JPWO2021125238A1 - Polyol composition, flame-retardant rigid polyurethane foam and its manufacturing method - Google Patents

Abstract

In the raw material liquid of the polyol composition and the flame-retardant rigid polyurethane foam containing a flame retardant containing a predetermined phosphinic acid-based metal salt and / or phosphoric acid-based metal salt, aggregation of powder in the liquid is suppressed and , A polyol composition capable of obtaining a rigid polyurethane foam having excellent flame retardancy, and a flame retardant rigid polyurethane foam using the same, and a method for producing the same. The polyol composition of the present invention comprises a polyol compound containing an aromatic polyester polyol, a flame retardant containing one or more compounds selected from the group consisting of a predetermined phosphinic acid-based metal salt and a phosphoric acid-based metal salt, and a flame retardant. , Neuburg Contains dispersants containing siliceous particles.

Description

The present invention relates to a polyol composition used for producing a flame-retardant rigid polyurethane foam, and 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 characteristic of being easily burned. Fire accidents often occur in which hard polyurethane foam spreads due to sparks in welding fusing work during construction work, renovation work, and demolition work.
As a measure to reduce such a fire accident, various measures for imparting flame retardancy to the 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, for example, a phosphinic acid-based metal salt used as a flame retardant for a polyurethane resin for synthetic leather in Patent Document 1 as a more effective flame retardant. 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 dissolved in the polyol compound and the 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 cause aggregation 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 to which a flame retardant is added in advance (polyol). Premix) or a raw material solution for rigid polyurethane foam is used.
In the polyol composition prepared by pre-dispersing the powdery flame retardant as described above or the raw material liquid of the rigid polyurethane foam, the dispersion may be agglomerated at the time of use, and a large amount is required for redispersion. It may require a work load and may make uniform redispersion difficult.

Therefore, when the powdery flame retardant containing the phosphinic acid-based metal salt is used, the aggregation of the powder (solid) in the raw material liquid of the polyol composition or the rigid polyurethane foam is suppressed, and the raw material composition is uniform. It is required to have excellent handleability in obtaining a product. 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 a 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 the aggregation of powder in the liquid as a raw material liquid for foam, and a flame retardant rigid polyurethane using the same. It is an object of the present invention to provide a foam and a method for producing the same.

INDUSTRIAL APPLICABILITY The present invention can effectively suppress the aggregation of powdery flame retardants by using a predetermined dispersant in a polyol composition containing a flame retardant containing a predetermined phosphinic acid-based metal salt. Moreover, it is based on the finding that a rigid polyurethane foam having excellent flame retardancy can be obtained.
Further, even in the polyol composition containing the flame retardant containing the phosphoric acid-based metal salt, the aggregation of the powdery flame retardant can be effectively suppressed by using the dispersant containing the Neuburg silica soil particles. Moreover, 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 [9].
[1] A polyol composition used for producing a flame-retardant rigid polyurethane foam, which is a polyol compound containing an aromatic polyester polyol, a phosphinic acid-based metal salt represented by the following formula (1), and a phosphoric acid-based compound. A polyol composition containing a flame retardant containing one or more compounds selected from the group consisting of metal salts, and a dispersant containing Neuburg silica soil particles.

(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 polyol compound contains a Mannich-based polyol.
[3] The polyol composition according to the above [1] or [2], wherein the Neuburg silica soil particles are contained in an amount of 1 to 50 parts by mass with respect to a total of 100 parts by mass of the solid content in the flame retardant.
[4] The polyol composition according to any one of the above [1] to [3], which comprises a foaming agent.
[5] The polyol composition according to the above [4], wherein the foaming agent contains at least one of a hydrofluoroolefin and a hydrochlorofluoroolefin.
[6] The polyol composition according to any one of the above [1] to [5], which comprises a catalyst.
[7] The polyol composition according to any one of the above [1] to [6], which comprises a defoaming agent.

[8] A flame-retardant rigid polyurethane foam which is a reaction product with the polyol composition according to any one of the above [1] to [7] and a polyisocyanate compound.
[9] The polyol composition according to any one of [1] to [7] above is mixed with a polyisocyanate compound, foamed and cured to obtain a flame-retardant rigid polyurethane foam, which is flame-retardant. Manufacturing method of rigid polyurethane foam.

