WO2021125237A1

WO2021125237A1 - Polyol composition, flame-retardant hard polyurethane foam and method for producing same

Info

Publication number: WO2021125237A1
Application number: PCT/JP2020/047016
Authority: WO
Inventors: 達也奥谷; 貴臣江原; 久保田　幸雄
Original assignee: 日清紡ケミカル株式会社
Priority date: 2019-12-17
Filing date: 2020-12-16
Publication date: 2021-06-24
Also published as: TW202130689A; JPWO2021125237A1

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 its manufacturing method

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

Rigid polyurethane foam has excellent heat insulating performance, is also excellent in workability and economy, and is widely used as a heat insulating material for buildings from the viewpoint of energy saving and improvement of comfort.

On the other hand, the rigid polyurethane foam is an organic polymer material and has a feature of being easily burned. Sparks during welding fusing work during construction, renovation, and demolition work often cause fire accidents in which rigid polyurethane foam spreads.
As a measure to reduce such fire accidents, various measures for imparting flame retardancy to rigid polyurethane foam are being studied.

For example, a technique is known in which red phosphorus or a phosphoric acid ester is added as a flame retardant to a rigid polyurethane foam to make it flame retardant.
However, red phosphorus is an ignitable substance, and sufficient care must be taken when handling it to ensure safety.
In addition, with red phosphorus and phosphoric acid ester, there is a limit to the degree of improvement in flame retardancy of rigid polyurethane foam, and it is difficult to impart better flame retardancy and bring rigid polyurethane foam closer to nonflammable materials. A flame retardant was sought.

In response to such problems, the present inventors have difficulty in containing a phosphinic acid-based metal salt as a more effective flame retardant, for example, which is used as a flame retardant for polyurethane resin for synthetic leather in Patent Document 1. We considered applying a flame retardant.

Japanese Unexamined Patent Publication No. 2016-79375

However, the flame retardant containing the phosphinic acid-based metal salt described in Patent Document 1 is also soluble in the polyol compound and polyisocyanate compound which are the raw materials of the rigid polyurethane foam, like the conventional flame retardants such as red phosphorus. It is a powdery flame retardant that is difficult to handle and has a large specific gravity, and tends to settle or aggregate in the raw material liquid of the rigid polyurethane foam.

In the production of flame-retardant rigid polyurethane foam, blending a flame retardant at the manufacturing site increases the burden of on-site work. Therefore, in general, a polyol composition (polyol) to which a flame retardant is added in advance. Premix) or a raw material solution of rigid polyurethane foam is used.
The polyol composition or the raw material liquid for rigid polyurethane foam prepared by pre-dispersing the powdery flame retardant as described above may cause sedimentation, agglomerate or solidify during use, and may be re-aggregated. A large workload may be required for dispersion, and uniform redispersion may be difficult.

Therefore, when using the powdery flame retardant containing the phosphinic acid-based metal salt, the powder (solid) may settle or aggregate in the raw material liquid of the polyol composition or the rigid polyurethane foam. Is suppressed, and it is required to be excellent in handleability in obtaining a uniform raw material composition. The same can be said for powdered flame retardants containing phosphoric acid-based metal salts.

The present invention has been made to solve the above technical problems, and is a polyol composition containing a flame retardant containing a predetermined phosphinic acid-based metal salt and / or phosphoric acid-based metal salt, and a flame-retardant rigid polyurethane. A polyol composition capable of obtaining a rigid polyurethane foam having excellent flame retardancy while suppressing powder settling and agglomeration in the raw material liquid of the foam, and a flame retardant rigid polyurethane foam using the same. It is an object of the present invention to provide the manufacturing method.

According to the present invention, in a polyol composition containing a flame retardant containing a predetermined phosphinic acid-based metal salt, the precipitation and aggregation of the powdery flame retardant can be effectively suppressed by using the predetermined polyol compound. It is based on the finding that a rigid polyurethane foam capable of being formed and having excellent flame retardancy can be obtained.
Further, even in a polyol composition containing a flame retardant containing a phosphoric acid-based metal salt, by using the same polyol compound, sedimentation and aggregation of the powdery flame retardant can be effectively suppressed, and moreover, it can be effectively suppressed. , It has been found that a rigid polyurethane foam having excellent flame retardancy can be obtained.

