so that it might become a direction. A predetermined amount was injected so that the total density was 28 kg / m ³ to 29 kg / m ^3, and the injection site was closed to pack-fill, thereby forming a urethane foam.

<Evaluation of rigid polyurethane foam>
[Tables 9 to 13]
For each rigid polyurethane foam obtained by box-free foaming in each production example, gel time (seconds), box-free density (unit: kg / m ³ ) as density, compressive strength (unit: MPa), dimensional change as dimensional stability The rate (unit:%) and the thermal conductivity (unit: mW / m · K) were measured by the following methods, respectively.
Moreover, the following evaluation was performed as storage stability. The results are shown in Tables 9 to 13.

The gel time was measured by inserting a wire into a foam in the middle of foaming and measuring the time (seconds) until stringing occurred when the foam was pulled up.
The total density (box-free density) was measured from the mass and volume according to JIS K7222 (1998 edition).
(Evaluation of compressive strength)
The compressive strength was measured according to JIS A9511. The sample piece cut out the core part of foaming foam, and the magnitude | size was 5 cm x 5 cm x 5 cm. Further, the compressive strength in the direction parallel to (//) and the direction perpendicular to the gravity direction (⊥) was measured. In Tables 9 to 13, “// + ⊥” represents the compression strength obtained by adding the compression strength in the parallel direction (//) and the compression strength in the vertical direction (⊥).

(Evaluation of dimensional stability)
Measured by a method according to ASTM D 2126-75, and when the foaming agent is water only, two conditions of high temperature dimensional stability and wet heat dimensional stability are evaluated, and when water and a hydrocarbon compound are used in combination as the foaming agent Evaluates two conditions of -30 ° C low temperature dimensional stability and wet heat dimensional stability. When water and a hydrofluorocarbon compound are used in combination as a foaming agent, 0 ° C low temperature dimensional stability and -30 ° C low temperature dimensional stability 2 The conditions were evaluated.
The hard polyurethane foam of each example was used as a sample, and after curing for 1 hour, a length (X) of 100 mm × width (Y) 150 mm × thickness (T) 75 mm was cut out and used. For high temperature dimensional stability, the specimen is stored at 70 ° C., wet heat dimensional stability at 70 ° C. and 95% relative humidity, and low temperature dimensional stability at −30 ° C. or 0 ° C. for 24 hours or 50 hours. The increased length (thickness) was expressed as a dimensional change rate (unit:%) with respect to the length (thickness) before storage. In the dimensional change rate, a negative value means shrinkage; a large absolute value means a large dimensional change.
In addition, based on the dimensional change rate (unit%) in all six directions in each of three directions (X, Y, T) under two conditions, the dimensional stability was evaluated according to the following evaluation criteria.
Evaluation criteria A: The maximum absolute value among the dimensional change rates in the six directions was less than 1%.
A: The maximum absolute value among the dimensional change rates in 6 directions was 1% or more and less than 5%.
Δ: The maximum absolute value among the dimensional change rates in 6 directions was 5% or more and less than 10%.
X: The maximum absolute value among the dimensional change rates in the six directions was 10% or more.

(Evaluation of thermal insulation performance)
The thermal conductivity (unit: mW / m · K) is in accordance with JIS A1412, using a thermal conductivity measuring device (product name: Auto Lambda HC-074, manufactured by Eihiro Seiki Co., Ltd.) at an average temperature of 20 ° C. It was measured.
The heat insulation performance was evaluated according to the following evaluation criteria.
Evaluation criteria The following criteria were used when the foaming agent was water only.
○: Thermal conductivity was 27 or less.
X: Thermal conductivity was more than 27.
When water and a hydrocarbon compound were used in combination as the blowing agent, the following criteria were used.
○: Thermal conductivity was 22 or less.
X: Thermal conductivity was more than 22.
When water and a hydrofluorocarbon compound were used in combination as the blowing agent, the following criteria were used.
○: Thermal conductivity was 21 or less.
X: Thermal conductivity was more than 21.

