TWI448543B - A flame retardant resin composition and a molded article derived - Google Patents
A flame retardant resin composition and a molded article derived Download PDFInfo
- Publication number
- TWI448543B TWI448543B TW098143102A TW98143102A TWI448543B TW I448543 B TWI448543 B TW I448543B TW 098143102 A TW098143102 A TW 098143102A TW 98143102 A TW98143102 A TW 98143102A TW I448543 B TWI448543 B TW I448543B
- Authority
- TW
- Taiwan
- Prior art keywords
- group
- component
- substituent
- independently
- resin composition
- Prior art date
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
本發明係關於一種使用具有高度難燃性及良好物性之採用源自植物原料之難燃性樹脂組成物及由其而來之成形品。更加詳細的說是關於一種含有規定的有機磷化合物而且實質無鹵素的難燃性樹脂組成物及由其而來之成形品。The present invention relates to a flame retardant resin composition derived from a plant material which is highly flame retardant and has good physical properties, and a molded article therefrom. More specifically, it relates to a flame retardant resin composition containing a predetermined organic phosphorus compound and substantially halogen-free, and a molded article therefrom.
用以獲得樹脂製的成形品之原料,一般使用聚丙烯(PP)、丙烯腈-丁二烯-苯乙烯(ABS)、聚醯胺(PA6、PA66)、聚酯(PET、PBT)、聚碳酸酯(PC)等樹脂。然而,該等樹脂是使用由石油資源獲得的原料製造而成,近年來,石油資源的枯竭或地球環境等問題一直被擔心,使用由植物等生物起源物質製得的原料之樹脂的製造受到要求。尤其在考量地球環境問題時,推斷使用源自植物原料的樹脂,即便在使用後被燒掉若考慮植物生育時吸收之二氧化碳的量,從碳收支中立之所謂碳中和的想法出發,亦是對地球環境的負荷低之樹脂。In order to obtain a raw material of a resin molded article, polypropylene (PP), acrylonitrile-butadiene-styrene (ABS), polyamine (PA6, PA66), polyester (PET, PBT), and poly are generally used. A resin such as carbonate (PC). However, these resins are manufactured using raw materials obtained from petroleum resources. In recent years, problems such as depletion of petroleum resources or the global environment have been a concern, and the production of resins using raw materials derived from biologically derived substances such as plants is required. . In particular, when considering the global environmental problem, it is inferred that the resin derived from plant material is used, even if it is burned after use, considering the amount of carbon dioxide absorbed by the plant when it is born, the idea of carbon neutrality neutral from the carbon balance is also It is a resin with a low load on the global environment.
另一方面,使用該等源自植物原料之樹脂利用到工業材料,尤其是電力/電子相關用部件、OA相關用部件或汽車部件時,從安全上的問題出發必須賦予難燃性。On the other hand, when these resins derived from plant materials are used for industrial materials, particularly electric power/electronic related components, OA related components, or automobile parts, it is necessary to impart flame retardancy from the viewpoint of safety.
目前,使用源自植物原料的樹脂,尤其是關於聚乳酸樹脂的難燃化做了種種嘗試,已經達到某種程度的難燃化。然而,該等難燃化處方係使用大量的難燃劑者,損害了樹脂本來的物性。At present, various attempts have been made to use a resin derived from a plant material, particularly a flame retardancy of a polylactic acid resin, and a certain degree of flame retardancy has been achieved. However, these incombustible prescriptions use a large amount of flame retardant, which impairs the physical properties of the resin.
另一方面,採用源自植物原料之樹脂,除聚乳酸樹脂以外,使用可以從能夠由糖質製造的醚二醇殘基製得的原料之聚碳酸酯樹脂受到研究。On the other hand, a polycarbonate resin derived from a plant material as a raw material which can be obtained from an ether diol residue which can be produced from a saccharide is used in addition to a polylactic acid resin.
例如,下述式(a)For example, the following formula (a)
所示之醚二醇,容易由例如糖類及澱粉等製作,已知3種立體異構體。The ether diol shown is easily produced from, for example, saccharides and starch, and three kinds of stereoisomers are known.
立體異構體列舉下述式(b)所示之,1,4:3,6-二脫水-D-山梨醇(本說明書中以下稱為「異山梨醇」)。The stereoisomers include 1,4:3,6-dianhydro-D-sorbitol (hereinafter referred to as "isosorbide" in the present specification) represented by the following formula (b).
另外列舉下述式(c)所示之,1,4:3,6-二脫水-D-甘露醇(本說明書中以下稱為「異甘露醇」)。Further, 1,4:3,6-dianhydro-D-mannitol (hereinafter referred to as "isomannitol" in the present specification) represented by the following formula (c) is exemplified.
另外列舉下述式(d)所示之,1,4:3,6-二脫水-L-艾杜醇(本說明書中以下稱為「異艾杜醇」)。Further, 1,4:3,6-dianhydro-L-idumitol (hereinafter referred to as "isoindole" in the present specification) represented by the following formula (d) is exemplified.
異山梨醇、異甘露醇、異艾杜醇分別由D-葡萄糖、D-甘露糖、L-艾杜糖製得。例如異山梨醇的情形,可透過將D-葡萄糖加以氫化後,使用酸觸媒經脫水製得。Isosorbide, isomannide, and isoidide are prepared from D-glucose, D-mannose, and L-idulose, respectively. For example, in the case of isosorbide, D-glucose can be hydrogenated and then dehydrated using an acid catalyst.
到此為止上述的醚二醇中,特別研究了在中心使用寡聚物之異山梨醇並將其組合到聚碳酸酯中。其中,尤其就異山梨醇之均聚碳酸酯(homo-polycarbonate)於專利文獻1、2中做了記載。Among the above-mentioned ether diols, it has been particularly studied to use an isosorbide of an oligomer at a center and to combine it into a polycarbonate. Among them, in particular, homo-polycarbonate of isosorbide is described in Patent Documents 1 and 2.
其中在專利文獻1中,報告了使用熔融酯交換法之具有203℃熔點之均聚碳酸酯樹脂。然而該聚合物僅具有不充足的機械性質。Among them, Patent Document 1 discloses a homopolycarbonate resin having a melting point of 203 ° C using a melt transesterification method. However, the polymer has only insufficient mechanical properties.
作為耐熱性高的例子,專利文獻2中報告有由升溫速度為10℃/分鐘的示差熱量測定之玻璃轉移溫度在170℃以上的聚碳酸酯,惟有作為對比粘度高的成形材料考量時熔融粘度過高之問題。As an example of high heat resistance, Patent Document 2 reports a polycarbonate having a glass transition temperature of 170 ° C or higher measured by a differential calorific value of a heating rate of 10 ° C /min, and is considered as a melt viscosity when considering a molding material having a high contrast viscosity. Too high a problem.
另一方面,專利文獻3中,就異山梨醇與直鏈脂肪族二醇的共聚合聚碳酸酯進行了記載。On the other hand, in Patent Document 3, a copolymerized polycarbonate of isosorbide and a linear aliphatic diol is described.
關於這些由異山梨醇形成之聚碳酸酯,其等之每一篇文獻都未就難燃性做任何研究。Regarding these polycarbonates formed from isosorbide, each of the literatures does not do any research on flame retardancy.
(專利文獻1)英國專利申請公開第1079686號說明書(Patent Document 1) British Patent Application Publication No. 1079686
(專利文獻2)國際公開第2007/013463號公報(Patent Document 2) International Publication No. 2007/013463
(專利文獻3)國際公開第2004/111106號公報(Patent Document 3) International Publication No. 2004/111106
本發明的第1目的是,提供一種採用具有高度難燃性及良好物性之源自植物原料的難燃性樹脂組成物及由其而來之成形品。A first object of the present invention is to provide a flame retardant resin composition derived from a plant material having high flame retardancy and good physical properties, and a molded article therefrom.
本發明的第2目的是,提供一種含有規定的有機磷化合物而且實質無鹵素的難燃性樹脂組成物及由其而來之成形品。A second object of the present invention is to provide a flame retardant resin composition containing a predetermined organic phosphorus compound and substantially halogen-free, and a molded article therefrom.
根據本發明人等的研究,本發明之目的是,利用含有100重量分之至少含有50質量%的包含以下述式(A-1)表示的單元之聚碳酸酯(A-1成分)之樹脂成分(A成分)及含有1~100重量分之以下述式(1)表示的有機磷化合物(B)成分之難燃性樹脂組成物來達成。According to the study of the present inventors, the object of the present invention is to use a resin containing at least 50% by mass of a polycarbonate (A-1 component) containing at least 50% by mass of a unit represented by the following formula (A-1). The component (component A) and the flame retardant resin composition containing the organophosphorus compound (B) component represented by the following formula (1) in an amount of from 1 to 100 parts by weight are obtained.
(式中,X1 、X2 各自獨立,係以下述式(2)表示的芳香族取代烷基)(wherein, X 1 and X 2 are each independently and are an aromatic substituted alkyl group represented by the following formula (2))
(式中,AL為碳數1~5的分枝狀或直鏈狀脂肪族烴基。Ar為苯基、萘基或蒽基,其等亦可具有取代基。Ar可以鍵結到AL中的任意碳原子上。n為1~3的整數。)(In the formula, AL is a branched or linear aliphatic hydrocarbon group having 1 to 5 carbon atoms. Ar is a phenyl group, a naphthyl group or an anthracenyl group, and the like may have a substituent. Ar may be bonded to the AL. On any carbon atom, n is an integer from 1 to 3.)
若依據本發明,不會損害樹脂本來的特性,獲得達成高難燃性的採用源自植物原料之難燃性樹脂組成物。According to the present invention, a flame retardant resin composition derived from a plant material can be obtained without impairing the original properties of the resin and achieving high flame retardancy.
以下就本發明之難燃性樹脂組成物做更加詳細地說明。Hereinafter, the flame retardant resin composition of the present invention will be described in more detail.
(樹脂成分:A成分)(resin component: component A)
本發明中之樹脂成分,主要含有聚碳酸酯(A-1成分)。樹脂成分中聚碳酸酯(A-1成分)的含量,合宜的是至少50重量%,較佳為至少60重量%,更佳為至少70重量%,最佳為至少80重量%,特別好的是至少90重量%。The resin component in the present invention mainly contains polycarbonate (component A-1). The content of the polycarbonate (component A-1) in the resin component is desirably at least 50% by weight, preferably at least 60% by weight, more preferably at least 70% by weight, most preferably at least 80% by weight, particularly preferably It is at least 90% by weight.
樹脂成分(A成分)中亦可含有其他樹脂(A-2成分)。其他樹脂(A-2成分)的含量,合宜的是50重量%以下,較佳為40重量%以下,更佳為30重量%以下,最佳為20重量%以下,特別好的是10重量%以下。後面就其他樹脂(A-2成分)做詳細的說明。Other resin (component A-2) may be contained in the resin component (component A). The content of the other resin (component A-2) is preferably 50% by weight or less, preferably 40% by weight or less, more preferably 30% by weight or less, most preferably 20% by weight or less, particularly preferably 10% by weight or less. the following. The other resin (component A-2) will be described in detail later.
(聚碳酸酯:A-1成分)(Polycarbonate: component A-1)
本發明中之聚碳酸酯(A-1成分),包含以下述式(A-1)表示之碳酸酯單元。全碳酸酯單元中,以下述式(A-1)表示之單元的比例,以50莫耳%以上為佳,60莫耳%以上較佳,70莫耳%以上更佳,80莫耳%以上特別適合,90莫耳%以上是最好的。The polycarbonate (component A-1) in the present invention contains a carbonate unit represented by the following formula (A-1). In the percarbonate unit, the ratio of the unit represented by the following formula (A-1) is preferably 50 mol% or more, more preferably 60 mol% or more, more preferably 70 mol% or more, and more preferably 80 mol% or more. Particularly suitable, 90% or more is the best.
聚碳酸酯(A-1成分),準據ASTM D6866 05測定之生物起源物質含有率,合宜的是25%以上,較佳為50%以上,更佳為70%以上。在本發明的性質方面,生物起源物質含有率越高越好,低於25%時難謂是生物量材料。The polycarbonate (component A-1) is preferably contained in an amount of 25% or more, preferably 50% or more, more preferably 70% or more, as measured according to ASTM D6866 05. In terms of the nature of the present invention, the higher the content of the biologically derived substance, the better, and when it is less than 25%, it is difficult to refer to the biomass material.
在二氯甲烷100ml中溶解聚碳酸酯(A-1成分)0.7g之溶液的20℃比粘度之下限,以0.14以上為佳,較佳為0.20以上,更佳為0.22以上。另外上限以0.45以下為佳,較佳為0.37以下,更佳為0.34以下。比粘度若低於0.14則很難使由本發明之樹脂組成物製得的成形品具有充足的機械強度。另外比粘度若高於0.45則熔融流動性過高,具有成形時必要的流動性之熔融溫度會高於分解溫度。The lower limit of the specific viscosity at 20 ° C of the solution of 0.7 g of the polycarbonate (component A-1) in 100 ml of dichloromethane is preferably 0.14 or more, more preferably 0.20 or more, still more preferably 0.22 or more. Further, the upper limit is preferably 0.45 or less, preferably 0.37 or less, more preferably 0.34 or less. When the specific viscosity is less than 0.14, it is difficult to impart sufficient mechanical strength to the molded article obtained from the resin composition of the present invention. Further, if the specific viscosity is higher than 0.45, the melt fluidity is too high, and the melting temperature which is required for fluidity at the time of molding is higher than the decomposition temperature.
另外,聚碳酸酯(A-1成分),250℃下以毛細管流變儀測定之熔融粘度,在剪切速率為600sec-1 的條件下以0.08×103 ~2.4×103 Pa‧s的範圍為佳,0.1×103 ~2.0×103 Pa‧s的範圍較佳,0.1×103 ~1.5×103 Pa‧s的範圍更佳。熔融粘度若在該範圍內則機械強度優良,使用本發明之樹脂組成物進行成形時沒有成形時之銀的生成等是良好的。Further, the polycarbonate (component A-1) has a melt viscosity measured by a capillary rheometer at 250 ° C, and is 0.08 × 10 3 to 2.4 × 10 3 Pa ‧ at a shear rate of 600 sec -1 . The range is preferably from 0.1 × 10 3 to 2.0 × 10 3 Pa s, and the range of from 0.1 × 10 3 to 1.5 × 10 3 Pa s is more preferable. When the melt viscosity is within this range, the mechanical strength is excellent, and the formation of silver at the time of molding without using the resin composition of the present invention is good.
聚碳酸酯(A-1成分),其玻璃轉移溫度(Tg)的下限以100℃以上為佳,較佳為120℃以上,另外上限以165℃以下為佳。Tg若不足100℃則耐熱性(尤其是由吸濕產生之耐熱性)差,若超過165℃則使用本發明之樹脂組成物進行成形時的熔融流動性差。Tg藉TA Instruments公司製DSC(型號DSC2910)來進行測定。In the polycarbonate (component A-1), the lower limit of the glass transition temperature (Tg) is preferably 100 ° C or higher, preferably 120 ° C or higher, and the upper limit is preferably 165 ° C or lower. When Tg is less than 100 ° C, heat resistance (especially heat resistance due to moisture absorption) is inferior, and when it exceeds 165 ° C, melt flowability at the time of molding using the resin composition of the present invention is inferior. Tg was measured by DSC (Model DSC2910) manufactured by TA Instruments.
另外,聚碳酸酯(A-1成分),其5%重量減少溫度的下限以300℃以上為佳,較佳為320℃以上,另外上限以400℃以下為佳,較佳為390℃以下,更佳為380℃以下。5%重量減少溫度若在上述範圍內,則使用本發明之樹脂組成物進行成形時幾乎沒有樹脂的分解,是適合的。5%重量減少溫度藉TA Instruments公司製TGA(型號TGA2950)進行測定。Further, the lower limit of the 5% weight loss temperature of the polycarbonate (component A-1) is preferably 300 ° C or higher, more preferably 320 ° C or higher, and the upper limit is preferably 400 ° C or lower, preferably 390 ° C or lower. More preferably, it is 380 ° C or less. When the 5% weight loss temperature is within the above range, it is suitable that almost no decomposition of the resin is carried out by molding using the resin composition of the present invention. The 5% weight reduction temperature was measured by TGA (model TGA2950) manufactured by TA Instruments.
聚碳酸酯(A-1成分),玻璃轉移溫度(Tg)以100℃~165℃,而且5%重量減少溫度(Td)以300℃~400℃為佳。The polycarbonate (component A-1) preferably has a glass transition temperature (Tg) of from 100 ° C to 165 ° C and a 5% weight loss temperature (Td) of from 300 ° C to 400 ° C.
聚碳酸酯(A-1成分),可以由以下述式(a)Polycarbonate (component A-1), which can be obtained by the following formula (a)
表示之醚二醇及碳酸二酯藉熔融聚合法加以製造。醚二醇具體例舉,以下述式(b)、(c)及(d)表示之異山梨醇、異甘露醇、異艾杜醇等。The ether diol and the carbonic acid diester shown are produced by a melt polymerization method. Specific examples of the ether diol include isosorbide, isomannide, and isoidide represented by the following formulas (b), (c), and (d).
