JPH05171027A - Polyol dispersion and its preparation - Google Patents

Abstract

PURPOSE:To prepare a polyol dispersion which has a low viscosity and an excellent dispersion stability and is useful as a material for preparing a polyurethane foam meeting the requirements of fire regulations by dispersing two kinds of specific powder in a polyol which is liq. at normal temp. CONSTITUTION:2-50 pts.wt. powder which comprises at least one triazine compd. (deriv.) selected from the group consisting of compds. of the formula (wherein R<1>, R<2>, and R<3> are each NH2, OH, or 5C or lower alkyl), is solid at normal temp., and has a mean particle diameter of 1-100mum and 1-50 pts.wt. powder which is a polymer which is solid at normal temp., contains at least 20wt.% powder having particle diameters of 10mum or lower, and has a true density of 0.9-1.3g/cm<3> at 20 deg.C (e.g. a PS powder) are dispersed in 50-97 pts.wt. polyol which is liq. at normal temp. (e.g. a polyether polyol obtd. by the addition reaction of propylene oxide and ethylene oxide with glycerin).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a dispersed polyol composition in which a powdered triazine compound or a derivative thereof is stably dispersed, which is suitable for producing a flame-retardant polyurethane foam, and a method for producing the same. More specifically, when a powder of a triazine compound or a derivative thereof is dispersed in a polyol, specific polymer particles are allowed to coexist in a dispersion system, and a dispersed polyol composition having improved dispersibility and a method for producing the same. It is about.

[0002]

BACKGROUND OF THE INVENTION Since the subway fire in the UK in 1988,
Measures against flame retardancy of polyurethane foams have become particularly important. Focusing on developed countries such as Europe, America and Japan,
The flame-retardant regulation of furniture and railway vehicles is being introduced, and the development of flexible urethane foam that complies with this flame-retardant regulation has become an important issue.

As a method for producing a polyurethane foam which complies with the flame retardancy regulation, a softness imparted with flame retardancy has already been obtained by mixing an appropriate amount of a melamine compound such as melamine or methylolated melamine into a polyurethane foam as a flame retardant. Urethane foam is being developed. The basic technique of flame retarding by mixing a melamine compound derivative such as melamine or formalin-modified melamine into urethane foam is described in JP-A-47-5,589 and JP-A-47-5,843. , Which is a known technique.
Further, a method of adding a triazine compound other than melamine as a flame retardant, such as cyanuric acid in German Patent Nos. 3,234,038 and 3,235,571, and cyanuric acid salt of melamine in JP-A-56-817. It is disclosed.

As described above, it is known to produce a urethane foam which complies with flame retardancy regulations by using a triazine compound such as melamine or a derivative thereof as a flame retardant. The production method includes a method of adding a powder of a flame retardant of a triazine compound when a polyol, a polyisocyanate, a catalyst, a crosslinking agent, a foam stabilizer, etc. are mixed and reacted, and a flame retardant of the triazine compound is previously added to the polyol. There is a method of mixing and reacting what is dispersed therein with polyisocyanate or the like. In the former method, since the powdery flame retardant and the polyol or the like are stirred for a short time, the dispersion state of the flame retardant varies, and it is difficult to obtain a uniform urethane foam. In addition, the raw materials for ordinary urethane foam are all liquid substances, and when adding a mixed system of powdered flame retardant to the conventional equipment designed for that purpose, major equipment modifications must be made. .. On the other hand, the latter method has an advantage that neither the problem of mixing with other raw materials nor the problem of the device occurs. That is, a method of previously dispersing a powdered flame retardant of a triazine compound in a polyol is an effective method for urethane foam production, and a dispersed polyol composition in which a powdered triazine compound is uniformly and stably dispersed in a polyol. Has a high industrial utility value.

However, it is not easy to uniformly and stably disperse the powdered triazine compound in the polyol. For example, when a melamine powder having an average particle diameter of several tens of μm that is industrially available is dispersed in a polyol, the melamine compound particles are precipitated and separated from this dispersion within a few hours, and therefore must be used immediately after preparation. I have to. In addition, when the melamine particles are settled and separated, the settling material is solidified at the bottom, which makes redispersion difficult. Several methods have been proposed so far to solve these problems.

