JPH07157653A - Nonhalogen flame retardant for polyurethane resin and its production - Google Patents

Abstract

PURPOSE:To obtain a new flame retardant which imparts a high flame retardancy to a polyurethane resin without detriment to the characteristics of the resin. CONSTITUTION:This flame retardant is obtd. by melt reacting a polyurethane resin, a polyepoxy compd., and a phenol resin and/or at least one nonhalogen flame retardant selected from epoxy-reactive phosphorus, nitrogen, and boron compds.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a non-halogen flame retardant for polyurethane resins and a method for producing the same, which is non-halogen produced by adding the non-halogen flame retardant of the present invention to a polyurethane resin. It is possible to impart a high degree of flame retardancy.

[0002]

2. Description of the Related Art Polyurethane resin is tough and wear resistant,
It has excellent oil resistance, solvent resistance, and rubber elasticity, so it is a foam,
It is widely used as a material for elastic bodies, paints, adhesives, elastic fibers, and synthetic leather. Polyurethane resin is generally a polymer that burns easily, so furniture that requires flame retardancy,
In order to use it for applications such as rugs, it is necessary to make it flame-retardant by some method. Conventionally, halogen-based flame retardants, phosphorus-based flame retardants, etc. have been used for flame retarding polyurethane. However, halogen-based flame retardants have high flame-retardant effects, but they have drawbacks such as environmental problems and the generation of harmful gases during combustion.Phosphorus-based flame retardants have physical properties such as heat resistance, tensile strength and impact strength deterioration of resins. And the flame retardant causes bleeding. From the above, it is most preferable that the polyurethane resin can be made flame retardant by the polymer alloy of the polyurethane resin and the halogen-free resin flame retardant.

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a non-halogen flame retardant which improves the flame retardancy of a polyurethane resin without halogen, with almost no deterioration in properties.

[0004]

The present inventors have proposed a method of simply blending a polyurethane resin (A) with a phenol resin and / or a halogen-free flame-retardant compound (C) in order to make the polyurethane resin flame-retardant. I thought about
It has been found that this method has an insufficient effect of improving the flame retardancy, and further has a drawback that characteristics such as bleeding, fluidity and impact strength are deteriorated. Therefore, as a result of further intensive study, by adding an epoxy compound (B) which reacts with both of the polyurethane resin (A) and the phenol resin and / or the halogen-free flame-retardant compound (C), and subjecting them to a melt reaction. The inventors have found that the conventional drawbacks such as bleeding, fluidity and impact resistance are improved without impairing the flame retardancy, thus completing the present invention. That is, the present invention includes (A) a polyurethane resin, (B) an epoxy compound having two or more epoxy groups in the molecule, and (C) a phenol resin.
A non-halogen system for polyurethane resin, characterized by being melt-reacted with one or more non-halogen flame-retardant compounds selected from phosphorus, nitrogen and boron compounds having a functional group capable of reacting with an epoxy group. The present invention relates to a flame retardant and a manufacturing method thereof.

The polyurethane resin used as the component (A) of the present invention is not particularly limited and is commercially available. The most frequently used method is to prepare diisocyanate and a dihydric alcohol. This is an addition reaction, and urethane rubber, urethane foam, urethane resin, and other properties can be produced by changing the type of raw material. Among these, urethane rubber having rubber elasticity is most preferably used.

The epoxy compound used as the component (B) of the present invention is an important component having a function of connecting the polyurethane resin (A) with the phenol resin and / or the halogen-free flame-retardant compound (C). The epoxy compound (B) of the present invention is not particularly limited and is commercially available, and any compound having two or more epoxy groups in the molecule can be used. Specific examples include bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolac type epoxy resin, cycloaliphatic epoxy resin, glycidyl ester type epoxy resin, copolymer of ethylene and glycidyl methacrylate, or ethylene / acrylic acid copolymer. Polymer, ethylene / methacrylic acid copolymer, ethylene / acrylate copolymer, terpolymer of ethylene / methacrylic acid copolymer and glycidyl methacrylate, epoxidized styrene-ethylene / butylene-styrene block copolymer , Epoxidized styrene-ethylene isoprene-
Examples thereof include styrene block copolymers. Among these, a bisphenol A type liquid resin having an epoxy equivalent of 170 to 300 is preferably used.

