JP2012188499A - Flame retardant composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a flame retardant composition which can impart excellent flame retardancy to a polymer, has high safety without including halogen elements and a phosphorus element which adversely affect the environment and the human body, and has good moldability without damaging the fundamental properties of the polymer.SOLUTION: The flame retardant composition comprises: a polymer containing at least any one of a thermoplastic resin having at least any one of a carbonate bond, an ester bond, and an amide bond, and an elastomer; urea, and at least any one of an organic acid ammonium salt and an inorganic acid ammonium salt; and, based on 100 pts.mass of the polymer, the content of the urea is 20-70 pts.mass and the content of the at least any one of the organic acid ammonium salt and the inorganic ammonium salt is 10-70 pts.mass.

Description

  The present invention relates to a flame retardant composition that has excellent flame retardancy and is suitably used for, for example, parts of various home appliance OA products.

  Polymer materials such as polymers used in products such as home appliances and office automation (OA) equipment have UL standards (Under Writers Laboratories Inc. Standard) for each part in the United States, and it is difficult to achieve UL-94. It must meet the flame retardancy specified by the flame standard. Recently, not only in the United States but also in most countries including Japan, this UL standard has been adopted, and construction materials, automobiles and train cars are also required to be flame retardant according to their respective standards. ing. In particular, as a polymer material, nitrile rubber, which is one of typical general-purpose rubbers, is known to have extremely high flammability as it is used as a solid fuel for rockets and missiles. Therefore, extremely high technology is required to make such rubber flame-retardant.

Currently, the following three types of principles are generally considered as flame retardant methods, and they are used according to the application and the type of polymer material.
The first method is to add about 10% to 25% by mass of a halogen compound to the polymer material, thereby acting as an oxidation reaction negative catalyst for the combustion flame, and reducing the combustion rate to impart flame retardancy. Is.
In the second method, a silicone compound is added to the polymer material by several mass% to several tens of mass%, or a phosphoric acid compound is added by several mass% to several tens mass%, and the surface of the resin is burned. By causing the silicone compound to bleed or causing a dehydrogenation reaction in the resin, char (carbonized layer) is generated on the surface and combustion is stopped by forming a heat insulating film.
The third method is to add about 80 to 150 parts by mass of a metal hydroxide such as magnesium hydroxide or aluminum hydroxide with respect to 100 parts by mass of the polymer material. The entire polymer material is cooled by cooling due to an endothermic reaction at the time of decomposition and the latent heat of vaporization of the generated water to stop combustion.

However, the first method has a problem that dioxins are generated by a halogen compound when a sufficient amount of oxygen and combustion temperature are not given when burning as waste.
In the second method, in the case of a phosphoric acid ester compound, water pollution due to phosphoric acid contained in combustion ash may be caused by waste plastic. In addition, when a large amount of a silicone compound is added, there are problems that the original physical properties of the resin are changed, the strength is lowered, and the cost is increased.
The third method has a problem that the polymer material is hydrolyzed because the metal hydroxide is added with a large amount of inorganic salt, and the mechanical properties are extremely fragile.

Also, ammonium polyphosphate coated or microencapsulated with one or more compounds selected from urea, thiourea, ethyleneurea and ethylenethiourea and a co-condensation resin of melamine and formaldehyde with respect to 100 parts by weight of the synthetic resin emulsion It is disclosed that a flame retardant synthetic resin emulsion containing 10 parts by weight to 300 parts by weight of the resin is excellent in flame retardancy (see Patent Document 1).
However, the flame retardant synthetic resin emulsion does not improve flame retardancy by microencapsulation, and the flame retardancy is not sufficient. In addition, such a microencapsulation method is very inferior in cost, and further, there is a problem that the microencapsulation work itself is a work with a significant environmental load.

Therefore, the present inventor previously added a tannin compound to the thermoplastic resin, so that the tannin compound captures radicals generated in the resin, so that the heat stabilizing effect is high, and it is extremely effective as a flame retardant. It has been proposed (see Patent Documents 2 to 5).
However, it is known that the combustion of the resin generates gas when the resin is decomposed, and this gas continuously reacts with oxygen in the air to continue the combustion. At present, it is difficult to impart a sufficiently satisfactory level of flame retardancy only by improving stability.

