JP2010095565A - Composition for manufacturing flame-retardant hard polyurethane foam, method of manufacturing flame-retardant hard polyurethane foam using the composition, and flame-retardant hard polyurethane foam obtained by the manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composition for manufacturing a flame-retardant hard polyurethane foam that solves such a problem that adhesive properties and flame retardancy of the foam are deteriorated when water is used as a sole expanding agent, a manufacturing method of the flame-retardant hard polyurethane foam using the composition, and the flame-retardant hard polyurethane foam obtained by the manufacturing method. <P>SOLUTION: The composition comprising a polyol (A), a catalyst (B), an expanding agent (C), a foam stabilizer (D) and a flame-retardant (E) is used as the composition for manufacturing the flame-retardant hard polyurethane foam, wherein (1) the polyol (A) is a composition comprising a glycerin-based polyol having a number-average molecular weight of 400-2,000 and a phthalic acid-based polyester polyol and the total amount of them is at least 50 wt.% based on the whole polyol; (2) the catalyst (B) is a composition comprising a quaternary ammonium salt catalyst (provided that the salt contains no hydroxyalkyl group) and a tertiary amine catalyst; and (3) the expanding agent (C) is water and the used amount thereof is at least 4 pts.wt. based on 100 pts.wt. of the polyol (A). <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a composition for producing a flame retardant rigid polyurethane foam using only water as a foaming agent, a method for producing a flame retardant rigid polyurethane foam using the composition, and a flame retardant obtained from the production method. It relates to a flexible polyurethane foam.

  Rigid polyurethane foam is widely used as a heat insulating material for electric refrigerators, building materials and the like because it has excellent heat insulating properties and self-adhesive properties. In these heat insulating materials, an organic flon compound is used as a foaming agent in order to maintain heat insulating performance. For building materials, rigid polyurethane foams with an isocyanurate ring structure introduced by trimerization of organic polyisocyanate have been frequently used due to demand for flame retardancy.

  Rigid polyurethane foams used for these applications are generally obtained by a method of mixing and reacting a blended composition in which a polyol component, a catalyst, a foaming agent, a foam stabilizer and a flame retardant are mixed with an organic polyisocyanate.

  In recent years, from the viewpoint of protecting the global environment, without using chlorofluorocarbons or hydrochlorofluorocarbons as blowing agents, hydrofluorocarbons or hydrocarbons and carbon dioxide generated by the reaction of isocyanate and water are used as blowing agents. The manufacturing method of rigid polyurethane foam is directed (see, for example, Patent Document 1 and Patent Document 2).

  However, the global warming problem has been greatly screamed, and the demand for rigid polyurethane foam that does not use organic compounds such as hydrofluorocarbons and hydrocarbons as a foaming agent has expanded. Rigid polyurethane foams that use carbon dioxide generated by the reaction between isocyanate and water as a blowing agent, that is, rigid polyurethane foams that use only water as the blowing agent, are attracting attention (for example, see Patent Document 3). ).

  However, when water is used as a foaming agent, the defects and foams tend to cause poor adhesion to the face material and reduced flame retardance due to an increase in urea bonds due to the reaction of water and isocyanate, resulting in higher density. Problems have been pointed out.

  In order to solve these problems, various special polyols and catalysts have been studied, but have not yet been a sufficient solution.

Japanese Patent Application Laid-Open No. 2003-89714 Japanese Patent Application Laid-Open No. 2005-126695 JP 2006-307192 A Specification

  The present invention has been made in view of the above-described background art, and its purpose is to provide a flame-retardant rigid polyurethane that can solve the problem of reduced foam adhesion and flame retardancy when only water is used as a foaming agent. It is providing the composition for foam manufacture, the manufacturing method of a flame-retardant rigid polyurethane foam using this composition, and the flame-retardant rigid polyurethane foam obtained by this manufacturing method.

  As a result of intensive studies to solve these problems, the present inventors have found that these problems can be solved by using a composition for producing a water-foamed rigid polyurethane foam having a specific configuration, The present invention has been completed.