According to the present invention, in the raw material liquid of a polyol composition containing a flame retardant of a predetermined phosphinic acid-based metal salt and a flame-retardant rigid polyurethane foam, aggregation of powder in the liquid is suppressed and the handling property is excellent. Polyol compositions can be provided.
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, aggregation of the powdery flame retardant can be effectively suppressed, and moreover, excellent flame retardancy is achieved. A rigid polyurethane foam having the above can be obtained.

Hereinafter, the polyol composition of the present invention, a flame-retardant rigid polyurethane foam using the same, and a 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 is a polyol compound containing an aromatic polyester polyol, a phosphinic acid-based metal salt represented by the following formula (1). It contains a flame retardant containing one or more compounds selected from the group consisting of phosphoric acid-based metal salts, and a dispersant containing Neuburg silica soil particles.

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 blending the dispersant, the raw material liquid of the flame-retardant rigid polyurethane foam containing the flame retardant containing the phosphinic acid-based metal salt and / or the phosphoric acid-based metal salt represented by the formula (1) is contained in the liquid. Agglomeration of powder can be effectively suppressed. As a result, it is possible to reduce the work load for uniformly mixing the raw material liquid of the polyol composition and the flame-retardant rigid polyurethane foam at the time of producing the flame-retardant rigid polyurethane foam, and the powder in the raw material liquid can be reduced. It is possible to enhance the uniform dispersibility of. Further, the excellent flame retardancy of the flame retardant in the obtained flame-retardant rigid polyurethane foam 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 better 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 contains an aromatic polyester polyol, and preferably contains a Mannich-based polyol.
The agglomeration of the powder in the raw material liquid of the flame-retardant rigid polyurethane foam is well suppressed by the dispersant, but the agglomeration of the powder is caused by containing the Mannig-based polyol as the polyol compound together with the dispersant. , Can be suppressed more effectively.

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 and hardness. , 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 polyvalent 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 terephthalates 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 60.0 to 100 parts by mass, and further preferably 70.0 in 100 parts by mass of the polyol compound. ~ 100 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.

When the Mannig-based polyol is contained in the polyol compound, the content thereof is the polyol composition from the viewpoint of suppressing the aggregation of powder in the polyol composition and obtaining a rigid polyurethane foam having good flame retardancy. It is preferably 1.0 to 20.0 parts by mass, more preferably 2.0 to 15.0 parts by mass, and further preferably 3.0 to 10.0 parts by mass in 100 parts by mass of the substance.
From the same viewpoint, the ratio of the content of the Mannig-based polyol to the content of the aromatic polyester polyol is preferably 0.10 to 1.00, more preferably 0.15 to 0. 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 Mannich-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 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 retardant made of 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.
The phosphoric acid-based metal salt is also in the form of powder, and by using a dispersant containing Neuburg silica soil particles, a good effect of suppressing aggregation in the polyol composition can be obtained.

From the viewpoint of further improving the 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 contained.
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 50 parts by mass with respect to 100 parts by mass of the phosphinic acid-based metal salt. It is less than the mass part.

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 obtained. 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 the flame retardant in the polyol composition from the viewpoint of obtaining a rigid polyurethane foam having good flame retardancy. Of the total 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.

The flame retardant may contain a liquid phosphoric acid ester from the viewpoint of obtaining an initial carbonization suppressing effect during heating and 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 causes aggregation and the like in the raw material liquid of a rigid polyurethane foam like the powdery phosphinic acid-based metal salt, phosphoric acid-based metal salt, and red phosphorus. Although this is not the case, the phosphinic acid-based metal salt is superior in the effect of imparting flame retardancy to the rigid polyurethane foam. 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, and further preferably 45 in 100 parts by mass of the flame retardant. It is less than the mass part.

<Dispersant>
The dispersant in the polyol composition contains Neuburg silica soil particles.
The Neuburg silica soil particles in the present invention are natural bonds of particulate negative microcrystalline and amorphous silica and plate-shaped kaolinite, and are also called silitin or silicoloid. For example, it can be obtained as a product such as Siritin V85, Siritin V88, Siritin N82, Siritin N85, Siritin N87, Siritin Z86, Siritin Z89, and Siricolloid P87 manufactured by Hoffman Minerals.