JP 2001-323170 A Japanese Patent No. 3046962 Japanese Patent No. 3046963 Japanese Patent No. 3046964 Japanese Patent No. 3607901

  An object of the present invention is to solve the above-described problems and achieve the following objects. That is, the present invention can impart excellent flame retardancy to the polymer, does not contain halogen elements and phosphorus elements that adversely affect the environment and the human body, is highly safe, and does not impair the basic physical properties of the polymer. An object of the present invention is to provide a flame retardant composition having good moldability.

  As a result of intensive studies by the inventor in order to solve the above-mentioned problems, a polymer containing at least one of a thermoplastic resin and an elastomer having at least one of a carbonate bond, an ester bond, and an amide bond, urea, At least one of an organic acid ammonium salt and an inorganic acid ammonium salt, and the content of the urea is 20 parts by mass to 70 parts by mass with respect to 100 parts by mass of the polymer, and the organic acid ammonium salt and The flame retardant composition having an inorganic acid ammonium salt content of at least 10 parts by mass to 70 parts by mass can impart excellent flame retardancy to the polymer, and adversely affects the environment and the human body. Contains no element or phosphorus element, is highly safe, and has good moldability without impairing the basic physical properties of the polymer And finding the door, leading to the completion of the present invention.

The present invention is based on the above findings by the present inventors, and means for solving the above problems are as follows. That is,
<1> a polymer containing at least one of a thermoplastic resin and an elastomer having at least one of a carbonate bond, an ester bond, and an amide bond, urea, at least one of an organic acid ammonium salt and an inorganic acid ammonium salt, And the content of the urea is 20 parts by mass to 70 parts by mass with respect to 100 parts by mass of the polymer, and the content of at least one of the organic acid ammonium salt and the inorganic acid ammonium salt is 10 masses It is a flame retardant composition characterized by being part to 70 parts by mass.
<2> The flame retardant composition according to <1>, wherein the organic acid ammonium salt is a salt composed of any one of an aliphatic organic acid, an aromatic organic acid, and a complex thereof, and ammonia.
<3> The flame retardant composition according to <2>, wherein the aliphatic organic acid is a polyvalent carboxylic acid.
<4> The flame retardant composition according to any one of <1> to <3>, wherein the inorganic acid ammonium salt is at least one selected from ammonium sulfate, ammonium sulfite, and ammonium thiosulfate.
<5> The flame retardant composition according to any one of <1> to <4>, which contains at least two organic acid ammonium salts.
<6> The flame retardant composition according to any one of <1> to <5>, containing at least two inorganic acid ammonium salts.
<7> The thermoplastic resin according to any one of <1> to <6>, wherein the thermoplastic resin contains at least one selected from polycarbonate resin, polybutylene terephthalate resin, polyethylene terephthalate resin, polyamide resin, and polylactic acid. It is a flame retardant composition.

According to the present invention, by using urea or ammonium salt, the conventional problems can be solved, the object can be achieved, and excellent flame retardancy can be imparted to the polymer. It is possible to provide a flame retardant composition that does not contain a halogen element or a phosphorus element that adversely affects the human body, has high safety, and has good moldability without impairing the basic physical properties of the polymer.
In addition, the urea and the ammonium salt are colorless and transparent compounds, and are hardly colored with respect to the polymer, and are characterized by hardly changing the appearance characteristics of the resin.

(Flame retardant composition)
The flame retardant composition of the present invention contains at least a polymer, urea, and at least one of an organic acid ammonium salt and an inorganic acid ammonium salt, and further contains other components as necessary.
Hereinafter, urea and at least one of organic acid ammonium salt and inorganic acid ammonium salt may be referred to as “flame retardant”.

<Polymer>
The polymer contains at least one of a thermoplastic resin and an elastomer.
There is no restriction | limiting in particular as content of the said polymer of the said flame-retardant composition, According to the objective, it can select suitably.

<< Thermoplastic resin >>
The thermoplastic resin means a polymer that becomes soft when heated to either the glass transition temperature or the melting point and can be molded into a desired shape.

