JP5151952B2 - Resin composition and resin molded body. - Google Patents

Description

  The present invention relates to a resin composition and a resin molded body.

  Conventionally, a flame retardant is mixed in a resin material that requires flame retardancy for flame retardancy. As the flame retardant mixed with the resin material, for example, halogen compounds and phosphorus compounds are widely known. However, particularly in the case of petroleum-based resin materials, there is a tendency to avoid mixing halogen compounds that may generate dioxins during incineration. Therefore, in recent years, phosphorus compounds are often used as flame retardants as an alternative to halogen compounds.

  Furthermore, as a resin material using a flame retardant other than a halogen compound and a phosphorus compound, for example, Patent Document 1 blended a synergistic mixture of a sterically hindered amine stabilizer and an isocyanurate flame retardant or a melamine-based flame retardant. Flame retardant polylactic acid polymer compositions have been proposed. Patent Document 2 proposes a flame retardant resin composition using a styrene resin, an alkylene oxide adduct of a dihydroxyaryl compound, and a boron oxide and / or an aminotriazine sulfate compound. Further, Patent Document 3 proposes a flame retardant resin composition using an aromatic polymer into which a sulfonic acid group and / or a sulfonic acid group is introduced as a flame retardant.

JP 2006-528254 Gazette Japanese Patent Laid-Open No. 2005-220318 JP 2005-272539 A

  The present invention provides a resin composition capable of forming a resin molded article having excellent flame retardancy without using a halogen compound and a phosphorus compound as a flame retardant, and a resin molded article using the same. With the goal.

According to one aspect of the present invention, a resin and a sulfuric acid guanidine content is not more than 30 parts by mass or more 0.1 part by mass relative to the resin 100 parts by mass, with respect to the content resin 100 parts by And a bistetrazole compound having a decomposition temperature of not less than 3 parts by mass and not more than 60 parts by mass and having a decomposition temperature of 300 ° C. or more.

The invention according to claim 2 is the resin composition according to claim 1, wherein the resin is acrylonitrile-butadiene-styrene copolymer or polylactic acid .

Invention of Claim 3 is resin , the guanidine sulfate whose content is 0.1 to 30 mass parts with respect to 100 mass parts of said resin, and content is with respect to 100 mass parts of said resin And a bistetrazole compound having a decomposition temperature of not less than 3 parts by mass and not more than 60 parts by mass and having a decomposition temperature of 300 ° C. or more.

The invention according to claim 4 is the resin molded article according to claim 3 , wherein the resin is acrylonitrile-butadiene-styrene copolymer or polylactic acid .

  The invention according to claim 1 is capable of forming a resin molded article having excellent flame retardancy as compared with a resin composition not having this configuration without using a halogen compound and a phosphorus compound as a flame retardant. Has the effect of being.

  The invention according to claim 2 can achieve the effect of the invention according to claim 1 in which formation of a resin molded article having excellent flame retardancy is possible without using a halogen compound and a phosphorus compound as a flame retardant. It has the effect that it can be effectively realized.

Invention of Claim 3 has the effect that it can have the outstanding flame retardance compared with the resin molding which does not have this structure, without using a halogen compound and a phosphorus compound as a flame retardant.

The invention according to claim 4 can effectively achieve the effect of the invention according to claim 3 that it can have excellent flame retardancy without using a halogen compound and a phosphorus compound as a flame retardant. Have

  Hereinafter, preferred embodiments of the present invention will be described in detail.

The resin composition according to the present embodiment includes a resin, guanidine sulfate, and a bistetrazole compound having a decomposition temperature of 300 ° C. or higher.
However, the content of guanidine sulfate is 0.1 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the resin, and the content of the bistetrazole compound having a decomposition temperature of 300 ° C. or more is 100 parts by mass of the resin. On the other hand, it shall be 3 to 60 mass parts.

