TW202130689A - Polyol composition, flame-retardant hard polyurethane foam and method for producing same - Google Patents

Abstract

Provided are: a polyol composition which contains a flame retardant containing a prescribed phosphinic acid metal salt and/or a phosphate metal salt, said polyol composition making it possible to obtain a hard polyurethane foam which exhibits excellent flame retardancy and also being capable of suppressing particle precipitation and flocculation in a liquid in the case of said polyol composition and a starting material solution for a flame-retardant hard polyurethane foam; a flame-retardant hard polyurethane foam which uses the same; and a method for producing said foam. This polyol composition contains a polyol compound and a flame retardant. The polyol compound contains an aromatic polyester polyol and a Mannich polyol. The flame retardant contains one or more types of compound selected from the group consisting of a prescribed phosphinic acid metal salt and a phosphate metal salt.

Description

Polyol composition, flame-retardant rigid polyurethane foam and manufacturing method thereof

The present invention relates to a polyol composition used for the production of a flame-retardant rigid polyurethane foam, a flame-retardant rigid polyurethane foam using the polyol composition, and a method for manufacturing the same.

Rigid polyurethane foam has excellent heat insulation performance, processability and economy, etc. It is widely used as heat insulation material in buildings from the viewpoint of energy saving and improvement of habitability. .

On the other hand, rigid polyurethane foam is an organic polymer material and has a so-called easy to burn characteristic. Due to sparks from welding and hot cutting operations in construction and renovation projects, and demolition projects, fire accidents of rigid polyurethane foam prolonged burning often occur. Various ideas for imparting flame retardancy to rigid polyurethane foams have been reviewed as a countermeasure to reduce such fire accidents.

For example, a technique of adding red phosphorus or phosphoric acid ester as a flame retardant to a rigid polyurethane foam to make it flame retardant is known. However, red phosphorus is a flammable substance, so it must be handled with sufficient care to ensure safety. In addition, red phosphorus and phosphoric acid esters have a limited degree of improvement in the flame retardancy of rigid polyurethane foams, and it is desired to provide more excellent flame retardancy and to make rigid polyurethane foams. The foam is close to the flame retardant of the non-combustible material.

For this problem, the present inventors have reviewed and applied. For example, in Patent Document 1, it is used as a flame retardant for polyurethane resins for synthetic leather. Burning agent, as a more effective flame retardant. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] JP 2016-79375 A

[The problem to be solved by the invention]

However, the flame retardant containing the phosphinic acid-based metal salt described in Patent Document 1 is also hardly soluble in the raw material of rigid polyurethane foam like the conventional flame retardant such as red phosphorus. Among the polyol compounds or polyisocyanate compounds, it is a powdery flame retardant with a high specificity, which is prone to sedimentation and agglomeration in the raw material liquid of the rigid polyurethane foam.

In the manufacture of flame-retardant rigid polyurethane foam, blending of flame-retardant at the manufacturing site will increase the burden of on-site operations. Therefore, generally, a polyol composition with flame-retardant added in advance is used (Polyol premix) or rigid polyurethane foam raw material liquid. As mentioned above, the polyol composition or the raw material liquid of the rigid polyurethane foam prepared by pre-dispersing the powdery flame retardant may also cause sedimentation, agglomeration or solidification during use. , And in order to redistribute, it will require a lot of work load, and it will become difficult to redistribute evenly.

Therefore, when using the aforementioned powdery flame retardant containing phosphinic acid-based metal salt, it is desired to suppress the powder ( (Solid) sedimentation, aggregation, and excellent handleability in obtaining a uniform raw material composition. The same applies to the powdery flame retardant containing phosphoric acid-based metal salt.

The present invention was made in order to solve the above-mentioned technical problems, and aims to provide a polyol composition, a flame-retardant rigid polyurethane foam using the same, and a method for producing the same. The polyol composition contains The polyol composition containing the designated phosphinic acid-based metal salt and/or phosphoric acid-based metal salt of the flame retardant and the raw material liquid of the flame retardant rigid polyurethane foam can inhibit the sedimentation of the powder and Agglomerate, and a rigid polyurethane foam with excellent flame retardancy can be obtained. [Means to solve the problem]

The present invention is based on the discovery of the following: In a polyol composition containing a flame retardant containing a designated phosphinic acid-based metal salt, by using a designated polyol compound, it is possible to effectively suppress powdery Settling and aggregation of the flame retardant, and obtaining a rigid polyurethane foam with excellent flame retardancy. In addition, it was found that in a polyol composition containing a flame retardant containing a phosphoric acid-based metal salt, by using the same polyol compound, the sedimentation and aggregation of the powdered flame retardant can also be effectively suppressed, and A rigid polyurethane foam with excellent flame retardancy is obtained.

That is, the present invention provides the following [1] to [8]. [1] A polyol composition, which is a polyol composition used for the production of flame-retardant rigid polyurethane foam, which contains a polyol compound and a flame retardant, and the polyol compound contains aromatic Polyester polyol and Mannich polyol, the flame retardant includes one or more selected from the group consisting of phosphinic acid-based metal salts and phosphoric acid-based metal salts represented by the following formula (1) The compound.