The thermoplastic resin has at least one of a carbonate bond, an ester bond, and an amide bond. Use of such a thermoplastic resin is preferable in that excellent flame retardancy can be obtained. On the other hand, a thermoplastic resin having no carbonate bond, ester bond, and amide bond such as acrylonitrile butadiene styrene resin (ABS) and polystyrene (PS) cannot obtain flame retardancy.
Examples of the thermoplastic resin having at least one of the carbonate bond, ester bond, and amide bond include polycarbonate resin (PC), polybutylene terephthalate resin (PBT), polyethylene terephthalate resin (PET), and polyamide resin (PA). Polylactic acid (PLA) is preferable in that it can impart high flame retardancy and has many uses that require flame retardancy such as films, sheets, and fibers. In addition, you may use resin called the alloy blend containing these.

There is no restriction | limiting in particular as the acquisition method of the said thermoplastic resin, What was synthesize | combined suitably may be used and a commercial item may be used.
Examples of commercially available thermoplastic resins include polycarbonate resin (Teijin Chemicals Ltd., trade name “Panlite”), polybutylene terephthalate (Polyplastics Co., Ltd., trade name “Juranex”), polyethylene terephthalate (Kuraray Co., Ltd.) Company, trade name “Kurapet”), polyamide resin (Toray Industries, Inc., trade name “Amilan”), polylactic acid (Mitsui Chemicals, trade name “Lacia”), and the like.

Moreover, you may further contain at least 1 sort (s) selected from thermoplastic resins other than the said polycarbonate resin, the said polybutylene terephthalate resin, the said polyethylene terephthalate resin, the said polyamide resin, and the said polylactic acid.
Examples of such thermoplastic resins include PC / ABS alloy, ABS alloy, PC / PBT alloy, PC / PET alloy, PC / PS alloy, and the like. These may be used alone or in combination of two or more. By containing these thermoplastic resins, economic efficiency or physical properties may be improved.

<< Elastomer >>
The elastomer refers to a polymer substance that exhibits rubber elasticity at room temperature. That is, it means a polymer substance that stretches more than twice when stretched at room temperature, and instantaneously returns to its original shape when the external force is removed. The elastomer is roughly classified into rubber and thermoplastic elastomer.

-Rubber-
The rubber is a material that undergoes large deformation with a small force at room temperature and quickly returns to its original shape when the force is removed, that is, a material exhibiting rubber elasticity, or a raw material polymer that can be made into such a material. Means.

The rubber is not particularly limited and can be appropriately selected depending on the purpose. For example, epoxidized natural rubber, raw natural rubber latex, vulcanized natural rubber latex, and methyl methacrylate (MMA) are graft copolymerized. Examples include natural rubber latex, nitrile butadiene rubber, acrylic rubber, chlorosulfonated polyethylene rubber, chloroprene rubber, hydrin rubber, neoprene rubber, and ethylene propylene rubber. These may be used alone or in combination of two or more.
Among these, the nitrile butadiene rubber (NBR), acrylic rubber (ACM), chlorosulfonated polyethylene rubber (CSM), chloroprene rubber (CR), hydrin rubber (ECO), epoxidized natural rubber (modified NR), Ethylene propylene (EPDM) is particularly preferable because it can be used cost-effectively and practically.

There is no restriction | limiting in particular as an acquisition method of the said rubber | gum, What was synthesize | combined suitably may be used and a commercial item may be used.
Examples of commercially available rubbers include nitrile butadiene rubber (made by Nippon Zeon Co., Ltd., trade name “Nipol 2850”), acrylic rubber (made by Nippon Zeon Co., Ltd., trade name “Nipol”), and chlorosulfonated polyethylene rubber. (DuPont, trade name “Hypalon”), Chloroprene rubber (Showa Denko, trade name “Shoprene”), Hydrin rubber (Daiso, trade name “Epichromer”), Epoxidized natural rubber (MMG) (Thailand), trade name “epoxyprene”), ethylene propylene (manufactured by JSR Corporation, trade name “EPR”) and the like.

-Thermoplastic elastomer-
There is no restriction | limiting in particular as said thermoplastic elastomer, According to the objective, it can select suitably, For example, a styrene-type elastomer (PSE), an ethylene vinyl acetate type | system | group elastomer (EVM), a polyester-type elastomer, a polyolefin-type elastomer, etc. Can be mentioned. These may be used alone or in combination of two or more.
Among these, as the thermoplastic elastomer, styrene elastomer (PSE) and ethylene vinyl acetate elastomer (EVM) are preferable because they are inexpensive and easily available.