這些源自糖質的醚二醇,亦是由自然界的生物量製得之物質,是一種被稱為可再生資源者。異山梨醇,在將由澱粉製得之D-葡萄糖加以氫化後,使其脫水藉而製得。其他的醚二醇,除起始物質以外亦是藉同樣的反應製得。These saccharide-derived ether diols are also made from natural biomass and are known as renewable resources. Isosorbide is obtained by hydrogenating D-glucose prepared from starch and then dehydrating it. Other ether diols are obtained by the same reaction in addition to the starting materials.
尤其,碳酸酯單元以由包含源自異山梨醇(1,4:3,6-二脫水-D-山梨醇)的單元形成之聚碳酸酯為佳。異山梨醇是可以由澱粉等簡單製作出之醚二醇,作為資源可以豐富的獲得,此外與異甘露醇或異艾杜醇比較,製造的容易性、性質、用途的廣度亦全部優異。In particular, the carbonate unit is preferably a polycarbonate formed of a unit derived from isosorbide (1,4:3,6-dianhydro-D-sorbitol). Isosorbide is an ether diol which can be easily produced from starch or the like, and is abundantly obtained as a resource. In addition, compared with isomannide or isoidide, the ease of production, the nature, and the breadth of use are all excellent.
聚碳酸酯(A-1成分),亦可在不損害其特性的範圍內與脂肪族二醇或芳香族雙酚類進行共聚合。適當的使用碳數3~12的直鏈脂肪族二醇,碳數6~20的脂環式二醇作為這種脂肪族二醇。具體例舉,1,3-丙烷二醇、1,4-丁烷二醇、1,6-己烷二醇等直鏈二醇類或,環己二醇、環己二甲醇等脂環式伸烷類等。其中以1,3-丙烷二醇、1,4-丁烷二醇、1,6-己二醇及環己二甲醇為佳。另外因為本發明之樹脂組成物,具有由植物等可再生資源製得的原料之上述式(a)為主成分,故亦適當的使用源自植物的二醇類。具體列舉有包含萜烯成分之二醇類。The polycarbonate (component A-1) may be copolymerized with an aliphatic diol or an aromatic bisphenol within a range not impairing the properties. As the aliphatic diol, a linear aliphatic diol having 3 to 12 carbon atoms and an alicyclic diol having 6 to 20 carbon atoms are suitably used. Specific examples thereof include a linear diol such as 1,3-propane diol, 1,4-butane diol or 1,6-hexane diol, or an alicyclic ring such as cyclohexanediol or cyclohexanedimethanol. Alkane and the like. Among them, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, and cyclohexanedimethanol are preferred. Further, since the resin composition of the present invention contains the above formula (a) which is a raw material obtained from a renewable resource such as a plant as a main component, a plant-derived glycol is also suitably used. Specific examples include glycols containing a terpene component.
芳香族雙酚類列舉有,2,2-雙(4-羥基苯基)丙烷(通稱“雙酚A”)、1,1-雙(4-羥基苯基)環己烷、1,1-雙(4-羥基苯基)-3,3,5-三甲基環己烷、4,4'-(對苯基二異亞丙基)二酚(4,4'-(m-Phenylenediisopropyridene)diphenol)、9,9-雙(4-羥基-3-甲基苯基)茀、2,2-雙(4-羥基-3-甲基苯基)丙烷、2,2-雙(4-羥基苯基)-4-甲基戊烷、1,1-雙(4-羥基苯基)癸烷、1,3-雙{2-(4-羥基苯基)丙基}苯等。该等脂肪族二醇類、芳香族雙酚類可以單獨或組合使用。The aromatic bisphenols are exemplified by 2,2-bis(4-hydroxyphenyl)propane (commonly known as "bisphenol A"), 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1- Bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 4,4'-(p-phenyldiisopropylidene)diphenol (4,4'-(m-Phenylenediisopropyridene) Diphenol), 9,9-bis(4-hydroxy-3-methylphenyl)anthracene, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxyl Phenyl)-4-methylpentane, 1,1-bis(4-hydroxyphenyl)decane, 1,3-bis{2-(4-hydroxyphenyl)propyl}benzene, and the like. These aliphatic diols and aromatic bisphenols may be used singly or in combination.
另外聚碳酸酯(A-1成分),在不損害其特性的範圍內亦可以導入端基。這種端基,可在聚合時添加對應的羥基化合物藉而導入。端基以用下述式(i)或(ii)表示之端基為佳。Further, the polycarbonate (component A-1) can be introduced into the end group without impairing its properties. Such a terminal group can be introduced by adding a corresponding hydroxy compound at the time of polymerization. The terminal group is preferably an end group represented by the following formula (i) or (ii).
上述式(i)(ii)中,R4 為碳原子數4~30的烷基、碳原子數7~30的芳烷基、碳原子數4~30的全氟烷基,或下述式(iii)。合宜的是碳原子數4~20的烷基、碳原子數4~20的全氟烷基,或下述式(iii)。尤其以碳原子數8~20的烷基,或下述式(iii)為佳。In the above formula (i) (ii), R 4 is an alkyl group having 4 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, a perfluoroalkyl group having 4 to 30 carbon atoms, or the following formula: (iii). Conveniently, it is an alkyl group having 4 to 20 carbon atoms, a perfluoroalkyl group having 4 to 20 carbon atoms, or the following formula (iii). In particular, an alkyl group having 8 to 20 carbon atoms or the following formula (iii) is preferred.
Y以選自單鍵結、醚鍵結、硫醚鍵結、酯鍵結、胺鍵結及醯胺鍵結組成的族群之至少一種鍵結為佳。較佳為選自單鍵結、醚鍵結及酯鍵結組成的族群之至少一種鍵結。其中以單鍵結、酯鍵結為佳。a為1~5的整數,合適的是1~3的整數,尤其以1為佳。Y is preferably at least one bond selected from the group consisting of a single bond, an ether bond, a thioether bond, an ester bond, an amine bond, and a guanamine bond. It is preferably at least one bond selected from the group consisting of a single bond, an ether bond, and an ester bond. Among them, a single bond and an ester bond are preferred. a is an integer of 1-5, suitably an integer of 1-3, especially 1 is preferable.
另外,上述式(iii)中,R5 、R6 、R7 、R8 及R9 各自獨立,係選自碳原子數1~10的烷基、碳原子數6~20的環烷基、碳原子數2~10的烯基,碳原子數6~10的芳基及碳原子數7~20的芳烷基組成的族群之至少一種的基團。合宜的是各自獨立,選自碳原子數1~10的烷基及碳原子數6~10的芳基組成的族群之至少一種的基團。尤其以各自獨立,選自甲基及苯基組成的族群之至少一種的基團為佳。b為0~3的整數,以1~3的整數為佳,尤其以2~3的整數為佳。c為4~100的整數,以4~50的整數為佳,尤其以8~50的整數為佳。Further, in the above formula (iii), R 5 , R 6 , R 7 , R 8 and R 9 are each independently selected from the group consisting of an alkyl group having 1 to 10 carbon atoms and a cycloalkyl group having 6 to 20 carbon atoms. A group of at least one of an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms. It is preferable that each is independently a group selected from at least one of a group consisting of an alkyl group having 1 to 10 carbon atoms and an aryl group having 6 to 10 carbon atoms. In particular, it is preferred that the groups are at least one selected from the group consisting of a methyl group and a phenyl group. b is an integer of 0 to 3, preferably an integer of 1 to 3, and particularly preferably an integer of 2 to 3. c is an integer of 4 to 100, preferably an integer of 4 to 50, and particularly preferably an integer of 8 to 50.
因為聚碳酸酯(A-1成分),在主鏈結構中具有使用由植物等可再生資源製得的原料之碳酸酯單元,故以該等之羥基化合物或由植物等可再生資源製得之原料為佳。由植物製得之羥基化合物,例舉由植物油製得之碳數14以上的長鏈烷醇類(鯨蠟醇、硬質醇、山嵛醇)等。Since the polycarbonate (component A-1) has a carbonate unit using a raw material obtained from a renewable resource such as a plant in the main chain structure, it is obtained from such a hydroxy compound or a renewable resource such as a plant. Raw materials are preferred. The hydroxy compound produced by the plant is exemplified by a long-chain alkanol (cetyl alcohol, hard alcohol, behenyl alcohol) having a carbon number of 14 or more, which is obtained from vegetable oil.
另外,混合包含以前述式(a)表示的醚二醇之雙羥基化合物和碳酸二酯,進行高溫減壓下除去由酯交換反應生成的醇或酚之熔融聚合,可藉而獲得聚碳酸酯(A-1成分)。Further, a bishydroxy compound and a carbonic acid diester containing an ether diol represented by the above formula (a) are mixed, and a melt polymerization of an alcohol or a phenol produced by a transesterification reaction is carried out under high temperature and reduced pressure, whereby a polycarbonate can be obtained. (A-1 ingredient).
反應溫度,為抑制醚二醇的分解,製得著色少的高粘度樹脂,以使用盡可能低溫的條件為佳,惟為了適當的促進聚合反應,聚合溫度以180℃~280℃的範圍為佳,較佳為180℃~270℃的範圍。The reaction temperature is to suppress the decomposition of the ether diol, and to obtain a high-viscosity resin having little coloration, and it is preferred to use a condition as low as possible, but in order to appropriately promote the polymerization reaction, the polymerization temperature is preferably in the range of 180 ° C to 280 ° C. It is preferably in the range of 180 ° C to 270 ° C.
另外,以在反應初期以常壓加熱醚二醇與碳酸二酯,使發生預反應後,慢慢減壓且在反應後期將系統減壓至1.3×10-3 ~1.3×10-5 MPa左右,容易使生成的醇或酚除去之方法為佳。反應時間通常為1~4小時左右。Further, the ether diol and the carbonic acid diester are heated at normal pressure in the initial stage of the reaction to cause a pre-reaction, and then the pressure is gradually reduced, and the system is depressurized to about 1.3 × 10 -3 to 1.3 × 10 -5 MPa at the later stage of the reaction. Preferably, the method of removing the produced alcohol or phenol is preferred. The reaction time is usually about 1 to 4 hours.
再者,為提高聚合速度可以使用聚合觸媒。聚合觸媒舉例如氫氧化鈉、氫氧化鉀、碳酸鈉、碳酸鉀、碳酸氫鈉、二元酚的鈉鹽或鉀鹽等鹼金屬化合物等。另外還例舉氫氧化鈣、氫氧化鋇、氫氧化鎂等鹼土類金屬化合物等。還例舉四甲基氫氧化銨、四乙基氫氧化銨、四丁基氫氧化銨、三甲胺、三乙胺等含氮鹼性化合物等。該等可以單獨使用,亦可組合2種以上使用。其中,以倂用含氮鹼性化合物與鹼金屬化合物使用為佳。Further, a polymerization catalyst can be used in order to increase the polymerization rate. The polymerization catalyst may, for example, be an alkali metal compound such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate or a sodium or potassium salt of a dihydric phenol. Further, an alkaline earth metal compound such as calcium hydroxide, barium hydroxide or magnesium hydroxide is exemplified. Further, a nitrogen-containing basic compound such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, trimethylamine or triethylamine may, for example, be mentioned. These may be used alone or in combination of two or more. Among them, it is preferred to use a nitrogen-containing basic compound and an alkali metal compound.
該等聚合觸媒的使用量,分別相對於碳酸二酯成分1莫耳,合宜的是在1×10-9 ~1×10-3 當量,較佳在1×10-8 ~5×10-4 當量的範圍內選擇。反應體系以相對於氮等原料、反應混合物、反應生成物保持在無活性的氣體氛圍氣為佳。氮以外的無活性氣體,可以例舉氬等。而且,亦可依需要加入抗氧化劑等添加劑。The amount of the polymerization catalyst used is preferably 1 × 10 -9 to 1 × 10 -3 equivalents, preferably 1 × 10 -8 to 5 × 10 - per mol of the carbonic acid diester component, respectively. Choose within a range of 4 equivalents. The reaction system is preferably maintained in an inert gas atmosphere with respect to a raw material such as nitrogen, a reaction mixture, and a reaction product. An inert gas other than nitrogen may, for example, be argon or the like. Further, an additive such as an antioxidant may be added as needed.
製造聚碳酸酯(A-1成分)時使用之碳酸二酯,列舉有亦可被取代之碳數6~20的芳基、芳烷基或碳數1~18的烷基等酯。具體例舉碳酸二苯酯、碳酸雙(氯苯基)酯、碳酸間甲苯酯、碳酸二萘酯、碳酸雙(對丁基苯基)酯、碳酸二甲酯、碳酸二乙酯、碳酸二丁酯等,其中以碳酸二苯酯為佳。The carbonic acid diester used in the production of the polycarbonate (component A-1) includes an ester such as an aryl group having 6 to 20 carbon atoms, an aralkyl group or an alkyl group having 1 to 18 carbon atoms which may be substituted. Specific examples thereof include diphenyl carbonate, bis(chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis(p-butylphenyl) carbonate, dimethyl carbonate, diethyl carbonate, and carbonic acid. Butyl ester and the like, among which diphenyl carbonate is preferred.
將碳酸二酯混合成相對於全部醚二醇化合物用莫耳比計以1.02~0.98為佳,較佳為1.01~0.98,更佳為1.01~0.99。碳酸二酯的莫耳比若多於1.02,則碳酸酯殘基作為末端封閉發揮作用而無法獲得足夠的聚合度,不適宜。另外碳酸二酯的莫耳比小於0.98時,無法獲得足夠的聚合度而不適宜。The carbonic acid diester is preferably mixed in an amount of from 1.02 to 0.98, more preferably from 1.01 to 0.98, still more preferably from 1.01 to 0.99, based on the molar ratio of the total of the ether diol compound. When the molar ratio of the carbonic acid diester is more than 1.02, it is not preferable that the carbonate residue acts as a terminal blocking to obtain a sufficient degree of polymerization. Further, when the molar ratio of the carbonic acid diester is less than 0.98, a sufficient degree of polymerization cannot be obtained, which is not preferable.
亦可在由上述製造法製得之聚碳酸酯(A-1成分)中添加觸媒失活劑。有效地使用公知的觸媒失活劑作為觸媒失活劑,惟其中以磺酸的銨鹽、鏻鹽為佳。而且以十二烷基苯磺酸四丁基鏻鹽等十二烷基苯磺酸的上述鹽類或對甲苯磺酸四丁基銨鹽等對甲苯磺酸的上述鹽類為佳。另外適當的使用磺酸酯之苯磺酸甲酯、苯磺酸乙酯、苯磺酸丁酯、苯磺酸辛酯、苯磺酸苯基酯、對甲苯磺酸甲酯、對甲苯磺酸乙酯、對甲苯磺酸丁酯、對甲苯磺酸辛酯、對甲苯磺酸苯基酯等。其中最好使用十二烷基苯磺酸四丁基鏻鹽。該等觸媒失活劑的使用量,可以以相對選自鹼金屬化合物及/或鹼土類金屬化合物之前述聚合觸媒1莫耳之0.5~50莫耳的比例,合宜的是0.5~10莫耳的比例,更好的是0.8~5莫耳的比例使用。A catalyst deactivator may also be added to the polycarbonate (component A-1) obtained by the above production method. A known catalyst deactivator is effectively used as the catalyst deactivator, and among them, an ammonium salt or a phosphonium salt of a sulfonic acid is preferred. Further, the above salts of dodecylbenzenesulfonic acid such as tetrabutylphosphonium dodecylbenzenesulfonate or the above salts of p-toluenesulfonic acid such as tetrabutylammonium p-toluenesulfonate are preferred. Further suitable use of sulfonate methyl benzenesulfonate, ethyl benzenesulfonate, butyl benzenesulfonate, octyl benzenesulfonate, phenyl benzenesulfonate, methyl p-toluenesulfonate, ethyl p-toluenesulfonate Ester, butyl p-toluenesulfonate, octyl p-toluenesulfonate, phenyl p-toluenesulfonate, and the like. Among them, tetrabutylphosphonium dodecylbenzenesulfonate is preferably used. The amount of the catalyst deactivator to be used may be 0.5 to 50 moles per mole of the polymerization catalyst of the alkali metal compound and/or the alkaline earth metal compound, preferably 0.5 to 10 moles. The ratio of the ear is preferably 0.8 to 5 moles.
(其他熱可塑性樹脂:A-2成分)(Other thermoplastic resin: component A-2)
樹脂成分(A成分),除聚碳酸酯(A-1成分)以外,亦可含有其他的熱可塑性樹脂(A-2成分)。如前述A成分中之其他樹脂(A-2成分)的含量,合宜的是50重量%以下,較佳為40重量%以下,更佳為30重量%以下,最佳的是20重量%以下,特別好的是10重量%以下。The resin component (component A) may contain other thermoplastic resin (component A-2) in addition to the polycarbonate (component A-1). The content of the other resin (component A-2) in the component A is preferably 50% by weight or less, preferably 40% by weight or less, more preferably 30% by weight or less, and most preferably 20% by weight or less. Particularly preferably, it is 10% by weight or less.