(Evaluation of storage stability)
After mixing polyol components other than polyol D according to the blending ratio of each production example, polymer-dispersed polyol, PTFE powder, or polyol D was added and mixed to prepare 300 g of mixed polyol, which was placed in a glass bottle with a lid. Then, it is stored at 23 ° C for 1 week, 1 month, 6 weeks and 2 months, and 100 g of the upper layer liquid is extracted from the upper layer of the mixed polyol after storage with a syringe, and the middle layer liquid is discarded so that 100 g of the lower layer liquid can be taken from the lower layer. Then, a mixed polyol of 100 g of the lower layer solution was collected from the lower layer.
Next, in the above <Manufacture of rigid polyurethane foam>, in the same manner as in <Manufacture of rigid polyurethane foam> except that 100 parts by mass of the upper layer liquid or 100 parts by mass of the lower layer liquid was used instead of 100 parts by mass of the polyol component. A polyurethane foam was produced.
And the storage stability was evaluated based on the following evaluation criteria from the characteristic of the obtained rigid polyurethane foam.
When the storage stability is poor, the polymer-dispersed polyol migrates to the upper layer or the lower layer during storage, and the upper and lower compositions of the mixed polyol are different, which affects the characteristics of the rigid polyurethane foam produced using this. Therefore, the storage stability can be evaluated from the foamed state when each of the upper layer liquid and the lower layer liquid is used, or the dimensional change rate of the obtained rigid polyurethane foam.
Evaluation criteria (circle): The foaming defect was not seen in any which foamed the upper layer liquid and the lower layer liquid, and the absolute value of the dimensional change rate of the rigid polyurethane foam was all less than 5%.
X: Foaming failure was observed in any of the foamed upper layer liquid and lower layer liquid, or the absolute value of the dimensional change rate of any of the rigid polyurethane foams was 5% or more.

[Table 14]
Evaluation of the rigid polyurethane foam in Table 14 was performed by the following method. That is, gel time (second) and box free density (unit: kg / m ³ ) were measured by the same method as described above.
About the rigid polyurethane foam by panel foaming, the molded foam was taken out after 20 minutes from the start of foaming, and after curing for 24 hours, the overall density, compressive strength, dimensional stability, thermal conductivity and storage stability were evaluated. The total density was expressed as a value (unit: kg / m ³ ) obtained by dividing the foam weight by the volume of the filled aluminum mold. The compressive strength was measured by the following method. Dimensional stability was evaluated by measuring the dimensional change rate (unit:%) under the following two conditions: high temperature dimensional stability and wet heat dimensional stability. Thermal conductivity and storage stability were evaluated by the same method as described above. These results are shown in Table 14.

(Compressive strength of panel foam)
Cut from the core of the molded foam into a length (X) of 40 mm × width (Y) of 40 mm × thickness (T) of 40 mm, and compressive strength is measured in three directions of X, Y, and T according to JIS A 9511. It was measured.
(Evaluation of dimensional stability of panel foam)
High temperature dimensional stability is cut out from the core of the molded foam into length (X) 200 mm × width (Y) 100 mm × thickness (T) 25 mm, and wet heat dimensional stability is length (X) with the surface skin left. It was cut out into 200 mm × horizontal (Y) 150 mm × thickness (T) 50 mm, and measured and evaluated in the same manner as in the above dimensional stability evaluation method.

As is apparent from the results shown in Tables 9 to 14, Production Examples 20 to 37 and Production Examples 20 to 37 using the polymer dispersed polyols F2, F5 to F7 and F9 to F17 produced by the method for producing a polymer dispersed polyol of the present invention were produced. In Examples 42 to 47 and Production Examples 51, 52, 56, 57, 61, and 62, the storage stability (6 weeks) was excellent, and the heat insulation performance and dimensional stability of the rigid polyurethane foam were both good.
In particular, a production example using a polymer-dispersed polyol (F2, F5 to F7, F9 to F15) in which the polyol Y1 (polyol G) is used in an amount of 5% to 70% when the entire polyol (Y) is 100% by mass. 20-28 and Production Examples 29-35, Production Examples 42-47, Production Examples 51, 52, 56, 57, 61, 62 used polymer-dispersed polyols (F18, F19) prepared without using polyol Y1. Compared to Production Examples 38, 39, 48, 53, 58, and 63, the same good dimensional stability and heat insulation performance can be obtained even though the amount of the polymer-dispersed polyol is small. This is also considered to contribute to excellent storage stability (6 weeks, 2 months).
Thus, in the method for producing a polymer-dispersed polyol, the content of the oxyethylene group in the polyether polyol (Y) is 15% by mass or more, the polyol Y1 having a hydroxyl value of 200 to 800 mgKOH / g and the hydroxyl value of 5 to 84 mgKOH / g. It has been found that by including acrylonitrile or vinyl acetate as a monomer having g of polyol Y2 and having a polymerizable unsaturated group, a further remarkable storage stability improvement effect can be obtained.