The phenol resin which is a resin having good flame retardancy used as the component (C) of the present invention is not particularly limited and is commercially available, and an acid catalyst is added to phenol and formalin. Either a non-thermally reactive novolac type phenolic resin obtained by reacting with a resin or a thermally reactive resol type phenolic resin obtained by adding an alkaline catalyst to phenol or formalin and reacting to obtain a resin can be used. However, among these, the non-thermoactive novolac type phenol resin is particularly preferable. The phosphorus, nitrogen and boron compounds having a functional group capable of reacting with the epoxy group used as the component (C) of the present invention are not particularly limited and are generally commercially available. Examples of the functional group include: Those having a hydroxyl group, a carboxyl group, an acid anhydride group and an amino group are preferably used. Specific examples of the compound include polyphosphoric acid, ammonium polyphosphate, phosphorus compounds such as phosphoric acid ester containing amino group, hydroxyl group, or carboxyl group, boric acid, boron compounds such as zinc borate, melamine or melamine cyanurate compound. Melamine-based derivatives such as melamine phosphate and melamine borate, guanidine or guanidine-based derivatives such as guanidine sulfamate and guanidine phosphate, and the like. These non-halogen flame retardant compounds may be used alone or in combination of two or more.

(A), (B) used in the present invention,
The catalyst (D) that accelerates the reaction of the component (C) is not particularly limited and is commercially available, and examples thereof include dimethylimidazole for imidazoles and diazabicycloundecene and dimethylbenzyl for amines and their derivatives. Examples of amines, organic phosphines and their derivatives include triphenylphosphine.

The non-halogen flame retardant for polyurethane resin of the present invention comprises (A) a polyurethane resin, (B) an epoxy compound having two or more epoxy groups in the molecule, and (C) a phenol resin and / or an epoxy group. The present invention relates to a non-halogen flame retardant for a polyurethane resin, which is characterized by being melt-reacted with a non-halogen flame retardant compound such as phosphorus, nitrogen, or a boron having a reactive functional group, preferably a polyurethane resin ( A) and phenol resin and / or halogen-free flame-retardant compound (C)
The compounding ratio of is 80:20 to 20:80 by weight,
The compounding ratio of the epoxy compound (B) and the phenol resin and / or the halogen-free flame-retardant compound (C) is the equivalent ratio (B
/ C) in an amount of 0.05 to 2 and subjected to a melt reaction, and relates to a non-halogen flame retardant for a polyurethane resin, more preferably (A),
A catalyst for promoting the reaction between the components (B) and (C) 0.01-
It is obtained by blending 5 parts by weight and melting and reacting at 150 ° C. to 250 ° C. for 10 minutes to 30 minutes with a pressure kneader or a Banbury mixer. In the halogen-free flame retardant for polyurethane resin of the present invention, the polyurethane resin (A)
It is preferable to mix the phenol resin and / or the halogen-free flame-retardant compound (C) in a ratio of 80:20 to 20:80. If the proportion of the phenolic resin and / or the halogen-free flame-retardant compound as the component (C) exceeds 80 wt%, the fluidity, impact resistance and mechanical properties tend to be insufficiently improved, and if it falls below 20 wt%, it is difficult. The effect of improving the flammability tends to be insufficient. Also, epoxy compound (B)
The compounding ratio of the phenol resin and / or the halogen-free flame-retardant compound (C) is 0.05 to 0.5 in terms of an equivalent ratio (B / C).
It is preferable to blend in 2 and when the equivalent ratio is less than 0.05, the action of connecting the polyurethane resin (A) and the phenol resin and / or the non-halogen flame retardant compound (B) becomes insufficient, and bleeding occurs. When the equivalent ratio exceeds 2, the flame retardancy tends to be insufficient.
The catalyst that promotes the reaction between (A), (B) and (C) is 0.
If it is less than 01 parts by weight, the effect of promoting the reaction tends to be insufficient, and if it exceeds 5 parts by weight, the effect does not change so much.

As described above, the non-halogen flame retardant for polyurethane resin of the present invention has the effect of improving the flame retardancy without causing the deterioration of the characteristics of the polyurethane resin. The reason is (A). The component (B) epoxy compound having a function of connecting the component polyurethane resin and the component (C) phenol resin and / or the halogen-free flame-retardant compound is added to the polyurethane resin (A) little by little. And a phenol resin and / or a compound produced by melt-reacting with a non-halogen flame-retardant compound (C), which has a compatibility with a polyurethane resin in one molecule, and a phenol. Since it has a component that has an affinity for resins and / or halogen-free flame-retardant compounds, it has good flame-retardant properties in thermoplastic resins. A (B) it is considered to be because the phenol resin and / or a non-halogenated flame retardant compound components made it possible to microdispersion. The non-halogen flame retardant for polyurethane resin of the present invention further contains other compounding agents such as an antioxidant, a light stabilizer, depending on the use and purpose.
Pigments, dyes, release agents, plasticizers, reinforcing agents and extenders can be added. The halogen-free flame retardant for polyurethane resin of the present invention is preferably used in combination with an inorganic flame retardant such as magnesium hydroxide or aluminum hydroxide.