該A-2成分例舉,聚酯樹脂(PEst)、聚苯醚樹脂(PPE)、聚碳酸酯樹脂(PC)、聚醯胺樹脂(PA)、聚烯烴樹脂(PO)、苯乙烯系樹脂、聚苯硫醚樹脂(PPS)及聚醚醯亞胺樹脂(PEI)組成的族群之至少一種的熱可塑性樹脂。這些A-2成分中,合宜的是聚酯樹脂(PEst)、聚苯醚樹脂(PPE)、聚碳酸酯樹脂(PC)、聚醯胺樹脂(PA)、聚烯烴樹脂(PO)及苯乙烯系樹脂。The component A-2 is exemplified by a polyester resin (PEst), a polyphenylene ether resin (PPE), a polycarbonate resin (PC), a polyamide resin (PA), a polyolefin resin (PO), and a styrene resin. A thermoplastic resin of at least one of the group consisting of polyphenylene sulfide resin (PPS) and polyether sulfimide resin (PEI). Among these A-2 components, polyester resin (PEst), polyphenylene ether resin (PPE), polycarbonate resin (PC), polyamide resin (PA), polyolefin resin (PO), and styrene are preferable. Resin.
接著就該A-2成分之熱可塑性樹脂做具體說明。Next, the thermoplastic resin of the component A-2 will be specifically described.
A-2成分之聚酯樹脂(PEst),例舉選自芳香族聚酯樹脂或脂肪族聚酯樹脂的1種或2種以上之混合物。合宜的是芳香族聚酯樹脂,係以芳香族二羧酸為主之二羧酸成分與,碳數2~10的脂肪族二醇為主之二醇成分形成之聚酯。合宜的二羧酸成分的80莫耳%以上,較佳為90莫耳%以上係由芳香族二羧酸成分形成。另一方面,二醇成分合宜的80莫耳%以上,較佳為90莫耳%以上係由碳數2~10的脂肪族二醇成分形成。The polyester resin (PEst) of the component A-2 is exemplified by one or a mixture of two or more selected from the group consisting of an aromatic polyester resin and an aliphatic polyester resin. Conveniently, the aromatic polyester resin is a polyester formed from a dicarboxylic acid component mainly composed of an aromatic dicarboxylic acid and a diol component mainly composed of an aliphatic diol having 2 to 10 carbon atoms. 80 mol% or more, preferably 90 mol% or more of a suitable dicarboxylic acid component is formed of an aromatic dicarboxylic acid component. On the other hand, the diol component is preferably 80 mol% or more, preferably 90 mol% or more, and is formed of an aliphatic diol component having 2 to 10 carbon atoms.
芳香族二羧酸成分可以例舉合適的例子為對苯二甲酸、間苯二甲酸、鄰苯二甲酸、甲基對苯二甲酸、甲基間苯二甲酸及2,6-萘二羧酸等。該等可以使用1種或2種以上。芳香族二羧酸以外的次級二羧酸可例舉,己二酸、癸二酸、癸烷二羧酸、壬二酸、十二烷二羧酸、環己烷二羧酸等脂肪族二羧酸或脂環族二羧酸等。Suitable examples of the aromatic dicarboxylic acid component are terephthalic acid, isophthalic acid, phthalic acid, methyl terephthalic acid, methyl isophthalic acid and 2,6-naphthalene dicarboxylic acid. Wait. These may be used alone or in combination of two or more. The secondary dicarboxylic acid other than the aromatic dicarboxylic acid may, for example, be an aliphatic acid such as adipic acid, sebacic acid, decane dicarboxylic acid, sebacic acid, dodecane dicarboxylic acid or cyclohexane dicarboxylic acid. Dicarboxylic acid or alicyclic dicarboxylic acid, and the like.
碳數2~10的脂肪族二醇可以列舉,乙二醇、丙二醇、丁二醇、1,6-己二醇、新戊二醇等脂肪族二醇。還可以列舉1,4-環己烷二甲醇等脂環族二醇。碳數2~10的脂肪族二醇以外的二醇,可以列舉p,p'-二羥乙氧基雙酚A、聚氧乙二醇等。Examples of the aliphatic diol having 2 to 10 carbon atoms include aliphatic diols such as ethylene glycol, propylene glycol, butylene glycol, 1,6-hexanediol, and neopentyl glycol. Further, an alicyclic diol such as 1,4-cyclohexanedimethanol may be mentioned. Examples of the diol other than the aliphatic diol having 2 to 10 carbon atoms include p,p'-dihydroxyethoxy bisphenol A and polyoxyethylene glycol.
芳香族聚酯樹脂的合適例為,具有由主要的二羧酸成分為選自對苯二甲酸及2,6-萘二羧酸的至少1種之二羧酸和,主要的二醇成分為選自乙二醇、丙二醇及丁二醇的至少1種之二醇形成之酯單元的聚酯。A suitable example of the aromatic polyester resin is that the main dicarboxylic acid component is at least one dicarboxylic acid selected from the group consisting of terephthalic acid and 2,6-naphthalenedicarboxylic acid, and the main diol component is A polyester of an ester unit formed from a diol of at least one selected from the group consisting of ethylene glycol, propylene glycol and butylene glycol.
具體的芳香族聚酯樹脂,以選自聚對苯二甲酸乙二醇酯樹脂、聚對苯二甲酸丁二醇酯樹脂、聚對萘二甲酸乙二醇酯樹脂、聚對萘二甲酸丁二醇酯樹脂、聚對苯二甲酸環己烷二甲酯樹脂、聚對苯二甲酸丙二醇酯樹脂及聚對萘二甲酸丙二醇酯樹脂組成的族群之至少1種為佳。a specific aromatic polyester resin selected from the group consisting of polyethylene terephthalate resin, polybutylene terephthalate resin, polyethylene naphthalate resin, and poly(p-naphthalene dicarboxylate) At least one of a group consisting of a glycol ester resin, a polybutylene terephthalate resin, a polytrimethylene terephthalate resin, and a polyparaphthalic acid propylene glycol ester resin is preferred.
最好的是選自聚對苯二甲酸乙二醇酯樹脂、聚對苯二甲酸丁二醇酯樹脂及聚對萘二甲酸乙二醇酯樹脂組成的族群之至少1種。尤其以聚對苯二甲酸丁二醇酯樹脂最好。Most preferably, it is at least one selected from the group consisting of polyethylene terephthalate resin, polybutylene terephthalate resin, and polyethylene naphthalate resin. In particular, polybutylene terephthalate resin is preferred.
另外,本發明之芳香族聚酯樹脂,亦可使用以上述重複單元為硬鏈段的主要重複單元之聚酯彈性體。Further, as the aromatic polyester resin of the present invention, a polyester elastomer in which the above repeating unit is a main repeating unit of a hard segment can also be used.
以對苯二甲酸丁二醇酯或2,6-萘二羧酸酯丁二醇酯為硬鏈段的主要重複單元之聚酯彈性體的軟鏈段,例如,二羧酸是由選自對苯二甲酸、間苯二甲酸、癸二酸及己二酸的至少1種之二羧酸形成,二醇成分由選自碳數5~10的長鏈二醇及H(OCH2 CH2 )i OH(i=2~5)組成的族群之至少1種的二醇形成,還可以使用由熔點100℃以下或非晶性的聚酯或聚己內酯形成者。a soft segment of a polyester elastomer having a main repeating unit of a hard segment of butylene terephthalate or 2,6-naphthalenedicarboxylate butane, for example, a dicarboxylic acid selected from Forming at least one dicarboxylic acid of terephthalic acid, isophthalic acid, sebacic acid, and adipic acid, the diol component is selected from long-chain diols having a carbon number of 5 to 10 and H (OCH 2 CH 2 ) A diol having at least one of a group consisting of i OH (i = 2 to 5) is formed, and a polyester or polycaprolactone having a melting point of 100 ° C or less or amorphous may be used.
再者,主成分是全二羧酸成分或全二醇成分的80莫耳%以上,合適的是90莫耳%以上的成分,主要的重複單元是全重複單元的80莫耳%以上,合適的是90莫耳%以上之重複單元。Further, the main component is 80 mol% or more of the total dicarboxylic acid component or the total diol component, and suitably 90 mol% or more, and the main repeating unit is 80 mol% or more of the total repeating unit, suitably It is a repeating unit of 90 mol% or more.
芳香族聚酯樹脂的分子量,如果具有可以作為通常成形品使用之固有粘度即可,在35℃,鄰氯苯酚中測定之固有粘度合適的是0.5~1.6dl/g,更佳為0.6~1.5dl/g。The molecular weight of the aromatic polyester resin may be an intrinsic viscosity which can be used as a normal molded article, and the intrinsic viscosity measured at 35 ° C in o-chlorophenol is suitably 0.5 to 1.6 dl/g, more preferably 0.6 to 1.5. Dl/g.
另外芳香族聚酯樹脂,末端羧基(-COOH)量為1~60當量/T(1T聚合物)是有利的。該末端羧基量,可以藉例如電位差滴定法以鹼溶液滴定間甲酚溶液來求算。Further, the aromatic polyester resin is advantageous in that the amount of terminal carboxyl groups (-COOH) is from 1 to 60 equivalents/T (1 T polymer). The amount of the terminal carboxyl group can be calculated by titrating the m-cresol solution with an alkali solution, for example, by potentiometric titration.
A-2成分之聚苯醚樹脂,可以使用通常已知的PPE樹脂。這種PPE樹脂的具體例,例舉(2,6-二甲基-1,4-伸苯基)醚、(2,6-二乙基-1,4-伸苯基)醚、(2,6-二丙基-1,4-伸苯基)醚、(2-甲基-6-乙基-1,4-伸苯基)醚、(2-甲基-6-丙基-1,4-伸苯基)醚、(2,3,6-三甲基-1,4-伸苯基)醚等單聚物及/或共聚物。列舉特別好的是(2,6-二甲基-1,4-伸苯基)醚。另外,亦可是在該等PPE上接枝聚合苯乙烯化合物之共聚物。這種PPE的製造法並無特殊限定,可以利用例如美國專利第3,306,874號記載之方法使用第一銅鹽與胺類的錯和物作為觸媒,將2,6-二甲苯酚加以氧化聚合藉而容易地製造。As the polyphenylene ether resin of the component A-2, a commonly known PPE resin can be used. Specific examples of such a PPE resin include (2,6-dimethyl-1,4-phenylene)ether, (2,6-diethyl-1,4-phenylene)ether, (2). ,6-dipropyl-1,4-phenylene)ether, (2-methyl-6-ethyl-1,4-phenylene)ether, (2-methyl-6-propyl-1) a monomer and/or a copolymer such as 4-phenylene ether or (2,3,6-trimethyl-1,4-phenylene) ether. Particularly preferred is (2,6-dimethyl-1,4-phenylene) ether. Alternatively, a copolymer of a styrene compound may be graft polymerized on the PPE. The method for producing such a PPE is not particularly limited, and 2,6-xylenol can be used as a catalyst by using a method of the first copper salt and an amine as a catalyst, for example, as described in U.S. Patent No. 3,306,874. It is easily produced by oxidative polymerization.
PPE樹脂的分子量尺度之還原粘度ηsp /C(0.5g/dl,甲苯溶液,30℃測定)為0.2~0.7dl/g,合宜的是0.3~0.6dl/g。還原粘度在該範圍的PPE樹脂成形加工性、機械物性的平衡良好,透過調整PPE製造時之觸媒量等,可以容易地調整還原粘度。The reduced viscosity η sp /C (0.5 g / dl, toluene solution, measured at 30 ° C) of the molecular weight scale of the PPE resin is 0.2 to 0.7 dl / g, preferably 0.3 to 0.6 dl / g. The PPE resin having a reduced viscosity in this range has a good balance between moldability and mechanical properties, and the reducing viscosity can be easily adjusted by adjusting the amount of the catalyst during the production of PPE.
A-2成分的聚碳酸酯樹脂(PC),列舉使用二氯甲烷等溶劑藉各種二羥芳基化合物與二氯化碳的界面聚合反應來製得者。另外還例舉藉二羥芳基化合物與碳酸二苯酯的酯交換反應製得者。代表為2,2'-雙(4-羥基苯基)丙烷與二氯化碳的反應製得之聚碳酸酯。The polycarbonate resin (PC) of the component A-2 is obtained by an interfacial polymerization reaction of various dihydroxyaryl compounds and carbon dichloride using a solvent such as dichloromethane. Further, a transesterification reaction of a dihydroxyaryl compound with diphenyl carbonate is also exemplified. Representative of a polycarbonate obtained by the reaction of 2,2'-bis(4-hydroxyphenyl)propane with carbon dichloride.
形成聚碳酸酯原料的二羥芳基化合物有,雙(4-羥基苯基)甲烷、1,1'-雙(4-羥基苯基)乙烷、2,2'-雙(4-羥基苯基)丙烷、2,2'-雙(4-羥基苯基)丁烷、2,2'-雙(4-羥基苯基)辛烷、2,2'-雙(4-羥基-3-甲基苯基)丙烷、2,2'-雙(4-羥基-3-叔丁基苯基)丙烷、2,2'-雙(3,5-二甲基-4-羥基苯基)丙烷、2,2'-雙(4-羥基-3-環己基苯基)丙烷、2,2'-雙(4-羥基-3-甲氧基苯基)丙烷、1,1'-雙(4-羥基苯基)環戊烷、1,1'-雙(4-羥基苯基)環己烷、1,1'-雙(4-羥基苯基)環十二烷、4,4'-二羥基苯基醚、4,4'-二羥基-3,3'-二甲基苯基醚、4,4'-二羥基二苯基硫醚、4,4'-二羥基-3,3'-二甲基二苯基硫醚、4,4'-二羥基二苯基亞碸、4,4'-二羥基二苯基碸、雙(4-羥基苯基)酮等。該等二羥芳基化合物可以單獨或組合2種以上使用。The dihydroxyaryl compounds forming the polycarbonate starting material are bis(4-hydroxyphenyl)methane, 1,1'-bis(4-hydroxyphenyl)ethane, 2,2'-bis(4-hydroxybenzene). Propane, 2,2'-bis(4-hydroxyphenyl)butane, 2,2'-bis(4-hydroxyphenyl)octane, 2,2'-bis(4-hydroxy-3-methyl Phenyl)propane, 2,2'-bis(4-hydroxy-3-tert-butylphenyl)propane, 2,2'-bis(3,5-dimethyl-4-hydroxyphenyl)propane, 2,2'-bis(4-hydroxy-3-cyclohexylphenyl)propane, 2,2'-bis(4-hydroxy-3-methoxyphenyl)propane, 1,1'-bis (4- Hydroxyphenyl)cyclopentane, 1,1'-bis(4-hydroxyphenyl)cyclohexane, 1,1'-bis(4-hydroxyphenyl)cyclododecane, 4,4'-dihydroxy Phenyl ether, 4,4'-dihydroxy-3,3'-dimethylphenyl ether, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxy-3,3'- Dimethyldiphenyl sulfide, 4,4'-dihydroxydiphenylarylene, 4,4'-dihydroxydiphenylanthracene, bis(4-hydroxyphenyl)ketone, and the like. These dihydroxyaryl compounds may be used alone or in combination of two or more.
合宜的二羥芳基化合物有,形成耐熱性高的芳香族聚碳酸酯之雙酚類、2,2'-雙(4-羥基苯基)丙烷等雙(羥基苯基)烷、雙(4-羥基苯基)環己烷等雙(羥基苯基)環烷、二羥基二苯基硫醚、二羥基二苯基碸、二羥基二苯基酮等。最好的二羥芳基化合物是,形成雙酚A型芳香族聚碳酸酯之2,2'-雙(4-羥基苯基)丙烷。Suitable dihydroxyaryl compounds include bisphenols which form aromatic polycarbonates having high heat resistance, bis(hydroxyphenyl)alkanes such as 2,2'-bis(4-hydroxyphenyl)propane, and bis (4). Bis(hydroxyphenyl)cycloalkane such as -hydroxyphenyl)cyclohexane, dihydroxydiphenyl sulfide, dihydroxydiphenylanthracene, dihydroxydiphenylketone or the like. The most preferred dihydroxyaryl compound is 2,2'-bis(4-hydroxyphenyl)propane which forms a bisphenol A type aromatic polycarbonate.
另外,若在不損害耐熱性、機械強度等之範圍內,在製造雙酚A型芳香族聚碳酸酯時,亦可用其他的二羥芳基化合取代雙酚A的一部分。Further, when a bisphenol A type aromatic polycarbonate is produced in a range that does not impair heat resistance, mechanical strength, or the like, a part of bisphenol A may be substituted by another dihydroxyaryl compound.