That is, the present invention provides the following [1] to [8].
[1] A polyol composition used for producing a flame-retardant rigid polyurethane foam, which contains a polyol compound and a flame retardant, and the polyol compound contains an aromatic polyester polyol and a Mannig-based polyol, and the flame retardant. Is a polyol composition containing one or more compounds selected from the group consisting of a phosphinic acid-based metal salt represented by the following formula (1) and a phosphoric acid-based metal salt.

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

[7] A flame-retardant rigid polyurethane foam which is a reaction product with the polyol composition according to any one of the above [1] to [6] and a polyisocyanate compound.
[8] A flame-retardant rigid polyurethane foam obtained by mixing the polyol composition according to any one of the above [1] to [6] with a polyisocyanate compound, foaming and curing. Manufacturing method of rigid polyurethane foam.

According to the present invention, in a polyol composition containing a flame retardant containing a predetermined phosphinic acid-based metal salt and a raw material liquid for a flame-retardant rigid polyurethane foam, sedimentation and aggregation of powder in the liquid are suppressed and handled. It is possible to provide a polyol composition having excellent properties.
Further, by using the polyol composition, a rigid polyurethane foam having excellent flame retardancy can be obtained.
Further, according to the present invention, even in a polyol composition containing a flame retardant containing a phosphoric acid-based metal salt, sedimentation and aggregation of powder in the liquid can be effectively suppressed, and moreover, excellent flame retardancy is achieved. A rigid polyurethane foam having a property can be obtained.

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

[Polyol composition]
The polyol composition of the present invention is a polyol composition used for producing a flame-retardant rigid polyurethane foam, and contains a predetermined polyol compound and a predetermined flame retardant.
The polyol compound contains an aromatic polyester polyol and a Mannig-based polyol, and the flame retardant is composed of a group consisting of a phosphinic acid-based metal salt represented by the following formula (1) and a phosphoric acid-based metal salt. Contains one or more selected compounds.

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

By using the polyol composition, a liquid in a raw material liquid of a flame-retardant rigid polyurethane foam containing a flame retardant containing a phosphinic acid-based metal salt and / or a phosphoric acid-based metal salt represented by the formula (1). It is possible to effectively suppress the sedimentation and aggregation of the powder inside. This makes it possible to reduce the work load for uniformly mixing the polyol composition and the raw material liquid of the flame-retardant rigid polyurethane foam during the production of the flame-retardant rigid polyurethane foam, and the powder in the raw material liquid. It is possible to enhance the uniform dispersibility of. Further, in the flame-retardant rigid polyurethane foam produced by using the raw material liquid, the excellent flame retardancy of the flame retardant is also maintained.

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

As the polyol compound used for producing the flame-retardant rigid polyurethane foam, an aromatic polyol is mainly used from the viewpoint of good flame retardancy. Aromatic polyols can impart more excellent flame retardancy than polypropylene glycol or the like used as a general polyurethane foam raw material.

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

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

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

(Aromatic polyester polyol)
Examples of the aromatic polyester polyol include compounds obtained by polycondensation of an aromatic polyunsaturated carboxylic acid and a polyhydric alcohol. The aromatic polyester polyol may be used alone or in combination of two or more.
Specific examples of the aromatic polyvalent carboxylic acid include aromatic polyvalent carboxylic acids such as phthalic acid, terephthalic acid, orthophthalic acid, isophthalic acid, trimellitic acid, hemmellitic acid, and pyromellitic acid. Specific examples of polyhydric alcohols include ethylene glycol, propanediol, butanediol, diethylene glycol, dipropylene glycol, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, decamethylene glycol, neopentyl glycol, 3-methyl-1, Examples thereof include 5-pentanediol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, and bisphenol A.
Further, examples of the aromatic polyester polyol include those obtained by transesterifying polyalkylene terephthalate such as polyethylene terephthalate and polybutylene terephthalate with a polyhydric alcohol.

The aromatic polyester polyol is preferably contained in the largest proportion of the polyol compounds from the viewpoint of obtaining a rigid polyurethane foam having good flame retardancy.
The content of the aromatic polyester polyol in the polyol compound is preferably 50.0 parts by mass or more, more preferably 52.0 to 90.0 parts by mass, still more preferably 55, based on 100 parts by mass of the polyol compound. It is 0.0 to 85.0 parts by mass.