  That is, the present invention provides a composition for producing a flame-retardant rigid polyurethane foam, a method for producing a flame-retardant rigid polyurethane foam using the composition, and a flame-retardant rigid obtained by the production method as described below. Polyurethane foam.

[1] A composition for producing a flame-retardant rigid polyurethane foam comprising a polyol (A), a catalyst (B), a foaming agent (C), a foam stabilizer (D), and a flame retardant (E),
(1) The polyol (A) is a composition containing a glycerin-based polyol having a number average molecular weight of 400 to 2,000 and a phthalic acid-based polyester polyol, the total of which is 50% by weight or more in the total polyol. ,
(2) The catalyst (B) is a composition containing a quaternary ammonium salt catalyst (but never having a hydroxyalkyl group) and a tertiary amine catalyst, and (3) a blowing agent ( A composition for producing a flame-retardant rigid polyurethane foam, wherein C) is water and the amount used is 4 parts by weight or more per 100 parts by weight of polyol (A).

  [2] A quaternary ammonium salt catalyst is tetramethylammonium acetate, tetramethylammonium formate, tetraethylammonium acetate, tetraethylammonium formate, tetrapropylammonium acetate, tetrapropylammonium formate, tetrabutylammonium acetate , Tetrabutylammonium formate, methyltriethylammonium acetate, methyltriethylammonium formate, methyltripropylammonium acetate, methyltripropylammonium formate, methyltributylammonium acetate, methyltributylammonium formate, trimethyldodecylammonium formate And one or more selected from the group consisting of trimethyldodecyl ammonium acetate Flame-retardant rigid polyurethane foam composition for the preparation of.

[3] A tertiary amine catalyst is N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine, bis (2-dimethylaminoethyl) ether, N, N-dimethylaminoethoxyethanol, N, N— Dimethylaminoethoxyethoxyethanol, N, N-dimethylaminoethyl-N′-methylaminoethanol, N, N, N′-trimethyl-N′-hydroxyethylbisaminoethyl ether, N, N-dimethylaminoethyl-N ′ -Methylaminoethyl-N "-methylaminoisopropanol, N- (2-hydroxyethyl) -N'-methylpiperazine, and one or more selected from the group consisting of N, N-dimethylaminohexanol [4] The composition for producing a flame-retardant rigid polyurethane foam according to [1] or [2] above, The amount of the catalyst (B) used is in the range of 0.5 to 50 parts by weight with respect to 100 parts by weight of the polyol (A), according to any one of the above [1] to [3] Composition for producing flame-retardant rigid polyurethane foam.

  [5] A composition for producing a flame-retardant rigid polyurethane foam according to any one of [1] to [4] above, and a polyisocyanate containing diphenylmethane diisocyanate and a diphenylmethane diisocyanate-based polynuclear condensate are combined with an isocyanate group (NCO ) And a hydroxyl group (OH) reactive with an isocyanate group at a molar ratio (NCO / OH) of 1.8 or more, a method for producing a flame-retardant rigid polyurethane foam.

[6] A flame-retardant rigid polyurethane foam obtained by the production method described in [5] above, having a foam density of 100 kg / m ³ or less and an oxygen index of 26% or more.

  According to the present invention, even when only water is used as a foaming agent from the viewpoint of protecting the global environment, a rigid polyurethane foam having good foam adhesive strength and high flame retardancy can be obtained.

  In addition, the composition for producing a flame-retardant rigid polyurethane foam of the present invention can be provided for long-term production because there is no problem that the blended liquid is separated.

  Furthermore, the flame retardant rigid polyurethane foam of the present invention is excellent in economic efficiency because the density of the foam can be reduced.

  The composition for producing a flame-retardant rigid polyurethane foam of the present invention comprises a polyol (A), a catalyst (B), water as a foaming agent (C), a foam stabilizer (D), and a flame retardant (E). It is a waste.

  The polyol (A) used in the composition of the present invention includes a glycerin-based polyol having a number average molecular weight of 400 to 2,000 and a phthalic acid-based polyester polyol, and the total thereof is 50% by weight or more based on the total polyol. It is a polyol composition.