聚碳酸酯的分子量不必做特殊限制,惟因為過低強度會不足,過高熔融粘度會變高而難以成形,故以粘度平均分子量表示通常為10,000~50,000,合宜的是15,000~30,000。此處之粘度平均分子量(M)係將在20℃下100ml二氯甲烷中溶解0.7g聚碳酸酯之溶液求算出之比粘度(ηsp )帶入下式而求得者。The molecular weight of the polycarbonate is not particularly limited, but the excessively high strength may be insufficient, and the excessively high melt viscosity may become high and difficult to form, so the viscosity average molecular weight is usually 10,000 to 50,000, and preferably 15, 000 to 30,000. Here, the viscosity average molecular weight (M) is obtained by taking the specific viscosity (η sp ) calculated by dissolving a solution of 0.7 g of polycarbonate in 100 ml of dichloromethane at 20 ° C into the following formula.
ηsp /C=[η]+0.45×[η]2 Cη sp /C=[η]+0.45×[η] 2 C
[η]=1.23×10-4 M0.83 [η]=1.23×10 -4 M 0.83
(但是,[η]為極限粘度,C以聚合物濃度計為0.7)(However, [η] is the intrinsic viscosity, and C is 0.7 in terms of polymer concentration)
簡單說明製造聚碳酸酯之基本方法。使用碳酸酯前驅物質二氯化碳之界面聚合法(溶液聚合法),通常在酸結合劑及有機溶劑的存在下進行反應。使用例如氫氧化鈉或氫氧化鉀等鹼金屬的氫氧化物或嘧啶等胺類化合物作為酸結合劑。使用例如二氯甲烷、氯苯等鹵化烴作為有機溶劑。另外為促進反應可以使用例如第三級胺或第四級銨鹽等觸媒。分子量調節劑適宜使用例如苯酚或對叔丁基苯酚這種烷基取代苯酚等末端停止劑。反應溫度通常為0~40℃,反應時間為數分鐘~5小時,反應中的pH以保持在10以上為佳。結果獲得之分子鏈末端不必全部具有源自末端停止劑的結構。A brief description of the basic method of making polycarbonate. The reaction is carried out by an interfacial polymerization method (solution polymerization method) using a carbonate precursor carbon dichloride, usually in the presence of an acid binder and an organic solvent. As the acid binder, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide or an amine compound such as pyrimidine is used. A halogenated hydrocarbon such as dichloromethane or chlorobenzene is used as the organic solvent. Further, a catalyst such as a tertiary amine or a fourth-order ammonium salt may be used to promote the reaction. As the molecular weight modifier, a terminal stopper such as phenol or p-tert-butylphenol such as an alkyl-substituted phenol is suitably used. The reaction temperature is usually from 0 to 40 ° C, the reaction time is from several minutes to 5 hours, and the pH during the reaction is preferably maintained at 10 or more. As a result, it is not necessary for all of the molecular chain ends obtained to have a structure derived from a terminal stopper.
使用碳酸二酯作為碳酸酯前驅物之酯交換反應(熔融聚合法),在無活性氣體的存在下邊加熱規定比例的二元苯酚與碳酸二酯邊攪拌,餾除生成之醇或酚之方法進行。反應溫度與生成之醇或酚類的沸點等較不同,惟通常為120~350℃的範圍。反應從初期開始減壓餾除生成之醇或酚類的同時完成反應。在這種反應的初期階段與二元苯酚等同時或在反應的中途階段添加末端停止劑。另外為促進反應可以使用現在公知的酯交換反應中使用之觸媒。該酯交換反應中使用之碳酸二酯舉例如,碳酸二苯酯、碳酸二萘酯、碳酸二甲酯、碳酸二乙酯、碳酸二丁酯等。其等中以碳酸二苯酯為佳。A transesterification reaction (melt polymerization method) using a carbonic acid diester as a carbonate precursor, and heating a predetermined ratio of a dihydric phenol and a carbonic acid diester in the presence of an inert gas, and distilling off the produced alcohol or phenol . The reaction temperature is different from the boiling point of the produced alcohol or phenol, and is usually in the range of 120 to 350 °C. The reaction is completed while distilling off the produced alcohol or phenol under reduced pressure from the initial stage. A terminal stopper is added simultaneously with the dihydric phenol or the like or in the middle of the reaction in the initial stage of the reaction. Further, in order to promote the reaction, a catalyst which is currently used in a transesterification reaction can be used. The carbonic acid diester used in the transesterification reaction may, for example, be diphenyl carbonate, dinaphthyl carbonate, dimethyl carbonate, diethyl carbonate or dibutyl carbonate. Among them, diphenyl carbonate is preferred.
A-2成分之聚醯胺樹脂(PA),可以舉例如環狀內醯胺的開環聚合物、胺基羧酸的聚合物、二元酸與二胺的縮聚物等。具體例舉尼龍6、尼龍66、尼龍46、尼龍610、尼龍612、尼龍11、尼龍12等脂肪族聚醯胺、其等之共聚物或混合物。另外可以例舉聚己二醯間苯二甲胺(poly(metaxylene adipamide))、聚(對苯二甲醯己二胺)(poly(hexamethylene terephthalamide))、聚(對苯二甲醯壬二胺)(poly(nona-methylene terephthalamide))、聚(間苯二甲醯己二胺)(poly(hexamethylene isophthalamide)、聚(間苯二甲醯丁二胺)(poly(tetramethylene isophthalamide)等脂肪族-芳香族聚醯胺、該等之共聚物或混合物。本發明可以使用之聚醯胺並無特殊限定。The polyamine resin (PA) of the component A-2 may, for example, be a ring-opening polymer of a cyclic indoleamine, a polymer of an aminocarboxylic acid, a polycondensate of a dibasic acid and a diamine, or the like. Specific examples thereof include aliphatic polyamides such as nylon 6, nylon 66, nylon 46, nylon 610, nylon 612, nylon 11, nylon 12, and the like, or copolymers or mixtures thereof. Further, poly(metaxylene adipamide), poly(hexamethylene terephthalamide), poly(p-xylylenediamine), poly(p-xylylenediamine) (poly(nona-methylene terephthalamide), poly(hexamethylene isophthalamide), poly(tetramethylene isophthalamide), etc. The aromatic polyamine, the copolymer or the mixture of the above. The polyamine which can be used in the present invention is not particularly limited.
這種聚醯胺樹脂的分子量,在98%硫酸中,濃度1%,25℃下測定之相對粘度,合宜的是1.7~4.5,較佳為2.0~4.0,更佳為2.0~3.5。The molecular weight of such a polyamide resin is preferably from 1.7 to 4.5, preferably from 2.0 to 4.0, more preferably from 2.0 to 3.5, in a 98% sulfuric acid concentration of 1% and a relative viscosity measured at 25 °C.
A-2成分的聚烯烴樹脂為,乙烯、丙烯、丁烯等烯烴類單聚物或共聚物,或該等烯烴類與可以發生共聚合之單體成分形成之共聚物。具體例舉,聚乙烯、聚丙烯、乙烯-醋酸乙烯酯共聚物、乙烯-丙烯酸乙酯共聚物、乙烯-丙烯酸共聚物、乙烯-甲基丙烯酸甲酯共聚合、乙烯-α-烯烴共聚物、乙烯-丙烯共聚物、乙烯-丁烯共聚物等。關於該等聚烯烴樹脂的分子量並無特殊限定,惟高分子量者難燃性良好。The polyolefin resin of the component A-2 is an olefin-based monomer or copolymer such as ethylene, propylene or butene, or a copolymer of the olefins and a monomer component which can be copolymerized. Specific examples include polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid copolymer, ethylene-methyl methacrylate copolymerization, ethylene-α-olefin copolymer, An ethylene-propylene copolymer, an ethylene-butene copolymer, or the like. The molecular weight of the polyolefin resin is not particularly limited, but the high molecular weight is excellent in flame retardancy.
A-2成分之苯乙烯系樹脂為,苯乙烯、α-甲基苯乙烯或乙烯基甲苯等的芳香族乙烯單體的單聚物或共聚物,這些單體與丙烯腈、甲基丙烯酸甲酯等乙烯單體的共聚物,使苯乙烯及/或苯乙烯衍生物在聚丁二烯等二烯系橡膠、乙烯‧丙烯系橡膠、丙烯酸酯系橡膠等中,或使苯乙烯及/或苯乙烯衍生物與其他乙烯單體發生接枝聚合而成者。The styrene resin of the component A-2 is a monomer or copolymer of an aromatic vinyl monomer such as styrene, α-methylstyrene or vinyltoluene, and these monomers are combined with acrylonitrile and methacrylic acid. a copolymer of a vinyl monomer such as an ester, such that the styrene and/or styrene derivative is in a diene rubber such as polybutadiene, an ethylene/acrylic rubber, an acrylate rubber, or the like, or styrene and/or The styrene derivative is grafted with other ethylene monomers.
苯乙烯系樹脂的具體例舉例如,聚苯乙烯、耐衝擊性聚苯乙烯(HIPS)、丙烯腈‧苯乙烯共聚物(AS樹脂)、丙烯腈‧丁二烯‧苯乙烯共聚物(ABS樹脂)、甲基丙烯酸甲酯‧丁二烯‧苯乙烯共聚物(MBS樹脂)、甲基丙烯酸甲酯‧丙烯腈‧丁二烯‧苯乙烯共聚物(MABS樹脂)、丙烯腈‧丙烯酸酯橡膠‧苯乙烯共聚物(AAS樹脂)、丙烯腈‧乙烯丙烯系橡膠‧苯乙烯共聚物(AES樹脂)等樹脂,或該等之混合物。Specific examples of the styrene resin include, for example, polystyrene, impact polystyrene (HIPS), acrylonitrile ‧ styrene copolymer (AS resin), acrylonitrile ‧ butadiene ‧ styrene copolymer (ABS resin) ), methyl methacrylate ‧ butadiene ‧ styrene copolymer (MBS resin), methyl methacrylate ‧ acrylonitrile ‧ butadiene ‧ styrene copolymer (MABS resin), acrylonitrile ‧ acrylate rubber A resin such as a styrene copolymer (AAS resin), an acrylonitrile, an ethylene propylene rubber, a styrene copolymer (AES resin), or a mixture thereof.
從耐衝擊性的觀點出發,以橡膠改質苯乙烯系樹脂為佳,橡膠改質苯乙烯系樹脂是橡膠狀聚合物在由乙烯芳香族系聚合物形成之基體中分散成粒子狀而成之聚合物,在橡膠狀聚合物的存在下加入芳香族乙烯單體、依需要之乙烯系單體,藉公知的塊狀聚合、塊狀懸濁聚合、溶液聚合或乳化聚合製得單體混合物。From the viewpoint of impact resistance, a rubber-modified styrene resin is preferable, and a rubber-modified styrene resin is a rubber-like polymer which is dispersed into a particle form in a matrix formed of a vinyl aromatic polymer. The polymer is obtained by adding an aromatic vinyl monomer or a vinyl monomer as needed in the presence of a rubbery polymer, and preparing a monomer mixture by a known bulk polymerization, bulk suspension polymerization, solution polymerization or emulsion polymerization.
前述橡膠狀聚合物的例子,可以例舉聚丁二烯、聚(苯乙烯-丁二烯)、聚(丙烯腈-丁二烯)等二烯系橡膠及將上述二烯橡膠加以氫化形成之飽和橡膠、異戊二烯橡膠、氯丁烯橡膠、聚丙烯酸丁酯等丙烯酸酯系橡膠,及乙烯-丙烯-二烯寡聚物三元共聚物(EPDM)等,尤其以二烯系橡膠為佳。Examples of the rubber-like polymer may, for example, be a diene rubber such as polybutadiene, poly(styrene-butadiene) or poly(acrylonitrile-butadiene), and hydrogenated the above diene rubber. Acrylate rubber such as saturated rubber, isoprene rubber, chloroprene rubber, polybutyl acrylate, and ethylene-propylene-diene oligomer terpolymer (EPDM), especially diene rubber good.
上述橡膠狀聚合物存在下使可能發生接枝聚合的單體混合物中的必須成分之芳香族乙烯單體,例如有苯乙烯、α-甲基苯乙烯、對甲基苯乙烯等,苯乙烯是最好的。The above-mentioned rubbery polymer has an aromatic vinyl monomer which is an essential component in a monomer mixture which may cause graft polymerization, and examples thereof include styrene, α-methylstyrene, p-methylstyrene, etc., and styrene is the best.
依需要可以添加的乙烯單體例舉,丙烯腈、甲基丙烯酸甲酯等。Examples of the ethylene monomer which may be added as needed are acrylonitrile, methyl methacrylate and the like.
橡膠改質苯乙烯樹脂中之橡膠狀聚合物為,1~50重量%,合宜的是2~40重量%。可以發生接枝聚合的單體混合物為99~50重量%,合宜的是98~60重量%。The rubbery polymer in the rubber-modified styrene resin is from 1 to 50% by weight, preferably from 2 to 40% by weight. The monomer mixture which can undergo graft polymerization is 99 to 50% by weight, preferably 98 to 60% by weight.
A-2成分之聚苯硫醚樹脂(PPS)具有以下述表示之重複單元。The polyphenylene sulfide resin (PPS) of the component A-2 has a repeating unit represented by the following.
式中,n為1以上的整數,50~500的整數以100~400的整數較佳,直鏈狀、交聯狀的每一種皆可。In the formula, n is an integer of 1 or more, and an integer of 50 to 500 is preferably an integer of 100 to 400, and each of a linear form and a crosslinked form may be used.
聚苯硫醚樹脂之製造方法的例子例舉使聚二氯苯與二硫化鈉反應之方法。可以透過將低聚合度的聚合物加以聚合後,在空氣的存在下加熱,進行部分交聯並加以高分子量化的方法來製造交聯狀者,可以藉聚合時進行高分子量化之方法來製造直鏈狀者。An example of the method for producing the polyphenylene sulfide resin is a method of reacting polydichlorobenzene with sodium disulfide. It can be produced by polymerizing a polymer having a low degree of polymerization, heating it in the presence of air, partially cross-linking, and mass-producing a cross-linking method, and polymerizing it by polymerization. Straight chain.
A-2成分的聚醚醯亞胺樹脂(PEI),具有以下述式表示之重複單元。The polyether oxime resin (PEI) of the component A-2 has a repeating unit represented by the following formula.
式中Ar1 表示芳香族二羥基化合物殘基,Ar2 表示芳香族二胺殘基。芳香族二羥基化合物,例舉前述聚碳酸酯樹脂的說明中顯示之芳香族二羥基化合物,尤其以雙酚A為佳。芳香族二胺例舉,間苯二胺、對苯二胺、4,4'-二胺聯苯、3,4'-二胺聯苯、4,4'-二胺二苯醚、3,4'-二胺二苯醚、二胺二苯甲烷、二胺二苯碸及二胺二苯硫醚等。In the formula, Ar 1 represents an aromatic dihydroxy compound residue, and Ar 2 represents an aromatic diamine residue. The aromatic dihydroxy compound is exemplified by the aromatic dihydroxy compound shown in the description of the above polycarbonate resin, and particularly preferably bisphenol A. The aromatic diamine is exemplified by m-phenylenediamine, p-phenylenediamine, 4,4'-diamine biphenyl, 3,4'-diamine biphenyl, 4,4'-diamine diphenyl ether, and 3. 4'-diamine diphenyl ether, diamine diphenylmethane, diamine diphenyl hydrazine and diamine diphenyl sulfide.
前述式中的n表示5~1,000的整數,以10~500的整數為佳。n in the above formula represents an integer of 5 to 1,000, and preferably an integer of 10 to 500.
另外,聚醚醯亞胺樹脂之製造方法的例子,記載於美國專利第3,847,867號、美國專利第3,847,869號、美國專利第3,850,885號、美國專利第3,852、242號及美國專利第3,855,178號等。Further, examples of the production method of the polyether oxime resin are described in U.S. Patent No. 3,847,867, U.S. Patent No. 3,847,869, U.S. Patent No. 3,850,885, and U.S. Patent No. 3 , 852, 242 and U.S. Patent No. 3,855,178, and the like.
前述之種種A-2成分中,以聚酯樹脂(PEst)、聚苯醚樹脂(PPE)、聚碳酸酯樹脂(PC)、聚醯胺樹脂(PA)或苯乙烯系樹脂為佳。Among the above various A-2 components, a polyester resin (PEst), a polyphenylene ether resin (PPE), a polycarbonate resin (PC), a polyamide resin (PA) or a styrene resin is preferred.
(有機磷化合物:B成分)(Organic Phosphorus Compound: Component B)
本發明中,作為B成分使用之有機磷化合物,以下述式(1)表示。In the present invention, the organophosphorus compound used as the component B is represented by the following formula (1).
式中,X1 、X2 各自獨立,係以下述式(2)表示之芳香族取代烷基。In the formula, X 1 and X 2 are each independently an aromatic substituted alkyl group represented by the following formula (2).
式中,AL係碳數1~5的分枝狀或直鏈狀脂肪族烴基。脂肪族烴基以烷二基(alkanediyl)、烷三基、烷四基為佳。Ar為苯基、萘基或蒽基,其等亦可具有取代基。Ar可以鍵結到AL中的任意碳原子上。n為1~3的整數。In the formula, AL is a branched or linear aliphatic hydrocarbon group having 1 to 5 carbon atoms. The aliphatic hydrocarbon group is preferably an alkanediyl group, an alkanetriyl group or an alkanetetrayl group. Ar is a phenyl group, a naphthyl group or an anthracenyl group, and the like may have a substituent. Ar can be bonded to any carbon atom in the AL. n is an integer of 1-3.
B成分,合宜的是選自以下述式(3)及(4)表示之有機磷化合物族群之1種或2種以上的混合物。The component B is preferably one or a mixture of two or more selected from the group of organophosphorus compounds represented by the following formulas (3) and (4).
式中,R2 、R5 各自獨立,為苯基、萘基或蒽基,其等亦可具有取代基。取代基例舉,甲基、乙基、丙基、丁基等碳數1~6的烷基,氟原子、氯原子、溴原子等鹵素原子,苯基、萘基等碳數6~12的芳基等。In the formula, R 2 and R 5 each independently represent a phenyl group, a naphthyl group or an anthracenyl group, and the like may have a substituent. Examples of the substituent include an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group or a butyl group; a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom; and a carbon number of 6 to 12 such as a phenyl group or a naphthyl group; Aryl and the like.
R1 、R3 、R4 、R6 各自獨立,係氫原子、碳數1~4的分枝狀或直鏈狀烷基、亦可具有取代基之苯基、亦可具有取代基之萘基或亦可具有取代基之蒽基。烷基例舉甲基、乙基、丙基、丁基等。取代基例舉甲基、乙基、丙基、丁基等碳數1~6的烷基,氟原子、氯原子、溴原子等鹵素原子,苯基、萘基等碳數6~12的芳基等。R 1 , R 3 , R 4 and R 6 are each independently a hydrogen atom, a branched or linear alkyl group having 1 to 4 carbon atoms, a phenyl group which may have a substituent, and a naphthalene which may have a substituent. Or a thiol group which may also have a substituent. The alkyl group is exemplified by methyl, ethyl, propyl, butyl and the like. Examples of the substituent include an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group or a butyl group; a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom; and a aryl group having 6 to 12 carbon atoms such as a phenyl group or a naphthyl group. Base.
式中,Ar1 及Ar2 各自獨立,為苯基、萘基或蒽基,其等亦可具有取代基。取代基例舉,甲基、乙基、丙基、丁基等碳數1~6的烷基,氟原子、氯原子、溴原子等鹵素原子,苯基、萘基等碳數6~12的芳基等。In the formula, Ar 1 and Ar 2 are each independently a phenyl group, a naphthyl group or an anthracenyl group, and the like may have a substituent. Examples of the substituent include an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group or a butyl group; a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom; and a carbon number of 6 to 12 such as a phenyl group or a naphthyl group; Aryl and the like.
R11 、R12 、R13 及R14 各自獨立,為氫原子、碳數1~3的脂肪族烴基、亦可具有取代基之苯基、亦可具有取代基之萘基或亦可具有取代基之蒽基。取代基例舉甲基、乙基、丙基、丁基等碳數1~6的烷基,氟原子、氯原子、溴原子等鹵素原子,苯基、萘基等碳數6~12的芳基等。R 11 , R 12 , R 13 and R 14 are each independently a hydrogen atom, an aliphatic hydrocarbon group having 1 to 3 carbon atoms, a phenyl group which may have a substituent, a naphthyl group which may have a substituent or may have a substitution. Base base. Examples of the substituent include an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group or a butyl group; a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom; and a aryl group having 6 to 12 carbon atoms such as a phenyl group or a naphthyl group. Base.
AL1 及AL2 各自獨立,為碳數1~4的分枝狀或直鏈狀脂肪族烴基。脂肪族烴基可例舉亞甲基、乙烯基、丙烯基等碳數1~4的烷二基。另外可例舉甲三基、乙三基、丙三基等碳數1~4的烷三基。另外還可例舉甲四基、乙四基、丙四基等碳數1~4的烷四基。Each of AL 1 and AL 2 is independently a branched or linear aliphatic hydrocarbon group having 1 to 4 carbon atoms. The aliphatic hydrocarbon group may, for example, be an alkylene group having 1 to 4 carbon atoms such as a methylene group, a vinyl group or a propylene group. Further, an alkyltriyl group having 1 to 4 carbon atoms such as a methyltriyl group, a trisyl group or a propyltriyl group may be mentioned. Further, an alkanetetrayl group having 1 to 4 carbon atoms such as a tetrakisyl group, an ethylenetetrayl group or a propyltetrayl group may also be mentioned.
Ar3及Ar4各自獨立,為苯基、萘基或蒽基,其等亦可具有取代基。取代基例舉,甲基、乙基、丙基、丁基等碳數1~6的烷基,氟原子、氯原子、溴原子等鹵素原子,苯基、萘基等碳數6~12的芳基等。Ar3 and Ar4 are each independently a phenyl group, a naphthyl group or an anthracenyl group, and the like may have a substituent. Examples of the substituent include an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group or a butyl group; a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom; and a carbon number of 6 to 12 such as a phenyl group or a naphthyl group; Aryl and the like.
p及q各自獨立,為0~3的整數。Ar3 及Ar4 可以各自鍵結到AL1 及AL2 的任意碳原子上。p and q are each independently and are an integer of 0 to 3. Ar 3 and Ar 4 may each be bonded to any of the carbon atoms of AL 1 and AL 2 .
而且,合宜的是以下述式(5)、(6)、(7)、(8)表示之磷系化合物。Further, a phosphorus-based compound represented by the following formulas (5), (6), (7), and (8) is preferable.
式中,R21 、R22 各自別獨立,為苯基、萘基或蒽基,其等亦可具有取代基。其中以苯基為佳。R21 及R22 的苯基、萘基或蒽基,其芳香環的氫原子亦可被取代,取代基可例舉甲基、乙基、丙基、丁基或者,該芳香環的鍵結基是以氧原子、硫原子或碳數1~4的脂肪族烴基為中間基團之碳數6~14的芳基。In the formula, R 21 and R 22 each independently represent a phenyl group, a naphthyl group or an anthracenyl group, and the like may have a substituent. Among them, phenyl is preferred. The phenyl, naphthyl or anthracenyl group of R 21 and R 22 may be substituted with a hydrogen atom of the aromatic ring, and the substituent may, for example, be a methyl group, an ethyl group, a propyl group or a butyl group, or a bond of the aromatic ring. The group is an aryl group having 6 to 14 carbon atoms and having an oxygen atom, a sulfur atom or an aliphatic hydrocarbon group having 1 to 4 carbon atoms as an intermediate group.
上述式(6)中,R31 及R34 各自獨立,為氫原子或碳數1~4的脂肪族烴基。以氫原子、甲基、乙基為佳,特別合適的是氫原子。R33 及R36 各自獨立,為碳數1~4的脂肪族烴基。以甲基或乙基為佳。R32 及R35 各自獨立,為苯基、萘基或蒽基,其等亦可具有取代基。以苯基為佳,隔著芳香族環上之碳原子鍵結到磷的部分以外的那個部分上都可以有取代基,為甲基、乙基、丙基(包含異構體)、丁基(包含異構體)或鍵結到該芳香族環的基團是以氧、硫或碳數1~4的脂肪族烴基為中間基團之碳數6~14的芳基。In the above formula (6), R 31 and R 34 are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 4 carbon atoms. A hydrogen atom, a methyl group or an ethyl group is preferred, and a hydrogen atom is particularly suitable. R 33 and R 36 are each independently and are an aliphatic hydrocarbon group having 1 to 4 carbon atoms. It is preferably a methyl group or an ethyl group. R 32 and R 35 are each independently a phenyl group, a naphthyl group or an anthracenyl group, and the like may have a substituent. Preferably, the phenyl group may have a substituent on the moiety other than the moiety bonded to the phosphorus via a carbon atom on the aromatic ring, and is a methyl group, an ethyl group, a propyl group (including an isomer), and a butyl group. The group (including an isomer) or a group bonded to the aromatic ring is an aryl group having 6 to 14 carbon atoms which is an intermediate group of oxygen, sulfur or an aliphatic hydrocarbon group having 1 to 4 carbon atoms.
上述式(6)中,R32 及R35 合適的具體例可以例舉,苯基、甲苯基、二甲苯基、三甲苯基、4-苯氧苯基、異丙苯基、萘基、4-苄苯基等,尤其以苯基為佳。In the above formula (6), specific examples of R 32 and R 35 may, for example, be phenyl, tolyl, xylyl, trimethyl, 4-phenoxyphenyl, cumyl, naphthyl, 4 -Benzylphenyl or the like, especially phenyl.
上述式(7)中,Ar1 及Ar2 各自獨立,為苯基、萘基或蒽基,其等亦可具有取代基。R11 、R12 、R13 及R14 各自獨立,係氫原子、碳數1~3的脂肪族烴基、亦可具有取代基之苯基、亦可具有取代基之萘基或亦可具有取代基之蒽基。以表示苯基為佳,隔著芳香族環上之碳原子鍵結到磷的部分以外的那個部分上都可以具有取代基,且為甲基、乙基、丙基(包含異構體)、丁基(包含異構體)或鍵結到該芳香族環的基團是以氧、硫或碳數1~4的脂肪族烴基為中間基團之碳數6~14的芳基。In the above formula (7), Ar 1 and Ar 2 are each independently a phenyl group, a naphthyl group or a fluorenyl group, and the like may have a substituent. R 11 , R 12 , R 13 and R 14 are each independently a hydrogen atom, an aliphatic hydrocarbon group having 1 to 3 carbon atoms, a phenyl group which may have a substituent, a naphthyl group which may have a substituent or may have a substitution. Base base. Preferably, the phenyl group may have a substituent on the portion other than the portion in which the carbon atom on the aromatic ring is bonded to the phosphorus, and is a methyl group, an ethyl group, a propyl group (including an isomer), The butyl group (including an isomer) or a group bonded to the aromatic ring is an aryl group having 6 to 14 carbon atoms which is an intermediate group of oxygen, sulfur or an aliphatic hydrocarbon group having 1 to 4 carbon atoms.
上述式(7)中,Ar1 及Ar2 之合適的具體例有,苯基、甲苯基、二甲苯基、三甲苯基、4-苯氧苯基、異丙苯基、萘基、4-苄苯基等,尤其以苯基為佳。In the above formula (7), specific examples of Ar 1 and Ar 2 are phenyl, tolyl, xylyl, trimethylphenyl, 4-phenoxyphenyl, cumylphenyl, naphthyl, and 4- Phenylphenyl or the like, especially phenyl is preferred.
上述式(7)中,AL1 及AL2 各自獨立,為碳數1~4的分枝狀或直鏈狀的脂肪族烴基。合宜的是碳數1~3的分枝狀或直鏈狀脂肪族烴基,尤其合適的是碳數1~2的分枝狀或直鏈狀脂肪族烴基。脂肪族烴基例舉,亞甲基、乙烯基、丙烯基等碳數1~4的烷二基。另外還例舉甲三基、乙三基、丙三基等碳數1~4的烷三基。另外亦列舉甲四基、乙四基、丙四基等碳數1~4的烷四基。In the above formula (7), each of AL 1 and AL 2 is independently a branched or linear aliphatic hydrocarbon group having 1 to 4 carbon atoms. Conveniently, a branched or linear aliphatic hydrocarbon group having 1 to 3 carbon atoms is preferable, and a branched or linear aliphatic hydrocarbon group having 1 to 2 carbon atoms is particularly preferable. The aliphatic hydrocarbon group is exemplified by an alkylene group having 1 to 4 carbon atoms such as a methylene group, a vinyl group or a propylene group. Further, an alkyltriyl group having 1 to 4 carbon atoms such as a trisyl group, a trisyl group or a propyltriyl group is also exemplified. Further, an alkanetetrayl group having 1 to 4 carbon atoms such as a tetrakis group, an ethyltetraki group or a propyltetrayl group is also mentioned.
上述式(7)中,AL1 及AL2 之合適的具體例有,亞甲基、乙烯基、亞乙基、伸丙基、亞丙基、異亞丙基等,尤其以亞甲基、乙烯基、亞乙基為佳。In the above formula (7), specific examples of AL 1 and AL 2 include methylene, vinyl, ethylene, propyl, propylene, isopropylidene, etc., especially methylene, Vinyl and ethylene are preferred.
上述式(7)中,Ar3 及Ar4 各自獨立,為苯基、萘基或蒽基,其等亦可具有取代基。合宜的是表示苯基,隔著芳香族環上的碳原子鍵結到磷的部分以外的那個部分上都可以具有取代基,且為甲基、乙基、丙基(包含異構體)、丁基(包含異構體)或者該芳香族環上的鍵結基團是以氧、硫或碳數1~4的脂肪族烴基為中間基團之碳數6~14的芳基。Ar3 及Ar4 可以分別鍵結到AL1 及AL2 的任意碳原子上。In the above formula (7), Ar 3 and Ar 4 are each independently a phenyl group, a naphthyl group or a fluorenyl group, and the like may have a substituent. It is preferred that the phenyl group has a substituent on the portion other than the portion in which the carbon atom on the aromatic ring is bonded to the phosphorus, and is a methyl group, an ethyl group, a propyl group (including an isomer), The butyl group (including an isomer) or a bonding group on the aromatic ring is an aryl group having 6 to 14 carbon atoms which is an intermediate group of oxygen, sulfur or an aliphatic hydrocarbon group having 1 to 4 carbon atoms. Ar 3 and Ar 4 may be bonded to any of the carbon atoms of AL 1 and AL 2 , respectively.
上述式(7)中,p及q各自獨立,為0~3的整數。p及q合宜的是0或1,特別合適的是0。In the above formula (7), p and q are each independently and are an integer of 0 to 3. Suitably p and q are 0 or 1, particularly suitably 0.
上述式(8)中,R41 及R44 各自獨立,為氫原子、碳數1~4的脂肪族烴基、亦可具有取代基之苯基、亦可具有取代基之萘基或亦可具有取代基之蒽基。以氫原子、碳數1~3的脂肪族烴基,或亦可具有取代基之苯基為佳。R41 及R44 為苯基時,隔著芳香族環上的碳原子鍵結到磷上的部分以外之任何都可以有取代基,且為甲基、乙基、丙基(包含異構體)、丁基(包含異構體)或者該芳香族環的鍵結基團係以氧、硫或碳數1~4的脂肪族烴基為中間基團之碳數6~14的芳基。In the above formula (8), R 41 and R 44 are each independently a hydrogen atom, an aliphatic hydrocarbon group having 1 to 4 carbon atoms, a phenyl group which may have a substituent, a naphthyl group which may have a substituent, or may have The base of the substituent. A hydrogen atom, an aliphatic hydrocarbon group having 1 to 3 carbon atoms, or a phenyl group which may have a substituent is preferred. When R 41 and R 44 are a phenyl group, any substituent other than a moiety bonded to the phosphorus via a carbon atom on the aromatic ring may have a substituent, and is a methyl group, an ethyl group, or a propyl group (including an isomer) The butyl group (including an isomer) or the bonding group of the aromatic ring is an aryl group having 6 to 14 carbon atoms which is an intermediate group of oxygen, sulfur or an aliphatic hydrocarbon group having 1 to 4 carbon atoms.
上述式(8)中,R41 及R44 之合適具體例可例舉,氫原子、甲基、乙基、丙基(包含異構體)、苯基、甲苯基、二甲苯基、三甲苯基、4-苯氧苯基、異丙苯基、萘基、4-苄苯基等,尤其以氫原子、甲基,或苯基為佳。In the above formula (8), a suitable specific example of R 41 and R 44 may, for example, be a hydrogen atom, a methyl group, an ethyl group, a propyl group (including an isomer), a phenyl group, a tolyl group, a xylyl group or a trimethylbenzene group. The group is 4-phenyloxyphenyl, cumylphenyl, naphthyl, 4-benzylphenyl or the like, and particularly preferably a hydrogen atom, a methyl group or a phenyl group.
R42 、R43 、R45 及R46 各自獨立,為苯基、萘基或蒽基,其等亦可具有取代基。合宜的是表示苯基,隔著芳香族環上的碳原子鍵結到磷上的部分以外的那個部分都可以具有取代基,且為甲基、乙基、丙基(包含異構體)、丁基(包含異構體)或該芳香族環的鍵結基團係以氧、硫或碳數1~4的脂肪族烴基為中間基團之碳數6~14的芳基。R 42 , R 43 , R 45 and R 46 are each independently a phenyl group, a naphthyl group or an anthracenyl group, and the like may have a substituent. It is preferred that the phenyl group has a substituent other than the moiety bonded to the phosphorus via a carbon atom on the aromatic ring, and is a methyl group, an ethyl group, a propyl group (including an isomer), The butyl group (including the isomer) or the bonding group of the aromatic ring is an aryl group having 6 to 14 carbon atoms which is an intermediate group of oxygen, sulfur or an aliphatic hydrocarbon group having 1 to 4 carbon atoms.