(In formula (1), M is Mg, Al, Ca, Ti, or Zn, R ¹ is a hydrogen atom, a linear alkyl group with 1 to 6 carbons or a phenyl group, and n is 2, 3 or 4.) [ 2] The polyol composition according to the above [1], which contains 20 to 95 parts by mass of the Mannich-based polyol with respect to 100 parts by mass of the total solid content in the flame retardant. [3] The polyol composition according to [1] or [2] above, which contains a foaming agent. [4] The polyol composition according to the above [3], wherein the blowing agent contains any one or more of hydrofluoroolefin and hydrochlorofluoroolefin. [5] The polyol composition according to any one of [1] to [4] above, which contains a catalyst. [6] The polyol composition according to any one of [1] to [5] above, which contains a foam stabilizer.

[7] A flame-retardant rigid polyurethane foam, which is a reaction product of the polyol composition described in any one of [1] to [6] above and a polyisocyanate compound. [8] A method for producing a flame-retardant rigid polyurethane foam, which comprises mixing the polyol composition described in any one of [1] to [6] above with a polyisocyanate compound to make It is foamed and hardened to obtain a flame-retardant rigid polyurethane foam. [Effects of Invention]

According to the present invention, a polyol composition can be provided in a raw material liquid containing a polyol composition containing a designated phosphinic acid-based metal salt of a flame retardant and a flame-retardant rigid polyurethane foam , Can inhibit the sedimentation and aggregation of the powder in the liquid, and has excellent handling properties. In addition, by using the aforementioned polyol composition, a rigid polyurethane foam having excellent flame retardancy can be obtained. Furthermore, according to the present invention, in a polyol composition containing a flame retardant containing a phosphoric acid-based metal salt, the sedimentation and agglomeration of powder in the liquid can also be effectively suppressed, and a rigid material with excellent flame retardancy can be obtained. Polyurethane foam.

[Form to implement the invention]

Hereinafter, the polyol composition of the present invention, the flame-retardant rigid polyurethane foam using the same, and the production method thereof will be described in detail.

[Polyol composition] The polyol composition of the present invention is a polyol composition used for the production of flame-retardant rigid polyurethane foam, which contains a designated polyol compound and a designated flame retardant. The polyol compound includes aromatic polyester polyol and Mannich polyol, and the flame retardant includes one or more selected from the group consisting of phosphinic acid-based metal salts represented by the following formula (1), and phosphoric acid It is a compound of the group of metal salts.

In the aforementioned formula (1), M is Mg, Al, Ca, Ti, or Zn, R ¹ is a hydrogen atom, a linear alkyl group having 1 to 6 carbons or a phenyl group, and n is 2, 3, or 4.

By using the aforementioned polyol composition, a flame-retardant rigid polyurethane foam containing a flame-retardant agent containing the phosphinic acid-based metal salt and/or phosphoric acid-based metal salt represented by the aforementioned formula (1) In the raw material liquid, the sedimentation and aggregation of the powder in the liquid can be effectively inhibited. According to this, when the flame-retardant rigid polyurethane foam is manufactured, the work load for uniformly mixing the polyol composition and the raw material liquid of the flame-retardant rigid polyurethane foam can be reduced. In addition, the uniform dispersibility of the powder in the raw material liquid can be improved. Moreover, in the flame-retardant rigid polyurethane foam manufactured using the said raw material liquid, the excellent flame retardance by the said flame-retardant agent can also be maintained.

＜Polyol compound＞ The polyol compound is a raw material compound of the flame-retardant rigid polyurethane foam, which constitutes the polyol composition of the present invention. The aforementioned polyol compound is an alcohol compound having two or more hydroxyl groups, and a polyurethane resin is produced by an addition polymerization reaction with a polyisocyanate compound.

From the viewpoint of good flame retardancy, aromatic polyols are mainly used for the polyol compounds used for the production of flame-retardant rigid polyurethane foams. Compared with polypropylene glycol or the like used as a raw material of general polyurethane foam, the aromatic polyol can impart more excellent flame retardancy.

From the viewpoint of obtaining a flame-retardant rigid polyurethane foam having good flame retardancy and hardness, the aforementioned aromatic polyol preferably has a hydroxyl value of 100 to 900 mgKOH/g, more preferably It is 150-800 mgKOH/g, more preferably 180-700 mgKOH/g.

The polyol compound in the present invention includes aromatic polyester polyol and Mannich polyol.

From the viewpoint of obtaining a flame-retardant rigid polyurethane foam having good flame retardancy and hardness, the total content of the polyol compound in 100 parts by mass of the polyol composition is preferably 10.0 ~60.0 parts by mass, more preferably 20.0-55.0 parts by mass, still more preferably 30.0-50.0 parts by mass.

(Aromatic polyester polyol) The aromatic polyester polyol includes, for example, a compound obtained by polycondensation of an aromatic polycarboxylic acid and a polyol. The aforementioned aromatic polyester polyol may be used alone or in combination of two or more kinds. Specific examples of aromatic polycarboxylic acids include phthalic acid, terephthalic acid, phthalic acid, isophthalic acid, trimellitic acid, hemimelic acid, pyromellitic acid, etc. Carboxylic acid and so on. Specific examples of polyols include ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, dipropylene glycol, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, and tetramethylene glycol. Methylene glycol, neopentyl glycol, 3-methyl-1,5-pentanediol, glycerin, trimethylolpropane, neopentylerythritol, sorbitol, bisphenol A, etc. In addition, for aromatic polyester polyols, polyalkylene terephthalate, such as polyethylene terephthalate and polybutylene terephthalate, can be esterified with polyols. Exchanger.

From the viewpoint of obtaining a rigid polyurethane foam having good flame retardancy, it is preferable that the aromatic polyester polyol is contained in the largest ratio among the polyol compounds. The content of the aromatic polyester polyol in the polyol compound is preferably 50.0 parts by mass or more in 100 parts by mass of the polyol compound, more preferably 52.0-90.0 parts by mass, and still more preferably 55.0~ 85.0 parts by mass.