First, a method of adding an alkyl sulfonate or the like when dispersing melamine having a particle size of 10 μm or less as described in German Patent Nos. 2,932,304 and 3,064,575 and European Patent No. 371,652. Alternatively, there is a method in which the amine described in US Pat. No. 4,644,015 is used and a dispersion stabilizer is used in combination. However, although the dispersion stability of the melamine particles is improved by the addition of the dispersion stabilizer, the viscosity of the dispersion is remarkably increased. For example, the dispersion of 25% by weight of the melamine particles has a viscosity of 2,600 to 4,000 cps (50
℃) and above, which is a major obstacle in handling the dispersion.

Alternatively, US Pat. No. 4,454,254
There is a method of dispersing finely divided melamine by the formalin modification reaction described in Japanese Patent Application Laid-Open No. 2-120,309. This method has a formalin-modified melamine particle size of 1
Since it has a regular spherical shape in the range of μm to several μm, the dispersion obtained has low viscosity but good dispersion stability. However, when a follow-up test of the examples of the above-mentioned patents was performed, by modifying the melamine with formalin, the flame retardancy of the urethane foam obtained was decreased as compared with unmodified melamine, and the dispersion stability of the particles was good. However, since the diameter of the dispersed particles is small, it was found that once settled, the melamine component solidified at the bottom and could not be redispersed. In addition, a method of adding melamine to a polymer dispersion polyol of British Patent No. 2,163,762 or a polyol composition in which a melamine powder of European Patent No. 358,427 is dispersed to carry out graft polymerization to produce a polymer polyol. There is a method characterized by that.

[0008]

In the case of melamine as a triazine compound and its derivative having an effect of improving flame retardancy of urethane foam, for example, melamine is 2 μm to several hundred μm.
The particles in the form of are available, but when this is dispersed in a polyol such as polyether polyol or polyester polyol, which is a raw material of the flexible urethane foam, and left at room temperature, after one day, at the latest after three days, However, it is in a state where sedimentation is confirmed. As a means for preventing this, it is considered that the viscosity of the dispersion is remarkably increased by using a highly viscous polyol or the content of melamine is increased, or the particle diameter of melamine is made smaller than 1 μm.
However, the former high-viscosity dispersion cannot be practically used for urethane foam production, and the latter requires a special crushing method, and even if such a thing is obtained, the polyol dispersion is highly The viscosity becomes so high that the urethane foam cannot be actually molded. Therefore, the polyol dispersion of the triazine compound, which is a raw material of the urethane foam conforming to the flame retardancy regulation, needs to be a polyol dispersion having a high dispersion stability and not having high viscosity.

The object of the present invention is to disperse particles of a triazine compound such as melamine, which is a flame retardant useful for improving the flame retardancy of urethane foam, or a derivative thereof in a polyol, 1) excellent dispersion stability, ) Dispersion has low viscosity, 3)
It is an object of the present invention to provide a dispersed polyol composition which satisfies all the requirements that redispersion after sedimentation is easy, 4) adjustment is easy, and 5) the obtained urethane foam has an excellent flame retardant effect.

[0010]

Means for Solving the Problems In order to solve the above problems, the present inventors have conducted an examination with reference to the already known theory of dispersion / sedimentation of a dispersion system. It is generally known that in an aqueous / non-aqueous dispersion system, the dispersion / sedimentation rate of dispersed particles is determined by factors such as the viscosity of the dispersion medium, the diameter of the dispersed particles, and the difference in specific gravity between the dispersion medium and the dispersed particles. The particles of this triazine compound were used as polyols (200-10,000 cps (25
When it is dispersed in the (.degree. C.) position, the sedimentation rate is determined by the size of the particle size of the triazine compound to be dispersed.
Then, in this dispersion system, it is found that the particles are so-called submicron particles, which are smaller than 1 μm, when the particle size that causes no semipermanent sedimentation is calculated. However, as described above, it is difficult to adjust the submicron particles by pulverization, the fineness of the particles significantly increases the viscosity of the dispersion, and further, the flame retardancy of the urethane foam obtained by the atomization decreases, so that it is simply dispersed. It is not practically preferable to form submicron particles and disperse them for the purpose of improving the property.

As a method of suppressing the sedimentation rate of particles without using a powder of a triazine compound having a submicron diameter, a method of coexisting particles having an extremely slow sedimentation rate in the dispersion system can be considered. The present inventors have conducted a dispersion experiment in which particles of a polymer, which are relatively easily available and do not cause sedimentation in the polyol used, are added to a polyol dispersion of triazine compound particles. It has been found that the dispersion polyol to which a polymer having a specific gravity and containing a specific particle size is added has a significantly improved dispersibility as compared with the dispersion polyol having no polymer added. Furthermore,
The present invention has been completed by developing a method for preparing this dispersion polyol composition.

That is, the present invention is as follows. (A) (A) Formula 1 (Formula 2)

[Chemical 2] (Wherein R ¹ , R ² and R ³ each represent —NH ₂ , —OH or a group selected from alkyl groups having 5 or less carbon atoms) and are solid at room temperature and are triazine compounds and triazine compound derivatives. One or a mixture of two or more selected from the above, and a powder material 2 to 5 having an average particle diameter of 1 to 100 μm
0 parts by weight, (B) 10 μm of a vinyl polymer that is solid at room temperature
1 to 50 parts by weight of a powder containing 20% by weight or more of particles having a particle size of m or less and having a true specific gravity of 0.9 to 1.3 g / cm ³ (20 ° C.), and (C) a polyol which is liquid at room temperature. 50-97
A dispersed polyol composition comprising 1 part by weight. (B) The dispersed polyol composition according to (A), in which the triazine compound of (A) is melamine, (iso) cyanuric acid and derivatives thereof. (C) The polymer particles of (B) are selected from the group consisting of styrene, acrylonitrile, and methyl methacrylate.
The dispersed polyol composition according to (a), which is a polymer of one kind or two or more kinds of monomers. (D) (A) 1 to 2 or more mixtures selected from triazine compounds and triazine compound derivatives which are solid at room temperature and are represented by the formula 1, and have an average particle diameter of 1 to 100 μm and a powder content of 2 to 50 wt. Part, (B) 10 at a room temperature solid polymer
Powders 1 to 50 containing 10% by weight or more of particles having a particle diameter of μm or less and having a true specific gravity of 0.9 to 1.3 g / cm ³ (20 ° C.)
Parts by weight and (C) Polyol 50-97 which is liquid at room temperature
The method for producing a dispersed polyol composition according to (A), characterized in that parts by weight are mixed. (E) The method for producing a dispersed polyol composition according to (D), wherein the triazine compound of (A) is melamine, cyanuric acid and their derivatives. (F) The method for producing a dispersed polyol composition according to (d), wherein the polymer particles of (B) are particles of a styrene-methyl methacrylate homopolymer or a styrene-methyl methacrylate / acrylonitrile copolymer particle. .. (G) 2 to 50 weight parts of a powdery material having an average particle size of 1 to 100 μm, which is one kind or a mixture of two or more kinds selected from triazine compounds and triazine compound derivatives which are solid at room temperature and which are represented by the formula (A) 1. Part, and (D) a polymer that is solid at room temperature
A powder material 1 containing 10% by weight or more of particles having a particle size of 0 μm1 or less and having a true specific gravity of 0.9 to 0.3 g / cm ³ (20 ° C.)
The method for producing a dispersed polyol composition according to (a) is characterized by mixing 50 to 98 parts by weight of a dispersed polyol uniformly dispersed in a polyol in an amount of 1 to 50% by weight in a polyol. (H) The method for producing a dispersed polyol composition according to (G), wherein the triazine compound (A) is melamine, (iso) cyanuric acid, or a derivative thereof. (I) The polymer of (D) is selected from the group consisting of styrene, acrylonitrile and methyl methacrylate 1
(G) A method for producing a dispersed polyol composition, which is a polymer of one kind or two or more kinds of monomers.

The triazine compound and its derivative used in the present invention include unmodified melamine, melamine modified with formalin or urea, melamine / formaldehyde resin, melamine salts such as melamine phosphate and melamine sulfate, melam, Melamine compounds such as melamine polynuclear bodies such as melem, cyanuric acid, isocyanuric acid, and salts thereof can be mentioned. Among the above, particularly preferred as a flame retardant for urethane foam is inexpensive, excellent in flame retardant effect, less generation of toxic gas during combustion, unmodified melamine, formalin-modified melamine with low addition ratio of formalin. , Isocyanuric acid and the like.
At the time of use, any of these is usually used alone, but in some cases, it is also possible to use a mixture of two or more.

The powder (A) such as a triazine compound has an average particle size of 1 to 100 μm. When the average particle size is less than 1 μm, the dispersion stability is improved,
This is not preferable because the viscosity of the dispersion becomes high. On the other hand, if the average particle size is larger than 100 μm, the dispersion stability is poor and the particles easily settle during storage. Further, in the present invention, if the average particle size is within this range, the particle size distribution of the particles is not particularly limited, but the content of coarse particles exceeding 100 μm is small, which contributes to improvement of dispersion stability.
It is preferable that the content of fine particles having a size of μm or less is large in terms of improving dispersion stability.

Examples of the polyol which is liquid at room temperature used in the present invention include compounds having active hydrogen such as ethylene glycol, glycerin, pentaerythritol, sucrose, and organic amines, and alkylenes such as ethylene oxide and propylene oxide. A polyether polyol having one or more oxide compounds added thereto, a polymer of tetrahydrofuran (PTMEG), or a polyester polyol can be used. Also, modified polyols such as polyether polyols, PTMEG, polyester polyols, and so-called polymer polyols, which are dispersions of vinyl polymer particles uniformly dispersed in these polyol compounds, can be used in the same manner as above. Is. When using, depending on the application
It is possible to use these polyol compounds as one kind or a mixture of two or more kinds, and to add other flame retardants, plasticizers, fillers, stabilizers, colorants and the like as required.

The polymer powder (B) which is solid at room temperature used in the present invention has a true specific gravity of 0.9 to 1.3 g / c.
m ³ (20 ° C.), the particle size composition of which includes 20% by weight or more of particles having a particle size of 10 μm or less. Those satisfying this condition are those whose true specific gravity is dispersed (0.98-1.15).
(g / cm ³ ), and by including fine particles having excellent dispersibility, the dispersibility in the polyol is extremely good, and an effect of suppressing sedimentation of particles coexisting in the dispersion occurs, and particles of the triazine compound are generated. The dispersibility of can be improved. Specifically, as a polymer having a true specific gravity in the range (true specific gravity in parentheses, g / cm ³ ), polyethylene (0.91-0.97), polypropylene (0.92-0.95), polystyrene, (1.04-1.12), Polyvinyl acetate (1.19), polyacetonitrile (1.17-1.18), vinyl polymers such as polymethylmethacrylate (1.18-1.19), polycarbonate (1.21), 6,6-nylon (1.
22-1.24), 6-nylon (1.13-1.24) and the like. Not only a homopolymer of one kind of monomer as in this example, but also a copolymer of two or more kinds of monomers may be used. Further, even if the true specific gravity of the homopolymer is out of this range, it can be used as long as the true specific gravity falls within this range by copolymerization with another monomer. However, conversely, even if the true specific gravity of the homopolymer is within this range, a copolymer whose true specific gravity deviates from this range by copolymerizing with another monomer is used in the present invention. Can not. Particularly preferred polymers for use in the dispersed polyol composition of the present invention are those of true specific gravity dispersed polyols (0.98-1.15).
It is a homopolymer of a monomer selected from acrylonitrile, styrene, and methyl methacrylate, or a copolymer thereof, which is very close to g / cm ³ ) and whose particle shape can be easily adjusted during polymerization preparation. These homopolymer and copolymer powders can be used alone or in combination of two or more. Polymers of the true specific gravity outside this range, for example, polyvinyl chloride (1.39g / cm ^3), as polyethylene terephthalate (1.34-1.39g / cm ^3),
Those with a large difference from the true specific gravity of the polyol (0.98-1.15 g / cm ³ ) have a large sedimentation rate of particles in the polyol,
Does not contribute to dispersion stability. Since the present polymer particles are added in order to suppress the sedimentation of particles of the triazine compound, those having a particle diameter in the range of 0.1 to 2 μm, which is effective in suppressing the sedimentation of the particles, should be added to all the polymer particles. The one containing 10% by weight or more of the amount is used. The amount of the polymer particles added is 1 to 50% by weight, preferably 2 to 20% by weight based on the total weight of the dispersion.
% By weight. If it is less than this range, the amount of fine particles in the dispersion system is too small to expect a dispersion stabilizing effect, and if it is more than the above range, the viscosity of the dispersion will be increased or the physical properties of the urethane foam obtained will be reduced. Let