上述式(8)中,R42 、R43 、R45 及R46 之合宜的具體例有,苯基、甲苯基、二甲苯基、三甲苯基、4-苯氧苯基、異丙苯基、萘基、4-苄苯基等,尤其以苯基為佳。In the above formula (8), specific examples of R 42 , R 43 , R 45 and R 46 are phenyl, tolyl, xylyl, trimethylphenyl, 4-phenoxyphenyl, cumene. Or naphthyl, 4-benzylphenyl, etc., especially phenyl.
以前述式(1)表示之有機磷化合物(B成分),相對於該等樹脂顯示極優異的難燃效果。在本發明人等已知的範圍內,習知由其等樹脂的無鹵素導致之難燃化,利用少量的難燃劑之難燃化是困難的,在實用上有很多問題點。The organophosphorus compound (component B) represented by the above formula (1) exhibits an extremely excellent flame retarding effect with respect to these resins. In the range known by the inventors of the present invention, it is known that it is difficult to ignite due to the halogen-free of the resin, and it is difficult to use a small amount of the flame retardant to be flammable, and there are many problems in practical use.
但是若依據本發明,驚奇的發現前述有機磷化合物(B成分),藉其本身單獨的少量使用容易達成該等樹脂的難燃化,亦不會損害樹脂本來的特性。However, according to the present invention, it has been surprisingly found that the above-mentioned organophosphorus compound (component B) is easily ignitable by a small amount of itself, and the original properties of the resin are not impaired.
然而本發明中除B成分以外,因為B成分使用比例的降低、成形品難燃性的改善、成形品物理性質的改良、成形品化學性質的提高或其他目的當然可以混合B成分以外的磷化合物、含氟樹脂或其他添加劑。就其等之其他混合成分在後面做具體的說明。However, in the present invention, in addition to the component B, the phosphorus component other than the component B can be mixed because the ratio of the component B is lowered, the flame retardancy of the molded article is improved, the physical properties of the molded article are improved, the chemical properties of the molded article are improved, or other purposes are of course possible. , fluorine-containing resin or other additives. The other mixed components such as these will be specifically described later.
本發明之樹脂組成物中的難燃劑之有機磷化合物(B成分),以前述式(1)表示,惟最好的代表化合物是以下述式(1-a)、(1-b)、(1-c)、(1-d)表示之化合物。The organophosphorus compound (component B) of the flame retardant in the resin composition of the present invention is represented by the above formula (1), and the most preferable representative compound is represented by the following formulas (1-a) and (1-b). Compounds represented by (1-c) and (1-d).
接著就本發明之前述有機磷化合物(B成分)的合成法做說明。B成分亦可是藉以下說明之方法以外的方法加以製造而成者。Next, the synthesis method of the above-mentioned organophosphorus compound (component B) of the present invention will be described. The component B may be produced by a method other than the method described below.
B成分藉例如,使三氯化磷在季戊四醇中反應,然後利用甲醇鈉等鹼金屬化合物來處理氧化反應物,接著使芳烷基鹵化物(aralkyl-halide)反應來製得。The component B is obtained, for example, by reacting phosphorus trichloride in pentaerythritol, and then treating the oxidation reactant with an alkali metal compound such as sodium methoxide, followed by reacting an aralkyl-halide.
另外,使芳烷基醇在由使芳烷基膦酸二氯化物在季戊四醇中反應之方法或,使三氯化磷在季戊四醇中反應製得之化合物中反應,接著在高溫下進行Arbuzov轉移之方法可藉而製得。後者的反應公示於例如美國專利第3,141,032號說明書、特開昭54-157156號公報、特開昭53-39698號公報中。Further, the aralkyl alcohol is reacted in a compound obtained by reacting an aralkylphosphonic acid dichloride in pentaerythritol or a compound obtained by reacting phosphorus trichloride in pentaerythritol, followed by Arbuzov transfer at a high temperature. The method can be obtained by borrowing. The latter reaction is disclosed in, for example, U.S. Patent No. 3,141,032, Japanese Patent Laid-Open Publication No. SHO-54-157156, and No. Sho 53-39698.
以下說明B成分的具體合成法,惟因為該合成法僅是說明,故本發明使用之B成分,除該等合成法以外,亦可是藉其之改變或其他合成法合成者。較具體的合成法在後述之製備例中加以說明。The specific synthesis method of the component B will be described below. However, since the synthesis method is merely illustrative, the component B used in the present invention may be synthesized by a modification or other synthesis method in addition to the synthesis methods. A more specific synthesis method will be described in the preparation examples described later.
(I) B成分中之前述(1-a)的有機磷化合物;使三氯化磷在季戊四醇中反應,然後利用甲醇鈉來處理由叔丁醇處理之氧化反應物,使溴苄反應藉以製得。(I) an organophosphorus compound of the above (1-a) in component B; reacting phosphorus trichloride in pentaerythritol, and then treating the oxidation reaction product treated with t-butanol with sodium methoxide to thereby react with benzyl bromide Got it.
(II) B成分中之前述(1-b)的有機磷化合物;使三氯化磷在季戊四醇中反應,然後利用甲醇鈉來處理由叔丁醇處理之氧化反應物,使1-溴乙基苯反應藉以製得。(II) the above-mentioned (1-b) organophosphorus compound in component B; reacting phosphorus trichloride in pentaerythritol, and then treating the oxidation reaction product treated with t-butanol with sodium methoxide to obtain 1-bromoethyl group The benzene reaction is obtained.
(III) B成分中之前述(1-c)的有機磷化合物;使三氣化磷在季戊四醇中反應,然後利用甲醇鈉來處理由叔丁醇處理之氧化反應物,使2-溴乙基苯反應藉以製得。(III) the above-mentioned (1-c) organophosphorus compound in component B; reacting tri-phosphorus phosphorus in pentaerythritol, and then treating the oxidation reaction product treated with t-butanol with sodium methoxide to obtain 2-bromoethyl group The benzene reaction is obtained.
(IV) B成分中之前述(1-d)的有機磷化合物;使二苯基甲基膦醯二氯在季戊四醇中反應藉而製得。(IV) The above-mentioned (1-d) organophosphorus compound in the component B; obtained by reacting diphenylmethylphosphonium dichloride in pentaerythritol.
另外其他方法,係使三氯化磷在季戊四醇中反應,在觸媒共存下加熱處理製得之生成物與二苯甲醇的反應生成物藉而製得。In addition, other methods are carried out by reacting phosphorus trichloride in pentaerythritol, and reacting the product obtained by heat treatment in the presence of a catalyst with diphenylmethanol.
前述B成分的酸價,合宜的是0.7mgKOH/g以下,較佳為0.5mgKOH/g以下。透過使用酸價在該範圍的B成分,製得難燃性及色相優異的成形品,而且製得熱安定性良好的成形品。B成分,以其酸價在0.4mgKOH/g以下者最佳。此處之酸價意指,中和1g樣品(B成分)中的酸成分所必須之KOH的量(mg)。The acid value of the component B is preferably 0.7 mgKOH/g or less, preferably 0.5 mgKOH/g or less. By using the component B having an acid value in this range, a molded article excellent in flame retardancy and hue is obtained, and a molded article having good heat stability is obtained. The component B is preferably the one having an acid value of 0.4 mgKOH/g or less. The acid value herein means the amount (mg) of KOH necessary to neutralize the acid component in the 1 g sample (component B).
而且,B成分使用其HPLC純度合宜的是至少90%,較佳為至少95%者。這種高純度在成形品的難燃性、色相,及熱安定性上優良。此處B成分的HPLC純度的測定,可以使用以下方法藉而有效的測定。Further, the component B is preferably used in an amount of at least 90%, preferably at least 95%, based on its HPLC purity. Such high purity is excellent in flame retardancy, hue, and thermal stability of the molded article. Here, the HPLC purity of the component B can be measured by the following method.
色譜柱使用野村化學公司製Develosil ODS-7 300mm×4mmΦ,色譜柱溫度為40℃。溶劑使用乙腈與水的6:4(容量比)的混合溶液,注入5μl。檢測器使用UV-260nm。The column was Develosil ODS-7 300 mm × 4 mm Φ manufactured by Nomura Chemical Co., Ltd., and the column temperature was 40 °C. The solvent was mixed with a 6:4 (volume ratio) solution of acetonitrile and water, and 5 μl was injected. The detector uses UV-260 nm.
除去B成分中雜質的方法,並無特殊限定,惟利用水、甲醇等溶劑進行再製漿(repulp)洗淨(利用溶劑反復進行數次洗淨、濾過)之方法是最有效的,而且成本亦是最有利的。The method of removing the impurities in the component B is not particularly limited, but the method of repulp washing with a solvent such as water or methanol (removing and filtering several times with a solvent) is most effective and cost. It is also the most advantageous.
B成分的含量,相對於樹脂成分(A成分)100重量分為1~100重量分,合宜的是2~90重量分,較佳為2~70重量分,更好的是3~50重量分的範圍。B成分的含量,根據所期望的難燃性水準、樹脂成分(A成分)的種類等來選擇其合適的範圍。構成該等組成物之A成分及B成分以外,只要不損害本發明之目的亦可依需要使用其他成分,可以使用其他的難燃劑、難燃助劑、含氟樹脂來改變B成分的混合量,多數情況下,透過該等的使用可以降低B成分的混合比例。本發明之難燃性樹脂組成物,在UL-94規格的難燃水準上,可以至少達成V-2。The content of the component B is 1 to 100 parts by weight, preferably 2 to 90 parts by weight, preferably 2 to 70 parts by weight, more preferably 3 to 50 parts by weight, per 100 parts by weight of the resin component (component A). The scope. The content of the component B is selected in accordance with the desired flame retardancy level, the type of the resin component (component A), and the like. In addition to the components A and B constituting the composition, other components may be used as needed without impairing the object of the present invention, and other flame retardants, flame retardant aids, and fluorine-containing resins may be used to change the mixture of the components B. The amount, in many cases, can reduce the mixing ratio of the B component by using these. The flame retardant resin composition of the present invention can at least achieve V-2 in the flame retardant level of the UL-94 specification.
(難燃性樹脂組成物的製備)(Preparation of a flame retardant resin composition)
本發明之難燃性樹脂組成物,可以透過使用V型混合機、高速混合機、高速浮上混合機、亨舍爾混合機等混合機將樹脂成分(A成分)、有機磷化合物(B成分)及依需要之其他成分加以預混合後,用混煉機加以熔融混合來製備。The flame retardant resin composition of the present invention can be a resin component (component A) or an organophosphorus compound (component B) by using a mixer such as a V-type mixer, a high-speed mixer, a high-speed float-up mixer, or a Henschel mixer. And pre-mixing other components as needed, and then melt-mixing with a kneader to prepare.
混煉機可以使用各種熔融混合機,例如捏合機、單軸或雙軸擠壓機等,其中使用雙軸擠壓機以220~280℃,合適的是230~270℃的溫度來熔融樹脂組成物,利用側面加料機(side feeder)將液體成分注入,押出,利用製粒機進行製粒化之方法適宜使用。The mixer can use various melt mixers, such as kneaders, uniaxial or biaxial extruders, etc., in which a biaxial extruder is used to melt the resin at a temperature of 220 to 280 ° C, suitably 230 to 270 ° C. The method of injecting and ejecting a liquid component by a side feeder and granulating by a granulator is suitably used.
(用途)(use)
本發明之難燃性樹脂組成物實質不含鹵素,具有非常高的難燃性能,作為成形家電製品部件、電力‧電子部件、汽車部件、機械‧機構部件、化妝品容器等各種成形品的材料是有用的。具體而言,在破碎機部件、開關部件、發動機部件、點火線圈機箱、電源插頭、電源插座、繞線管、連結器、繼電器箱、保險絲箱、返馳變壓器部件、聚焦部件(Focus block)、分配器蓋、導線連結器等。而且作為薄壁化發展的外罩(housing)、罩蓋(caging)或底盤(chassis),例如電子‧電力製品(例如電話機、電腦、列印機、傳真、複印機、電視、錄像機、聲頻機器等家電‧OA機器或該等之部件等)的外罩、罩蓋或底盤上是有用的。尤其作為要求有優良的耐熱性、難燃性之列印機的框體、固定單元部件、傳真等家電‧OA製品的機械‧機構部件等是有用的。The flame-retardant resin composition of the present invention contains substantially no halogen and has a very high flame retardancy. The materials for various molded articles such as molded household electrical appliance parts, electric power, electronic parts, automobile parts, machinery, mechanical parts, and cosmetic containers are useful. Specifically, in the crusher component, the switch component, the engine component, the ignition coil case, the power plug, the power socket, the bobbin, the connector, the relay box, the fuse box, the flyback transformer component, the focus block, the focus block, Dispenser cover, wire connector, etc. Moreover, as a housing, housing, or chassis for thinning, such as electronic appliances, such as telephones, computers, printers, fax machines, photocopiers, televisions, video recorders, audio equipment, and the like. ‧ OA machines or such components, etc. are useful on the cover, cover or chassis. In particular, it is useful as a machine body, a mechanical unit, a mechanical component, a mechanical component, a fixing unit, a facsimile, etc., which are required to have excellent heat resistance and flame retardancy.
成形方法之射出成形、吹氣模製、壓製成形等,並無特殊限制,惟合宜的是透過使用射出成形機將粒狀的樹脂組成物加以射出成形來製造。The injection molding, the blow molding, the press molding, and the like of the molding method are not particularly limited, and it is preferable to produce the granular resin composition by injection molding using an injection molding machine.
實施例Example
以下例舉實施例說明本發明,惟本發明並未限定該等實施例。另外,利用下述方法進行評價。The invention is illustrated by the following examples, which are not intended to limit the invention. In addition, evaluation was performed by the following method.
(1)難燃性(UL-94評價)(1) Flame retardancy (UL-94 evaluation)
難燃性使用厚度1/16英寸(1.6mm)的試驗片,作為難燃性的評價尺度,準據美國UL規格的UL-94中規定之垂直燃燒試驗來進行評價。每一個試驗片去除火焰後的燃燒會在10秒內滅火,而且,未發生脫脂棉著火者為V-0,30秒內滅火者為V-2,該標準以下者為notV。For the flame retardancy, a test piece having a thickness of 1/16 inch (1.6 mm) was used as an evaluation standard for flame retardancy, and it was evaluated according to the vertical burning test specified in UL-94 of the UL specification of the United States. The fire after each flame is removed from the test piece will be extinguished within 10 seconds. Moreover, if the cotton wool is not fired, it will be V-0, and within 30 seconds, the fire extinguisher will be V-2. The standard below is notV.
(2)酸價(2) Acid price
準據JIS-K-3504實施測定。The measurement was carried out in accordance with JIS-K-3504.
製備例1Preparation Example 1
2,4,8,10-四氧雜-3,9-二磷雜螺[5.5]十一烷、3,9-二苄基-3,9-二氧化物(FR-1)的製備。Preparation of 2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-dibenzyl-3,9-dioxide (FR-1).
在具備溫度計、電容器、滴下漏斗的反應容器中備好季戊四醇816.9g(6.0莫耳)、嘧啶19.0g(0.24莫耳)、甲苯2250.4g(24.4莫耳),加以攪拌。使用該滴下漏斗在該反應容器中添加三氯化磷1651.8g(12.0莫耳),完成添加後,以60℃進行加熱攪拌。反應後,冷卻至室溫,在製得之反應物中添加二氯甲烷26.50分,邊水冷邊滴下叔丁醇889.4g(12.0莫耳)及二氯甲烷150.2g(1.77莫耳)。用甲苯及二氯甲烷將製得之結晶洗淨濾過。以80℃,1.33×102 Pa將獲得之濾取物乾燥12小時,製得白色固體1341.1g(5.88莫耳)。藉31 P,1 H-NMR光譜確認製得之固體為2,4,8,10-四氧雜-3,9-二磷雜螺[5.5]十一烷、3,9-二氫-3,9-二氧化物。In a reaction vessel equipped with a thermometer, a capacitor, and a dropping funnel, 816.9 g (6.0 mol) of pentaerythritol, 19.0 g (0.24 mol) of pyrimidine, and 2250.4 g (24.4 mol) of toluene were prepared and stirred. To the reaction vessel, 1651.8 g (12.0 mol) of phosphorus trichloride was added to the reaction vessel, and after completion of the addition, the mixture was heated and stirred at 60 °C. After the reaction, the mixture was cooled to room temperature, and dichloromethane (26.50 ml) was added to the obtained reaction mixture, and 889.4 g (12.0 mol) of t-butyl alcohol and 150.2 g (1.77 mol) of dichloromethane were added dropwise with water. The obtained crystals were washed and filtered with toluene and dichloromethane. The obtained filtrate was dried at 80 ° C, 1.33 × 10 2 Pa for 12 hours to obtain 1341.1 g (5.88 mol) as a white solid. The solid obtained by the 31 P, 1 H-NMR spectrum was confirmed to be 2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-dihydro-3. , 9-dioxide.