On the other hand, in Production Examples 38, 39, 48, 53, 58, and 63 using polymer dispersed polyols F18 and F19 prepared without using polyol Y1, a relatively large amount of polymer dispersed polyol was added, so that a rigid polyurethane foam was obtained. Good thermal insulation performance and dimensional stability were obtained, but storage stability (6 weeks, 2 months) deteriorated.
As shown in Production Examples 40, 49, 54, 59 and 64, it was confirmed that the storage stability (1 week, 1 month, 6 weeks, 2 months) was poor when PTFE powder was used.
It was confirmed that the rigid polyurethane foams of Production Examples 41, 50, 55, 60, and 65 produced using Polyol D containing no polymer fine particles had poor dimensional stability.

The polymer-dispersed polyol obtained by the production method of the present invention can be used for production of rigid polyurethane foam. The polymer-dispersed polyol has good storage stability even when mixed with a low molecular weight polyol for rigid polyurethane foam.
Further, by using the polymer-dispersed polyol, it is possible to reduce the weight and obtain a rigid polyurethane foam excellent in both heat insulation performance and dimensional stability.

Claims (9)

In the method for producing a polymer-dispersed polyol for rigid polyurethane foam in which polymer fine particles are dispersed in a polyol by polymerizing a monomer having a polymerizable unsaturated group in the polyol (X),
The polyol (X) contains the following polyether polyol (Y), and the monomer having a polymerizable unsaturated group contains a fluorine-containing acrylate or a fluorine-containing methacrylate. .
The polyether polyol (Y) has an oxyethylene group content of 15% by mass or more, and the polyether polyol (Y) is a polyol Y1 having a hydroxyl value of 200 to 800 mgKOH / g and a polyol Y2 having a hydroxyl value of 5 to 84 mgKOH / g. only including, the blend ratio (Y1 / Y2) of the polyol Y1 and the polyol Y2 is a 5/95 to 70/30 (weight ratio). The method for producing a polymer-dispersed polyol according to claim 1, wherein the fluorine-containing acrylate or fluorine-containing methacrylate is a monomer represented by the following formula (1).

However, in Formula (1), ^Rf is a C1-C18 polyfluoroalkyl group, R is a hydrogen atom or a methyl group, Z is a bivalent coupling group which does not contain a fluorine atom, Z And R ^f are separated so that the carbon number of R ^f is small.   The method for producing a polymer-dispersed polyol according to claim 1 or 2, wherein the monomer having a polymerizable unsaturated group further contains at least one selected from the group consisting of acrylonitrile, vinyl acetate, and styrene. The said polyether polyol (Y) is a manufacturing method of the polymer dispersion | distribution polyol as described in any one of Claims 1-3 whose oxyethylene group content is 20 mass% or more. The method for producing a polymer-dispersed polyol according to any one of claims 1 to 4 , wherein the polyol Y2 is a polyoxyalkylene polyol obtained by addition polymerization of propylene oxide and ethylene oxide to a polyhydric alcohol. The polymer-dispersed polyol according to any one of claims 2 to 5 , wherein a ratio of the monomer represented by the formula (1) in all monomers having the polymerizable unsaturated group is 30 to 100% by mass. Production method. Monomer represented by the formula (1) is, R ^f is a polyfluoroalkyl group having 3 to 8 carbon atoms, Z is an alkylene group or an arylene group, according to any one of claims 2-6 A method for producing a polymer-dispersed polyol. Monomer represented by the formula (1) is either of the monomer represented by the following formula (1-1) to (1-3), a polymer according to any one of claims 2-7 A method for producing a dispersed polyol.

The manufacturing method of the polymer dispersion | distribution polyol as described in any one of Claims 1-8 whose density | concentration of the said polymer fine particle is 1-50 mass%.