[0011]

EXAMPLES The present invention will be described below with reference to examples, but these are merely examples and the present invention is not limited thereto. The tensile test is JIS K7311, the oxygen index is ASTM-D2863, and the combustion test is Underwriters Lab.
Oratories safety standard UL94 (○: burning time within 10 seconds, Δ: burning time of 10 seconds or more, × indicates complete burning). Further, the molding appearance was evaluated by visually observing the surface of the test piece. * Production example of non-halogen flame retardant (A to T) Put a predetermined amount of polyurethane resin of component (A) into a pressure kneader, and then add epoxy compound of component (B) little by little to polyurethane resin (A). After a predetermined amount is added and the mixture is melt-reacted in advance at 160 to 200 ° C. for 5 to 10 minutes, a phenol resin and / or a halogen-free flame-retardant compound (C) is further added, and the temperature is further set to 160 to 200 ° C.
A non-halogen flame retardant, i.e., was obtained by melting and reacting for ~ 15 minutes. The presence or absence of the reaction was confirmed by the difference in the infrared absorption spectrum peak intensity of the epoxy group before and after the reaction. The composition is shown in Table 1.

[0012] The raw material used was a urethane elastomer as the A component [PUE: Miractolan manufactured by Nippon Miractolan Co., Ltd.
E375MNAT], B component as epoxy compound [Eikaka Shell Co., Ltd. Epicoat 828 epoxy equivalent 189 g / eq], C component as phenol novolac resin [PN: Sumitomo Dures Co. PR-5147]
0 hydroxyl group equivalent 105 g / eq], guanidine phosphate [Awainone-301 amine equivalent 108 g / eq manufactured by Sanwa Chemical Co., Ltd.] and melamine, and triphenylphosphine [TPP] as a catalyst for the D component.

(Examples 1 to 6) Polyurethane resin [PU
E: Miractolan E19 manufactured by Nippon Miractolan Co., Ltd.
8] was mixed with a predetermined amount of non-halogen flame retardants a to c, magnesium hydroxide and the like, and kneaded with a twin-screw kneader to experimentally prepare the composition of the example. The blending and evaluation results are shown in Table 2.

(Comparative Examples 1 to 9) Polyurethane resin [PU
E: Miractolane E37 manufactured by Nippon Miractolan Co., Ltd.
5MNAT] and a predetermined amount of a phenol resin and / or a halogen-free flame-retardant compound, a halogen-free flame retardant nito, magnesium hydroxide and the like were mixed and kneaded with a twin-screw kneader to prepare a comparative composition composition. The blending and evaluation results are shown in Tables 3 and 4.

[0015]

[0016]

As is apparent from the table, the halogen-free flame retardant of the present invention is a novel flame retardant that imparts a high degree of flame retardancy while maintaining the characteristics of the polyurethane resin.

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Claims (7)

[Claims] 1. A polyurethane resin (A), which has 2 in the molecule.
Epoxy compound (B) having one or more epoxy groups and at least one non-halogen flame retardant selected from phosphorus, nitrogen and boron compounds having a functional group capable of reacting with a phenol resin and / or an epoxy group. A non-halogen flame retardant for a polyurethane resin, which is obtained by melting and reacting with a compound (C). 2. The weight ratio of the polyurethane resin (A) to the phenol resin and / or the halogen-free flame-retardant compound (C) is 80:20 to 20:80, and the epoxy compound (B) to the phenol. The compounding ratio of the resin and / or the halogen-free flame-retardant compound (C) is the equivalent ratio (B /
The non-halogen flame retardant for a polyurethane resin according to claim 1, wherein C) is 0.05 to 2. 3. A polyurethane resin (A), an epoxy compound (B) and a phenol resin and / or 100 parts by weight of a mixture of a halogen-free flame-retardant compound (C),
At least one catalyst (D) selected from the group consisting of imidazoles, amines and their derivatives, organic phosphines and their derivatives that accelerate the reaction of (A) or (C) with (B) is used in an amount of 0. The halogen-free flame retardant for polyurethane resin according to claim 1 or 2, which is obtained by adding 01 to 5 parts by weight and performing a melt reaction. 4. The non-halogen flame retardant for a polyurethane resin according to claim 1, 2 or 3, wherein the polyurethane resin (A) is a polyurethane elastomer. 5. The non-halogen flame retardant for polyurethane resin according to claim 1, 2, 3 or 4, wherein the epoxy compound (B) is a bisphenol A type liquid resin having an epoxy equivalent of 170 to 300. 6. A phenol resin and / or a halogen-free flame-retardant compound (C) is a phenol novolac resin,
Amino group, hydroxyl group, at least a phosphoric acid ester or polyphosphate having a functional group selected from carboxyl groups, boric acid, zinc borate, melamine, melamine derivatives, guanidine, at least selected from guanidine derivatives The halogen-free flame retardant for a polyurethane resin according to claim 1, which is one or more kinds of compounds. 7. The epoxy compound (B) is added little by little to the polyurethane resin (A) and melt-reacted in advance, and then the phenol resin and / or the halogen-free flame-retardant compound (C) is blended and further melt-reacted. A method for producing a halogen-free flame retardant for a polyurethane resin, comprising: