WO2013057841A1 - 難燃剤マスターバッチ及びそれを使用したスチレン系難燃性樹脂組成物の製造方法 - Google Patents
難燃剤マスターバッチ及びそれを使用したスチレン系難燃性樹脂組成物の製造方法 Download PDFInfo
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- WO2013057841A1 WO2013057841A1 PCT/JP2011/074355 JP2011074355W WO2013057841A1 WO 2013057841 A1 WO2013057841 A1 WO 2013057841A1 JP 2011074355 W JP2011074355 W JP 2011074355W WO 2013057841 A1 WO2013057841 A1 WO 2013057841A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2325/02—Homopolymers or copolymers of hydrocarbons
- C08J2325/04—Homopolymers or copolymers of styrene
Definitions
- the present invention relates to a flame retardant masterbatch used for imparting flame retardancy to a styrene resin, a method for producing a styrene flame retardant resin composition using the flame retardant masterbatch and a styrene resin, and
- the present invention relates to a method for manufacturing a molded product.
- a flame retardant masterbatch for obtaining a styrene flame retardant resin composition having UL flame retardant standard V-0 and a method for producing a styrene flame retardant resin composition using the same.
- Styrenic resins are used in a wide range of applications, taking advantage of their properties. Above all, styrene-based flame retardant resins with advanced flame retardancy are used in a wide variety of fields, including office automation equipment such as word processors, personal computers, printers, copiers, liquid crystal televisions, VTRs, and audio home appliances. in use.
- office automation equipment such as word processors, personal computers, printers, copiers, liquid crystal televisions, VTRs, and audio home appliances. in use.
- halogen-containing organic compounds that are inexpensive and excellent in physical property balance are often used as flame retardants.
- tetrabromobisphenol A, decabromodiphenyl ether, decabromodiphenylethane, brominated triazine, brominated epoxy, or a brominated epoxy resin having an epoxy group blocked with tribromophenol is used.
- brominated triazine-based 2,4,6-tris (2,4,6-trisbromophenoxy) -1,3,5-triazine flame retardant resin having good heat resistance, fluidity and physical property balance
- Examples of these flame retardants used in styrene resins include Patent Document 1, Patent Document 2, Patent Document 3, and Patent Document 4.
- this 2,4,6-tris (2,4,6-trisbromophenoxy) -1,3,5-triazine is granular, smaller in shape than styrenic resin pellets, and has a large specific gravity. Therefore, the flame retardant and the styrene resin pellet are easily classified and have a problem that it is difficult to mix them uniformly. For this reason, in order to mix uniformly, it is necessary to install another feed in all the extruder main bodies, and to melt-mix uniformly, and it has the problem that it is difficult to manufacture with a simple single screw or twin screw extruder.
- talc is a fine powder and has the problem of dust. In order to solve the dust problem when melt mixing, it is necessary to provide a dust collector in all the extruders.
- Japanese Unexamined Patent Publication No. 8-269275 Japanese Unexamined Patent Publication No. 2002-97328 Japanese Unexamined Patent Publication No. 2002-3688 Japan Special Table 2008-501849
- the subject of this invention is providing the method of manufacturing a styrene-type flame retardant resin composition by solving the said problem, manufacturing a flame retardant masterbatch, and melt-mixing the flame retardant masterbatch.
- each of a wide variety of styrene-based flame retardant resin compositions is provided with large and small twin-screw extruders with separate feed / dust collectors, good dispersibility of the flame retardant, and the desired flame retardant properties.
- a styrene-based flame retardant resin composition suitable for each purpose such as heat resistance and fluidity, particularly in a single-screw extruder, without substantially reducing the original properties of polystyrene-based resin such as mechanical properties. It is in.
- the gist of the present invention is as follows. 1. (A) 75 to 25 parts by mass of a styrene resin, (B) 15 to 50 parts by mass of 2,4,6-tris (2,4,6-tribromophenoxy) -1,3,5-triazine, C) 2 to 8 parts by mass of antimony trioxide, and (D) 5 to 17 parts by mass of talc, And the flame retardant masterbatch characterized by containing 0.5 to 2.0 mass parts of (E) antioxidant further with respect to a total of 100 mass parts of (A) thru
- C The flame retardant masterbatch according to 1 or 2 above, which is 3 to 8 parts by mass of antimony trioxide and (D) 7 to 17 parts by mass of talc. 4).
- the styrene-based flame retardant resin composition comprising 30 to 85 parts by mass of the flame retardant master batch (I) according to any one of 1 to 5 and 70 to 15 parts by mass of the styrene resin (II). Manufacturing method. 7).
- the styrene flame retardant resin composition comprising 30 to 60 parts by mass of the flame retardant masterbatch (I) according to any one of 1 to 5 and 70 to 40 parts by mass of the styrene resin (II). Manufacturing method.
- each of a wide variety of styrene-based flame retardant resin compositions can be provided with a large number of twin-screw extruders with separate feed / dust collectors
- An extruder also provides a styrene-based flame retardant resin composition suitable for each purpose. That is, the obtained styrene-based flame retardant resin composition is excellent in the balance of physical properties such as flame retardancy, impact strength, heat resistance, and fluidity, and even a composition obtained by using a single screw extruder for melt mixing.