There is no restriction | limiting in particular as an acquisition method of the said thermoplastic elastomer, What was synthesize | combined suitably may be used and a commercial item may be used.
Examples of commercially available thermoplastic elastomers include styrene elastomers (trade name “Tuftec” manufactured by Asahi Kasei Chemicals Corporation), ethylene vinyl acetate elastomers (Bayer Holding Co., Ltd., trade name “Revaprene”), and the like. .

<Urea>
Urea was found in mammalian urine and was named “urea”. Urea is commercially available as a good nitrogen fertilizer in field crops and rice crops, or synthesized in large quantities as a raw material for urea resin (urea resin) by copolymerization with formaldehyde.
The method for obtaining urea used in the present invention is not particularly limited, and it may be purified from urine of a mammal, may be appropriately synthesized, or may be a commercially available product. Good. Among these, it is preferable to use a commercially available product because it is simple. In the present invention, the urea does not have to be purified and has a high purity, which is advantageous in terms of cost.

  Although the content of the urea in the flame retardant composition is 20 parts by mass to 70 parts by mass with respect to 100 parts by mass of the polymer, 30 parts by mass to 50 parts by mass is preferable. If the urea content is less than 20 parts by mass, flame retardancy may not be imparted, and if it exceeds 70 parts by mass, the physical properties of the polymer may be deteriorated and the molding processability may be deteriorated. is there.

<Organic acid ammonium salt and / or inorganic acid ammonium salt>
<< Organic acid ammonium salt >>
The organic acid ammonium salt is a salt generated by the combination of ammonia and an organic acid.
There is no restriction | limiting in particular as said organic acid, Although it can select suitably according to the objective, Any of aliphatic organic acid, aromatic organic acid, and these composites are preferable.

-Aliphatic organic acids-
The aliphatic organic acid is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include adipic acid, succinic acid, malonic acid, tartaric acid, and the like, but when an organic acid ammonium salt is used. Those without deliquescence are preferred.

-Aromatic organic acids-
The aromatic organic acid is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include benzoic acid, phthalic acid, terephthalic acid, and benzenetricarboxylic acid.

  Among these, the organic acid ammonium salt is preferably a salt composed of an aliphatic organic acid and ammonia, and a salt composed of a polyvalent carboxylic acid and ammonia is compatible with many polymers such as elastomers and thermoplastic resins. The solubility is recognized, and is particularly preferable in that good compatibility with a thermoplastic polyester resin and a thermoplastic carbonate resin having a similar bond to an ester bond is recognized.

There is no restriction | limiting in particular as said polyvalent carboxylic acid, According to the objective, it can select suitably, For example, dicarboxylic acid, tricarboxylic acid, tetracarboxylic acid etc. are mentioned.
There is no restriction | limiting in particular as said dicarboxylic acid, According to the objective, it can select suitably, For example, quinoline dicarboxylic acid, carboxycinnamic acid, carboxyphenylacetic acid, naphthalene dicarboxylic acid, furandicarboxylic acid etc. are mentioned.
There is no restriction | limiting in particular as said tricarboxylic acid, According to the objective, it can select suitably, For example, a nitrile triacetic acid, a pyridine tricarboxylic acid, an aconitic acid etc. are mentioned.
There is no restriction | limiting in particular as said tetracarboxylic acid, According to the objective, it can select suitably, For example, ethylenedioxybisethylamine tetraacetic acid etc. are mentioned.

  In addition, as the organic acid, a heterocyclic compound may be used. There is no restriction | limiting in particular as said heterocyclic compound, According to the objective, it can select suitably, For example, nicotinic acid, furan carboxylic acid, thiophene carboxylic acid etc. are mentioned.

  The organic acid ammonium salt may be contained singly or in combination of two or more, but it is excellent flame retardant that two or more organic acid ammonium salts are contained. It is preferable at the point from which a property is acquired.

  Specific examples of the organic acid ammonium salt include ammonium hydrogen citrate, ammonium acetate, ammonium amidosulfate, ammonium benzoate, ammonium hydrogen carbonate, ammonium carbonate, ammonium oxalate, ammonium bicarbonate, ammonium adipate, ammonium succinate and the like. It is done.