  In the present invention, as the glycerin-based polyol, a polyol obtained by reacting alkylene oxide with glycerin as an initiator is suitably used. If the molecular weight is too small, the adhesiveness and fluidity deteriorate, and if it is too large, the strength of the foam decreases. Therefore, the number average molecular weight is preferably in the range of 400 to 2,000. More preferably, it is the range of 600-1200.

  In the present invention, as the phthalic acid-based polyester polyol, a conventionally known method is used by using phthalic acid such as orthophthalic acid, isophthalic acid, and phthalic anhydride and one or more compounds having two or more hydroxyl groups. The phthalic acid-recovered polyester polyol obtained by decomposing a phthalic acid-based polyester molded product such as polyethylene terephthalate or the like can be suitably used.

  Here, as the compound having two or more hydroxyl groups, for example, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, hexanediol, neopentyl glycol, trimethylolpropane, hexanetriol, Suitable examples include glycerin, pentaerythritol, and derivatives thereof.

  In the present invention, the preferred hydroxyl value of the phthalic polyester polyol is in the range of 100 to 800, more preferably in the range of 150 to 450.

  In the polyol (A) of the present invention, the total of the glycerin-based polyol and the phthalic acid-based polyester polyol is 50% by weight or more based on the total polyol. Glycerol polyol is effective for improving adhesiveness, but if its proportion is excessively large, flame retardancy is lowered. Phthalic acid-based polyester polyols are effective in improving flame retardancy and fluidity, but if their proportion is excessively large, adhesiveness and foam compressive strength are lowered. For this reason, it is preferable that a phthalic-acid type polyester polyol is contained in the range of 30 to 70 weight% in a polyol (A).

  In the polyol (A) of the present invention, the polyol used in addition to the glycerin-based polyol and the phthalic acid-based polyester polyol is not particularly limited as long as it does not contradict the gist of the present invention. For example, the conventionally known Mannich Examples include phenol-based polyols such as base polyols, flame-retardant polyols such as phosphorus-containing polyols and halogen-containing polyols, polyether polyols, and polymer polyols. Of these, Mannich base polyols and polyether polyols are preferred.

  As the Mannich base polyol in the present invention, for example, a polyether polyol obtained by modifying Mannich with phenol and / or a derivative thereof (hereinafter referred to as “Mannich modified polyol”) is preferable. That is, phenol or nonylphenol, alkylphenol and other phenol derivatives are modified with Mannich using secondary amines such as formaldehyde and diethanolamine, ammonia and primary amines, and ring-opening addition of alkylene oxides such as ethylene oxide and propylene oxide. A polyol obtained by polymerization is preferably used.

  As the polyether polyol in the present invention, for example, a polyol obtained by ring-opening addition polymerization of an alkylene oxide such as ethylene oxide or propylene oxide with an initiator such as ethylenediamine, tolylenediamine, sucrose, amino alcohol, diethylene glycol or the like. Are mentioned as preferred.

  Of these polyols, Mannich base polyols are particularly preferred because of their excellent balance between flame retardancy and adhesiveness. However, when used excessively, the foam fluidity deteriorates, resulting in a high-density foam. Therefore, when using Mannich base polyol, the ratio in polyol (A) has the preferable range of 10 to 50 weight%.

  The catalyst (B) used in the present invention contains a quaternary ammonium salt catalyst (but never having a hydroxyalkyl group) and a tertiary amine catalyst.

  In the present invention, the quaternary ammonium salt catalyst is not particularly limited as long as it is a quaternary ammonium salt compound having a specific structure not having a hydroxyalkyl group. Acetate, tetramethylammonium formate, tetraethylammonium acetate, tetraethylammonium formate, tetrapropylammonium acetate, tetrapropylammonium formate, tetrabutylammonium acetate, tetrabutylammonium formate, methyltriethylammonium acetate, methyl Triethylammonium formate, methyltripropylammonium acetate, methyltripropylammonium formate, methyltributylammonium acetate, methyltributylammonium formate, trimethyldode Le ammonium formate, trimethyl dodecyl ammonium acetate and the like. In the present invention, one compound selected from these may be used alone or in combination of two or more compounds.