  The resin is not particularly limited. For example, acrylonitrile-butadiene-styrene copolymer (ABS), methylpentene, thermoplastic vulcanized elastomer, thermoplastic polyurethane, styrene-isoprene-styrene block copolymer, silicone, styrene-ethylene. -Propylene-styrene block copolymer, styrene-ethylene-butylene-styrene block copolymer, styrene-butadiene-styrene block copolymer, styrene-butadiene rubber, styrene-butadiene copolymer, acrylonitrile-styrene copolymer, Polyvinyl pyrrolidone, polyvinyl alcohol, polyvinyl methyl ether, polyvinyl isobutyl ether, polyvinyl formal, polyvinyl butyral, polyvinyl acetate, polyvinyl alcohol, polytri Tylene terephthalate, polysulfone, polysulfone, polystyrene, polyphenylene sulfide, polyphenylene ether, polypropylene, polyphthalamide, polyoxymethylene, polymethylpentene, polymethyl methacrylate, polymethacrylonitrile, polymethoxyacetal, polyisobutylene, thermoplastic polyimide, Polyethylene terephthalate, polyether sulfone, polyethylene naphthalate, polyether nitrile, polyether imide, polyether ether ketone, polyethylene, polycarbonate, polybutylene terephthalate, polybutadiene styrene, polyparaphenylene benzobisoxazole, poly-n-butyl methacrylate, poly Benzimidazole, polybutadiene acrylonitrile, poly Ten-1, polyallylsulfone, polyarylate, polyacrylonitrile, thermoplastic polyester alkyd resin, thermoplastic polyamideimide, polyacrylic acid, polyamide, natural rubber, nitrile rubber, methyl methacrylate butadiene styrene copolymer, polyethylene, isoprene rubber, Ionomer, butyl rubber, furan resin, ethylene-vinyl alcohol copolymer, ethylene-vinyl acetate copolymer, ethylene-propylene-diene terpolymer, cellulose propionate, hydrin rubber, carboxymethylcellulose, cresol resin, cellulose acetate propio Nate, cellulose acetate butyrate, cellulose acetate, bismaleimide triazine, cis 1-4 polybutadiene synthetic rubber, acrylonitrile styrene acrylate Examples thereof include rate, acrylonitrile-styrene copolymer, acrylonitrile-ethylene-propylene-styrene copolymer, acrylate rubber, and polylactic acid. These can be used individually by 1 type or in combination of 2 or more types.

Moreover, as said resin, an acrylonitrile-butadiene-styrene copolymer (ABS) or polylactic acid (PLA) can be used suitably from a viewpoint of an elasticity modulus. According to the resin composition containing ABS, in addition to being excellent in flame retardancy and elastic modulus, it is possible to form a resin molded article excellent in impact resistance, cost, and the like. Further, according to the above resin composition comprising PLA, in addition to excellent flame retardancy and modulus, formation of the resin molded body can contribute in terms of life cycle assessment (LCA) to CO ₂ reduction is possible. These resin compositions are particularly suitable for forming a resin molded product for office equipment.

  Further, from the viewpoint of obtaining a resin molded article having excellent toner resistance and chemical resistance, it is preferable to use ABS, polycarbonate (PC) / ABS, or the like as the resin. These resin compositions are particularly suitable for forming a resin molded product for office equipment.

  The bistetrazole compound has a decomposition temperature of 300 ° C. or higher and a bistetrazole skeleton represented by the following formula (1).

  As said bistetrazole compound, the bistetrazole compound represented by following formula (2) is mentioned, for example.

  In said formula (2), X shows a metal atom, a hydrogen atom, or an organic cation, and n shows the integer of 1-2. X may have a bond with a nitrogen atom of a bistetrazole skeleton.

  As said metal atom, lithium, sodium, magnesium, potassium, calcium, manganese, copper, iron, zinc etc. are mentioned, for example. Among these, potassium is preferable in that the amount of generated gas is large and a further excellent flame retardancy is obtained.