<< Inorganic acid ammonium salt >>
The inorganic acid ammonium salt is a salt generated by the combination of ammonia and an inorganic acid.
Specific examples of the inorganic acid ammonium salt include ammonium sulfate, ammonium sulfite, ammonium thiosulfate, ammonium fluoride, ammonium chloride, ammonium phosphate, and ammonium metaphosphate.

The inorganic acid ammonium salt may be contained singly or in combination of two or more, but it is excellent flame retardant that two or more inorganic acid ammonium salts are contained. It is preferable at the point from which property is acquired.
In addition, it is preferable that at least two kinds of organic acid ammonium salts and at least two kinds of inorganic acid ammonium salts are contained in terms of obtaining more excellent flame retardancy.

  The content of at least one of the organic acid ammonium salt and inorganic acid ammonium salt in the flame retardant composition is 10 parts by mass to 70 parts by mass with respect to 100 parts by mass of the polymer. 60 mass parts is preferable and 40 mass parts-50 mass parts are more preferable. When the content of at least one of the organic acid ammonium salt and the inorganic acid ammonium salt is less than 10 parts by mass, flame retardancy may not be imparted. When the content exceeds 70 parts by mass, the physical properties of the polymer deteriorate. And moldability may deteriorate.

<Other ingredients>
The other components in the flame retardant composition are not particularly limited and may be appropriately selected from known additives according to the purpose. Examples thereof include fibers, minerals, and antibacterial agents. . These may be used alone or in combination of two or more.

-Fiber-
There is no restriction | limiting in particular as said fiber, According to the objective, it can select suitably, For example, organic fiber, such as inorganic fibers, such as glass fiber, carbon fiber, a whisker, Kevlar fiber, etc. are mentioned.

-Minerals-
The mineral is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include silica, talc, mica, wollastonite, clay, calcium carbonate and the like.

<Method for preparing flame retardant composition>
The method for preparing the flame retardant composition is not particularly limited and may be appropriately selected depending on the purpose. For example, the flame retardant (the urea, the organic acid ammonium salt and the inorganic salt in the polymer). And a method of adding at least one of acid ammonium salts).
The method of adding the flame retardant to the polymer is not particularly limited and may be appropriately selected depending on the purpose. For example, the flame retardant may be added directly to the polymer, Alternatively, a mixture (masterbatch) prepared by mixing the flame retardant at a high concentration in advance may be added.

<Molding method>
The method for molding the flame retardant composition is not particularly limited and can be appropriately selected from known methods according to the purpose. For example, film molding, extrusion molding, injection molding, blow molding, compression Examples thereof include molding, transfer molding, calendar molding, thermoforming, fluid molding, and lamination molding.

<Mechanism>
The flame retardant composition is bonded to the primary structure of the polymer by a coordination bond, hydrogen bond, or the like, and apparently causes a crosslinking reaction, whereby the constituent molecules of the polymer form a network and are used for heating during combustion. It is presumed that the combustion of the polymer can be suppressed and flame-retardant can be achieved by enduring and reducing the generated combustible combustion gas.
That is, in the combustion of the polymer, the low molecular weight compound is generated as a flammable combustion gas by the non-uniform thermal decomposition of the polymer, and the combustion continues as the flammable combustion gas continuously reacts with oxygen in the air. However, when the polymer is given either urea or at least one of organic carboxylic acid ammonium salt and inorganic acid ammonium salt, the molecular weight of the polymer is apparently increased, so that it occurs during thermal decomposition. It is estimated that the combustible combustion gas to be reduced is reduced, the combustion of the polymer is effectively suppressed, and flame retardancy can be imparted.

<Application>
The flame retardant composition of the present invention is excellent in flame retardancy and moldability, and can be formed into molded bodies of various shapes, structures, and sizes. For example, personal computers, printers, televisions, stereos, copiers, air conditioners It can be widely used as a part of various home appliances OA products such as refrigerators, washing machines and stereos.

  EXAMPLES The present invention will be specifically described below with reference to examples of the present invention, but the present invention is not limited to these examples.