(Mannich-based polyol)
The Mannich-based polyol in the present invention is an aromatic-based polyether obtained by addition-polymerizing an alkylene oxide to an aromatic-based polyol which is a product (Mannich condensate) obtained by the Mannich reaction of a phenol compound, an aldehyde compound and an amine compound. Refers to a polyol. The Mannich-based polyol may be used alone or in combination of two or more.
As the phenol compound, for example, phenol; alkylphenols such as cresol and nonylphenol are generally used.
As the aldehyde compound, for example, formaldehyde, acetaldehyde and the like are generally used.
Examples of the amine compound include aliphatic primary or secondary monoamines, such as alkanolamines such as monoethanolamine, diethanolamine and 1-amino-2-propanol; alkylamines such as methylamine and diethylamine. Etc. are commonly used.
As the alkylene oxide, for example, ethylene oxide, propylene oxide, butylene oxide and the like are generally used.
Specifically, the Mannich-based polyol can be produced by the production method described in International Publication No. 2010/147091 and the like.

The content of the Mannig-based polyol is preferably in 100 parts by mass of the polyol composition from the viewpoint of suppressing the precipitation and aggregation of powder in the polyol composition and obtaining a rigid polyurethane foam having good flame retardancy. Is 1.0 to 20.0 parts by mass, more preferably 2.0 to 18.0 parts by mass, and even more preferably 3.0 to 16.0 parts by mass.
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. It is 90, more preferably 0.20 to 0.80.

The polyol compound may contain, for example, an aromatic polyether polyol other than the Mannig-based polyol in addition to the aromatic polyester polyol and the Mannig-based polyol, but is a hard having good flame retardancy. From the viewpoint of obtaining a polyurethane foam, it is preferable not to contain an aliphatic polyol. From the same viewpoint, the total content of the aromatic polyester polyol and the Mannig-based polyol in 100 parts by mass of the polyol compound is preferably 90 parts by mass or more, more preferably 95 parts by mass or more, still more preferably 100 parts by mass. It is a department.

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

In the formula (1), M is Mg, Al, Ca, Ti or Zn, preferably Al or Zn, and 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 or a phenyl group having 1 to 6 carbon atoms, and is preferably a hydrogen atom, a methyl group, an ethyl group or a phenyl group.

The flame retardant may contain either the phosphinic acid-based metal salt or the phosphoric acid-based metal salt, or may contain both. From the viewpoint of the effect of the present invention, the flame retardant preferably contains the phosphinic acid-based metal salt.

The phosphinic acid-based metal salt is an inorganic phosphinate or an organic phosphinate, and is in the form of a powder. The phosphinic acid-based metal salt may be used alone or in combination of two or more.
The powdery flame retardant containing the phosphinic acid-based metal salt can impart more excellent flame retardancy to the rigid polyurethane foam as compared with the conventional flame retardants using red phosphorus, phosphoric acid ester, or the like.

The phosphoric acid-based metal salt is an inorganic phosphate or an organic phosphate, and is in the form of powder. The phosphoric acid-based metal salt is preferably a phosphoric acid ester metal salt. The metal atom (ion) in the phosphoric acid-based metal salt is preferably a salt of the same metal atom (ion) as the phosphinic acid-based metal salt. The phosphoric acid-based metal salt may be used alone or in combination of two or more.
By using the polyol compound in the powdery flame retardant containing the phosphoric acid-based metal salt, a good effect of suppressing sedimentation and suppressing aggregation in the polyol composition can be obtained.

From the viewpoint of further improving flame retardancy, the flame retardant may contain a component capable of acting as a flame retardant aid in addition to the phosphinic acid-based metal salt and the phosphoric acid-based metal salt, and may contain, for example, nitrogen. It preferably contains a compound.
Examples of the nitrogen-containing compound include melamine, melamine phosphate, melamine pyrophosphate, melamine polyphosphate, melamine phthalate, melamine cyanurate, benzoguanamine and the like. Of these, only one type or two or more types may be included.
When the nitrogen-containing compound is contained in the flame retardant, the content thereof is preferably 200 parts by mass or less, more preferably 100 parts by mass or less, still more preferably 100 parts by mass, based on 100 parts by mass of the phosphinic acid-based metal salt. It is 50 parts by mass or less.

However, ammonium polyphosphate is not preferable because it tends to delay the urethanization reaction in the production of rigid polyurethane foam. Ammonium polyphosphate tends to gel in the polyol composition and is not preferable in terms of suppressing aggregation. Further, in the polyol composition, phosphate ions are easily liberated, the free acid affects the catalytic activity in the urethanization reaction, the urethanization reaction is not sufficiently promoted, and a rigid polyurethane foam having good flame retardancy is produced. It is presumed that it cannot be obtained.