The Neuburg silica soil particles themselves do not dissolve in the polyol composition, but by using the Neuburg silica soil particles as a dispersant, the phosphinic acid-based metal salt and / or phosphoric acid-based powdery flame retardant is used. Even when the metal salt has settled, the settled powder does not easily aggregate and can be easily redispersed.
Therefore, when the Neuburg silica soil particles are added to the polyol composition during the production of the flame-retardant rigid polyurethane foam, the work load for uniformly mixing the polyol composition and the raw material liquid of the flame-retardant rigid polyurethane foam is increased. It can be reduced, and the uniform dispersibility of the powder in the raw material liquid can be enhanced.

From the viewpoint of more effectively suppressing the aggregation of the powder in the polyol composition, the dispersant may contain a surfactant or the like that exerts an aggregation inhibitory action in addition to the Neuburg silica soil particles.
The content of the Neuburg silica soil particles in the dispersant effectively suppresses the aggregation of the powder in the polyol composition and imparts good flame retardancy to the rigid polyurethane foam. It is preferably 90 parts by mass or more, more preferably 95 to 100 parts by mass, and further preferably 100 parts by mass in 100 parts by mass of the agent.
From the same viewpoint, the content of the Neuburg silica soil particles is preferably 1 to 50 parts by mass, more preferably 5 to 40 parts by mass, based on 100 parts by mass of the total solid content in the flame retardant. More preferably, it is 10 to 20 parts by mass.

<Other ingredients>
As a raw material for producing the flame-retardant rigid polyurethane foam, a foaming agent, a catalyst, a foam-regulating agent and the like are blended in addition to the polyol compound, the flame retardant and the polyisocyanate compound which are the main raw materials. 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 in.
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.

(Effervescent 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, HFO and HCFO are foaming agents whose demand is expected to increase in the future instead of HFC from the viewpoint of the effect 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 to generate carbon dioxide gas. Water is preferably contained 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 blending 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.

As the nurateization catalyst, for example, nitrogen-containing tris (dimethylaminomethyl) phenol, 2,4-bis (dimethylaminomethyl) phenol, 2,4,6-tris (dialkylaminoalkyl) hexahydro-S-triazine and the like are contained. 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 accelerating the nurateization reaction of isocyanate. It is ~ 8.0 parts by mass, more preferably 0.2 to 5.0 parts by mass.

(Defoamer)
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 rigid polyurethane foam can be used. Generally, a silicone-based defoaming agent 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. .1 to 8.0 parts by mass, more preferably 0.2 to 5.0 parts by mass.

Further, the polyol composition may contain a solvent, an additive such as a filler, a colorant, an antioxidant and the like, if necessary, as long as the effect of the present invention is not impaired.

[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 the phosphoric acid-based metal salt that easily aggregates is used, the flame retardant is used. Aggregation of powder can be effectively suppressed in the raw material liquid of the polyol composition and the flame-retardant rigid polyurethane foam. 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 is uniformly dispersed in the raw material liquid. It can enhance the 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, tolylen-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 MDI such as 2,2'-MDI, 2,4'-MDI, 4,4'-MDI, and 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.

<Manufacturing method of flame-retardant rigid polyurethane foam>
The molding and 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, mold molding, laminate molding, injection molding, and spray foaming can be applied. 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 the aggregation of the powder contained therein. Therefore, the redispersion when mixed with the polyisocyanate compound is performed by using, for example, a general stirrer using a stirring blade or the like. , 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 manufacturing 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)
RFK-556: terephthalic acid-based polyester polyol; "Maximol (registered trademark) RFK-556", manufactured by Kawasaki Kasei Chemicals, Inc .; hydroxyl value 224 mgKOH / g
(Mannich-based polyol)
NB-622: "Exenol (registered trademark) NB-622", manufactured by AGC Inc., hydroxyl value 500 mgKOH / g
<Flame retardant>
(A1) CM-6R: Powdered flame retardant containing phosphinic acid-based metal salt; "Fran CM-6R", manufactured by Daiwa Chemical Industry Co., Ltd. (a2) OP935: Phosphoric acid metal salt; "Exorit (registered trademark)" OP935 ", manufactured by Clarianto Chemicals Co., Ltd. (a3) R098-5: Phosphate ester metal salt (powder);" Nonnen (registered trademark) R098-5 ", manufactured by Maruhishi Yuka Kogyo Co., Ltd. (a'1) -TK-1000: Ammonium polyphosphate; "TK-1000", manufactured by Manac Co., Ltd.-TMCPP: Tris (β-chloropropyl) phosphate; "TMCPP", manufactured by Daihachi Chemical Industry Co., Ltd. <Dispersant>
(Neuburg silica soil particles)
(B1) P87: "Siricolloid P87", manufactured by Hoffman Minerals (b2) V85: "Siritin V85", manufactured by Hoffman Minerals (carbon black)
-MA220: "Carbon Black MA220", manufactured by Mitsubishi Chemical Corporation <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, Nurate-forming 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, polyester polyol RFK-556 35.2 parts by mass, catalyst (SX60, DM70 and K-15) 1.6 parts by mass, water (foaming agent) 0.3 parts by mass, TMCPP 15.6 parts by mass, And 1.6 parts by mass of the foaming agent was 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 (a1) and 2.0 parts by mass of Neuburg silica soil particles (b1) were added and stirred for 20 seconds, then 20.5 parts by mass of HCFO was added, and further. After stirring for 20 seconds, the mixture was kept warm in a constant temperature water bath at 20 ° C. to prepare a polyol composition.