- the desired molded product can be easily obtained and the appearance of the molded product is also good.
- the flame retardant masterbatch of the present invention comprises (A) a styrene resin, (B) 2,4,6-tris (2,4,6-trisbromophenoxy) -1,3,5-triazine, (C) three Contains antimony oxide, (D) talc, and (E) an antioxidant.
- the (A) styrene resin used in the flame retardant masterbatch of the present invention is preferably a rubber-modified styrene resin.
- the rubber-modified styrenic resin is obtained, for example, by dissolving a rubber-like polymer in a mixed liquid of an aromatic vinyl monomer and an inert solvent and stirring to perform bulk polymerization, suspension polymerization, solution polymerization, or the like.
- the molecular weight of the matrix portion is not particularly limited, but when the flame retardant master batch is produced or when the function as the flame retardant master batch is exhibited, the reduced viscosity ( ⁇ sp / C) of the matrix portion is 0.55 to It is preferably 0.85. Although there is no restriction
- the average particle diameter of the rubbery polymer is not particularly limited, but is preferably 0.4 to 6.0 ⁇ m. Deviating from these numerical ranges is not preferable because the function as a flame retardant masterbatch is difficult to be exhibited. Further, a mixture obtained by dissolving a rubbery polymer in a mixed liquid of an aromatic vinyl monomer and an inert solvent and a separately obtained aromatic vinyl polymer may be mixed. .
- the aromatic vinyl monomer mentioned above is mainly styrene, and examples thereof include o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, or a mixture thereof. . In particular, styrene is most preferred.
- examples of the rubber-like polymer include polybutadiene, styrene-butadiene copolymer, polyisoprene and the like, and among them, polybutadiene or styrene-butadiene copolymer is preferable.
- the high cis polybutadiene rubber means a polybutadiene rubber containing cis-1,4 bonds in a ratio of 90 mol% or more.
- the low-cis polybutadiene rubber means a polybutadiene rubber having a 1,4-cis bond content of preferably 10 to 40% by mass. Any rubbery polymer can be used.
- a rubber-modified styrene resin may be used by mixing a styrene-butadiene resin having a random structure, a styrene-butadiene resin having a block structure, or the like.
- the mixing amount of the styrene-butadiene resin is preferably such that the rubber content depending on the styrene-butadiene resin is 25% by mass or less as a proportion of the total rubber content in the rubber-modified styrene resin.
- the total rubber content in the rubber-modified styrenic resin is preferably 5 to 15% by mass.
- the content of the (A) styrenic resin used in the present invention is preferably 25 to 75 parts by mass, more preferably 30 to 30 parts per 100 parts by mass in total of (A) to (D) in the flame retardant masterbatch. 65 parts by mass.
- the content is less than 25 parts by mass, the amount of flame retardant increases, and when a styrene-based flame retardant resin composition is used, the Charpy impact strength and the heat distortion temperature become inferior. If the content exceeds 75 parts by mass, the resin component will increase and the flame retardancy will be poor. As a result, the addition amount of the flame retardant masterbatch must be increased to obtain a styrene-based flame retardant resin composition, resulting in poor efficiency as a flame retardant masterbatch.
- (B) 2,4,6-tris (2,4,6-tribromophenoxy) -1,3,5-triazine is used as a flame retardant.
- the content of the flame retardant master batch is 15 to 50 with respect to 100 parts by mass of the total of (A) to (D) in the flame retardant master batch.
- a mass part is preferable, More preferably, it is 25-50 mass parts.
- the flame retardancy is inferior, and if the addition amount of the flame retardant masterbatch is not increased, the flame retardancy of the styrene-based flame retardant resin composition will be inferior, and as a flame retardant masterbatch The economic effect is low.
- the content exceeds 50 parts by mass, the amount of flame retardant increases, and when a styrene-based flame retardant resin composition is used, the Charpy impact strength and the heat distortion temperature become inferior.
- (C) antimony trioxide which is a flame retardant aid used in the present invention, functions to further enhance the flame retardant effect of the (B) bromine-containing flame retardant.
- the flame retardant aid further includes, for example, antimony trioxide, antimony pentoxide, sodium antimonate and other antimony oxides, zinc borate, barium metaborate, anhydrous zinc borate, anhydrous boric acid, etc. Boron compounds, tin compounds such as zinc stannate and zinc hydroxystannate, molybdenum compounds such as molybdenum oxide and ammonium molybdate, zirconium compounds such as zirconium oxide and zirconium hydroxide, and zinc compounds such as zinc sulfide May be used.
- the content of (C) antimony trioxide is 2 to 8 parts by mass, preferably 3 to 8 parts by mass with respect to 100 parts by mass in total of (A) to (D) in the flame retardant masterbatch. Part. If content is less than 2 mass parts, when it is set as a styrene-type flame retardant resin composition, the effect which improves a flame-retardant effect is small. When the content exceeds 8 parts by mass, when a styrene-based flame retardant resin composition is used, the Charpy impact strength becomes inferior and the glowing behavior during combustion is increased, which is not preferable.