  In the present invention, among them, tetramethylammonium acetate, tetramethylammonium formate, tetraethylammonium acetate, tetraethylammonium formate, methyltriethylammonium acetate and methyltriethylammonium formate are preferred because of their high catalytic activity.

  In the present invention, the tertiary amine catalyst may be a conventionally known tertiary amine, and is not particularly limited. For example, N, N, N ′, N′-tetramethylethylenediamine, N, N , N ′, N′-tetramethylpropylenediamine, N, N, N ′, N′-tetramethylhexanediamine, N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine, N, N, N ′ , N ″, N ″ -pentamethyl- (3-aminopropyl) ethylenediamine, N, N, N ′, N ″, N ″ -pentamethyldipropylenetriamine, triethylenediamine, N, N, N ′, N′-tetra Methylguanidine, 1,3,5-tris (N, N-dimethylaminopropyl) hexahydro-S-triazine, 1,8-diazabicyclo [5.4.0] undecene-7, N, N -Dimethylpiperazine, dimethylcyclohexylamine, N-methylmorpholine, N-ethylmorpholine, bis (2-dimethylaminoethyl) ether, 1-methylimidazole, 1,2-dimethylimidazole, 1-isobutyl-2-methylimidazole, 1 -Dimethylaminopropylimidazole, N, N-dimethylaminoethanol, N, N-dimethylaminoisopropanol, N, N-dimethylaminoethoxyethanol, N, N-dimethylaminoethoxyethoxyethanol, N, N-dimethylaminoethyl-N '-Methylaminoethanol, N, N-dimethylaminopropyl-N'-methylaminoethanol, N, N, N'-trimethyl-N'-hydroxyethylbisaminoethyl ether, N, N-dimethylaminoethyl- '-Methylaminoethyl-N ″ -methylaminoethanol, N, N-dimethylaminoethyl-N′-methylaminoethyl-N ″ -methylaminoisopropanol, N, N-bis (3-dimethylaminopropyl) -N— Isopropanolamine, N- (3-dimethylaminopropyl) -N, N-diisopropanolamine, N- (2-hydroxyethyl) -N′-methylpiperazine, N, N-dimethylaminohexanol, 5-dimethylamino-3 -Methyl-1-pentanol and the like. In the present invention, one compound selected from these may be used alone or in combination of two or more compounds.

  In the present invention, among these, N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine, bis (2-dimethylaminoethyl) ether, N, N-dimethylaminoethoxyethanol, N, N-dimethyl Aminoethoxyethoxyethanol, N, N-dimethylaminoethyl-N′-methylaminoethanol, N, N, N′-trimethyl-N′-hydroxyethylbisaminoethyl ether, N, N-dimethylaminoethyl-N′- Methylaminoethyl-N ″ -methylaminoisopropanol, N- (2-hydroxyethyl) -N′-methylpiperazine, and N, N-dimethylaminohexanol are preferred because they increase the reactivity with water and improve fluidity.

  In this invention, it is preferable that the usage-amount of a catalyst (B) shall be the range of 0.5-50 weight part with respect to 100 weight part of polyol (A). The ratio of the quaternary ammonium salt catalyst to the tertiary amine catalyst is not particularly limited, but the quaternary ammonium salt catalyst / tertiary amine catalyst is usually 20 to 95/5 to 80 ( Weight ratio).

  The foaming agent (C) used in the present invention is only water. Since water reacts with the polyisocyanate component to produce carbon dioxide, it is used as a blowing agent. The amount of water used is 4 parts by weight or more, preferably 4 to 30 parts by weight, based on 100 parts by weight of the polyol (A). If the amount of water used is less than this range, foaming is insufficient and the density of the foam cannot be sufficiently reduced. On the other hand, if the amount of water used exceeds the above range, there may be a problem that foaming failure or flame retardancy is reduced.

  The foam stabilizer (D) used in the present invention is a conventionally known organosilicon surfactant, and specifically includes non-siloxanes such as organosiloxane-polyoxyalkylene copolymers and silicone-grease copolymers. Illustrative examples include ionic surfactants or mixtures thereof. The use amount thereof is preferably in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight of the polyol (A).