The following two methods can be mentioned as the method for preparing the triazine compound particle-dispersed polyol composition containing the polymer particles. One is a method in which polymer particles, which have been adjusted to have a predetermined particle shape in the process of producing the polymer in advance, are mixed with particles of a triazine compound, powders of a triazine compound or a derivative thereof, and a polyol. As an example of this method, water or alcohol dispersion of polystyrene particles obtained by emulsion polymerization of styrene, and polycarbonate particles finely pulverized in a non-solvent precipitation process after solution polymerization, are uniformly mixed with particles of a triazine compound and a polyol. It is a method of mixing. In advance, when prepared as a solid powder, it is sufficient to mix the triazine compound particles and the polyol as they are, but when using those prepared in the form of a dispersion composition dispersed in a liquid such as water or alcohol, The target dispersed polyol composition can be obtained by mixing the triazine compound particles and the polyol after being separated by filtration in advance, or by mixing the triazine compound particles, the polyol and the dispersion composition and then removing water and the like. ..

Another method is a method in which a polyol known as a polymer polyol having a trade name, which is obtained in advance by graft-polymerizing acrylonitrile or the like in a polyol, is directly mixed with particles of the triazine compound or the polyol. That is, polyether polyol, PTMEG,
In a liquid polyol such as polyester polyol, the true specific gravity of its homopolymer or copolymer such as styrene, acetonitrile, methyl methacrylate, etc. is 0.9 to 1.3 g / cm ³ (20 ° C). To prepare a polymer polyol by a method of polymerizing one or two or more vinyl monomers, and by selecting conditions such as polymerization temperature, composition of vinyl monomer, polymerization catalyst and additives at that time, 10 μm or less It is adjusted so as to be polymer particles containing 20% by weight or more of the particles. By mixing the obtained polymer polyol with the triazine compound particles and the polyol, the intended triazine compound particle-dispersed polyol composition can be prepared.

By the method as described above, it becomes possible to prepare a dispersed polyol composition in which particles of a triazine compound having excellent dispersibility are dispersed in a polyol, which has been impossible with conventional techniques. The dispersion polyol composition in which the particles of the triazine compound having such a composition are dispersed in the polyol has a lower viscosity of the dispersion and improved dispersion stability as compared with the conventional dispersion polyol composition. If the particles settle, they easily return to their original homogeneous dispersion. This is a drawback that the dispersed polyol composition obtained by the conventional technique has poor dispersibility, high dispersion viscosity, or does not easily return to its original dispersion state when dispersed particles settle. As opposed to having. INDUSTRIAL APPLICABILITY According to the present invention, a dispersion polyol composition optimal as a raw material for a flame-retardant regulation-compliant urethane foam containing a triazine compound as a flame retardant can be obtained.

[0020]

EXAMPLES The present invention will be described more specifically below with reference to Examples and Comparative Examples. Tables 1 to 4 collectively show Examples and Comparative Examples.