Example 1
<Preparation of flame retardant composition>
Nitrile butadiene rubber (NBR) as a polymer (trade name: Nipol 2850, manufactured by Nippon Zeon Co., Ltd.), 100 parts by mass, urea (manufactured by Nacalai Tesque Co., Ltd.), 45 parts by mass, and citrate as ammonium citrate (Aq) 45 parts by mass of diammonium oxyhydrogen (reagent grade 1, manufactured by Nacalai Tesque) was added. A predetermined amount is weighed and put into a kneader (Rheocord RC300P (Germany), HAAKE), and a predetermined amount of powdered sulfur and zinc oxide is added as a vulcanizing agent and kneaded at a rotation speed of 20 rpm and 30 ° C. It took out after 10 minutes, the flame-retardant composition of Example 1 was prepared, and the combustion test was done by the method shown below. The results are shown in Table 1.

<< Combustion test >>
The flame retardant composition was roughly cut with a nipper or the like, placed in a polypropylene 100 mL container, and dissolved in a shaker for about 3 hours using toluene as a solvent. This was applied to a polyimide film with a doctor blade to produce a sheet-like test piece having an area of about 50 mm × 200 mm and a rubber layer thickness of 0.30 mm ± 0.05 mm.
The obtained test piece was formed into a cylindrical shape having a diameter of about 10 mm, and indirect flame ignition was performed with a 10 mm methane flame in a UL94 combustion tester for 5 seconds. The time from the moment when the gas burner was moved until the flame disappeared was measured as the burning time.
Note that this combustion test is a test for confirming flame retardancy, and not all of the UL-94 tests are compliant.

(Comparative Example 1)
In the preparation of the flame retardant composition of Example 1, the flame retardant composition of Comparative Example 1 was prepared in the same manner as in Example 1 except that urea and ammonium citrate (Aq) were not added. A combustion test was performed in the same manner as in Example 1. The results are shown in Table 1.

(Comparative Examples 2-3)
In the preparation of the flame retardant composition of Example 1, comparison was made in the same manner as in Example 1 except that urea was not added and ammonium citrate (Aq) was changed to various ammonium salts shown in Table 1 below. The flame retardant compositions of Examples 2 to 3 were prepared and subjected to a combustion test in the same manner as in Example 1. The results are also shown in Table 1.

(Examples 2 to 16)
In the preparation of the flame retardant composition of Example 1, in the same manner as in Example 1 except that ammonium citrate (Aq) was changed to various ammonium salts shown in Table 1 below, Examples 2 to 16 A flame retardant composition was prepared, and a combustion test was conducted in the same manner as in Example 1. The results are also shown in Table 1.

  In Table 1, the abbreviated symbols of ammonium salts represent the meanings shown in Table 2 below. In addition, Table 2 also shows manufacturer names and grades of various ammonium salts.

  From the results of Table 1, Examples 1 to 16 in which urea and organic ammonium salt or inorganic ammonium salt were added to nitrile butadiene rubber (NBR) as a polymer, respectively, were compared without adding urea and / or ammonium salt. Compared with Examples 1 to 3, it was recognized that the burning time was greatly reduced, and it was found that the material has flame retardancy.

(Examples 17 to 24)
In the preparation of the flame retardant composition of Example 1, instead of nitrile butadiene rubber (NBR), as the polymer, various rubbers or thermoplastic elastomers shown in Table 3 below were used, and the amount of ammonium hydrogen citrate (Aq) added Except having changed to 30 mass parts, it carried out similarly to Example 1, and prepared the flame-retardant composition of Examples 17-24, and performed the combustion test by the method similar to Example 1. FIG. The results are also shown in Table 3.

(Comparative Examples 4 to 11)
In preparing the flame retardant compositions of Examples 17 to 24, the flame retardant compositions of Comparative Examples 4 to 11 were prepared in the same manner as in Examples 17 to 24 except that urea and ammonium salt were not added. A combustion test was conducted in the same manner as in Example 1. The results are shown in Table 3.

  In Table 3, the abbreviation symbols for rubber or thermoplastic elastomer have the meanings shown in Table 4 below, and the abbreviation symbols for ammonium salts have the same meaning as in Table 2. Table 4 also shows the manufacturer name, product name, and grade of each rubber or thermoplastic elastomer.

  From the results shown in Table 3, it was found that even if the type of the base polymer rubber or thermoplastic elastomer was different, it had excellent flame retardancy.

(Examples 25-29, Comparative Examples 12-13)
15 g of the thermoplastic resin shown in Table 5 below is used, and 100 parts by mass of this is used, and urea (manufactured by Nacalai Tesque Co., Ltd.) and ammonium citrate (Aq) (reagent grade 1, Nacalai Tesque Co., Ltd.) are used as shown in Table 5 below. It added in the addition amount shown in. This was roughly mixed to prepare flame retardant compositions of Examples 25 to 29 and Comparative Examples 12 to 13, and a combustion test was performed by the method described below. The results are also shown in Table 5.