(Mannich series polyol) The Mannich polyol in the present invention refers to an aromatic polyol of a product (Mannich condensate) obtained by Mannich reaction of a phenol compound, an aldehyde compound, and an amine compound, and an alkylene oxide (alkylene oxide) Aromatic polyether polyol formed by addition polymerization. The aforementioned Mannich-based polyol may be used alone or in combination of two or more kinds. As for the aforementioned phenol compound, for example, phenol; alkylphenols such as cresol and nonanol are generally used. As for the aforementioned aldehyde compound, for example, formaldehyde, acetaldehyde, etc. are generally used. The aforementioned amine compounds include, for example, aliphatic primary or secondary monoamines. Generally, alkanolamines such as monoethanolamine, diethanolamine, 1-amino-2-propanol, etc. are used; methylamine, diethanolamine, etc. Alkyl amines such as ethyl amine, etc. As for the aforementioned alkylene oxide, for example, ethylene oxide, propylene oxide, butylene oxide, etc. are generally used. The aforementioned Mannich-based polyol can be specifically produced by the production method described in International Publication No. 2010/147091 and the like.

From the viewpoint of suppressing the sedimentation and aggregation of the powder in the aforementioned polyol composition and obtaining a rigid polyurethane foam with good flame retardancy, the content of the aforementioned Mannich-based polyol is In 100 parts by mass of the aforementioned polyol composition, it is preferably 1.0 to 20.0 parts by mass, more preferably 2.0 to 18.0 parts by mass, and still more preferably 3.0 to 16.0 parts by mass. Also, from the same viewpoint, the ratio of the content of the Mannich-based polyol to the content of the aromatic polyester polyol is preferably 0.10 to 1.00, more preferably 0.15 to 0.90, and still more preferably It is 0.20～0.80.

The polyol compound may include, in addition to the aromatic polyester polyol and the Mannich polyol, for example, aromatic polyether polyols other than the Mannich polyol, etc., and From the viewpoint of obtaining a rigid polyurethane foam having good flame retardancy, it is preferable not to include an aliphatic polyol. From the same viewpoint, the total content of the aromatic polyester polyol and the Mannich polyol in 100 parts by mass of the polyol compound is preferably 90 parts by mass or more, more preferably 95 parts by mass Above, it is more preferably 100 parts by mass.

＜Flame Retardant＞ The flame retardant used in the polyol composition of the present invention includes one or more compounds selected from the group consisting of phosphinic acid-based metal salts and phosphoric acid-based metal salts represented by the following formula (1).

In the aforementioned formula (1), M is Mg, Al, Ca, Ti or Zn, preferably Al or Zn, more preferably Al. When M is Mg, Ca, or Zn, n=2, when M is Al, n=3, and when M is Ti, n=4. R ¹ is a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms, or a phenyl group, and preferably a hydrogen atom, a methyl group, an ethyl group, or a phenyl group.

The flame retardant may include any one of the phosphinic acid-based metal salt and the phosphoric acid-based metal salt, or may include both. From the viewpoint of the effects of the present invention, the flame retardant is preferably one containing the phosphinic acid-based metal salt.

The aforementioned phosphinic acid-based metal salt is an inorganic phosphinate or an organic phosphinate, and is in powder form. The aforementioned phosphinic acid-based metal salt may be used alone or in combination of two or more kinds. The aforementioned powdered flame retardant containing phosphinic acid-based metal salt, compared with conventional flame retardants using red phosphorus or phosphoric acid ester, can give rigid polyurethane foams more excellent difficulties. Flammability.

The aforementioned phosphoric acid-based metal salt is an inorganic phosphate or an organic phosphate, and is in the form of a powder. The aforementioned phosphoric acid-based metal salt is preferably a phosphoric acid ester metal salt. The metal atom (ion) in the aforementioned phosphoric acid-based metal salt is preferably a salt of the same metal atom (ion) as the aforementioned phosphinic acid-based metal salt. The aforementioned phosphoric acid-based metal salt may be used alone or in combination of two or more kinds. The powdery flame retardant containing the phosphoric acid-based metal salt also uses the polyol compound to obtain good sedimentation suppression and aggregation suppression effects in the polyol composition.

(benzoguanamine)等。此等之中，可僅包含1種，亦可包含2種以上。 前述難燃劑中包含前述含有氮的化合物的情形，其含量，相對於前述次膦酸系金屬鹽100質量份，較佳為200質量份以下，更佳為100質量份以下，進一步較佳為50質量份以下。From the viewpoint of further enhancing the flame retardancy, the flame retardant may contain, in addition to the phosphinic acid-based metal salt or phosphoric acid-based metal salt, a component capable of acting as a flame-retardant auxiliary agent. For example, Contains nitrogen-containing compounds. As for the aforementioned nitrogen-containing compounds, for example, melamine, melamine phosphate, melamine pyrophosphate, melamine polyphosphate, melamine phthalate, melamine cyanurate, benzoguanidine

(benzoguanamine) and so on. Among these, only one type may be included, or two or more types may be included. When the aforementioned flame retardant contains the aforementioned nitrogen-containing compound, its content relative to 100 parts by mass of the aforementioned phosphinic acid-based metal salt is preferably 200 parts by mass or less, more preferably 100 parts by mass or less, and still more preferably 50 parts by mass or less.