- (D) talc is used.
- the use of talc improves the heat resistance and rigidity of the styrene-based flame retardant resin composition, and as a flame retardant masterbatch, when the resin composition is produced by melting and mixing with a styrene resin, Of course, even a single screw extruder can easily obtain the desired styrene-based flame retardant resin composition.
- the content of (D) talc is 5 to 17 parts by mass, preferably 7 to 17 parts by mass with respect to a total of 100 parts by mass of (A) to (D) in the flame retardant masterbatch.
- (E) antioxidant is used for a flame retardant masterbatch.
- octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate ethylenebis (oxyethylene) bis [3- (5-t-butyl-4-hydroxy-m-tolyl) propionate
- a phenolic antioxidant such as pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] is used.
- the addition amount of the antioxidant is less than 0.5 parts by mass, when the styrene-based flame retardant resin composition is obtained using the flame retardant master batch of the present invention, the Charpy impact strength is hardly exhibited. Moreover, when it exceeds 2.0 mass parts, it will become easy to cause a heat resistant fall.
- the blending ratios of (A) to (D) are (A) 65 to 30 parts by mass of styrene resin, (B) 2,4,6-tris (2,4 , 6-tribromophenoxy) -1,3,5-triazine 25 to 50 parts by mass, (C) antimony trioxide 3 to 8 parts by mass, and (D) talc 7 to 17 parts by mass.
- colorants in order to obtain the flame retardant master batch of the present invention, colorants, heat stabilizers, ultraviolet absorbers, plasticizers, lubricants, antistatic agents, and the like can be further mixed as additives.
- (E) carbon black may be mixed as a pigment as necessary to form a flame retardant masterbatch. it can.
- the content of (E) carbon black in the styrene-based flame retardant resin composition is less than 0.5% by mass according to UL standards. Therefore, the (E) carbon black that can be added to the flame retardant masterbatch is preferably less than 1.7 parts by mass with respect to 100 parts by mass in total of the (A) to (D) in the flame retardant masterbatch, More preferably, it is 1.5 parts by mass or less.
- lubricant polyolefin waxes, higher fatty acid amides, higher carboxylic acid metal salts, and the like can be used as appropriate.
- the flame retardant master batch of the present invention For the production of the flame retardant master batch of the present invention, methods such as a Banbury mixer, a kneader, a single screw extruder, a twin screw extruder can be adopted.
- a flame retardant masterbatch in order to uniformly mix the flame retardant 2,4,6-tris (2,4,6-trisbromophenoxy) -1,3,5-triazine, Further, it is preferable to uniformly melt and mix using a feeder different from other raw materials.
- blending talc it is preferable to provide a dust collector for dust countermeasures of talc.
- the styrene resin used to obtain the styrene flame retardant resin composition is hereinafter referred to as styrene resin (II), and the flame retardant master batch detailed above is referred to as flame retardant master batch (I).
- the styrene resin (II) used to obtain the styrene flame retardant resin composition can be the same as (A) the styrene resin detailed in the flame retardant master batch (I), but the same composition. They do not have to be of the same type. Of course, they may be the same.
- a rubber-modified styrenic resin and / or an aromatic vinyl polymer is preferably used.
- the blending ratio of the flame retardant master batch (I) and the styrene resin (II) can be varied depending on the flame retardant class required for the obtained styrene flame retardant resin composition. Especially, it is preferable to mix
- the flame retardancy of the styrene-based flame retardant resin composition obtained by the production method of the present invention is the same as that of Subject No. 94 (hereinafter also abbreviated as UL-94) of US Underwriters Laboratories. In conformity evaluation, V-0 is preferable.
- flame retardant aids for additives generally used to obtain styrene-based flame retardant resin compositions
- it can be supplied as it is or added to the flame retardant master batch in advance.
- the total amount of the flame retardant master batch (I) and the styrene resin (II) Preferably, polytetrafluoroethylene (PTFE) is added in an amount of 0.4 parts by mass or less (excluding 0), more preferably 0.1 to 0.3 parts by mass with respect to 100 parts by mass. Is preferred. In this case, it is preferable that the flame retardant master batch (I), the styrene resin (II) and the polytetrafluoroethylene (PTFE) are premixed and then melted.
- PTFE polytetrafluoroethylene
- a flame retardant master batch deterioration of polytetrafluoroethylene (PTFE) is promoted when a styrene-based flame retardant resin composition is obtained.
- a Banbury mixer As a method of melt mixing used in the method for producing a styrene-based flame retardant resin composition of the present invention, a Banbury mixer, a kneader, a single screw extruder, a twin screw extruder, or the like can be adopted. It is preferable to use a melt extruder of a single screw extruder or a twin screw extruder.
- the cylinder temperature in melt extrusion can be performed at a temperature used when extruding a general styrene-based flame retardant resin composition, and is not particularly limited, but is preferably 200 to 250 ° C, and preferably 210 to 240 ° C. More preferred.