<< Combustion test >>
Using a heat press machine (mini press type 10 manufactured by Toyo Seiki Co., Ltd.) with polyimide films placed above and below the flame retardant composition and adjusted to a temperature according to the type of thermoplastic resin shown in Table 6 below. After sandwiching and pressing for 10 seconds at a gauge pressure of 10 MPa after 60 seconds, it was taken out and cooled to prepare a disk-shaped flame-retardant composition test piece having a diameter of about 80 mm and a thickness of 0.4 mm to 0.6 mm. .
The obtained test piece was set up vertically and ignited with a gas burner, and the combustion state was observed and evaluated according to the following criteria.
In addition, this combustion test is a test for confirmation of flame retardance, and not all comply with the UL-94 test.
〔Evaluation criteria〕
○: Burning time of 15 seconds or less ▲: It seems to disappear but did not disappear △: Slowly burned X: Either burning or drip flame was confirmed

(Comparative Examples 14-18)
In Examples 25-29, flame retardant compositions of Comparative Examples 14-18 were prepared in the same manner as in Examples 25-29, except that urea and ammonium salts were not added. Examples 25-29 A combustion test was conducted in the same manner as above. The results are shown in Table 5.

(Comparative Examples 19-22)
In Examples 25 to 29, except that urea was not added and the ammonium citrate salt (Aq) was changed to the ammonium salt of the type shown in Table 5 below, and the addition amount shown in Table 5 was changed, Example 25 to Example 25 The flame retardant compositions of Comparative Examples 19 to 22 were prepared in the same manner as in Example 29, and the combustion test was performed in the same manner as in Examples 25 to 29. The results are also shown in Table 5.

  In Table 5, the abbreviated symbols for thermoplastic resins have the meanings shown in Table 6 below, and the abbreviated symbols for ammonium salts have the same meanings as in Table 2. Table 6 also shows the manufacturer name, product name, grade, and press temperature of each thermoplastic resin.

From the results of Table 5, it was found that extremely excellent flame retardancy can be imparted to polycarbonate, polylactic acid, polybutylene terephthalate, polyamide, polyethylene terephthalate, and the like.
On the other hand, flame retardancy could not be imparted to polymers such as ABS and PS. This is presumably because, as described above, the polymers such as ABS and PS have extremely small polarity, so that the flame retardant and the constituent molecules of the polymer cannot form a network and flame retardancy cannot be obtained.

(Examples 30 to 39)
In the preparation of the flame-retardant composition of Example 1, Examples 30 to 30 were carried out in the same manner as in Example 1 except that the polymer, urea, and ammonium salt were changed to the types and addition amounts shown in Table 7 below. 39 flame retardant compositions were prepared and subjected to a combustion test in the same manner as in Example 1. The results are also shown in Table 7.
In Table 7, the abbreviation symbols for polymers have the same meaning as in Table 4, and the abbreviation symbols for ammonium salts have the same meaning as in Table 2.

  From the results in Table 7, it was found that effective flame retardancy can also be imparted by combining a plurality of types of ammonium salts.

(Examples 40 to 43)
In the preparation of the flame retardant compositions of Examples 25 to 29, the same procedures as in Examples 25 to 29 were conducted except that the thermoplastic resin, urea, and ammonium salt were changed to the types and addition amounts shown in Table 8 below. The flame retardant compositions of Examples 40 to 43 were prepared, and the combustion test was performed in the same manner as in Examples 25 to 29. The results are shown in Table 8.
In Table 8, the abbreviated symbols for thermoplastic resins have the same meaning as in Table 6, and the abbreviated symbols for ammonium salts have the same meaning as in Table 2.

  From the results of Table 8, it was found that effective flame retardancy can also be imparted by combining a plurality of types of ammonium salts.

(Examples 44 to 48)
In the preparation of the flame retardant composition of Example 1, ammonium salts were used in combinations shown in Table 9 below, and the addition amount of urea and / or ammonium salt was changed to the addition amount shown in Table 9 below. Prepared the flame retardant compositions of Examples 44 to 48 in the same manner as in Example 1, and conducted a combustion test in the same manner as in Example 1. The results are also shown in Table 9.