However, ammonium polyphosphate has a tendency to delay the urethane reaction during the manufacture of rigid polyurethane foam, which is not preferable. Ammonium polyphosphate is easy to gel in the polyol composition, and it is not good at the point of aggregation inhibition. In addition, in the polyol composition, the phosphate ions are easily released, and the free acid will affect the catalyst activity in the urethane reaction. It is presumed that the urethane reaction is not fully promoted, and good flame retardancy cannot be obtained. Of rigid polyurethane foam.

In the present invention, as a powdery flame retardant containing the aforementioned phosphinic acid-based metal salt and a nitrogen-containing compound, for example, commercially available products such as the "FRAN CM" series manufactured by Daiwa Chemical Industry Co., Ltd. can be suitably used. Taste.

In addition, from the viewpoint of obtaining a rigid polyurethane foam with good flame retardancy, the aforementioned powdered flame retardant containing a phosphinic acid-based metal salt and/or a phosphoric acid-based metal salt is In the total 100 parts by mass of the flame retardant in the aforementioned polyol composition, it is preferably 50 parts by mass or more, more preferably 52-100 parts by mass, and still more preferably 55-100 parts by mass. In addition, in view of the fact that the aforementioned powdered flame retardant containing phosphinic acid-based metal salt and/or phosphoric acid-based metal salt is easy to settle and agglomerate, the powdered flame retardant, that is, the solid content of the aforementioned flame retardant In 100 parts by mass of the aforementioned polyol composition, preferably 10.0-40.0 parts by mass, more preferably 12.0-35.0 parts by mass, and still more preferably 15.0-30.0 parts by mass. From the same point of view, the content of the Mannich-based polyol is preferably 20 to 95 parts by mass, more preferably 30 parts by mass relative to the total solid content of the flame retardant in the polyol composition, 100 parts by mass. -90 parts by mass, more preferably 35-80 parts by mass.

The aforementioned flame retardant may contain liquid phosphoric acid ester from the viewpoint of obtaining the effect of inhibiting carbonization in the initial stage of heating or burning of rigid polyurethane foam. For example, a halogen-containing phosphoric acid ester is generally used. Tris (β-chloropropyl) phosphate and the like. Tris (β-chloropropyl) phosphate is a liquid, and will not occur in the raw material liquid of rigid polyurethane foam like the aforementioned phosphinic acid metal salt or phosphoric acid metal salt and red phosphorus in powder form. Sedimentation, agglomeration, etc., but the effect of imparting flame retardancy to the rigid polyurethane foam is superior to the aforementioned powdered flame retardant containing the phosphinic acid-based metal salt. Therefore, when the aforementioned flame retardant contains liquid phosphate ester, its content in 100 parts by mass of the flame retardant is preferably 50 parts by mass or less, more preferably less than 50 parts by mass, and still more preferably 45 parts by mass or less.

＜Other ingredients＞ As far as the raw materials for the production of flame-retardant rigid polyurethane foams, in addition to the polyol compounds, flame retardants and polyisocyanate compounds as the main raw materials, blowing agents, catalysts, Foam stabilizer, etc. These components can be added separately from the polyol composition during the manufacture of the flame-retardant rigid polyurethane foam, but they can reduce the work on the production site of the flame-retardant rigid polyurethane foam. From the viewpoint of burden, it is preferably blended with the aforementioned polyol composition. Furthermore, the aforementioned polyol composition may contain additives such as solvents, colorants, antioxidants, etc., as necessary, within a range that does not hinder the effects of the present invention.

(Foaming agent) The foaming agent has a function of generating gas by the heat generated by the resinification reaction of forming a urethane bond by the reaction of the polyol compound and the polyisocyanate compound, and foaming the polyurethane resin. As the aforementioned foaming agent, for example, hydrofluoroolefin (HFO), hydrochlorofluoroolefin (HCFO), hydrofluorocarbon (HFC), water, and the like can be cited. These may be used individually by 1 type, and may use 2 or more types together. Among these, from the viewpoint of global warming suppression effect, etc., HFO and HCFO will replace HFC, and it is expected that there will be an increase in foaming agent in the future, so it is better to use these. Specifically, trans-1,3,3,3-tetrafluoropropene (trans-HFO-1234ze), 1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzz ), trans-1-chloro-3,3,3-trifluoropropene (HCFO-1233zd), etc.

The isocyanate group of the polyisocyanate compound also reacts with water to form a urea bond and a foaming reaction of carbon dioxide gas occurs. Water becomes the foaming inducer in the initial stage of the formation reaction of the rigid polyurethane foam, and since the density of the rigid polyurethane foam produced can be reduced, it is preferable to include water as the hair Foaming agent.

From the viewpoint of appropriately foaming the polyurethane resin, the blending amount of the aforementioned blowing agent is preferably 5.0 to 40.0 parts by mass, more preferably 10.0 to 100 parts by mass of the polyisocyanate compound. 30.0 parts by mass, more preferably 12.0-25.0 parts by mass. However, since water may hydrolyze the aromatic polyester polyol, the content of water is preferably less than that of other foaming agents. It is preferably 20.0 parts by mass or less, more preferably 0.8 to 15.0 parts by mass, and still more preferably 1.0 to 10.0 parts by mass relative to the total 100 parts by mass of the foaming agent other than water.

(catalyst) From the viewpoint of promoting the aforementioned resinification reaction and foaming reaction, it is suitable to use a tertiary amine catalyst in the formation reaction of the rigid polyurethane foam. In addition, from the viewpoint of the improvement of flame retardancy due to a part of nurate, a nurating catalyst can also be used. Regarding these catalysts, conventional catalysts used in the production of rigid polyurethane foams can be used. These may be used individually by 1 type, and may use 2 or more types together.