- a method of supplying the flame retardant master batch (I) and the styrene resin (II) of the present invention to a melt extruder a method of supplying a premixed mixture using a known apparatus such as a tumbler or V blender.
- a method of separately and quantitatively supplying both materials to the supply port of the extruder can be employed.
- the most versatile full flight screw can be used as the screw of the single screw extruder, a dalmage type, pin type, or Maddock type screw with higher kneading properties can also be used.
- the styrene resin (II) used to obtain the flame retardant master batch and the styrene resin (II) used to obtain the styrene flame retardant resin composition have the following characteristics: (A-1), (A-2) and / or (A-3) were used.
- composition of this rubber-modified styrenic resin is such that the reduced viscosity of the matrix portion is 0.75 dl / g, the content of the rubber-like polymer is 9.3% by mass, and the gel content of the rubber-like polymer is 27%.
- the rubber-like polymer has a volume average particle size of 2.53 ⁇ m, and the liquid paraffin content in the rubber-modified styrenic resin is 1.9% by mass.
- A-2) It is a rubber-modified styrenic resin using a shirosis polybutadiene rubber as a rubbery polymer.
- the composition of this rubber-modified styrenic resin has a reduced viscosity of 0.58 dl / g in the matrix portion, a rubber-like polymer content of 9.9% by mass, and a rubber-like polymer gel content of 30.
- the volume average particle size of the rubber-like polymer is 2.50 ⁇ m, and the content of liquid paraffin in the rubber-modified styrenic resin is 2.0% by mass.
- A-3) A styrene polymer (GP) having a reduced viscosity of 0.70 dl / g and a liquid paraffin content in the styrene resin of 2.5% by mass was used.
- styrene-butadiene copolymer (G) added to the rubber-modified styrene resin a styrene-butadiene-styrene block copolymer (trade name Toughprene 315P, manufactured by Asahi Kasei Chemicals Corporation) was used.
- the reduced viscosity, the gel content, the rubbery polymer content and the average particle size were measured by the following methods.
- the liquid paraffin content indicates the amount charged.
- Reduced viscosity ( ⁇ sp / C): A mixed solvent of 15 ml of methyl ethyl ketone and 15 ml of acetone was added to 1 g of rubber-modified styrenic resin and dissolved by shaking at a temperature of 25 ° C. for 2 hours. Subsequently, the insoluble matter was settled by centrifugation, the supernatant was taken out by decantation, 500 ml of methanol was added to precipitate the resin, and the insoluble matter was filtered and dried. The resin component obtained by the same operation was dissolved in toluene to prepare a sample solution having a polymer concentration of 0.4% (mass / volume).
- Rubbery polymer content The rubber-modified styrenic resin was dissolved in chloroform, a certain amount of iodine monochloride / carbon tetrachloride solution was added, and the mixture was left in the dark for about 1 hour. Subsequently, 15 mass / volume potassium iodide solution and 50 ml of pure water were added, excess iodine monochloride was titrated with 0.1N sodium thiosulfate / ethanol aqueous solution, and the amount of iodine monochloride added was calculated.
- (B) For the flame retardant, (B-1) 2,4,6-tris (2,4,6-tribromophenoxy) -1,3,5-triazine is a trade name of Daiichi Kogyo Seiyaku Co., Ltd. Pyroguard SR245 was used. As a comparative flame retardant, (B-2) trade name SAYTEX-8010 (hereinafter abbreviated as S8010) manufactured by Albemarle, which is ethylene bispentabromobenzene, was used.
- (F) As the carbon black a trade name RB962P manufactured by Koshigaya Kasei Co., Ltd. having a carbon black content of 40% by mass was used.
- PTFE polytetrafluoroethylene
- H a trade name PTFE31-JR manufactured by Mitsui / Dupont Fluorochemical Co., Ltd. was used. This is abbreviated as (H).
- the preliminary future product was fed into a twin screw extruder (Toshiki Machine Co., Ltd., TEM26SS) by separately feeding the pellet component and the powder component into strands, cooled with water, then led to a pelletizer and pelletized.
- the cylinder temperature was 200 ° C.
- the supply amount was 50 kg / hour.
- compositions of the flame retardant masterbatch used for the study in the present invention are shown in Table 1, Table 2, and Table 3 below.
- the flame retardant master batch (I), the styrene resin (II), and the (H) polytetrafluoroethylene (PTFE) obtained in the above are shown in Tables 4, 5, and 6 (parts by mass). All components were premixed in a tumbler. The preliminary mixture was supplied to a single screw extruder (PMS40-28 manufactured by IKG) and a twin screw extruder (TEM 26SS manufactured by Toshiba Machine Co., Ltd.) to form a strand, which was cooled with water and led to a pelletizer to be pelletized. At this time, the twin screw extruder was set to a cylinder temperature of 230 ° C. and a supply amount of 30 kg / hour.
- the single screw extruder was set to a cylinder temperature of 230 ° C. and a screw rotation speed of 100 rpm. Note that (H) polytetrafluoroethylene (PTFE) was added so that the pure amount of PTFE would be the blending amount.