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

Further, the powdery flame retardant containing the phosphinic acid-based metal salt and / or the phosphoric acid-based metal salt is a flame retardant of the polyol composition from the viewpoint of obtaining a rigid polyurethane foam having good flame retardancy. Of the total of 100 parts by mass, it is preferably 50 parts by mass or more, more preferably 52 to 100 parts by mass, and further preferably 55 to 100 parts by mass.
Further, in view of the fact that the powdery flame retardant containing the phosphinic acid-based metal salt and / or the phosphoric acid-based metal salt is likely to settle and aggregate, the powdery flame retardant, that is, the flame retardant The solid content of the above is preferably 10.0 to 40.0 parts by mass, more preferably 12.0 to 35.0 parts by mass, and further preferably 15.0 to 30 parts by mass in 100 parts by mass of the polyol composition. It is 0.0 parts by mass. From the same viewpoint, the content of the Mannich-based polyol is preferably 20 to 95 parts by mass, more preferably 20 parts by mass, based on 100 parts by mass of the total solid content of the flame retardant in the polyol composition. It is 30 to 90 parts by mass, more preferably 35 to 80 parts by mass.

The flame retardant may contain a liquid phosphoric acid ester from the viewpoint of obtaining an initial carbonization suppressing effect at the time of heating or burning of the rigid polyurethane foam. For example, Tris (β) which is a halogen-containing phosphoric acid ester. -Chloropropyl) phosphate and the like are generally used. Tris (β-chloropropyl) phosphate is a liquid, and like the powdered phosphinic acid-based metal salt, phosphoric acid-based metal salt, and red phosphorus, sedimentation and aggregation of hard polyurethane foam in the raw material liquid, etc. However, the effect of imparting flame retardancy to the rigid polyurethane foam is superior to the powdery flame retardant containing the phosphinic acid-based metal salt. Therefore, when the flame retardant contains a liquid phosphoric acid ester, the content thereof is preferably 50 parts by mass or less, more preferably less than 50 parts by mass, still more preferably 45 parts by mass of the flame retardant. It is less than a part by mass.

<Other ingredients>
As a raw material for producing a flame-retardant rigid polyurethane foam, in addition to the main raw materials, a polyol compound, a flame retardant and a polyisocyanate compound, a foaming agent, a catalyst, a foam stabilizer and the like are also blended. These components may be added separately from the polyol composition during the production of the flame-retardant rigid polyurethane foam, but from the viewpoint of reducing the work load at the production site of the flame-retardant rigid polyurethane foam, the polyol composition It is preferable that it is blended inside.
Further, if necessary, the polyol composition may contain a solvent, additives such as a colorant and an antioxidant, etc., as long as the effects of the present invention are not impaired.

(Foaming agent)
The foaming agent has an action of foaming a polyurethane resin by generating a gas by heat generation of a resinification reaction in which a polyol compound and a polyisocyanate compound react to form a urethane bond.
Examples of the foaming agent include hydrofluoroolefin (HFO), hydrochlorofluoroolefin (HCFO), hydrofluorocarbon (HFC), water and the like. These may be used alone or in combination of two or more. Of these, HFOs and HCFOs are foaming agents whose demand is expected to increase in the future instead of HFCs from the viewpoint of suppressing global warming, and it is preferable to use them. Specifically, trans-1,3,3,3-tetrafluoropropene (trans-HFO-1234ze), 1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzz), Examples thereof include trans-1-chloro-3,3,3-trifluoropropene (HCFO-1233zd).

The isocyanate group of the polyisocyanate compound also reacts with water to generate a urea bond and a foaming reaction that generates carbon dioxide gas. Water preferably contains water as a foaming agent because it induces foaming in the initial stage of the formation reaction of the rigid polyurethane foam and can reduce the density of the produced rigid polyurethane foam.

From the viewpoint of appropriately foaming the polyurethane resin, the total amount of the foaming agent is preferably 5.0 to 40.0 parts by mass, more preferably 10.0 to 100 parts by mass with respect to 100 parts by mass of the polyisocyanate compound. It is 30.0 parts by mass, more preferably 12.0 to 25.0 parts by mass.
However, water preferably has a lower content than other foaming agents because it may hydrolyze aromatic polyester polyols. It is preferably 20.0 parts by mass or less, more preferably 0.8 to 15.0 parts by mass, and further preferably 1.0 to 10.0 parts by mass with respect to 100 parts by mass of the total amount of the foaming agent other than water. It is a department.

(catalyst)
In the reaction for producing a rigid polyurethane foam, a tertiary amine catalyst is preferably used from the viewpoint of accelerating the resinification reaction and foaming reaction. Further, from the viewpoint of improving flame retardancy by partially nurate-forming, a nurate-forming catalyst can also be used. As these catalysts, known catalysts in the production of rigid polyurethane foam can be used. These may be used alone or in combination of two or more.

Examples of the tertiary amine catalyst include dimethylethanolamine, triethylenediamine, methyldicyclohexylamine, dimethylcyclohexylamine, pentamethyldiethylenetriamine, bis (2-dimethylaminoethyl) ether, diethylmethylbenzenediamine, and 1,2-dimethyl. Examples thereof include imidazole, 1,4-diazabicyclo [2.2.2] octane and the like.
The blending amount of the tertiary amine catalyst is preferably 0.1 to 10.0 mass by mass with respect to 100 parts by mass of the polyisocyanate compound from the viewpoint of appropriately promoting the resinification reaction and foaming reaction of the rigid polyurethane foam. Parts, more preferably 0.2 to 8.0 parts by mass, still more preferably 0.5 to 5.0 parts by mass.

Examples of the nucleolation catalyst include nitrogen such as tris (dimethylaminomethyl) phenol, 2,4-bis (dimethylaminomethyl) phenol, and 2,4,6-tris (dialkylaminoalkyl) hexahydro-S-triazine. Aromatic compounds; Carboxylic acid alkali metal salts such as potassium acetate and potassium 2-ethylhexylate; Tertiary ammonium salts such as trimethylammonium salt, triethylammonium salt and triphenylammonium salt; tetramethylammonium salt, tetraethylammonium and tetraphenyl Examples thereof include quaternary ammonium salts such as ammonium salts.
The blending amount of the nurateization catalyst is preferably 0.05 to 10.0 parts by mass, more preferably 0.1 part by mass with respect to 100 parts by mass of the polyisocyanate compound from the viewpoint of appropriately promoting the nurateization reaction of isocyanate. It is ~ 8.0 parts by mass, more preferably 0.2 to 5.0 parts by mass.

(Foaming agent)
The foam stabilizer is blended from the viewpoint of obtaining a homogeneous flame-retardant rigid polyurethane foam, and a known foam stabilizer in the production of the rigid polyurethane foam can be used. Generally, a silicone-based foam stabilizer is preferably used, and examples thereof include a siloxane-polyalkylene oxide copolymer.
The blending amount of the foam stabilizer is appropriately set according to the type of polyurethane resin to be produced, but is preferably 0.05 to 10.0 parts by mass, more preferably 0, with respect to 100 parts by mass of the polyisocyanate compound. It is .1 to 8.0 parts by mass, more preferably 0.2 to 5.0 parts by mass.

Further, if necessary, the polyol composition may contain a solvent, additives such as fillers, colorants, antioxidants, etc., as long as the effects of the present invention are not impaired.
From the viewpoint of more effectively suppressing the aggregation of powder in the polyol composition, among the fillers, particulate negative microcrystalline and amorphous silica and plate-shaped kaolinite are used as dispersants. It is preferable that Neuburg siliceous earth particles (also referred to as silitin or silicoloid), which is a natural bond, are blended in the polyol composition. The Neuburg silica soil particles themselves do not dissolve in the polyol composition, but due to the inclusion of the Neuburg silica soil particles, it is difficult to form a powder containing the phosphinic acid-based metal salt and / or the phosphoric acid-based metal salt. Even when the phosphoric acid has settled, the settled powder is difficult to solidify and can be easily redispersed. This makes it possible to improve the ease of handling of the polyol composition when producing a flame-retardant rigid polyurethane foam.

[Flame-retardant rigid polyurethane foam]
The flame-retardant rigid polyurethane foam of the present invention is a reaction product obtained by reacting the polyol composition with a polyisocyanate compound.
When a polyol composition that is not sufficiently uniform is used, it is difficult to obtain a homogeneous rigid polyurethane foam having good flame retardancy as a whole.
On the other hand, according to the polyol composition of the present invention, as described above, when a powdery flame retardant containing the phosphinic acid-based metal salt and / or phosphoric acid-based metal salt that easily precipitates is used. In the raw material liquid of the polyol composition and the flame-retardant rigid polyurethane foam, sedimentation and aggregation of powder can be effectively suppressed. Therefore, during the production of the flame-retardant rigid polyurethane foam, the work load for uniformly dispersing the raw material liquid of the polyol composition and the flame-retardant rigid polyurethane foam is reduced, and the powder in the raw material liquid is uniformly dispersed. You can improve your sex. Further, the good flame retardancy of the obtained flame retardant rigid polyurethane foam due to the flame retardant is also maintained.

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

Examples of the aromatic polyisocyanate include diphenyl ether-2,4'-diisocyanate, diphenyl ether-4,4'-diisocyanate, tolylen-2,4-diisocyanate, tolylene-2,6-diisocyanate, and 4,6-dimethyl-1. , 3-Phenylylene diisocyanate, 2,2'-diphenylmethane diisocyanate (2,2'-MDI), 2,4'-diphenylmethane diisocyanate (2,4'-MDI), 4,4'-diphenylmethane diisocyanate (4,4') -MDI) and the like, monomeric MDI, polymethylene polyphenyl polyisocyanate (crude MDI or polypeptide MDI), 3,3'-dimethyl-4,4'-biphenylenediocyanate, m-xylylene diisocyanate and the like can be mentioned.
The aliphatic polyisocyanate may be either an acyclic or alicyclic polyisocyanate, and examples thereof include tetramethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, and dicyclohexylmethane diisocyanate.
Of these, monomeric MDIs such as 2,2'-MDI, 2,4'-MDI, and 4,4'-MDI, Crude, from the viewpoint of reactivity and flame retardancy of the produced rigid polyurethane foam. MDI or polypeptide MDI is preferable, and among these, crude MDI or polypeptide MDI is preferably used from the viewpoint of availability, cost and the like.

The blending amount of the polyisocyanate compound in the raw material liquid of the flame-retardant rigid polyurethane foam is appropriately set according to the type of the polyisocyanate compound, but is sufficiently reactive with the polyol compound and when the raw material liquid is mixed. From the viewpoint of ease of handling and the like, the amount is preferably 50 to 200 parts by mass, more preferably 70 to 150 parts by mass, and further preferably 80 to 120 parts by mass with respect to 100 parts by mass of the polyol composition.

<Flame-retardant rigid polyurethane foam manufacturing method>
The molding foaming method in the method for producing the flame-retardant rigid polyurethane foam is not particularly limited, and for example, known methods such as slab molding, molding, laminating molding, injection molding, and spray foaming can be applied. it can. In each of these molding and foaming methods, the polyol composition and the polyisocyanate compound are mixed, foamed and cured to produce a homogeneous rigid polyurethane foam having good flame retardancy as a whole. Can be done.

As described above, the polyol composition suppresses sedimentation and aggregation of the contained powder. Therefore, for redispersion when mixing with the polyisocyanate compound, for example, a general stirrer using a stirring blade or the like is used. By using it, it can be easily made uniform without requiring a large shearing force or the like. That is, it can be easily and uniformly redistributed with a small work load. Therefore, by using the polyol composition, the efficiency of producing a flame-retardant rigid polyurethane foam can be improved.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto.

[Preparation of polyol composition]
Details of each raw material used for preparing the polyol compositions of the following Examples and Comparative Examples are shown below.
<polyol compound>
(Polyester polyol (a1))
(A1-1) RFK-556: Terephthalic acid-based polyester polyol; "Maximol (registered trademark) RFK-556", manufactured by Kawasaki Kasei Chemicals, Inc .; hydroxyl value 224 mgKOH / g
(A1-2) RFK-087: Terephthalic acid-based polyester polyol; "Maximol (registered trademark) RFK-087", manufactured by Kawasaki Kasei Chemicals Co., Ltd .; Hydroxyl value 200 mgKOH / g
(Mannich-based polyol (a2))
(A2-1) NB-622: "Exenol (registered trademark) NB-622", manufactured by AGC Inc., hydroxyl value 500 mgKOH / g
(A2-2) FB-800: "Exenol (registered trademark) FB-800", manufactured by AGC Inc., hydroxyl value 300 mgKOH / g
(Polyether polyol)
GR-30: TDA (Trinediamine) -based polyether polyol; "Actcol (registered trademark) GR-30", manufactured by Mitsui Kagaku SKC Polyurethane Co., Ltd., hydroxyl value 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-based metal salt; "Fran CM-6R", manufactured by Daiwa Chemical Industry Co., Ltd. (b2) OP935: Phosphonic acid-based metal salt; "Exolit (registered trademark) ) OP935 ", manufactured by Clarianto Chemicals Co., Ltd. (b3) R098-5: Phosphate ester metal salt (powder);" Nonnen (registered trademark) R098-5 ", manufactured by Maruhishi Yuka Kogyo Co., Ltd. (ammonium polyphosphate) )
-TK-1000: Ammonium polyphosphate; "TK-1000", manufactured by Manac Inc.-APP201: Ammonium polyphosphate; "KYLIN (registered trademark) APP201", SHIFFANG CHANGFENG CHEMICAL Co., Ltd.-TMCPP: Tris (β-chloropropyl) Phosphate; "TMCPP", manufactured by Daihachi Chemical Industry Co., Ltd. <foaming agent>
-HCFO: Trans-1-chloro-3,3,3-trifluoropropene (HCFO-1233zd); "Solstice® LBA", manufactured by Honeywell International, Inc.-Water <catalyst>
-SX60: Tertiary amine catalyst; "TOYOCAT (registered trademark) -SX60", manufactured by Tosoh Corporation ・ DM70: Tertiary amine catalyst; "TOYOCAT (registered trademark) -DM70", manufactured by Tosoh Corporation ・ K-15 : Potassium 2-ethylhexylate; "Dabco (registered trademark) K-15", manufactured by Ebonic, Nurateized catalyst <foaming agent>
L-6100: Silicone-based defoaming agent; "Niax (registered trademark) silicone L-6100", manufactured by Momentive Performance Materials, Inc.

(Example 1)
In a 500 mL plastic bottle, 28.5 parts by mass of polyester polyol (a1-1), 8.0 parts by mass of Mannig-based polyol (a2-1), 1.6 parts by mass of each of catalysts (SX60, DM70 and K-15), water. 0.3 parts by mass of (foaming agent), 16.0 parts by mass of TMCPP, and 1.6 parts by mass of foam stabilizer L-6100 were added, and the mixture was stirred at 3000 rpm for 20 seconds with an electric drill equipped with a cage-type stirrer. Hereinafter, the stirring method is the same.)
To this, 20.0 parts by mass of the flame retardant (b1) was added and stirred for 20 seconds, then 20.8 parts by mass of HCFO was added and stirred for another 20 seconds, and then in a constant temperature water bath at 20 ° C. The mixture was kept warm to prepare a polyol composition.

(Examples 2 to 7, Comparative Examples 1 to 7)
Polyol compositions were prepared in the same manner as in Example 1 with the raw material formulations shown in Table 1 below.

[Manufacturing of rigid polyurethane foam]
Using the polyol compositions of each of the above Examples and Comparative Examples, a rigid polyurethane foam was produced as follows.
As the polyisocyanate compound, polymethylene polyphenyl polyisocyanate (Polymeric MDI); "Millionate (registered trademark) MR-200", manufactured by Tosoh Corporation was used.
In a 500 mL descup, 100 parts by mass of the polyol composition in a uniform state by stirring and 102.5 parts by mass of the polyisocyanate compound were placed, and after stirring for 5 seconds, the obtained mixed solution (raw material solution for rigid polyurethane foam) was obtained. Was poured into a 15 cm square shape and allowed to stand for 30 minutes, and then demolded to obtain a rigid polyurethane foam.

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

<Sedimentability>
A 50 mL vial containing 30 g of the polyol composition was allowed to stand at room temperature (25 ° C.) for 21 days, and then the vial was shaken up and down 20 times and allowed to stand again. By observing the appearance, the height position (height from the liquid surface) of the upper surface of the solid matter settled after 1 day was measured.
These measured values were evaluated based on the following evaluation criteria.
(Evaluation criteria)
A: The height position of the upper surface of the sediment is less than 5 mm from the liquid surface B: The height position of the upper surface of the sediment is 5 mm or more and less than 8 mm from the liquid surface C: The height position of the upper surface of the sediment is 8 mm or more from the liquid surface In the case of evaluation A, it can be considered that the sedimentation has hardly progressed. In the case of evaluation B, sedimentation was slightly progressing, and in the case of evaluation C, sedimentation was remarkably progressing, and it was determined that the polyol composition was not suitable for practical use.