(Comparative Examples 23-27)
In the preparation of the flame retardant compositions of Examples 44 to 48, Comparative Examples 23 to 27 were performed in the same manner as Examples 44 to 48, except that the addition amount of the ammonium salt was changed to the addition amount shown in Table 9 below. A flame retardant composition was prepared and a combustion test was conducted in the same manner as in Example 1. The results are also shown in Table 9.

(Examples 49 to 52)
In the preparation of the flame retardant compositions of Examples 44 to 48, Examples 49 to 52 were performed in the same manner as Examples 44 to 48, except that the addition amount of urea was changed to the addition amount shown in Table 9 below. A flame retardant composition was prepared, and a combustion test was conducted in the same manner as in Example 1. The results are also shown in Table 9.

(Comparative Examples 28-31)
In the preparation of the flame retardant compositions of Examples 44 to 48, Comparative Example 28 was performed in the same manner as Examples 44 to 48, except that the addition amounts of urea and ammonium salt were changed to the addition amounts shown in Table 9 below. The flame-retardant composition of -31 was prepared, and the combustion test was done by the same method as Example 1. The results are also shown in Table 9.
In Table 9, the polymer abbreviations have the same meaning as in Table 4, and the ammonium salt abbreviations have the same meaning as in Table 2.

表９において、「＊」は、試料作製が困難又は不可のため、評価不可であったことを表す。

In Table 9, “*” represents that the evaluation was not possible because the sample preparation was difficult or impossible.

  From the results of Table 9, if the amount of urea and at least one of the organic ammonium salt and inorganic ammonium salt is too small, an appropriate flame retardant effect cannot be obtained, and if too large, the physical properties of the polymer deteriorate, I found out that I could not. Accordingly, at least one of an organic ammonium salt and an inorganic ammonium salt is contained in an amount of 10 parts by mass to 70 parts by mass, preferably 20 parts by mass to 60 parts by mass, and more preferably 40 parts by mass to 50 parts by mass. It turned out that the flame retardance which was excellent by containing 30 mass parts-70 mass parts, Preferably 30 mass parts-50 mass parts is obtained.

  From the results of Tables 1 to 9, a flame retardant containing urea and at least one of an organic ammonium salt and an inorganic ammonium salt is used as a thermoplastic resin having at least one of a carbonate bond, an ester bond, and an amide bond; It was found that the flame retardancy of the polymer can be effectively suppressed by adding it to the polymer containing at least one of the elastomers.

  The flame retardant composition of the present invention is excellent in flame retardancy and moldability, and can be formed into molded bodies of various shapes, structures, and sizes. For example, personal computers, printers, televisions, stereos, copiers, air conditioners It can be widely used as a part of various home appliances OA products such as refrigerators, washing machines and stereos.

Claims (7)

A polymer containing at least one of a thermoplastic resin and an elastomer having at least one of a carbonate bond, an ester bond, and an amide bond, urea, and an organic acid ammonium salt and / or an inorganic acid ammonium salt. ,
The content of the urea is 20 parts by mass to 70 parts by mass with respect to 100 parts by mass of the polymer, and the content of at least one of the organic acid ammonium salt and the inorganic acid ammonium salt is 10 parts by mass to 70 parts by mass. A flame retardant composition characterized by being a part.   The flame retardant composition according to claim 1, wherein the organic acid ammonium salt is a salt composed of any one of an aliphatic organic acid, an aromatic organic acid, and a complex thereof, and ammonia.   The flame retardant composition according to claim 2, wherein the aliphatic organic acid is a polyvalent carboxylic acid.   The flame retardant composition according to any one of claims 1 to 3, wherein the inorganic acid ammonium salt is at least one selected from ammonium sulfate, ammonium sulfite, and ammonium thiosulfate.   The flame retardant composition according to any one of claims 1 to 4, comprising at least two organic acid ammonium salts.   The flame retardant composition according to any one of claims 1 to 5, comprising at least two inorganic acid ammonium salts.   The flame retardant composition according to any one of claims 1 to 6, wherein the thermoplastic resin contains at least one selected from polycarbonate resin, polybutylene terephthalate resin, polyethylene terephthalate resin, polyamide resin, and polylactic acid.