- H polytetrafluoroethylene
- a styrene resin composition was obtained without using the flame retardant masterbatch (I) at a blending amount (part by mass) of the polymer and (H) polytetrafluoroethylene (PTFE) shown in Table 7. .
- Deflection temperature under load The deflection temperature under load was measured based on JIS K 7191. Measuring device: No. 148-HD-PC-3 (manufactured by Yasuda Seiki Co., Ltd.) Stress: 1.80 MPa Distance between fulcrums: 64mm Specimen size: Length 80mm Width 10mm Height 4mm Flatwise
- Melt flow rate (MFR) Melt flow rate (MFR) measured the obtained pellet based on JISK7210. Test temperature: 200 ° C Test load: 49.03N
- the test piece for evaluation of combustibility was formed as a 127 ⁇ 12.7 ⁇ 1.5 mm test piece for combustion using an injection molding machine (manufactured by Nippon Steel Works, J100E-P). At this time, the cylinder temperature was 190 ° C. and the mold temperature was 30 ° C.
- Table 4 shows the melt mixing method of the styrene-based flame retardant resin composition using the flame retardant masterbatch and the physical property values thereof.
- Table 7 shows the evaluation results of the styrene-based flame-retardant resin composition extruded with a single screw extruder without using a flame-retardant masterbatch.
- the styrene-based flame retardant resin composition obtained by the production method of the present invention is flame retardant, impact strength, heat resistance, It can be seen that the fluidity balance is good and the appearance is also good.
- the styrene-based flame retardant resin composition obtained in the comparative example that does not satisfy the requirements of the present invention is excellent in any of flame retardancy, impact strength, heat resistance, and fluidity, but all of them. It is clear that there is nothing better than
- Styrenic flame retardant resin compositions obtained using the flame retardant masterbatch have a good balance of flame retardancy, impact strength, heat resistance, and fluidity as shown in the examples of Tables 4 and 5, and further the appearance. Is also good.
- the flame retardant master batch of the present invention can be used for the production of a styrene-based flame retardant resin composition.
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Abstract
Description
このように、多岐の分野に使用されるので、UL難燃規格の難燃性レベルでも5V,V-0、V-1、V-2、HBのいずれが要求されるのか、加えて耐熱性、流動性、耐衝撃性等の全て物性が一定の水準以上を満たさなければならないのか、あるいはこれらの特性の中で難燃性に加えて特に耐熱性が必要なのか、さらに耐衝撃性が必要になるのか、など用途によって多様な特性が必要とされる。