  Although it does not specifically limit as a flame retardant (E) used for this invention, For example, propoxylated phosphoric acid obtained by addition reaction of phosphoric acid and alkylene oxide, propoxylated dibutyl pyrophosphoric acid, etc. Reactive flame retardants such as phosphorus-containing polyols, phosphate esters such as tricresyl phosphate, halogen-containing phosphate esters such as trischloroethyl phosphate and trischloropropyl phosphate, dibromopropanol, dibromoneopentyl glycol, tetrabromobisphenol Halogen-containing organic compounds such as A, and inorganic compounds such as antimony oxide, magnesium carbonate, calcium carbonate, and aluminum phosphate. Of these, halogen-containing phosphates are preferred, and trischloropropyl phosphate is particularly preferred because of its good stability and high flame retardancy. The amount of these flame retardants used varies depending on the required flame retardancy and is not particularly limited. However, considering the balance between flame retardancy and foam strength, the amount of polyol (A) is 100 parts by weight. A range of 10 to 500 parts by weight is preferred. When the amount of the flame retardant is large, the flame retardancy is improved, but when it is added excessively, the foam strength may be lowered.

  The composition of the present invention may contain other auxiliary agents as long as the effects of the present invention are obtained. As such an auxiliary agent, a coloring agent, an anti-aging agent, and other conventionally known additives can be further used. The type and amount of these additives may be within the normal usage range of the additive used.

  Next, the manufacturing method of the flame-retardant rigid polyurethane foam of this invention and the flame-retardant rigid polyurethane foam obtained from the manufacturing method of this invention are demonstrated.

  The flame retardant rigid polyurethane foam of the present invention is a flame retardant rigid polyurethane foam containing the polyol (A), catalyst (B), foaming agent (C), foam stabilizer (D) and flame retardant (E). It is obtained by mixing the composition for production and polyisocyanate and foam-molding.

  The polyisocyanate used in the present invention is diphenylmethane diisocyanate (hereinafter abbreviated as “MDI”) and diphenylmethane diisocyanate-based multinuclear condensate (hereinafter abbreviated as “MDI-based condensate”), and a mixture thereof. And modified products. In the present invention, the MDI-based condensate means a so-called polynuclear substance having at least three benzene rings and three isocyanate groups. Examples of the modified product of MDI and MDI condensate include, for example, urethanized products, urea compounds, allophanate compounds, biuret compounds, carbodiimides obtained by reacting MDI and / or MDI condensates with active hydrogen group-containing compounds. And uretoniminate, uretdione, isocyanurate, and the like. In the present invention, the active hydrogen group-containing compound means a polyfunctional compound having two or more active hydrogen groups (for example, hydroxyl group, amino group, etc.) in the molecule that can react with the isocyanate group of polyisocyanate. To do.

  In the present invention, the composition of the mixture of MDI and MDI condensate is not particularly limited, but it is preferable to contain 30% by weight or more of MDI condensate in the total polyisocyanate.

  In the present invention, the mixing ratio of the composition for producing a flame retardant rigid polyurethane foam and the polyisocyanate is such that the isocyanate group (NCO) in the polyisocyanate and the isocyanate group in the composition for producing the flame retardant rigid polyurethane foam are The molar ratio (NCO / OH) with the reactive hydroxyl group (OH) is a mixing ratio of 1.8 or more. An isocyanate index obtained by multiplying this molar ratio by 100 is 180 or more. This isocyanate index is preferably set to 500 or less because there is a possibility of causing a problem of increasing the density of the foam due to deterioration of the fluidity of the foam.

The flame-retardant rigid polyurethane foam of the present invention is characterized in that the foam density is 100 kg / m ³ or less and the oxygen index, which is an index of flame retardancy, is 26% or more. In the method for producing a flame-retardant rigid polyurethane foam of the present invention, the isocyanate index is set to 300 or more, and the amount of the flame retardant (E) used is 90 parts by weight or more with respect to 100 parts by weight of the polyol (A). Furthermore, a flame-retardant rigid polyurethane foam having an oxygen index of 30% or more with improved flame retardancy can also be obtained.