  The organic cation indicates an atomic group having a cationic functional group, for example, an atomic group having an ammonium group formed by a reaction of a primary, secondary or tertiary amine and an acid, or a quaternary ammonium group. And an atomic group having the same. Moreover, you may have a some cationic functional group in an atomic group. As the organic cation, an ammonium cation and a piperazine dication are preferable from the viewpoint that a large amount of gas is generated and a further excellent flame retardancy is obtained.

  As the bistetrazole compound, an amine salt of bistetrazole can be suitably used from the viewpoint of a large amount of generated gas and excellent flame retardancy, and from the viewpoint of easy synthesis and compatibility with the resin. The amine salt of bistetrazole is specifically a salt obtained by reacting a known basic amine compound such as ammonia, primary amine, secondary amine, tertiary amine, cyclic amine or aromatic amine with bistetrazole. For example, 5,5′-bi-1H-tetrazole / diammidine, 5,5′-bi-1H-tetrazole / piperazine, 5,5′-bi-1H-tetrazole / diguanidine and the like can be mentioned.

  The bistetrazole compound has a decomposition temperature of 300 ° C. or higher, preferably 325 ° C. or higher, more preferably 350 ° C. or higher. If the decomposition temperature is less than 300 ° C., decomposition gas is easily generated during molding, which may impair the appearance of the molded body. Here, the decomposition temperature means a thermal decomposition temperature measured according to a thermogravimetric analysis of JIS K0129.

  The generated gas amount of the bistetrazole compound is preferably 300 ml / g or more, and more preferably 340 ml / g or more. When the amount of generated gas is 300 ml / g or more, the flame retardancy of the resin molded product tends to be further improved. Here, the generated gas amount is measured by the following gas amount measurement test.

[Gas quantity measurement test]
1 g of a sample is accurately measured in a 100 ml three-necked flask, 20 ml of liquid paraffin is added as a dispersing agent, and the sample is uniformly dispersed using an ultrasonic cleaner. Next, a thermometer for measuring the gas phase and liquid layer temperature is attached to the three-necked flask, and a 300 ml U-shaped gas burette is connected via a three-way cock. The gas burette is filled with water so that the water surface heights of the left and right tubes (hereinafter referred to as “reference height”) are at the same position. After this, the flask is immersed in a silicon oil bath that has been previously maintained at the measurement temperature to generate gas. The generation of gas pushes down the water surface on one side of the U-shaped gas burette tube and pushes it up on the other. Next, the pushed water surface is pressurized from the upper part of the pipe and adjusted so that the height of the water surface of the left and right pipes is the same position. The height of the water surface of the right and left pipes after adjustment is defined as the “gas generation height”. From the gas generation height after 20 minutes from the gas generation due to the primary decomposition of the sample after the immersion, the apparent gas generation amount is calculated by the following equation (A). On the other hand, a blank test without a sample is performed in the same manner as described above, and an apparent gas generation amount based on the expansion of air is calculated. The amount of gas generated in the sample is calculated by subtracting the amount of gas generated in the blank from the amount of gas generated only when the sample is introduced. The amount of generated gas is converted to 20 ° C. and 1 atm, and is expressed as the amount of generated gas per 1 g of sample.
Apparent gas generation amount = (reference height-gas generation height) x U-tube cross-sectional area (A)

As the bistetrazole compound, for example, product names “Celtetra BHT-2NH ₃ ” and “Celtetra BHT-PIPE” manufactured by Eiwa Chemical Industry Co., Ltd. can be used.

  In the resin composition according to this embodiment, the content of the bistetrazole compound is preferably 3 parts by mass or more and 60 parts by mass or less, and preferably 4 parts by mass or more and 55 parts by mass or less with respect to 100 parts by mass of the resin. It is more preferable that If the content of the bistetrazole compound is less than 3 parts by mass, the flame retardancy of the resin molded product may not be sufficiently obtained, and if it is more than 60 parts by mass, the impact resistance may be significantly reduced.