これらの難燃剤がスチレン系樹脂に使用されている例は、特許文献1、特許文献2、特許文献3、特許文献4などが挙げられる。
すなわち、それぞれ多岐に渡るスチレン系難燃樹脂組成物を別フィード・集塵機付きの二軸押出機を大小多数備えることなく、難燃剤の分散性が良好で、所望の難燃特性を有し、しかも、機械物性など、ポリスチレン系樹脂本来の特性が実質上低下せず、耐熱性、流動性等などのそれぞれの目的にあったスチレン系難燃性樹脂組成物を特に単軸押出機でも提供することにある。
1.(A)スチレン系樹脂75乃至25質量部、(B)2,4,6-トリス(2,4,6-トリブロモフェノキシ)-1,3,5-トリアジン15乃至50質量部、(C)三酸化アンチモン2乃至8質量部、及び(D)タルク5乃至17質量部を含有し、
かつ、(A)乃至(D)の合計100質量部に対し、更に(E)酸化防止剤0.5乃至2.0質量部を含有することを特徴とする難燃剤マスターバッチ。
2.前記(A)乃至(D)の合計100質量部に対し、更に、(F)カーボンブラック1.67質量部未満(但し0は含まず。)を含有する前記1に記載の難燃剤マスターバッチ。
3.(A)スチレン系樹脂65乃至30質量部、(B)2,4,6-トリス(2,4,6-トリブロモフェノキシ)-1,3,5-トリアジン25乃至50質量部、(C)三酸化アンチモン3乃至8質量部、及び(D)タルク7乃至17質量部である前記1又は2に記載の難燃剤マスターバッチ。
4.(A)スチレン系樹脂が、スチレン-ブタジエンブロック共重合体及び/又はランダム共重合体を含有したゴム変性スチレン系樹脂である前記1乃至3のいずれかに記載の難燃剤マスターバッチ。
5.(E)酸化防止剤が、オクタデシル-3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオネートである前記1乃至4のいずれかに記載の難燃剤マスターバッチ。
6.前記1乃至前記5のいずれかに記載の難燃剤マスターバッチ(I)30乃至85質量部と、スチレン系樹脂(II)70乃至15質量部と、を溶融混合するスチレン系難燃性樹脂組成物の製造方法。
7.前記1乃至前記5のいずれかに記載の難燃剤マスターバッチ(I)30乃至60質量部と、スチレン系樹脂(II)70乃至40質量部と、を溶融混合するスチレン系難燃性樹脂組成物の製造方法。
9.単軸押出機で溶融混合する前記6乃至8のいずれかに記載のスチレン系難燃性樹脂組成物の製造方法。
10.二軸押出機で溶融混合する前記6乃至8のいずれかに記載のスチレン系難燃性樹脂組成物の製造方法。
11.前記スチレン系難燃性樹脂組成物のUL―94に基づく難燃性の評価がV-0である前記6乃至10のいずれかに記載のスチレン系難燃性樹脂組成物の製造方法。
すなわち、得られたスチレン系難燃性樹脂組成物は、難燃性、衝撃強度、耐熱性、流動性等の物性バランスに優れ、溶融混合に単軸押出機を使用して得た組成物でも容易に目的の成形品が得られ、成形品の外観も良好である。
更には、芳香族ビニル単量体と不活性溶媒の混合液にゴム状重合体を溶解して得られた重合体に、別途得られた芳香族ビニル重合体を混合した混合物であってもよい。
難燃剤マスターバッチにおける前記(A)乃至(D)の合計100質量部に対し、該(B)難燃剤の含有量は、難燃剤マスターバッチとしての機能性、経済性の観点から、15乃至50質量部が好ましく、さらに好ましくは25乃至50質量部である。含有量が15質量部未満であれば難燃性能が劣り、難燃剤マスターバッチの添加量を増やさなければスチレン系難燃性樹脂組成物の難燃性が劣ることになり、難燃剤マスターバッチとしての経済効果が低い。含有量が50質量部を超えると難燃剤が多くなり、スチレン系難燃性樹脂組成物とした場合、シャルピー衝撃強度、及び熱変形温度が劣るようになる。また、樹脂成分が少なくなり、難燃剤マスターバッチとしてスチレン系樹脂と溶融混合してスチレン系難燃性樹脂組成物を製造する際に、難燃剤の分散不良を発生しやすく好ましくない。
本発明で、難燃剤マスターバッチにおける前記(A)乃至(D)の合計100質量部に対し、(C)三酸化アンチモンの含有量は、2乃至8質量部であり、好ましくは3乃至8質量部である。含有量が2質量部未満であれば、スチレン系難燃性樹脂組成物とした場合、難燃効果を高める効果が小さい。含有量が8質量部を超えると、スチレン系難燃性樹脂組成物とした場合、シャルピー衝撃強度も劣るようになり、燃焼時のグローイング挙動を高めるので好ましくない。
難燃剤マスターバッチにおける前記(A)乃至(D)の合計100質量部に対し、(D)タルクの含有量は、5乃至17質量部であり、好ましくは7乃至17質量部である。含有量が5質量部未満であれば、得られたスチレン系難燃性樹脂組成物の耐熱性及び剛性を低下させるので難燃剤マスターバッチとしての効果が低い。含有量が17質量部を超えると、スチレン系難燃性樹脂組成物のシャルピー衝撃強度、耐熱性を低下させるので好ましくない。
例えばオクタデシル-3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオネート、エチレンビス(オキシエチレン)ビス[3-(5-t-ブチル-4-ヒドロキシ-m-トリル)プロピオネート、ペンタエリスリトールテトラキス[3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオネート]等のフェノール系酸化防止剤が使用される。また、2,2-メチレンビス(4,6-ジ-t-ブチルフェニル)オクチルホスファイト、ビス(2,6-ジ-t-ブチル-4-メチルフェニル)ペンタエリスリトールジホスファイト等のリン系酸化防止剤と併用してもよい。なかでも、オクタデシル-3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオネートを使用することが好ましい。