  As a method for producing the flame-retardant rigid polyurethane foam of the present invention, for example, the above-mentioned composition for producing flame-retardant rigid polyurethane foam and polyisocyanate are rapidly mixed and stirred, and then injected into a suitable container or mold for foaming. A flame-retardant rigid polyurethane foam can be produced by molding. As a specific manufacturing apparatus, any apparatus can be used as long as it can be uniformly mixed. For example, small mixers, low pressure or high pressure foaming machines for injection foaming, low pressure or high pressure foaming machines for slab foaming, low pressure or high pressure foaming machines for continuous lines, etc. A foaming device of the type can be used.

  The flame retardant rigid polyurethane foam of the present invention can be used in various applications. For example, heat insulation and structural materials related to construction, civil engineering, electrical equipment related, heat insulating materials such as freezer, refrigerator, freezer showcase, etc., plant and ship related, LPG, LNG tanker and pipeline heat insulating materials, vehicle related Applications such as cold storage and heat insulation for refrigerated vehicles can be mentioned.

  Hereinafter, the present invention will be described more specifically by way of examples and comparative examples. However, the present invention is not construed as being limited to these examples. In addition, (pbw) in the table indicates parts by weight of another agent when the polyol is 100 parts by weight.

  In the following examples and comparative examples, the measurement method for each measurement item is as follows.

・ Measurement items for reactivity.
Cream time: The rising start time of the foamed foam was measured visually.

    Gel time: The time required for the reaction to progress to a resinous substance from a liquid substance was measured.

-Foam core density:
The center portion of the foam that was free-foamed in a 2 L polyethylene cup was cut to a size of 7 cm × 7 cm × 15 cm, and the core density was calculated by accurately measuring the size and weight.

-Foam adhesive strength:
A 5 × 5 cm SUS304 plate was set on the upper surface of the foam that was free-foamed in a 2 L polyethylene cup, and foamed. One hour after foaming, the 90 ° peel strength of the set SUS304 plate was measured and used as the adhesive strength of the foam.

-Foam oxygen index:
A sample in which the core density of the foam was measured was measured according to JIS K7201.

・ Foam fluidity:
The mixed solution was poured into an aluminum mold having a size of 110 (L) × 30 (W) × 5 (t) cm to cause foaming. The foam length (cm) and foam weight were measured, and the foam length (cm) per 100 g of foam weight was defined as fluidity.

・ Compressive strength of foam:
The foam whose fluidity was measured was cut and measured according to JIS K7220.

Preparation of flame retardant rigid polyurethane foam manufacturing composition:
Preparation Example 1.
Phthalic acid-based polyester polyol (Oxid LP, product name: Terol-588, OH number = 227 mgKOH / g) 700 g, glycerin-based polyol 300 g (manufactured by Sanyo Chemical Co., Ltd., product name) GP600, OH value = 271 mgKOH / g) was added, and stirring was started at room temperature. Subsequently, 31 g of an ethylene glycol solution of 50% tetramethylammonium acetate as a catalyst and 14 g of N, N-dimethylaminoethyl-N′-methylaminoethanol and trischloropropyl phosphate as a flame retardant (manufactured by Akzo Nobel, product) Name: Phylol PCF) 200 g, 10 g of a silicone surfactant (product name: L5420, manufactured by Momentive Co., Ltd.) as a foam stabilizer, and finally 50 g of water as a foaming agent were added and stirring was continued. 1 was prepared.

Preparation Examples 2 to 17
Compositions P-2 to P-17 were prepared by blending the amounts of polyol species, catalyst, flame retardant, foam stabilizer and water shown in Table 1 by the same blending method as in Preparation Example 1.

  The obtained composition was placed in a 100 ml beaker and the liquid separation state was observed after 24 hours at room temperature, and the stability of the composition was evaluated as follows.

○: No liquid phase separation, good
X: Liquid phase separation is observed.

  These results are also shown in Table 1.