<Cohesiveness>
In the evaluation of sedimentation, the 50 mL vial bottle after standing for 21 days was laid on its side and allowed to stand for 5 minutes, and further allowed to stand for 5 minutes. The state of the solid matter sediment was confirmed by visual observation of the appearance.
These observation results were evaluated based on the following evaluation criteria.
(Evaluation criteria)
A: When the vial is tilted sideways, the sediment flows, and when it is raised again, it gradually returns to its original state. Even after standing for 5 minutes, the sediment does not completely return to its original state, but does not adhere to the inner wall surface of the vial.
B: When the vial is tilted sideways, the sediment flows, and when it is raised again, it gradually returns to its original state. Even after standing for 5 minutes, the sediment does not completely return to its original state, and deposits remain on the inner wall surface of the vial.
C: Even if the vial is tilted sideways, the sediment does not flow.
D: The solid content was gelled.
In the case of evaluation A, it can be said that the agglutination of the powder is well suppressed. On the other hand, in the cases of evaluations B to D, a sufficient agglutination suppressing effect was not obtained, and in the cases of evaluations C and D, it was determined that they were not suitable for practical use.

<Flame retardant>
From the rigid polyurethane foam produced above, a sample having a thickness of 98 mm × 98 mm × thickness (height) of 25 mm was cut out.
According to ISO 5660-1, with a corn calorimeter ("Corn calorimeter III", manufactured by Toyo Seiki Seisakusho Co., Ltd .; non-combustible material of base material: gypsum board (thickness 9.5 mm)), 50 kW / m with a corn. ^{The calorie of 2} was added to the sample, and at the same time, the sample was ignited by an ignition plug for 10 seconds, and the total calorific value when heated for 20 minutes was measured.
These measured values were evaluated based on the following evaluation criteria.
(Evaluation criteria)
A: The total calorific 8 MJ / m ² less B: the total calorific 8 MJ / m ² or more 11 mJ / m ² less than C: total calorific 11 mJ / m ² or more 20 MJ / m ² less than D: total calorific value 20 MJ / m ² or more In the case of evaluation A, it has the highest flame retardancy and is a level that can be said to be a non-combustible material. Next, in the case of evaluation B as well, the flame retardancy is sufficiently high, which is a level that can be said to be a semi-incombustible material.

As can be seen from the results shown in Table 1, by adding a Mannig-based polyol as the polyol compound (Examples 1 to 7), the compound is selected from the group consisting of a predetermined phosphinic acid-based metal salt and a phosphoric acid-based metal salt. It was confirmed that a rigid polyurethane foam containing a powdery flame retardant containing one or more compounds was suppressed from sedimentation and aggregation, and had a flame retardancy equivalent to or higher than that of a semi-incombustible material.
On the other hand, when the Mannich-based polyol is not added (Comparative Examples 1 to 5), the flame retardancy of the rigid polyurethane foam is good, but the sedimentation and aggregation of the powder in the polyol composition are sufficiently suppressed. I couldn't say it. Of these, when an aromatic polyether polyol other than the Mannig-based polyol is added (Comparative Examples 2 and 3), the effect of suppressing the sedimentation and aggregation of the powder in the polyol composition is inferior, and the flame retardant of the rigid polyurethane foam The sex was also inferior.
Further, when the flame retardant contained ammonium polyphosphate (Comparative Examples 6 and 7), the polyol composition gelled, and the flame retardancy of the rigid polyurethane foam was also inferior.

Claims

A polyol composition used in the production of flame-retardant rigid polyurethane foam.
Contains polyol compounds and flame retardants,
The polyol compound contains an aromatic polyester polyol and a Mannich-based polyol.
The flame retardant is a polyol composition containing one or more compounds selected from the group consisting of a phosphinic acid-based metal salt represented by the following formula (1) and a phosphoric acid-based metal salt.

(In the formula (1), M is Mg, Al, Ca, Ti or Zn, R 1 is a hydrogen atom, a linear alkyl group or a phenyl group having 1 to 6 carbon atoms, and n is 2 3 or 4)
The polyol composition according to claim 1, wherein the Mannich-based polyol is contained in an amount of 20 to 95 parts by mass with respect to a total of 100 parts by mass of the solid content in the flame retardant.
The polyol composition according to claim 1 or 2, which contains a foaming agent.
The polyol composition according to claim 3, wherein the foaming agent contains at least one 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 defoaming agent.
A flame-retardant rigid polyurethane foam which is a reaction product with the 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, wherein the polyol composition according to any one of claims 1 to 6 and a polyisocyanate compound are mixed, foamed and cured to obtain a flame-retardant rigid polyurethane foam. ..