難燃剤マスターバッチにおける前記(A)乃至(D)の合計100質量部に対し、これらの酸化防止剤の添加量は0.5乃至2.0質量部であり、1.0乃至2.0質量部であることが好ましい。酸化防止剤の添加量が0.5質量部未満であると本発明の難燃剤マスターバッチを使用してスチレン系難燃性樹脂組成物を得た場合、シャルピー衝撃強度が発現し難くなる。また2.0質量部を超えると、耐熱性の低下を招き易くなる。
本発明の難燃性マスターバッチにおいて、前記(A)乃至(D)の配合割合としては、(A)スチレン系樹脂65乃至30質量部、(B)2,4,6-トリス(2,4,6-トリブロモフェノキシ)-1,3,5-トリアジン25乃至50質量部、(C)三酸化アンチモン3乃至8質量部、及び
(D)タルク7乃至17質量部であるのが好ましい。
なお、スチレン系難燃性樹脂組成物を得るのに使用するスチレン系樹脂をスチレン系樹脂(II)、また、これまで詳述した難燃剤マスターバッチを難燃剤マスターバッチ(I)と以下称する。
スチレン系難燃性樹脂組成物を得るのに使用するスチレン系樹脂(II)は、難燃剤マスターバッチ(I)で詳述した(A)スチレン系樹脂と同様のものが使用出来るが、同一組成、同一種類のものである必要はない。勿論同一のものであっても良い。ゴム変性スチレン系樹脂及び/又は芳香族ビニル重合体が好ましく使用される。
本発明の製造方法で得られるスチレン系難燃性樹脂組成物の難燃性は、米国アンダーライターズ・ラボラトリーズ社のサブジェクト94号(以下、UL-94とも略記する。)の垂直燃焼試験方法に準拠する評価において、V-0であるのが好ましい。
(A-1):
ゴム状重合体にシス1、4結合を90モル%以上の比率で含有するハイシスポリブタジエンゴムを使用したゴム変性スチレン系樹脂である。このゴム変性スチレン系樹脂の組成は、マトリックス部分の還元粘度が0.75dl/gであり、ゴム状重合体の含有量が9.3質量%であり、ゴム状重合体のゲル含有量が27.0質量%であり、及びゴム状重合体の体積平均粒子径が2.53μmであり、更にゴム変性スチレン系樹脂中の流動パラフィン含有量が1.9質量%である。
(A-2):
ゴム状重合体にシローシスポリブタジエンゴムを使用したゴム変性スチレン系樹脂である。このゴム変性スチレン系樹脂の組成はマトリックス部分の還元粘度が0.58dl/gであり、並びにゴム状重合体の含有量が9.9質量%であり、ゴム状重合体のゲル含有量が30.5質量%であり、及びゴム状重合体の体積平均粒子径が2.50μmであり、更にゴム変性スチレン系樹脂中の流動パラフィン含有量が2.0質量%である。
(A-3):
還元粘度が0.70dl/gであり、スチレン系樹脂中の流動パラフィン含有量が2.5質量%であるスチレン重合体(GP)を使用した。
また、ゴム変性スチレン系樹脂に添加したスチレン-ブタジエン共重合体(G)には、スチレン-ブタジエン-スチレンブロック共重合体(旭化成ケミカルズ社製、商品名タフプレン315P)を使用した。
ゴム変性スチレン系樹脂1gにメチルエチルケトン15mlとアセトン15mlの混合溶媒を加え、温度25℃で2時間振とう溶解した。次いで、遠心分離で不溶分を沈降させ、デカンテーションにより上澄み液を取り出し、500mlのメタノールを加えて樹脂分を析出させ、不溶分を濾過乾燥した。同操作で得られた樹脂分をトルエンに溶解してポリマー濃度が0.4%(質量/体積)の試料溶液を調製した。この試料溶液、及び純トルエンを温度30℃の恒温でウベローデ型粘度計により溶液流下秒数を測定して、下式にて算出した。
ηsp/C=(t1/t0-1)/C
t0:純トルエン流下秒数
t1:試料溶液流下秒数
C:ポリマー濃度
1gのゴム変性スチレン系樹脂組成物をメチルエチルケトン15mlとアセトン15mlの混合溶媒に加え、温度25℃で2時間振とう溶解した。次いで、遠心分離して不溶分を沈降させ、デカンテーションにより上澄み液を除去して不溶分を得、温度70℃で15時間程度真空乾燥し、20分間デシケーター中で冷却した後、乾燥した不溶分の質量G(g)を測定して次の式でより求めた。
ゴム状重合体のゲル含有量(質量%)=(G/1)×100
ゴム変性スチレン系樹脂をクロロホルムに溶解させ、一定量の一塩化ヨウ素/四塩化炭素溶液を加え暗所に約1時間放置した。次いで、15質量/体積のヨウ化カリウム溶液と純水50mlを加え、過剰の一塩化ヨウ素を0.1Nチオ硫酸ナトリウム/エタノール水溶液で滴定し、付加した一塩化ヨウ素量から算出した。
二軸押出機(東芝機械社製、TEM26SS)を使用した場合は、形状がペレット状と粉体状の物を分けて、それぞれの形状成分をヘンシェルミキサー(三井三池化工社製、FM20B)にて予備混合し、別フィード供給してストランドとし、水冷してからペレタイザーへ導きペレット化した。この際、シリンダー温度230℃、供給量30kg/時間とした。
単軸押出機(IKG社製 PMS40-28)を使用した場合は、全成分をタンブラーにて予備混合し、ストランドとし、水冷してからペレタイザーへ導きペレット化した。この際、シリンダー温度230℃、スクリュー回転数100rpmとした。なお、(H)ポリテトラフルオロエチレン(PTFE)はPTFE純量が配合量となるように添加した。
難燃性の測定は、米国アンダーライターズ・ラボラトリーズ社のサブジェクト94号の垂直燃焼試験方法に準拠し、試験片厚さ1.5mmの燃焼性を評価した。評価結果は下記の様に表記した。
NG:V-0でない燃焼性(V-1、V-2、又はHB)を示すもの。
シャルピー衝撃強度は、JIS K 7111-1に基づき測定を行った。
測定装置:シャルピー試験機(東洋精機社製)
ノッチタイプ:タイプA
打撃方向:エッジワイズ
測定環境:23℃
荷重たわみ温度は、JIS K 7191に基づき測定を行った。
測定装置:No.148-HD-PC-3(安田精機社製)
応力:1.80MPa
支点間距離:64mm