[0021]

[Table 1]

[0022]

[Table 2]

[0023]

[Table 3]

[0024]

[Table 4]

Abbreviations and the like of the raw materials used in Examples and Comparative Examples are as follows. Polyol A: Polyether polyol having a hydroxyl value of 33.1 mg KOH / g obtained by adding propylene oxide and ethylene oxide to glycerin at a ratio of 85:15 (weight ratio) Polyol B: Obtained by adding propylene oxide to glycerin, Polyether polyol having a hydroxyl value of 55.8 mgKOH / g Melamine mixture: Melamine powder having an average particle diameter of 24 μm and melamine powder having an average particle diameter of 1.9 μm are mixed with 70/30.
(Mixing ratio by weight) Melamine mixture: Melamine powder having an average particle size of 24 μm and melamine powder having an average particle size of 1.9 μm were mixed with 80/20.
Uniform mixture (weight ratio) FAML: Formalin / melamine (3mol / 1mo
1) Formalin-modified melamine powder modified at a ratio of ICA: Isocyanuric acid powder PST (A): Polystyrene powder prepared by emulsion polymerization (particle size: 1.0 ± 0.1 μm) PST (B): Emulsion polymerization Polystyrene powder (particle size: 0.6 ± 0.1 μm) PST (C): Polystyrene powder prepared by dispersion polymerization (particle size: 15 ± 2 μm) PE (A): Polyethylene powder (particle size: 5 to 5) 8 μm) PE (B): Powdered polyethylene (particle size: 8 to 12 μm
m) PE (C): Powdered polyethylene (particle size: 10-20
m) PC: powdered polycarbonate (particle size: 5 to 8 μm) PVC: powdered polyvinyl chloride (particle size: 3 to 12 μm) POP-C: In polyol A, styrene and acrylonitrile 50:50 (weight ratio) are radically polymerized. 20.0% by weight of polymer with the polymer polyol prepared by
Included Particle size of dispersion polymer <1 μm 34.7% (number ratio) 1 to 5 μm 47.2% 5 to 10 μm 14.3%> 10 μm 3.8% POP-D: Styrene and acrylonitrile in Polyol B Polymer polyol prepared by radical polymerization of 70:30 (weight ratio), containing 20.0% by weight of polymer Particle size of dispersion polymer <1 μm 13.3% (number ratio) 1 to 5 μm 61. 4% 5 to 10 μm 22.8%> 10 μm 2.5% POP-E: Polymer B prepared by radically polymerizing styrene and acrylonitrile 20:80 (weight ratio) in Polyol B. 0.0% by weight Particle size of dispersion polymer <1 μm 12.9% (number ratio) 1 to 5 μm 2.7% 5 to 10 μm 10.2%> 10 μm 74.2%

The particle size of the polymer is determined by electron micrograph (SEM
Or it was determined by visual observation or image analysis by TEM).
The viscosity, dispersion stability and average particle size were measured by the following methods. (Viscosity) The dispersion whose temperature is adjusted to 25 ° C. is measured using a B-type viscometer (Tokyo Keiki BM-type viscometer). (Dispersion Stability) Visual Method: A sample placed in a graduated cylinder having a height of 10 cm is placed at 25 ° C., and after 1 week, the height of a sedimentation part containing a triazine compound is measured and calculated by the following formula. Dispersion stability (%) = height of sedimentation part (cm) / 10 cm × 10
0 Solid content method: A sample placed in a graduated cylinder having a height of 10 cm is placed at 25 ° C., and after 1 week, 0 to 2 cm (bottom) from the bottom, 4 to 6 cm (middle) from the bottom, 8 to 10 from the bottom. Each part of (upper part) is sucked up, and the solid content insoluble in methanol is measured by extraction with methanol. (Average Particle Size) With a SK Laser Micron Sizer 700S, the powder is dispersed in methanol to measure the particle size distribution, and the weight average value is taken as the average particle size. The number of parts in the examples is parts by weight.

Comparative Example 1 70 parts of polyol A is charged into a reactor equipped with a stirrer, a nitrogen line and a charging port, and nitrogen substitution is carried out. Then, 30 parts of melamine (average particle size: 24 μm) is gradually charged from the charging port. After charging the whole amount, the mixture was stirred for 2 hours while purging with nitrogen. After the stirring was completed, the white dispersion polyol composition was taken out from the reactor, and the viscosity and the dispersion stability were measured. As a result, the viscosity of the dispersion was 2380 cps.
The dispersion stability after 1 week was 83% by the visual method, 3.4% by the solid content method, 17.8% in the middle portion, and 52.4% in the lower portion.
At that time, clear sedimentation of particles was observed.