表１より明らかなように、本発明の難燃性硬質ポリウレタンフォーム製造用組成物（Ｐ−１〜Ｐ−９）は液が分離せず安定性が良い。一方、ポリオールとしてフタル酸系ポリエステルポリオール単独を調合した組成物Ｐ−１４と、分子量３０００のグリセリン系ポリオールを調合した組成物Ｐ−１３は液の分離が見られ安定性が悪い。

As is clear from Table 1, the flame retardant rigid polyurethane foam production compositions (P-1 to P-9) of the present invention have good stability because the liquid does not separate. On the other hand, composition P-14 in which phthalic polyester polyol alone was prepared as a polyol and composition P-13 in which glycerin polyol with a molecular weight of 3000 was prepared showed liquid separation and poor stability.

Example 1 to Example 9, Comparative Example 1 to Comparative Example 8.
After thoroughly stirring the composition for producing a flame-retardant rigid polyurethane foam obtained in the preparation example, the composition and the polyisocyanate were mixed at the mixing ratio shown in Table 2 at a liquid temperature of 20 ° C. and 6000 rpm using a lab mixer. And a foaming reaction was carried out by stirring for 5 seconds to produce a flame retardant rigid polyurethane foam. At this time, the raw materials (the composition and polyisocyanate shown in Table 2) were foamed in a 2 L polyethylene cup, and the reactivity and adhesive strength were measured. Further, the core density and oxygen index of the obtained flame-retardant rigid polyurethane foam were measured.

  Next, the foam scale was raised, and the mixed raw material was put into a mold whose temperature was adjusted to 50 ° C. by the same operation as described above, and foam molding was performed. The flame-retardant rigid polyurethane foam was demolded 10 minutes after the raw material mixed in the mold was put, and the fluidity of the obtained foam was measured. Furthermore, the foam whose flowability was measured was cut and the compressive strength of the foam was measured. These results are also shown in Table 2.

  In addition, the measuring method of each above-mentioned measuring item in an Example and a comparative example is as follows.

・ Reactivity measurement.
Cream time: The rising start time of the foamed foam was measured visually.

    Gel time: The time required for the reaction to progress to a resinous substance from a liquid substance was measured.

-Foam core density:
The center of the foam foamed in a 2 L polyethylene cup was cut into a size of 7 cm × 7 cm × 15 cm, and the core density was calculated by accurately measuring the size and weight.

-Foam adhesive strength:
When foaming in a 2 L polyethylene cup, a 5 × 5 cm SUS304 plate was adhered to the upper surface of the foamed foam, and the 90-degree peel strength of the SUS304 plate after 10 minutes of foaming was measured to obtain the adhesive strength of the foam.

-Foam oxygen index:
A sample in which the core density of the foam was measured was measured according to JIS K7201.

・ Foam fluidity:
The mixed solution was poured into an aluminum mold having a size of 110 (L) × 30 (W) × 5 (t) cm to cause foaming. The foam length (cm) and foam weight were measured, and the foam length (cm) per 100 g of foam weight was defined as fluidity.

・ Compressive strength of foam:
The foam whose fluidity was measured was cut and measured according to JIS K7220.

表２の実施例１〜実施例９より明らかなように、本発明の難燃性硬質ポリウレタンフォームは、酸素指数が２６％以上である。更にイソシアネートインデックスが３００以上で且つ難燃剤が多くなると酸素指数が３０％を超えるまで高難燃性となっている（実施例７〜実施例９）。また、フォームのコア密度は低密度（３０〜４０ｋｇ程度）であり、フォームの流動性に優れ、フォームの接着強度は１．０ｋｇ／ｃｍ^２以上と高くなっている。

As is clear from Examples 1 to 9 in Table 2, the flame retardant rigid polyurethane foam of the present invention has an oxygen index of 26% or more. Furthermore, when the isocyanate index is 300 or more and the number of flame retardants is increased, the flame retardancy is high until the oxygen index exceeds 30% (Examples 7 to 9). Further, the core density of the foam is low (about 30 to 40 kg), the foam has excellent fluidity, and the adhesive strength of the foam is as high as 1.0 kg / cm ² or more.