試験片サイズ:長さ80mm 幅10mm 高さ4mm フラットワイズ
メルトフローレート(MFR)は、得られたペレットをJIS K 7210に基づき測定を行った。
試験温度:200℃
試験荷重:49.03N
射出成形機(日本製鋼所社製、J100E-P)にて90mm角板(厚み2mm)に成形し、成形品の表面に成形不良(ブツ・フラッシュ等)の有無を観察して外観を評価した。この際、シリンダー温度230℃、金型温度30℃とした。
○:成形品表面の不良(ブツ・フラッシュ)が見られないもの。
×:成形品表面の不良(ブツ・フラッシュ)が見られたもの。
シャルピー衝撃強度用試験片、及び荷重たわみ温度試験片として、射出成形機(日本製鋼所社製、J100E-P)にて、JIS K 7139に記載のA型試験片(ダンベル)を作製した。成形条件はJIS K 6926-2に準拠して行った。シャルピー衝撃強度用試験片は、該ダンベル片の中央部より切り出し、切削でノッチ(タイプA、r=0.25mm)を入れ、試験に用いた。また、荷重たわみ温度試験片は、該ダンベル片の中央部より切り出し、試験に用いた。
しかし、本発明の要件を満足しない比較例で得られたスチレン系難燃性樹脂組成物は、難燃性、衝撃強度、耐熱性、流動性の何れかに優れることはあっても、その全てに優れていることはないことがわかる。
Claims (11)
- (A)スチレン系樹脂75乃至25質量部、
(B)2,4,6-トリス(2,4,6-トリブロモフェノキシ)-1,3,5-トリアジン15乃至50質量部、
(C)三酸化アンチモン2乃至8質量部、及び
(D)タルク5乃至17質量部を含有し、
かつ、(A)乃至(D)の合計100質量部に対し、更に
(E)酸化防止剤0.5乃至2.0質量部を含有することを特徴とする難燃剤マスターバッチ。 - 前記(A)乃至(D)の合計100質量部に対し、更に、(F)カーボンブラック1.7質量部未満(但し0は含まず。)を含有する請求項1に記載の難燃剤マスターバッチ。
- (A)スチレン系樹脂65乃至30質量部、
(B)2,4,6-トリス(2,4,6-トリブロモフェノキシ)-1,3,5-トリアジン25乃至50質量部、
(C)三酸化アンチモン3乃至8質量部、及び
(D)タルク7乃至17質量部である請求項1又は2に記載の難燃剤マスターバッチ。 - (A)スチレン系樹脂が、スチレン-ブタジエンブロック共重合体及び/又はランダム共重合体を含有したゴム変性スチレン系樹脂である請求項1乃至3のいずれか1項に記載の難燃剤マスターバッチ。
- (E)酸化防止剤が、オクタデシル-3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオネートである請求項1乃至4のいずれか1項に記載の難燃剤マスターバッチ。
- 請求項1乃至5のいずれか1項に記載の難燃剤マスターバッチ(I)30乃至85質量部と、スチレン系樹脂(II)70乃至15質量部とを、溶融混合するスチレン系難燃性樹脂組成物の製造方法。
- 請求項1乃至5のいずれか1項に記載の難燃剤マスターバッチ(I)30乃至60質量部と、スチレン系樹脂(II)70乃至40質量部とを溶融混合するスチレン系難燃性樹脂組成物の製造方法。
- 難燃剤マスターバッチ(I)とスチレン系樹脂(II)の合計量100質量部に対して、更にポリテトラフルオロエチレン(PTFE)を0.4質量部以下(但し0は含まず。)を添加して溶融混合する請求項6又は7に記載のスチレン系難燃性樹脂組成物の製造方法。
- 単軸押出機で溶融混合する請求項6乃至8のいずれか1項に記載のスチレン系難燃性樹脂組成物の製造方法。
- 二軸押出機で溶融混合する請求項6乃至8のいずれか1項に記載のスチレン系難燃性樹脂組成物の製造方法。
- 前記スチレン系難燃性樹脂組成物のUL―94に基づく難燃性の評価がV-0である請求項6乃至10のいずれか1項に記載のスチレン系難燃性樹脂組成物の製造方法。
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JP2015187226A (ja) * | 2014-03-27 | 2015-10-29 | 東洋スチレン株式会社 | スチレン系難燃性樹脂組成物及びこれを用いてなる成形体 |
EP3260492A4 (en) * | 2015-02-17 | 2018-10-24 | Adeka Corporation | Method for producing resin additive composition and resin additive composition |
US10253176B2 (en) | 2015-02-17 | 2019-04-09 | Adeka Corporation | Method for producing resin additive composition and resin additive composition |
CN114716715A (zh) * | 2022-04-06 | 2022-07-08 | 江阴市宏丰塑业有限公司 | 一种轻质耐磨的pbt复合材料及其制备方法 |
CN114716715B (zh) * | 2022-04-06 | 2023-09-22 | 江苏普非尔塑料科技有限公司 | 一种轻质耐磨的pbt复合材料及其制备方法 |
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JPWO2013057841A1 (ja) | 2015-04-02 |
CN103890083A (zh) | 2014-06-25 |
CN103890083B (zh) | 2016-03-16 |
JP5872577B2 (ja) | 2016-03-01 |
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