  In the resin composition according to the present embodiment, the content of guanidine sulfate is preferably 0.1 parts by mass or more and 30 parts by mass or less, and 0.1 parts by mass or more and 25 parts by mass with respect to 100 parts by mass of the resin. It is more preferable that the amount is not more than parts. When the content of guanidine sulfate is less than 0.1 parts by mass, the flame retardancy of the resin molded product may not be sufficiently obtained, and when it is more than 30 parts by mass, the impact resistance may be significantly reduced.

  In the resin composition according to this embodiment, the total content of the bistetrazole compound and guanidine sulfate is preferably 3 parts by mass or more and 75 parts by mass or less with respect to 100 parts by mass of the resin. More preferably, it is 75 parts by mass or less. If the total content of the bistetrazole compound and guanidine sulfate is less than 3 parts by mass, the flame retardancy of the resin molded product may not be sufficiently obtained. In some cases, the strength of the resin molded body may be reduced.

  The resin composition concerning this embodiment may contain additives other than each component mentioned above. Examples of additives include radical trapping agents, char forming agents, anti-drip agents, impact resistance improvers, compatibilizers, reinforcing agents, antioxidants, weathering agents, plasticizers, lubricants, colorants, crystal nucleating agents, Examples include foaming agents, antistatic agents, preservatives, and the like. Although content of these additives will not be restrict | limited especially if it is a range which does not impair the effect of this invention, It is preferable that it is 50 mass parts or less with respect to 100 mass parts of said resins.

  Moreover, it is preferable that the resin composition concerning this embodiment does not contain a halogen compound substantially from a viewpoint of an environmental problem, and it is preferable not to contain a phosphorus compound substantially from a viewpoint of recyclability. In addition, it is preferable that content of the halogen compound and phosphorus compound in the said resin composition is 0.5 mass% or less, respectively on the basis of the resin composition whole quantity.

  Next, the resin molded body according to the present embodiment will be described. The resin molded body according to the present embodiment includes a resin, guanidine sulfate, and a bistetrazole compound having a decomposition temperature of 300 ° C. or higher. For example, the resin molded body can be obtained by molding the above-described resin composition.

  The resin molded body may be formed by, for example, known methods such as injection molding, injection compression molding, press molding, extrusion molding, blow molding, calendar molding, coating molding, cast molding, dipping molding, and the like. Can be obtained at In the present embodiment, the resin composition is preferably molded at less than 300 ° C., more preferably 250 ° C. or less so that the bistetrazole compound is not decomposed.

  From the viewpoint of flame retardancy, the resin molded body of this embodiment preferably has a specific gravity of 1.0 or more and 2.5 or less when the resin is an acrylonitrile-butadiene-styrene copolymer. Moreover, when the said resin is polylactic acid, it is preferable that the specific gravity of a resin molding is 1.2 or more and 2.5 or less.

  The use of the resin molding is not particularly limited. For example, housings such as home appliances and office equipment or various parts thereof, wrapping films, storage cases such as CD-ROMs and DVDs, tableware, food trays, and beverage bottles And chemical wrap materials.

  The resin molded article is very useful from the viewpoint of environmental problems and recyclability because sufficient flame retardancy can be obtained without using a halogen compound as a flame retardant and a phosphorus compound having a strong hygroscopic property. is there. Furthermore, since the resin molded body can sufficiently suppress deterioration due to heat, it is very useful as a casing of a copying machine, a printer, or the like having a high temperature portion inside.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example.