  On the other hand, Comparative Example 1 to Comparative Example 3 are cases in which the polyol (A) of the present invention is used but a catalyst (composition) other than the catalyst (B) of the present invention is used. Compared with Example 4 and Example 5, the oxygen index and adhesive strength of the flame-retardant rigid polyurethane foam are reduced (Comparative Example 1 and Comparative Example 2), and the foamed foam cannot be molded (Comparative Example 3).

  Comparative Examples 4 to 7 are cases where the catalyst (B) of the present invention was used but a polyol (composition) other than the polyol (A) of the present invention was used. Compared with Example 3 and Example 7, the compressive strength and adhesive strength of the flame-retardant rigid polyurethane foam are reduced (Comparative Example 4 and Comparative Example 5), the oxygen index is lowered (Comparative Example 6), and the foam flow The density of the foam has been increased due to a decrease in properties (Comparative Example 7).

  Further, Comparative Example 8 is a case where a polyol other than the polyol (A) of the present invention is used and a catalyst composition other than the catalyst (B) of the present invention is used. Compared to Example 7, there is a higher density of foam due to a decrease in foam fluidity.

Claims (6)

A composition for producing a flame-retardant rigid polyurethane foam comprising a polyol (A), a catalyst (B), a foaming agent (C), a foam stabilizer (D), and a flame retardant (E),
(1) The polyol (A) is a composition containing a glycerin-based polyol having a number average molecular weight of 400 to 2,000 and a phthalic acid-based polyester polyol, the total of which is 50% by weight or more in the total polyol. ,
(2) The catalyst (B) is a composition containing a quaternary ammonium salt catalyst (but never having a hydroxyalkyl group) and a tertiary amine catalyst, and (3) a blowing agent ( A composition for producing a flame-retardant rigid polyurethane foam, wherein C) is water and the amount used is 4 parts by weight or more per 100 parts by weight of polyol (A). Quaternary ammonium salt catalysts are tetramethylammonium acetate, tetramethylammonium formate, tetraethylammonium acetate, tetraethylammonium formate, tetrapropylammonium acetate, tetrapropylammonium formate, tetrabutylammonium acetate, tetrabutyl Ammonium formate, methyltriethylammonium acetate, methyltriethylammonium formate, methyltripropylammonium acetate, methyltripropylammonium formate, methyltributylammonium acetate, methyltributylammonium formate, trimethyldodecylammonium formate, and trimethyl The flame retardant according to claim 1, wherein the flame retardant is one or more selected from the group consisting of dodecyl ammonium acetate. Rigid polyurethane foam composition for producing. Tertiary amine catalyst is N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine, bis (2-dimethylaminoethyl) ether, N, N-dimethylaminoethoxyethanol, N, N-dimethylaminoethoxy Ethoxyethanol, N, N-dimethylaminoethyl-N′-methylaminoethanol, N, N, N′-trimethyl-N′-hydroxyethylbisaminoethyl ether, N, N-dimethylaminoethyl-N′-methylamino It is one or more selected from the group consisting of ethyl-N ″ -methylaminoisopropanol, N- (2-hydroxyethyl) -N′-methylpiperazine, and N, N-dimethylaminohexanol. The composition for producing a flame-retardant rigid polyurethane foam according to claim 1 or 2 4. The difficulty according to claim 1, wherein the amount of the catalyst (B) used is in the range of 0.5 to 50 parts by weight with respect to 100 parts by weight of the polyol (A). A composition for producing a flammable rigid polyurethane foam. A composition for producing a flame-retardant rigid polyurethane foam according to any one of claims 1 to 4, a polyisocyanate containing diphenylmethane diisocyanate and a diphenylmethane diisocyanate polynuclear condensate, an isocyanate group (NCO), and an isocyanate A method for producing a flame-retardant rigid polyurethane foam in which a molar ratio (NCO / OH) of a group to a reactive hydroxyl group (OH) is 1.8 or more. A flame retardant rigid polyurethane foam obtained by the production method according to claim 5, having a foam density of 100 kg / m ³ or less and an oxygen index of 26% or more.