在具備溫度計、電容器、滴下漏斗的反應容器中備好製得之2,4,8,10-四氧雜-3,9-二磷雜螺[5.5]十一烷、3,9-二氫-3,9-二氧化物1341.0g(5.88莫耳)、DMF6534.2g(89.39莫耳),加以攪拌。在該反應容器中在水冷下添加甲醇鈉648.7g(12.01莫耳)。在水冷下攪拌2小時後,在室溫下進行5小時攪拌。然後除去DMF後,添加DMF2613.7g(35.76莫耳),在水冷下向該反應混合物中滴下溴苄2037.79g(11.91莫耳)。水冷下攪拌3小時後,除去DMF,加水8L,濾取析出之固體,用2L水洗淨2次。將製得之粗精製物與甲醇4L加入至具備電容器、攪拌機之反應容器中,迴流約2小時。冷卻至室溫後,濾過結晶藉以進行分離,用2L甲醇洗淨後,以120℃、1.33×102 Pa將製得之濾取物乾燥19小時,製得白色的鱗片狀結晶1863.5g(4.56莫耳)。利用31 P、1 H-NMR光譜及元素分析確認製得之結晶為2,4,8,10-四氧雜-3,9-二磷雜螺[5.5]十一烷、3,9-二苄基-3,9-二氧化物。收率為76%,31 P-NMR純度為99%。另外,利用本文記載之方法測定之HPLC純度為99%。酸價為0.06mgKOH/g。Prepare 2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-dihydrogen in a reaction vessel equipped with a thermometer, a capacitor, and a dropping funnel. -3,9-dioxide 1341.0 g (5.88 mol), DMF 6534.2 g (89.39 mol), and stirred. In the reaction vessel, 648.7 g (12.01 mol) of sodium methoxide was added under water cooling. After stirring for 2 hours under water cooling, stirring was carried out for 5 hours at room temperature. Then, after removing DMF, DMF 2613.7 g (35.76 mol) was added, and to the reaction mixture, bromobenzyl 2037.79 g (11.91 mol) was added dropwise under water cooling. After stirring for 3 hours under water cooling, DMF was removed, 8 L of water was added, and the precipitated solid was collected by filtration and washed twice with 2 L of water. The obtained crude product and 4 L of methanol were placed in a reaction vessel equipped with a capacitor and a stirrer, and refluxed for about 2 hours. After cooling to room temperature, the crystals were filtered to separate them, and after washing with 2 L of methanol, the obtained filtrate was dried at 120 ° C, 1.33 × 10 2 Pa for 19 hours to obtain white scaly crystals of 1863.5 g (4.56). Moore). The crystals obtained by 31 P, 1 H-NMR spectroscopy and elemental analysis were confirmed to be 2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-di. Benzyl-3,9-dioxide. The yield was 76%, and the 31 P-NMR purity was 99%. In addition, the HPLC purity determined by the method described herein was 99%. The acid value was 0.06 mgKOH/g.
1 H-NMR(DMSO-d6 ,300MHz):δ7.2-7.4(m,10H),4.1-4.5(m-8H),3.5(d,4H),31 P-NMR(DMSO-d6 ,120MHz):δ23.1(S),熔點:255-256℃,元素分析計算值:C,55.89;H,5.43,測定值:C,56.24;H,5.35 1 H-NMR (DMSO-d 6, 300MHz): δ7.2-7.4 (m, 10H), 4.1-4.5 (m-8H), 3.5 (d, 4H), 31 P-NMR (DMSO-d 6, 120MHz): δ23.1(S), melting point: 255-256°C, calculated for elemental analysis: C, 55.89; H, 5.43, measured: C, 56.24; H, 5.35
製備例2Preparation Example 2
2,4,8,10-四氧雜-3,9-二磷雜螺[5.5]十一烷、3,9-二苄基-3,9-二氧化物(FR-2)的製備Preparation of 2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-dibenzyl-3,9-dioxide (FR-2)
在具有攪拌機、溫度計、電容器的反應容器中,填充3,9-二苄氧基-2,4,8,10-四氧雜-3,9-二磷雜螺[5.5]十一烷22.55g(0.055莫耳)、溴苄19.01g(0.11莫耳)及二甲苯33.54g(0.32莫耳),室溫下邊攪拌,邊吹氮乾燥。接著用油浴開始加熱,以迴流溫度(約130℃)加熱4小時,攪拌。加熱完成後,冷卻至室溫,加入二甲苯20mL,然後攪拌30分鐘。濾過析出之結晶藉以分離,用二甲苯20mL洗淨2次。將製得之粗精製物與甲醇40mL加入至具備電容器、攪拌機之反應容器中,迴流約2小時。冷卻至室溫後,藉濾過結晶來進行分離,用甲醇20mL洗淨後,以120℃,1.33×102 Pa乾燥製得之濾取物19小時,獲得白色鱗片狀結晶。利用質譜分析、1 H、31 P核磁共振光譜分析及元素分析確認生成物為雙苄基季戊四醇二膦酸酯。產量為20.60g,收率為91%,31 P-NMR純度為99%。另外,以本文記載之方法測定之HPLC純度為99%。酸價為0.05mgKOH/g。In a reaction vessel with a stirrer, thermometer, and capacitor, filled with 3,9-dibenzyloxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane 22.55 g (0.055 mol), benzyl bromide 19.01 g (0.11 mol) and xylene 33.54 g (0.32 mol), and stirred at room temperature while drying with nitrogen. Heating was then started with an oil bath, and the mixture was heated at a reflux temperature (about 130 ° C) for 4 hours and stirred. After the completion of the heating, the mixture was cooled to room temperature, and 20 mL of xylene was added, followed by stirring for 30 minutes. The precipitated crystals were separated by filtration and washed twice with 20 mL of xylene. The obtained crude product and 40 mL of methanol were placed in a reaction vessel equipped with a capacitor and a stirrer, and refluxed for about 2 hours. After cooling to room temperature, the mixture was separated by filtration, and washed with methanol (20 mL), and then filtered and dried at 120 ° C, 1.33 × 10 2 Pa for 19 hours to obtain white flaky crystals. The product was confirmed to be bisbenzyl pentaerythritol diphosphonate by mass spectrometry, 1 H, 31 P nuclear magnetic resonance spectroscopy and elemental analysis. The yield was 20.60 g, the yield was 91%, and the 31 P-NMR purity was 99%. Further, the HPLC purity measured by the method described herein was 99%. The acid value was 0.05 mgKOH/g.
1 H-NMR(DMSO-d6 ,300MHz):δ7.2-7.4(m,10H),4.1-4.5(m,8H),3.5(d,4H),31 P-NMR(DMSO-d6 ,120MHz):δ23.1(S),熔點:257℃ 1 H-NMR (DMSO-d 6 , 300 MHz): δ 7.2-7.4 (m, 10H), 4.1-4.5 (m, 8H), 3.5 (d, 4H), 31 P-NMR (DMSO-d 6 , 120MHz): δ23.1(S), melting point: 257°C
製備例3Preparation Example 3
2,4,8,10-四氧雜-3,9-二磷雜螺[5.5]十一烷、3,9-二α-甲苄基-3,9-二氧化物(FR-3)的製備2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-di-α-benzyl-3-,9-dioxide (FR-3) Preparation
在備有溫度計、電容器、滴下漏斗的反應容器中備好季戊四醇816.9g(6.0莫耳)、嘧啶19.0g(0.24莫耳)、甲苯2250.4g(24.4莫耳),加以攪拌。使用該滴下漏斗在該反應容器中添加三氯化磷1651.8g(12.0莫耳),添加完成後,以60℃進行加熱攪拌。反應後,冷卻至室溫,在製得之反應物中添加二氯甲烷5180.7g(61.0莫耳),邊水冷邊滴下叔丁醇889.4g(12.0莫耳)及二氯甲烷150.2g(1.77莫耳)。用甲苯及二氯甲烷將製得之結晶洗淨濾過。以80℃,1.33×102 Pa將製得之濾取物乾燥12小時,獲得白色固體1341.1g(5.88莫耳)。藉31 P、1 HNMR光譜確認製得之固體為2,4,8,10-四氧雜-3,9-二磷雜螺[5.5]十一烷、3,9-二氫-3,9-二氧化物。In a reaction vessel equipped with a thermometer, a capacitor, and a dropping funnel, 816.9 g (6.0 mol) of pentaerythritol, 19.0 g (0.24 mol) of pyrimidine, and 2250.4 g (24.4 mol) of toluene were prepared and stirred. To the reaction vessel, 1651.8 g (12.0 mol) of phosphorus trichloride was added using the dropping funnel, and after the addition was completed, the mixture was heated and stirred at 60 °C. After the reaction, the mixture was cooled to room temperature, and 5180.7 g (61.0 mol) of dichloromethane was added to the obtained reaction mixture, and 889.4 g (12.0 mol) of t-butanol and 150.2 g of methylene chloride (1.77 mol) were added dropwise while cooling with water. ear). The obtained crystals were washed and filtered with toluene and dichloromethane. The obtained filtrate was dried at 80 ° C, 1.33 × 10 2 Pa for 12 hours to obtain 1341.1 g (5.88 mol) of a white solid. The solid obtained by 31 P, 1 H NMR spectroscopy confirmed 2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-dihydro-3,9 - dioxide.
在備有溫度計、電容器、滴下漏斗的反應容器中備好製得之2,4,8,10-四氧雜-3,9-二磷雜螺[5.5]十一烷、3,9-二氫-3,9-二氧化物1341.0g(5.88莫耳)、DMF6534.2g(89.39莫耳),加以攪拌。在該容器中在水冷下添加甲醇鈉648.7g(12.01莫耳)。以水冷攪拌2小時後,在室溫下進行5小時攪拌。然後除去DMF後,添加DMF2613.7g(35.76莫耳),在水冷下向該反應混合物中滴下1-溴乙基苯2204.06g(11.91莫耳)。水冷下攪拌3小時後,除去DMF,加水8L,濾取析出之固體,用2L水洗淨2次。將製得之粗精製物與甲醇4L加入至備有電容器、攪拌機之反應容器中,迴流約2小時。冷卻至室溫後,濾過結晶藉以進行分離,用2L甲醇洗淨後,以120℃、1.33×102 Pa將製得之濾取物乾燥19小時,製得白色的鱗片狀結晶1845.9g(4.23莫耳)。利用31 P-NMR、1 H-NMR光譜及元素分析確認製得之結晶為2,4,8,10-四氧雜-3,9-二磷雜螺[5.5]十一烷、3,9-二α-甲苄基-3,9-二氧化物。31 PNMR純度為99%。另外,利用本文記載的方法測定之HPLC純度為99%。酸價為0.03mgKOH/g。Prepare 2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-di in a reaction vessel equipped with a thermometer, a capacitor, and a dropping funnel. Hydrogen-3,9-dioxide 1341.0 g (5.88 mol), DMF 6534.2 g (89.39 mol), and stirred. In the vessel, 648.7 g (12.01 mol) of sodium methoxide was added under water cooling. After stirring for 2 hours with water cooling, stirring was carried out for 5 hours at room temperature. Then, after removing DMF, DMF 2613.7 g (35.76 mol) was added, and 1-bromoethylbenzene 2204.06 g (11.91 mol) was added dropwise to the reaction mixture under water cooling. After stirring for 3 hours under water cooling, DMF was removed, 8 L of water was added, and the precipitated solid was collected by filtration and washed twice with 2 L of water. The obtained crude product and 4 L of methanol were placed in a reaction vessel equipped with a capacitor and a stirrer, and refluxed for about 2 hours. After cooling to room temperature, the crystals were filtered to separate, and after washing with 2 L of methanol, the obtained filtrate was dried at 120 ° C, 1.33 × 10 2 Pa for 19 hours to obtain white flaky crystals of 1845.9 g (4.23). Moore). The crystals obtained were confirmed to be 2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9 by 31 P-NMR, 1 H-NMR spectroscopy and elemental analysis. - bis-methylbenzyl-3,9-dioxide. The 31 P NMR purity was 99%. Further, the HPLC purity measured by the method described herein was 99%. The acid value was 0.03 mgKOH/g.
1 H-NMR(CDCl3 ,300MHz):δ7.2-7.4(m,10H),4.0-4.2(m,4H),3.4-3.8(m,4H),3.3(qd,4H),1.6(ddd,6H),31 P-NMR(CDCl3 ,120MHz):δ28.7(S),熔點:190-210℃,元素分析計算值:C,57.80;H:6.01,測定值:C,57.83;H,5.96 1 H-NMR (CDCl 3 , 300 MHz): δ 7.2-7.4 (m, 10H), 4.0-4.2 (m, 4H), 3.4-3.8 (m, 4H), 3.3 (qd, 4H), 1.6 (ddd , 6H), 31 P-NMR (CDCl 3 , 120 MHz): δ 28.7 (S), m.p.: 190-210 ° C, calc.: C, 57.80; H: 6.01, measured: C, 57.83; , 5.96
製備例4Preparation Example 4
2,4,8,10-四氧雜-3,9-二磷雜螺[5.5]十一烷、3,9-二(2-苯乙基)-3,9-二氧化物(FR-4)的製備2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis(2-phenylethyl)-3,9-dioxide (FR- 4) Preparation
在備有溫度計、電容器、滴下漏斗的反應容器中備好季戊四醇816.9g(6.0莫耳)、嘧啶19.0g(0.24莫耳)、甲苯2250.4g(24.4莫耳),加以攪拌。使用該滴下漏斗在該反應容器中添加三氯化磷1651.8g(12.0莫耳),添加完成後,以60℃進行加熱攪拌。反應後,冷卻至室溫,在製得之反應物中添加二氯甲烷5180.7g(61.0莫耳),邊水冷邊滴下叔丁醇889.4g(12.0莫耳)及二氯甲烷150.2g(1.77莫耳)。用甲苯及二氯甲烷將製得之結晶洗淨濾過。以80℃,1.33×102 Pa將製得之濾取物乾燥12小時,獲得白色固體1341.1g(5.88莫耳)。藉31 P、1 H-NMR光譜確認製得之固體為2,4,8,10-四氧雜-3,9-二磷雜螺[5.5]十一烷、3,9-二氫-3,9-二氧化物。In a reaction vessel equipped with a thermometer, a capacitor, and a dropping funnel, 816.9 g (6.0 mol) of pentaerythritol, 19.0 g (0.24 mol) of pyrimidine, and 2250.4 g (24.4 mol) of toluene were prepared and stirred. To the reaction vessel, 1651.8 g (12.0 mol) of phosphorus trichloride was added using the dropping funnel, and after the addition was completed, the mixture was heated and stirred at 60 °C. After the reaction, the mixture was cooled to room temperature, and 5180.7 g (61.0 mol) of dichloromethane was added to the obtained reaction mixture, and 889.4 g (12.0 mol) of t-butanol and 150.2 g of methylene chloride (1.77 mol) were added dropwise while cooling with water. ear). The obtained crystals were washed and filtered with toluene and dichloromethane. The obtained filtrate was dried at 80 ° C, 1.33 × 10 2 Pa for 12 hours to obtain 1341.1 g (5.88 mol) of a white solid. The solid obtained by the 31 P, 1 H-NMR spectrum was confirmed to be 2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-dihydro-3. , 9-dioxide.
在備有溫度計、電容器、滴下漏斗的反應容器中備好製得之2,4,8,10-四氧雜-3,9-二磷雜螺[5.5]十一烷、3,9-二氫-3,9-二氧化物1341.0g(5.88莫耳)、DMF6534.2g(89.39莫耳),加以攪拌。在該容器中在水冷下添加甲醇鈉648.7g(12.01莫耳)。在水冷下攪拌2小時後,在室溫下進行5小時攪拌。然後除去DMF後,添加DMF2613.7g(35.76莫耳),在水冷下向該反應混合物中滴下(2-溴乙基)苯2183.8g(11.8莫耳)。水冷下攪拌3小時後,除去DMF,加水8L,濾取析出之固體,用2L水洗淨2次。將製得之粗精製物與甲醇4L加入至備有電容器、攪拌機之反應容器中,迴流約2小時。冷卻至室溫後,濾過結晶藉以進行分離,用2L甲醇洗淨後,以120℃、1.33×102 Pa將製得之濾取物乾燥19小時,製得白色粉末1924.4g(4.41莫耳)。利用31 P-NMR、1 H-NMR光譜及元素分析確認製得之固體為2,4,8,10-四氧雜-3,9-二磷雜螺[5.5]十一烷、3,9-二(2-苯乙基)-3,9-二氧化物。31 P-NMR純度為99%。另外,利用本文記載的方法測定之HPLC純度為99%。酸價為0.03mgKOH/g。Prepare 2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-di in a reaction vessel equipped with a thermometer, a capacitor, and a dropping funnel. Hydrogen-3,9-dioxide 1341.0 g (5.88 mol), DMF 6534.2 g (89.39 mol), and stirred. In the vessel, 648.7 g (12.01 mol) of sodium methoxide was added under water cooling. After stirring for 2 hours under water cooling, stirring was carried out for 5 hours at room temperature. Then, after removing DMF, DMF 2613.7 g (35.76 mol) was added, and 2183.8 g (11.8 mol) of (2-bromoethyl)benzene was added dropwise to the reaction mixture under water cooling. After stirring for 3 hours under water cooling, DMF was removed, 8 L of water was added, and the precipitated solid was collected by filtration and washed twice with 2 L of water. The obtained crude product and 4 L of methanol were placed in a reaction vessel equipped with a capacitor and a stirrer, and refluxed for about 2 hours. After cooling to room temperature, the crystals were filtered to separate them, and after washing with 2 L of methanol, the obtained filtrate was dried at 120 ° C, 1.33 × 10 2 Pa for 19 hours to obtain a white powder of 1924.4 g (4.41 m). . The solids obtained were confirmed to be 2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9 by 31 P-NMR, 1 H-NMR spectroscopy and elemental analysis. - bis(2-phenylethyl)-3,9-dioxide. The 31 P-NMR purity was 99%. Further, the HPLC purity measured by the method described herein was 99%. The acid value was 0.03 mgKOH/g.