Comparative Examples 2 to 11 In Comparative Example 1, the polyol, the triazine compound, and the additives were added (Comparative Examples 6 and 7 only) to prepare dispersed polyol compositions.

Example 1 A reactor equipped with a stirrer and a nitrogen line was charged with a mixture of 65 parts of polyol A and 5 parts of PST (A) that had been uniformly mixed in advance, and the atmosphere was replaced with nitrogen. A melamine mixture was used as the triazine compound, and a dispersed polyol composition was obtained by the same procedure as in Comparative Example. The viscosity of the dispersion was 4120 cps, and the dispersion stability after 1 week showed that no sedimentation of particles was observed by the visual method, and the solid content method showed the upper 3
The percentages were 4.1%, 34.8% in the middle part, and 36.1% in the lower part, and it was confirmed that the dispersion stability was improved as compared with Comparative Example 4. In addition, a sediment layer of 14 mm was confirmed at the bottom after one month of the wetting, but it was easily restored to the original uniform dispersion by stirring.

Examples 2 and 3 A dispersed polyol composition was prepared in the same manner as in Example 1, except that the addition amount of polystyrene was changed. In all cases, no sedimentation of particles was observed by visual observation.

Example 4 In Example 1, PST (A) was changed to PST (B) to prepare a dispersed polyol composition. No sedimentation of particles was observed by visual inspection.

Example 5 A dispersed polyol composition was prepared in the same manner as in Example 1 except that the melamine had an average particle size of 24 μm. Comparative Example 1
It was confirmed that the dispersion stability was improved in comparison with the above.

Comparative Example 12 A dispersion polyol composition was prepared in the same manner as in Example 1 except that PST (A) was changed to PST (C). As a result of a dispersion stability test by a visual method, a sedimentation layer was found on the upper part.

Examples 6 and 7 In Example 1, polystyrene was changed to polyethylene to prepare a dispersed polyol composition. As in Example 1, the dispersion stability was good.

Comparative Example 12 In Example 6, polyethylene (PE) was used instead of polyethylene to prepare a dispersed polyol composition. The dispersion stability was good by the visual method, but when measured by the solid content method, a difference in the solid content concentration was observed between the upper part and the lower part.

Example 8 and Comparative Example 14 In Example 1, polystyrene was replaced with polycarbonate and polyvinyl chloride to prepare a dispersed polyol composition. In the case of polycarbonate, the dispersion stability was good, but in the case of polyvinyl chloride, the sedimentation of particles was remarkable.

Example 9 A dispersed polyol composition was prepared in the same manner as in Comparative Example 9 except that the amount of polyol used was changed and polystyrene was added in Comparative Example 9. It was confirmed that the dispersion stability was improved as compared with Comparative Examples 8 and 9.

Example 10 A dispersed polyol composition was prepared in the same manner as in Comparative Example 11, except that the amount of polyol used was changed and polystyrene was added. An improvement in dispersion stability was observed as compared with Comparative Examples 10 and 11.

Example 11 20 parts of polyol A and 50 parts of POP-C are charged into a reactor equipped with a stirrer, a nitrogen line and a charging port, and nitrogen substitution is carried out. Then, 30 parts of melamine (mixing) is gradually charged from the charging port. After charging the whole amount, the mixture was stirred for 2 hours while purging with nitrogen. After the stirring was completed, the white dispersion polyol composition was taken out from the reactor, and the viscosity and the dispersion stability were measured. As a result, the viscosity of the dispersion is 375
At 0 cps, the dispersion stability after 1 week was such that no sedimentation of particles was observed by the visual method, and 39.1% in the upper part, 38.5% in the middle part, and 39.5% in the lower part by the solid content method. Compared to 4,
An improvement in dispersion stability was observed.

Examples 12 and 13 Dispersed polyol compositions were prepared in the same manner as in Example 11, except that the amount of polyol used, the type of melamine, and the amount of polymer polyol added were changed. Both
An improvement in dispersibility was recognized as compared with Comparative Examples 1 to 7.