Regarding the aforementioned tertiary amine catalyst, for example, dimethylethanolamine, triethylenediamine, methyldicyclohexylamine, dimethylcyclohexylamine, pentamethyldiethylenetriamine, bis(2- Dimethylaminoethyl)ether, diethylmethylphenylenediamine, 1,2-dimethylimidazole, 1,4-diazabicyclo[2.2.2]octane, etc. From the viewpoint of appropriately promoting the resinification reaction and foaming reaction of the rigid polyurethane foam, the blending amount of the aforementioned tertiary amine catalyst is preferably 0.1 relative to 100 parts by mass of the polyisocyanate compound ~10.0 parts by mass, more preferably 0.2 to 8.0 parts by mass, still more preferably 0.5 to 5.0 parts by mass.

等之含有氮的芳香族化合物；乙酸鉀、2-乙基己基酸鉀等之羧酸鹼金屬鹽；三甲基銨鹽、三乙基銨鹽、三苯基銨鹽等之三級銨鹽；四甲基銨鹽、四乙基銨、四苯基銨鹽等之四級銨鹽等。 由使適度促進異氰酸酯之三聚異氰酸酯化反應的觀點來看，前述三聚異氰酸酯化觸媒之摻合量，相對於聚異氰酸酯化合物100質量份，較佳為0.05～10.0質量份，更佳為0.1～8.0質量份，進一步較佳為0.2～5.0質量份。Regarding the aforementioned trimerized isocyanate catalyst, for example, ginseng (dimethylaminomethyl)phenol, 2,4-bis(dimethylaminomethyl)phenol, 2,4,6-ginseng (Dialkylaminoalkyl)hexahydro-S-tri

Nitrogen-containing aromatic compounds; alkali metal salts of carboxylic acids such as potassium acetate and potassium 2-ethylhexyl acid; tertiary ammonium salts such as trimethylammonium salt, triethylammonium salt, triphenylammonium salt, etc. ; Quaternary ammonium salts such as tetramethylammonium salt, tetraethylammonium salt, tetraphenylammonium salt, etc. From the viewpoint of moderately promoting the isocyanuration reaction of isocyanate, the blending amount of the aforementioned isocyanuration catalyst is preferably 0.05 to 10.0 parts by mass, and more preferably 0.1, relative to 100 parts by mass of the polyisocyanate compound. -8.0 parts by mass, more preferably 0.2-5.0 parts by mass.

(Foam stabilizer) From the viewpoint of obtaining a homogeneous flame-retardant rigid polyurethane foam, a foam stabilizer can be blended, and a conventional foam stabilizer in the production of rigid polyurethane foam can be used. Generally speaking, a silicone-based foam stabilizer is suitable for use, for example, siloxane-polyalkylene oxide copolymer (siloxane-polyalkylene oxide copolymer) and the like can be cited. The blending amount of the aforementioned foam stabilizer is appropriately set according to the type of polyurethane resin to be produced, but it is preferably 0.05 to 10.0 parts by mass, and more preferably 0.1 to 8.0 relative to 100 parts by mass of the polyisocyanate compound. Parts by mass, more preferably 0.2 to 5.0 parts by mass.

Furthermore, the aforementioned polyol composition may contain additives such as solvents, fillers, colorants, antioxidants, etc., as necessary, within a range that does not hinder the effects of the present invention. In addition, from the viewpoint of more effectively suppressing the aggregation of the powder in the polyol composition, among the fillers, it is preferable to blend particulate cryptomicrocrystalline in the polyol composition. And Noibo silica particles (also called Silitin or Silikolloid), a natural combination of amorphous silica and plate-shaped kaolin, are used as a dispersant. Although the Noyborg silica particles themselves are not soluble in the aforementioned polyol composition, by blending the Noyborg silica particles, even if the aforementioned powders containing phosphinic acid-based metal salts and/or phosphoric acid-based metal salts are When the flame retardant is settling, the settled powder is difficult to solidify and can be easily redispersed. According to this, when manufacturing a flame-retardant rigid polyurethane foam, the ease of handling of the polyol composition can be improved.

[Flame retardant rigid polyurethane foam] The flame-retardant rigid polyurethane foam of the present invention is a reaction product obtained by reacting the aforementioned polyol composition with a polyisocyanate compound. In the case of using an inadequately uniform polyol composition, it is difficult to obtain a homogeneous rigid polyurethane foam having good flame retardancy overall. On the other hand, the polyol composition according to the present invention, as described above, can be used in the polyol when a powdery flame retardant containing the aforementioned phosphinic acid-based metal salt and/or phosphoric acid-based metal salt that is easy to settle is used. In the raw material liquid of the alcohol composition and the flame-retardant rigid polyurethane foam, the sedimentation and agglomeration of the powder are effectively inhibited. According to this, when the flame-retardant rigid polyurethane foam is manufactured, the work load for uniformly dispersing the aforementioned polyol composition and the raw material liquid of the flame-retardant rigid polyurethane foam can be reduced , In addition, it can improve the uniform dispersibility of the powder in the raw material liquid. In addition, good flame retardancy due to the flame retardant in the obtained flame retardant rigid polyurethane foam can also be maintained.