(Examples 1-8)
A resin composition in which the components shown in Table 1 below were blended in the blending amounts (unit: parts by mass) shown in the same table was kneaded with a twin screw extruder (Toshiba Machine Co., Ltd., 58SS), and an injection molding machine (Nissei) Resin Kogyo Co., Ltd. (NEX360) is injection-molded under conditions of a cylinder temperature of 235 ° C. and a mold temperature of 60 ° C., and an ISO multipurpose dumbbell test piece (test part thickness 4 mm, width 10 mm) and UL (thickness 2) 0.0 mm) test piece.

(Comparative Examples 1-9)
A resin composition in which the components shown in Table 2 below were blended in the blending amounts (unit: parts by mass) shown in the same table was kneaded with a twin screw extruder (Toshiba Machine Co., Ltd., 58SS), and an injection molding machine (Nissei) Resin Kogyo Co., Ltd. (NEX360) is injection-molded under conditions of a cylinder temperature of 235 ° C. and a mold temperature of 60 ° C., and an ISO multipurpose dumbbell test piece (test part thickness 4 mm, width 10 mm) and UL (thickness 2) 0.0 mm) test piece.

In Tables 1 and 2 below, ABS indicates acrylonitrile-butadiene-styrene copolymer (manufactured by Japan A & L, AT-05, bulk polymer), PLA indicates polylactic acid (Unitika, TE7000), BHT -2NH ₃ represents 5,5′-bi-1H-tetrazole diammonium (manufactured by Eiwa Kasei Co., Ltd., Celltetra BHT-2NH ₃ , decomposition temperature 325 ° C., generated gas amount 520 ml / g), and BHT-PIPE is 5, 5'-bi-1H-tetrazole / piperazine (manufactured by Eiwa Kasei Co., Ltd., Cell Tetra BHT-PIPE, decomposition temperature 350 ° C., generated gas amount 340 ml / g) is shown, P5T is 5-phenyltetrazole (manufactured by Eiwa Kasei Co., Ltd., Cell Tetra P5T) The decomposition temperature is 230 ° C. and the amount of generated gas is 180 ml / g). The guanidine sulfate used was manufactured by Kanto Chemical.

[Characteristic evaluation test of resin molding]
Using each test piece (resin molding) obtained in Examples 1 to 8 and Comparative Examples 1 to 9, a characteristic evaluation test was performed according to the following procedure. The results are shown in Tables 3 and 4.

<Evaluation of flame retardancy (heat generation rate)>
Using the ISO multipurpose dumbbell test piece, the heat generation rate (kW / m ² ) was measured with a cone calorimeter (manufactured by Toyo Seiki Co., Ltd., CONE III) in accordance with ISO 5660-1.

<Evaluation of flame retardancy (UL-94)>
Using the UL test piece, a horizontal and vertical combustion test of UL-94 was performed. In addition, the result of a combustion test is a high level in order of V-0, V-1, V-2, and HB, and the flame retardance more than V-2 is often requested | required.

<Evaluation of Charpy impact strength>
Charpy impact strength (kJ / m ² ) was measured with a digital impact resistance tester (DG-C, manufactured by Toyo Seiki Co., Ltd.) using the ISO multipurpose dumbbell test piece.

Claims (4)

And resin,
Guanidine sulfate having a content of 0.1 to 30 parts by mass with respect to 100 parts by mass of the resin ;
A bistetrazole compound having a content of 3 parts by mass or more and 60 parts by mass or less with respect to 100 parts by mass of the resin, and a decomposition temperature of 300 ° C. or more ;
A resin composition comprising:   The resin composition according to claim 1, wherein the resin is acrylonitrile-butadiene-styrene copolymer or polylactic acid. And resin,
Guanidine sulfate having a content of 0.1 to 30 parts by mass with respect to 100 parts by mass of the resin ;
A bistetrazole compound having a content of 3 parts by mass or more and 60 parts by mass or less with respect to 100 parts by mass of the resin, and a decomposition temperature of 300 ° C. or more ;
A resin molded body. The resin molded product according to claim 3 , wherein the resin is an acrylonitrile-butadiene-styrene copolymer or polylactic acid.