(Examples 2 to 6, Comparative Examples 1 to 6)
Polyol compositions were prepared in the same manner as in Example 1 with the raw material formulations shown in Table 1 below.
In Comparative Example 2, carbon black, which is known as a sedimentation inhibitor when the flame retardant is red phosphorus, was used as the dispersant.

[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 added. 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.

<Cohesiveness>
A 50 mL vial containing 30 g of the polyol composition was allowed to stand at room temperature (25 ° C.) for 21 days, then the vial was laid on its side and allowed to stand for 5 minutes, and then left to stand for 5 minutes. The state of solid sediment was confirmed by visual observation of the appearance.
These observation results were evaluated based on the following evaluation criteria.
(Evaluation criteria)
AA: When the vial is tilted sideways, the sediment flows, and when it is raised again, it returns to its original state within 1 minute.
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: The sediment does not flow even if the vial is tilted sideways.
D: The solid content was gelled.
In the case of evaluation AA or A, it can be said that the aggregation of powder is well suppressed, and in the case of evaluation AA, the effect of suppressing aggregation is particularly excellent. On the other hand, in the cases of evaluations B to D, a sufficient effect of suppressing aggregation 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 cone 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 cone. ^{The calorie of 2} was added to the sample, and at the same time, the sample was ignited with 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 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 Neuburg silica soil particles as a dispersant (Examples 1 to 6), the mixture was selected from the group consisting of a predetermined phosphinic acid-based metal salt and a phosphoric acid-based metal salt. It was found that a rigid polyurethane foam containing one or more of these compounds was suppressed from agglomeration of a powdery flame retardant and had a flame retardancy equal to or higher than that of a semi-incombustible material. When a Mannich-based polyol was used in combination as the polyol compound (Examples 2 to 4), it was confirmed that a particularly excellent aggregation inhibitory effect was obtained.
On the other hand, when Neuburg silica soil particles are not added (Comparative Examples 1, 3 and 4) or when carbon black is added as a dispersant (Comparative Example 2), the flame retardancy of the rigid polyurethane foam is good, but The effect of suppressing the aggregation of powder in the polyol composition was not sufficient.
Further, when the flame retardant contained ammonium polyphosphate (Comparative Examples 5 and 6), the polyol composition caused gelation and solidification, and the flame retardancy of the rigid polyurethane foam was also inferior.

Claims (9)

A polyol composition used in the production of flame-retardant rigid polyurethane foam.
Polyol compounds, including aromatic polyester polyols,
A flame retardant 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, and
A polyol composition containing a dispersant containing Neuburg silica soil particles.

(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 polyol compound contains a Mannich-based polyol. The polyol composition according to claim 1 or 2, wherein the Neuburg silica soil particles are contained in an amount of 1 to 50 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 any one of claims 1 to 3, comprising a foaming agent. The polyol composition according to claim 4, wherein the foaming agent contains at least one of hydrofluoroolefin and hydrochlorofluoroolefin. The polyol composition according to any one of claims 1 to 5, which comprises a catalyst. The polyol composition according to any one of claims 1 to 6, which comprises 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 7 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 7 and a polyisocyanate compound are mixed, foamed and cured to obtain a flame-retardant rigid polyurethane foam. ..