＜Polyisocyanate compound＞ The polyisocyanate compound is an isocyanate compound having two or more isocyanate groups, and a polyurethane resin is produced by the addition polymerization reaction with the aforementioned polyol compound. The aforementioned polyisocyanate compound may be either an aromatic polyisocyanate or an aliphatic polyisocyanate, and one of these may be used alone, or two or more of them may be used in combination.

As for the aromatic polyisocyanate, for example, diphenylether-2,4'-diisocyanate, diphenylether-4,4'-diisocyanate, tolylene-2,4-diisocyanate, Phenyl-2,6-diisocyanate, 4,6-dimethyl-1,3-phenyl-diisocyanate, 2,2'-diphenylmethane diisocyanate (2,2'-MDI), MDI and polymethylene of monomers such as 2,4'-diphenylmethane diisocyanate (2,4'-MDI) and 4,4'-diphenylmethane diisocyanate (4,4'-MDI) Polyphenyl polyisocyanate (crude MDI or polymer MDI), 3,3'-dimethyl-4,4'-biphenyldiisocyanate, meta-xylene diisocyanate, etc. Regarding the aliphatic polyisocyanate, it can be either acyclic or alicyclic polyisocyanate, for example, tetramethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, two Cyclohexylmethane diisocyanate, etc. Among these, from the viewpoints of reactivity and the flame retardancy of the rigid polyurethane foam produced, 2,2'-MDI, 2,4'-MDI, 4, Monomer MDI such as 4'-MDI, crude MDI, or polymer MDI. Among them, crude MDI or polymer MDI is suitably used from the viewpoints of ease of availability and cost.

The blending amount of the polyisocyanate compound in the raw material liquid of the aforementioned flame-retardant rigid polyurethane foam is appropriately set according to the type of the polyisocyanate compound, but is determined by the sufficient reactivity with the aforementioned polyol compound and the aforementioned From the viewpoints of ease of handling during mixing of the raw material liquid, it is preferably 50 to 200 parts by mass, more preferably 70 to 150 parts by mass, and still more preferably 80 to 100 parts by mass of the aforementioned polyol composition. 120 parts by mass.

<Method for manufacturing flame-retardant rigid polyurethane foam> The molding foaming method in the manufacturing method of the aforementioned flame-retardant rigid polyurethane foam is not particularly limited. For example, slab molding, mold-molding, and laminate molding can be applied. , Injection molding, spray foaming and other well-known methods. In each of these molding and foaming methods, by mixing the aforementioned polyol composition with the aforementioned polyisocyanate compound, foaming and hardening, it is possible to produce a homogeneous rigid polyurethane with good flame retardancy. Ester foam.

As mentioned above, since the sedimentation and aggregation of the powder contained are suppressed, the polyol composition is redispersed when it is mixed with the polyisocyanate compound. For example, using a general mixer using a stirring blade, etc., it is not necessary to re-disperse it. Shear force, etc., and easily homogenize. That is, it is easy to uniformly redisperse with a small workload. Therefore, by using the aforementioned polyol composition, the production efficiency of the flame-retardant rigid polyurethane foam can be improved. [Example]

Hereinafter, the present invention will be described in detail with examples, but the present invention is not limited to these.

[Preparation of polyol composition] The details of each raw material used in the preparation of the polyol composition of the following examples and comparative examples are shown below. ＜Polyol compound＞ (Polyester polyol (a1)) (a1-1) RFK-556: Terephthalic acid polyester polyol; "MAXIMOL (registered trademark) RFK-556", manufactured by Kawasaki Chemical Industry Co., Ltd., with a hydroxyl value of 224mgKOH/g (a1-2) RFK-087: Terephthalic acid polyester polyol; "MAXIMOL (registered trademark) RFK-087", manufactured by Kawasaki Chemical Industry Co., Ltd.; hydroxyl value 200mgKOH/g (Mannich polyol (a2)) (a2-1) NB-622: "EXCENOL (registered trademark) NB-622", manufactured by AGC Co., Ltd., with a hydroxyl value of 500mgKOH/g (a2-2) FB-800: "EXCENOL (registered trademark) FB-800", manufactured by AGC Co., Ltd., with a hydroxyl value of 300mgKOH/g (Polyether polyol) ・GR-30: TDA (toluene diamine)-based polyether polyol; "Actocol (registered trademark) GR-30", manufactured by Mitsui Chemicals SKC Polyurethane Co., Ltd., with a hydroxyl value of 400 mgKOH/g ＜Flame Retardant＞ (Phosphinic acid-based metal salt or phosphoric acid-based metal salt (b)) (b1) CM-6R: Powdered flame retardant containing phosphinic acid metal salt; "FRAN CM -6R", manufactured by Daiwa Chemical Industry Co., Ltd. (b2) OP935: phosphinic acid series metal salt; "Exolit (registered trademark) OP935", manufactured by Clariant Chemicals Co., Ltd. (b3) R098-5: Phosphate metal salt (powder); "Nonnen (registered trademark) R098-5", manufactured by Marubi Oil Chemical Co., Ltd. (Ammonium Polyphosphate) ・TK-1000: Ammonium polyphosphate; "TK-1000", manufactured by MANAC Co., Ltd. ・APP201: Ammonium polyphosphate; "KYLIN (registered trademark) APP201", manufactured by SHIFANG CHANGFENG CHEMICAL ・TMCPP: Tris (β-chloropropyl) phosphate; "TMCPP", manufactured by Dahachi Chemical Industry Co., Ltd. ＜Blowing agent＞ ・HCFO: Trans-1-chloro-3,3,3-trifluoropropene (HCFO-1233zd); "Solstice (registered trademark) LBA", manufactured by Honeywell International Inc. ·water ＜Catalyst＞ ・SX60: Tertiary amine catalyst; "TOYOCAT (registered trademark)-SX60", manufactured by TOSOH Co., Ltd. ・DM70: Tertiary amine catalyst; "TOYOCAT (registered trademark)-DM70", manufactured by TOSOH Co., Ltd. ・K-15: Potassium 2-ethylhexyl acid; "Dabco (registered trademark) K-15", manufactured by Evonik Corporation, trimeric isocyanate catalyst ＜Foam stabilizer＞ ・L-6100: Silicone foam stabilizer; "Niax (registered trademark) silicone L-6100", manufactured by Momentive Performance Materials Inc.

(Example 1) In a 500mL polyethylene bottle, put 28.5 parts by mass of polyester polyol (a1-1), 8.0 parts by mass of Mannich polyol (a2-1), and 1.6 parts each of catalysts (SX60, DM70 and K-15) Parts by mass, 0.3 parts by mass of water (foaming agent), 16.0 parts by mass of TMCPP, and 1.6 parts by mass of foam stabilizer L-6100, stirred at 3000 rpm for 20 seconds with an electric drill equipped with a cage stirrer (below, stirring method) same). 20.0 parts by mass of the flame retardant (b1) was added thereto, stirred for 20 seconds, and then 20.8 parts by mass of HCFO was added, and after stirring for 20 seconds, the mixture was kept in a constant temperature water tank at 20°C to prepare a polyol composition.

(Examples 2-7, Comparative Examples 1-7) The raw materials shown in Table 1 below were blended in the same manner as in Example 1, and polyol compositions were prepared individually.

[Manufacturing of rigid polyurethane foam] Using the polyol composition of each of the foregoing Examples and Comparative Examples, a rigid polyurethane foam was produced in the following manner. In addition, as the polyisocyanate compound, polymethylene polyphenyl polyisocyanate (MDI of polymer); "MILLIONATE (registered trademark) MR-200", manufactured by TOSOH Co., Ltd. was used. In a 500 mL recyclable measuring cup, 100 parts by mass of the polyol composition and 102.5 parts by mass of the polyisocyanate compound in a uniformly stirred state are placed, and after stirring for 5 seconds, the obtained mixture (hard polyurethane hair The raw material liquid of the foam body) was poured into a 15 cm square mold, allowed to stand for 30 minutes, and then demolded to obtain a rigid polyurethane foam.

[Evaluation] The polyol composition prepared in each of the above-mentioned Examples and Comparative Examples and the rigid polyurethane foam produced using the same were evaluated for the following items. These evaluation results are summarized and presented in Table 1 below.

＜Sinkability＞ After the 50 mL vial containing 30 g of the polyol composition was allowed to stand at room temperature (25° C.) for 21 days, the vial was shaken up and down 20 times, and the vial was allowed to stand again. Observe the appearance, and measure the height position (the height from the liquid surface) of the sediment of the solid content after 1 day. Evaluate these measured values based on the following evaluation criteria. (Evaluation criteria) A: The height position above the sediment is less than 5mm from the liquid surface B: The height of the upper surface of the sediment is 5mm or more and less than 8mm from the liquid surface C: The height of the top of the sediment is 8mm or more from the liquid surface In the case of evaluation A, it can be seen that almost no settlement progressed. In the case of evaluation B, slight sedimentation progressed, and in the case of evaluation C, significant sedimentation progressed, and it was determined that the polyol composition was not practically suitable.

＜Cohesion＞ In the aforementioned evaluation of sedimentation, the 50 mL vial was left to stand for 5 minutes after standing for 21 days, and then stand upright for 5 minutes. Observed by visual appearance, the state of the solid content sedimentation was confirmed. Based on the following evaluation criteria, evaluate these observation results. (Evaluation criteria) A: When the vial is poured to the side, the sediment flows, and when it stands upright again, it slowly returns to its original state. Even if it is left to stand for 5 minutes, the sediment will not return to its original state at all, but will not adhere to the inner wall surface of the vial. B: When the vial is poured to the side, the sediment flows, and when it stands up again, it slowly returns to its original state. Even if it is left for 5 minutes, the sediment will not return to its original state at all, but there will be adherents remaining on the inner wall of the vial. C: Even if the vial is poured on its side, the sediment does not flow. D: The solid content will gel. In the case of Evaluation A, it can be said that the aggregation of the powder is well suppressed. On the other hand, when evaluating B to D, it was judged that a sufficient aggregation suppression effect was not obtained, and when evaluating C and D, it was judged not to be suitable for practical use.

<Flame retardancy> From the rigid polyurethane foam produced above, a sample of 98 mm×98 mm×thickness (height) 25 mm was cut out. According to ISO 5660-1, using a cone calorimeter ("Cone calorimeter III", manufactured by Toyo Seiki Seisakusho Co., Ltd.; non-combustible base material: gypsum board (thickness 9.5mm)), 50KW/ m ² of heat, and at the same time, the spark plug is used to ignite for 10 seconds, and the total heat of heating for 20 minutes is measured. Evaluate these measured values based on the following evaluation criteria. (Evaluation criteria) A: Total heating value is less than 8MJ/m ² B: Total heating value is 8MJ/m ² or more and less than 11MJ/m ² C: Total heating value is 11MJ/m ² or more and less than 20MJ/m ² D: Total heating value When the amount of 20MJ/m ² or more is evaluated as A, the flame retardancy is the highest, which can be described as a non-combustible material. Secondly, in the case of evaluation B, the flame retardancy is also sufficiently high, which can be described as a quasi-non-combustible material.

[Table 1] Blending composition [mass parts] Example Comparative example 1 2 3 4 5 6 7 1 2 3 4 5 6 7 Polyol compound Polyester polyol (a1) (a1-1)RFK-556 28.5 24.0 21.0 28.5 - 28.5 28.5 36.5 32.0 24.0 36.5 36.5 28.5 28.5 (a1-2)RFK-087 - - - - 28.5 - - - - - - - - - Mannich series polyol (a2) (a2-1)NB-622 8.0 17.3 15.1 - 8.0 8.0 8.0 - - - - - 8.0 8.0 (a2-2)FB-800 - - - 8.0 - - - - - - - - - - ＜(a2)/(a1)＞ ＜0.28＞ ＜0.72＞ ＜0.72＞ ＜0.28＞ ＜0.28＞ ＜0.28＞ ＜0.28＞ - - - - - ＜0.28＞ ＜0.28＞ ((a2)/(b)×100) (40) (87) (50) (40) (40) (40) (40) - - - - - - - Polyether polyol GR-30 - - - - - - - - 9.3 17.3 - - - - Flame retardant Phosphinic acid-based metal salt or phosphoric acid-based metal salt (b) (b1)CM-6R 20.0 20.0 30.0 20.0 20.0 - - 20.0 20.0 20.0 - - - - (b2)OP935 - - - - - 30.0 - - - - 30.0 - - - (b3)R098-5 - - - - - - 30.0 - - - - 30.0 - - Ammonium Polyphosphate TK-1000 - - - - - - - - - - - - 30.0 - APP201 - - - - - - - - - - - - - 30.0 TMCPP 16.0 16.0 14.0 16.0 16.0 6.0 6.0 16.0 16.0 16.0 6.0 6.0 6.0 6.0 Foaming agent HCFO 20.8 16.0 14.0 20.8 20.8 20.8 20.8 20.8 16.0 16.0 20.8 20.8 20.8 20.8 water 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 catalyst SX60 1.6 1.6 1.4 1.6 1.6 1.6 1.6 1.6 1.6 1.6 1.6 1.6 1.6 1.6 DM70 1.6 1.6 1.4 1.6 1.6 1.6 1.6 1.6 1.6 1.6 1.6 1.6 1.6 1.6 K-15 1.6 1.6 1.4 1.6 1.6 1.6 1.6 1.6 1.6 1.6 1.6 1.6 1.6 1.6 Foam stabilizer L-6100 1.6 1.6 1.4 1.6 1.6 1.6 1.6 1.6 1.6 1.6 1.6 1.6 1.6 1.6 Settlement A A A B A A A C C C B B C D Cohesion A A A A A A A B C C B B D D Flammability A B B B A B B A C D B B C C

As shown in the results shown in Table 1, it was confirmed that by adding Mannich-based polyols as polyol compounds (Examples 1 to 7), the inclusion of one or more selected from the group consisting of specified phosphinic acid-based metal salts and phosphoric acid was suppressed It is the sedimentation and aggregation of the powdery flame retardant of the compound of the metal salt group, and a rigid polyurethane foam having flame retardancy equivalent to or higher than that of a quasi-incombustible material is obtained. On the other hand, in the case where Mannich-based polyol was not added (Comparative Examples 1 to 5), the flame retardancy of rigid polyurethane foam was good, but it could not be said to sufficiently inhibit the content of the polyol composition. Settling and agglomeration of powder. Among these, in the case of adding aromatic polyether polyols other than Mannich polyols (Comparative Examples 2 and 3), the effect of suppressing the sedimentation and aggregation of the powder in the polyol composition is poor, and the rigid polymer The flame retardancy of urethane foam is also poor. In addition, when the flame retardant contains ammonium polyphosphate (Comparative Examples 6 and 7), the polyol composition is gelled, and the flame retardancy of the rigid polyurethane foam is also poor.

without.

without.

without.

Claims (8)

A polyol composition, which is a polyol composition used in the manufacture of flame-retardant rigid polyurethane foam, which contains a polyol compound and a flame retardant, and the polyol compound includes an aromatic polyester Polyols and Mannich-based polyols, and the flame retardant includes one or more selected from the group consisting of phosphinic acid-based metal salts and phosphoric acid-based metal salts represented by the following formula (1) Group of compounds,

(In formula (1), M is Mg, Al, Ca, Ti, or Zn, R ¹ is a hydrogen atom, a linear alkyl group having 1 to 6 carbons or a phenyl group, and n is 2, 3, or 4). The polyol composition of claim 1, which contains 20 to 95 parts by mass of the Mannich-based polyol relative to 100 parts by mass of the total solid content in the flame retardant. Such as the polyol composition of claim 1 or 2, which contains a foaming agent. The polyol composition of claim 3, wherein the blowing agent contains any one or more of hydrofluoroolefin and hydrochlorofluoroolefin. The polyol composition according to any one of claims 1 to 4, which contains a catalyst. The polyol composition according to any one of claims 1 to 5, which contains a foam stabilizer. A flame-retardant rigid polyurethane foam, which is a reaction product of a polyol composition according to any one of claims 1 to 6 and a polyisocyanate compound. A method for producing a flame-retardant rigid polyurethane foam, which mixes the polyol composition according to any one of claims 1 to 6 with a polyisocyanate compound to foam and harden, and A flame-retardant rigid polyurethane foam was obtained.