Example 14 and Comparative Example 15 In Example 13, a dispersed polyol composition was prepared by changing the kind of polyol and the kind of polymer polyol. In the case of POP-D, the dispersion stability was good, but in the case of POP-E, there was a difference in the concentration between the upper and lower particles in the solid content method.

Example 15 In Example 14, a dispersion polyol composition was prepared by changing the amount of polyol used and the triazine compound to formalin-modified melamine, and changing the amount used and the type of polymer polyol. As in Example 14, the dispersion stability was good.

Example 16 In Example 13, the triazine compound was changed to isocyanuric acid to prepare a dispersed polyol. As in Example 13, the dispersion stability was good.

[0044]

Industrial Applicability According to the present invention, it becomes possible to easily prepare a triazine compound-dispersed polyol composition which is useful as a urethane foam raw material which complies with flame retardancy regulations. Further, the dispersion polyol composition has a low viscosity and improved dispersion stability as compared with those prepared by the conventional technique, and is extremely useful in urethane production.

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Claims (9)

[Claims] 1. (A) Formula 1 (Formula 1) (In the formula, R ¹ , R ² and R ³ each represent —NH ₂ , —OH or a group selected from alkyl groups having 5 or less carbon atoms.) A triazine compound and a triazine compound which are solid at room temperature One or a mixture of two or more kinds selected from the derivatives, and the powder material 2 having an average particle diameter of 1 to 100 μm 2
50 parts by weight, (B) 20% by weight or more of a polymer that is solid at room temperature and has a particle size of 10 μm or less, and has a true specific gravity of 0.9.
1 to 50 parts by weight of powder substance of ~ 1.3 g / cm ³ (20 ° C),
And (C) a dispersed polyol composition comprising 50 to 97 parts by weight of a polyol that is liquid at room temperature. 2. The dispersed polyol composition according to claim 1, wherein the triazine compound (A) is melamine, (iso) cyanuric acid or a derivative thereof. 3. The dispersed polyol composition according to claim 1, wherein the polymer particle (B) is a polymer of one or more monomers selected from the group consisting of styrene, acrylonitrile and methyl methacrylate. .. 4. (A) One or a mixture of two or more selected from triazine compounds and triazine compound derivatives which are solid at room temperature represented by formula (1) and have an average particle size of 1 to 100.
2 to 50 parts by weight of a powder material having a particle size of 10 μm and (B) a polymer which is a solid at room temperature and has a particle size of 10 μm or less, and a true specific gravity of 0.9 to 1.3 g / cm ³ (20 C.) 1 to 50 parts by weight of powdered material and (C) 50 to 97 parts by weight of a liquid polyol at room temperature are mixed, The method for producing a dispersed polyol composition according to claim 1. 5. The method for producing a dispersed polyol composition according to claim 4, wherein the triazine compound (A) is melamine, (iso) cyanuric acid or a derivative thereof. 6. The dispersed polyol composition according to claim 4, wherein the polymer particles (B) are particles of a styrene homopolymer of methyl methacrylate or a copolymer of styrene, a methyl methacrylate and acrylonitrile. Production method. 7. (A) One or a mixture of two or more selected from triazine compounds and triazine compound derivatives which are solid at room temperature and are represented by formula (A), and have an average particle size of 1 to 100.
2 to 50 parts by weight of a powder having a particle diameter of 10 μm and (D) a polymer which is a solid at room temperature and has a particle diameter of 10 μm 1 or less, and has a true specific gravity of 0.9 to 0.3 g / cm ³ ( 1 to 50 parts by weight of powdered material of 20 ° C.) in polyol in a weight ratio of 1 to 5
The method for producing a dispersed polyol composition according to claim 1, wherein 50 to 98 parts by weight of the dispersed polyol uniformly dispersed in 0% is mixed. 8. The method for producing a dispersed polyol composition according to claim 7, wherein the triazine compound (A) is melamine, (iso) cyanuric acid or a derivative thereof. 9. The dispersed polyol composition according to claim 7, wherein the polymer (D) is a polymer of one or more monomers selected from the group consisting of styrene, acrylonitrile, and methyl methacrylate. Manufacturing method.