1 H-NMR(CDCl3 ,300MHz):δ7.1-7.4(m,10H),3.85-4.65(m,8H),2.90-3.05(m,4H),2.1-2.3(m,4H),31 P-NMR(CDCl3 ,120MHz):δ31.5(S),熔點:245-246℃,元素分析計算值:C,57.80;H,6.01,測定值:C,58.00;H,6.07 1 H-NMR (CDCl 3, 300MHz): δ7.1-7.4 (m, 10H), 3.85-4.65 (m, 8H), 2.90-3.05 (m, 4H), 2.1-2.3 (m, 4H), 31 P-NMR (CDCl 3 , 120 MHz): δ 31.5 (m), m.p.: 245 - 246 C, calc.
製備例5Preparation Example 5
2,4,8,10-四氧雜-3,9-二磷雜螺[5.5]十一烷、3,9-二(2-苯乙基)-3,9-二氧化物(FR-5)的製備2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis(2-phenylethyl)-3,9-dioxide (FR- 5) Preparation
在具有攪拌機、溫度計、電容器的反應容器中,填充3,9-二(苯基乙氧基)-2,4,8,10-四氧雜-3,9-二磷雜螺[5.5]十一烷436.4g(1.0mol)及2-溴乙基苯370.1g(2.0mol),室溫下邊攪拌,邊吹氮乾燥。接著用油浴開始加熱,以油浴溫度180℃保持10小時。然後除去油浴冷卻至室溫。在製得之白色固體狀反應物中加入甲醇2000ml攪拌洗淨後,使用燒結玻璃過濾器過濾白色粉末。接著將濾過之白色粉末與甲醇4000ml加入至具備電容器、攪拌機之反應容器中,迴流約2小時。冷卻至室溫後,藉濾過結晶來進行分離,用甲醇2000mL洗淨後,以100Pa、120℃將製得之白色粉末乾燥8小時,獲得2,4,8,10-四氧雜-3,9-二磷雜螺[5.5]十一烷、3,9-二(2-苯乙基)-3,9-二氧化物362.3g。藉質譜分析、1 H、31 P核磁共振光譜分析及元素分析確認生成物為雙2,4,8,10-四氧雜-3,9-二磷雜螺[5.5]十一烷、3,9-二(2-苯乙基)-3,9-二氧化物。收率為83%,HPLC純度為99.3%,酸價為0.41KOHmg/g。In a reaction vessel with a stirrer, thermometer, and capacitor, filled with 3,9-bis(phenylethoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5] 436.4 g (1.0 mol) of mono-alkane and 370.1 g (2.0 mol) of 2-bromoethylbenzene were stirred at room temperature, and dried with nitrogen. Heating was then started with an oil bath and maintained at an oil bath temperature of 180 ° C for 10 hours. The oil bath was then removed and cooled to room temperature. To the obtained white solid reaction, 2000 ml of methanol was added and stirred, and the white powder was filtered using a sintered glass filter. Next, the filtered white powder and 4000 ml of methanol were placed in a reaction vessel equipped with a capacitor and a stirrer, and refluxed for about 2 hours. After cooling to room temperature, separation was carried out by filtration through crystallization, and after washing with methanol 2000 mL, the obtained white powder was dried at 100 Pa and 120 ° C for 8 hours to obtain 2,4,8,10-tetraoxa-3. 9-Diphosphaspiro[5.5]undecane, 3,9-bis(2-phenylethyl)-3,9-dioxide 362.3 g. Mass spectrometry, 1 H, 31 P NMR spectroscopy and elemental analysis confirmed that the product was bis 2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3, 9-bis(2-phenylethyl)-3,9-dioxide. The yield was 83%, the HPLC purity was 99.3%, and the acid value was 0.41 KOH mg/g.
1 H-NMR(CDCl3 ,300MHz):δ7.1-7.4(m,10H),3.85-4.65(m,8H),2.90-3.05(m,4H),2.1-2.3(m,4H),31 P-NMR(CDCl3 ,120MHz):δ31.5(S),熔點:245-246℃ 1 H-NMR (CDCl 3, 300MHz): δ7.1-7.4 (m, 10H), 3.85-4.65 (m, 8H), 2.90-3.05 (m, 4H), 2.1-2.3 (m, 4H), 31 P-NMR (CDCl 3 , 120 MHz): δ 31.5 (S), m.p.: 245-246.
製備例6Preparation Example 6
2,4,8,10-四氧雜-3,9-二磷雜螺[5.5]十一烷、3,9-雙(二苯甲基)-3,9-二氧化物(FR-6)的製備2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis(diphenylmethyl)-3,9-dioxide (FR-6 Preparation
在具有攪拌裝置、攪拌翼、迴流冷卻管、溫度計的三個10升燒瓶中,備好二苯甲基膦酰二氯2058.5g(7.22莫耳)和季戊四醇468.3g(3.44莫耳)、嘧啶1169.4g(14.8莫耳)、三氯甲烷8200g,在氮氣流下加熱至60℃,攪拌6小時。反應完成後,用二氯甲烷代替三氯甲烷,在該反應混合物中加入6L蒸餾水加以攪拌,使白色粉末析出。藉吸收濾過來進行濾取,使用甲醇洗淨製得之白色物後,以100℃、1.33×102 Pa乾燥10小時,製得白色固體1156.2g。利用31 P-NMR、1 H-NMR光譜及元素分析確認製得之固體為2,4,8,10-四氧雜-3,9-二磷雜螺[5.5]十一烷、3,9-雙(二苯甲基)-3,9-二氧化物。31 P-NMR純度為99%。另外,利用本文記載的方法測定之HPLC純度為99%。酸價為0.3mgKOH/g。In three 10-liter flasks with stirring device, stirring wing, reflux cooling tube, thermometer, 2058.5 g (7.22 mol) of diphenylmethylphosphonochloride and 468.3 g (3.44 mol) of pentaerythritol and pyrimidine 1169.4 were prepared. g (14.8 mol) and 8200 g of chloroform were heated to 60 ° C under a nitrogen stream and stirred for 6 hours. After completion of the reaction, methylene chloride was used instead of chloroform, and 6 L of distilled water was added to the reaction mixture, followed by stirring to precipitate a white powder. The mixture was filtered by absorption, and the obtained white material was washed with methanol, and then dried at 100 ° C and 1.33 × 10 2 Pa for 10 hours to obtain 1156.2 g of a white solid. The solids obtained were confirmed to be 2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9 by 31 P-NMR, 1 H-NMR spectroscopy and elemental analysis. - bis(diphenylmethyl)-3,9-dioxide. The 31 P-NMR purity was 99%. Further, the HPLC purity measured by the method described herein was 99%. The acid value was 0.3 mgKOH/g.
1 H-NMR(DMSO-d6,300MHz):δ7.20-7.60(m,20H),5.25(d,2H),4.15-4.55(m,8H),31 P-NMR(DMSO-d6,120MHz):δ20.9,熔點:265℃,元素分析計算值:C,66.43;H,5.39,測定值:C,66.14;H,5.41 1 H-NMR (DMSO-d6, 300MHz): δ 7.20-7.60 (m, 20H), 5.25 (d, 2H), 4.15-4.55 (m, 8H), 31 P-NMR (DMSO-d6, 120MHz) : δ 20.9, m.p.: 265 ° C, calc.: C, 66.43; H, 5.39, found: C, 66.14; H, 5.41
製備例7Preparation Example 7
2,4,8,10-四氧雜-3,9-二磷雜螺[5.5]十一烷、3,9-雙(二苯甲基)-3,9-二氧化物(FR-7)的製備2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis(diphenylmethyl)-3,9-dioxide (FR-7 Preparation
在3個燒瓶中安裝攪拌機、溫度計及電容器,氮氣流下,在該燒瓶中加入3,9-雙(二苯基甲氧基)-2,4,8,10-四氧雜-3,9-二磷雜螺[5.5]十一烷40.4g(0.072莫耳)、二苯甲基溴35.5g(0.14莫耳)、二甲苯48.0g(0.45莫耳),以迴流溫度(約130℃)加熱3小時,加以攪拌。加熱完成後冷卻至室溫,加入30mL二甲苯,接著攪拌30分鐘。藉濾過析出之結晶來分離,用30mL二甲苯洗淨2次。將製得之粗精製物與100mL甲醇放入茄型燒瓶中,安裝電容器,迴流約1小時。冷卻至室溫後,將結晶濾過藉以分離,用50mL甲醇洗淨2次後,以120℃進行減壓乾燥。利用31 P-NMR、1 H-NMR光譜及元素分析確認製得之固體為2,4,8,10-四氧雜-3,9-二磷雜螺[5.5]十一烷、3,9-雙(二苯甲基)-3,9-二氧化物。製得之固體為白色粉末,產量為36.8g,收率為91%。31 P-NMR純度為99%。另外,利用本文記載的方法測定之HPLC純度為99%。酸價為0.07mgKOH/g。A stirrer, a thermometer and a capacitor were installed in three flasks, and under a nitrogen flow, 3,9-bis(diphenylmethoxy)-2,4,8,10-tetraoxa-3,9- was added to the flask. Diphosphorus [5.5] undecane 40.4g (0.072 moles), diphenylmethyl bromide 35.5g (0.14 moles), xylene 48.0g (0.45 moles), heated at reflux temperature (about 130 ° C) Stir for 3 hours. After the completion of the heating, it was cooled to room temperature, and 30 mL of xylene was added, followed by stirring for 30 minutes. The precipitated crystals were separated by filtration, and washed twice with 30 mL of xylene. The obtained crude product and 100 mL of methanol were placed in an eggplant type flask, and a capacitor was mounted and refluxed for about 1 hour. After cooling to room temperature, the crystals were filtered and separated, washed twice with 50 mL of methanol, and then dried under reduced pressure at 120 °C. The solids obtained were confirmed to be 2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9 by 31 P-NMR, 1 H-NMR spectroscopy and elemental analysis. - bis(diphenylmethyl)-3,9-dioxide. The solid obtained was a white powder, the yield was 36.8 g, and the yield was 91%. The 31 P-NMR purity was 99%. Further, the HPLC purity measured by the method described herein was 99%. The acid value was 0.07 mgKOH/g.
1 H-NMR(DMSO-d6 ,300MHz):δ7.2-7.6(m,20H),6.23(d,J=9Hz,2H),3.89-4.36(m,6H),3.38-3.46(m,2H),31 P-NMR(CDCl3 ,120MHz):δ20.9(S),熔點:265℃,元素分析計算值:C,66.43;H,5.39,測定值:C,66.14;H,5.41 1 H-NMR (DMSO-d 6 , 300 MHz): δ 7.2-7.6 (m, 20H), 6.23 (d, J = 9 Hz, 2H), 3.89 - 4.36 (m, 6H), 3.38 - 3.46 (m, 2H), 31 P-NMR ( CDCl 3, 120MHz): δ20.9 (S), melting point: 265 ℃, elemental analysis Calcd: C, 66.43; H, 5.39 , measurement values: C, 66.14; H, 5.41
製備例8Preparation Example 8
聚碳酸酯(PC-1)的製備Preparation of polycarbonate (PC-1)
在反應容器中加入異山梨醇7307重量分(50莫耳)和碳酸二苯酯10709重量分(50莫耳),備好聚合觸媒之四甲基氫氧化銨4.8重量分(相對於碳酸二苯酯成分1莫耳為1×10-4 莫耳),及氫氧化鈉5.0×10-3 重量分(相對於碳酸二苯酯成分1莫耳為0.25×10-6 莫耳),在氮氛圍氣常壓下使其加熱熔融至180℃。7307 parts by weight (50 moles) of isosorbide and 10709 parts by weight (50 moles) of diphenyl carbonate were added to the reaction vessel, and 4.8 parts by weight of tetramethylammonium hydroxide of the polymerization catalyst was prepared (relative to carbonic acid two) The phenyl ester component 1 mole is 1 × 10 -4 moles, and the sodium hydroxide 5.0 × 10 -3 weight fraction (relative to the diphenyl carbonate component 1 mole is 0.25 × 10 -6 moles), in the nitrogen The atmosphere was heated and melted to 180 ° C under normal pressure.
攪拌下,以30分鐘的時間將反應槽內慢慢減壓,邊餾除生成的苯酚邊進行減壓至13.3×10-3 MPa。在該狀態下使反應進行20分鐘後再升溫至200℃,然後以20分鐘的時間慢慢減壓,邊餾除苯酚邊在4.00×10-3 MPa下使反應進行20分鐘,接著升溫至220℃,使反應進行30分鐘,再升溫至250℃使反應進行30分鐘。Under stirring, the reaction vessel was gradually depressurized for 30 minutes, and the resulting phenol was distilled off to reduce the pressure to 13.3 × 10 -3 MPa. In this state, the reaction was allowed to proceed for 20 minutes, and the temperature was further raised to 200 ° C. Then, the pressure was gradually reduced over a period of 20 minutes, and the reaction was allowed to proceed for 20 minutes at 4.00 × 10 -3 MPa while distilling off the phenol, followed by raising the temperature to 220. The reaction was allowed to proceed for 30 minutes at ° C, and the temperature was raised to 250 ° C to carry out the reaction for 30 minutes.
接著慢慢減壓,以2.67×10-3 MPa10分鐘,1.33×10-3 MPa10分鐘连续進行反應,然後減壓,若到達4.00×10-5 MPa,則慢慢升溫至260℃,最終以260℃、6.66×10-5 MPa使反應1小時。將反應後的聚合物加以製粒化,獲得比粘度為0.33的顆粒。該顆粒的玻璃轉移溫度為165℃,5%重量減少溫度為355℃。Then, the pressure was gradually reduced, and the reaction was continuously carried out at 2.67 × 10 -3 MPa for 10 minutes and 1.33 × 10 -3 MPa for 10 minutes, and then the pressure was reduced. When it reached 4.00 × 10 -5 MPa, the temperature was gradually raised to 260 ° C, and finally 260. The reaction was allowed to proceed for 1 hour at ° C, 6.66 × 10 -5 MPa. The polymer after the reaction was granulated to obtain particles having a specific viscosity of 0.33. The pellet had a glass transition temperature of 165 ° C and a 5% weight loss temperature of 355 ° C.
製備例9Preparation Example 9
聚碳酸酯(PC-2)的製備Preparation of polycarbonate (PC-2)
除最終以255℃、6.66×10-5 MPa使其反應30分鐘以外與製備例8同樣地處理,製得比粘度為0.23的顆粒。該顆粒的玻璃轉移溫度為158℃,5%重量減少溫度為353℃。The pellets having a specific viscosity of 0.23 were obtained in the same manner as in Production Example 8 except that the reaction was finally carried out at 255 ° C and 6.66 × 10 -5 MPa for 30 minutes. The pellet had a glass transition temperature of 158 ° C and a 5% weight loss temperature of 353 ° C.
製備例10Preparation Example 10
聚碳酸酯(PC-3)的製備Preparation of polycarbonate (PC-3)
除異山梨醇6722重量分(46莫耳)與碳酸二苯酯10709重量分(50莫耳)與1,3-丙二醇304重量分(4莫耳)以外與參考例8同樣地處理製得比粘度為0.28的顆粒。該顆粒的玻璃轉移溫度為146℃,5%重量減少溫度為342℃。The same procedure as in Reference Example 8 except that isosorbide 6722 parts by weight (46 moles) and diphenyl carbonate 10709 parts by weight (50 moles) and 1,3-propanediol 304 parts by weight (4 moles) were prepared. Particles having a viscosity of 0.28. The pellet had a glass transition temperature of 146 ° C and a 5% weight loss temperature of 342 ° C.
實施例、比較例中使用之各成分使用下述物質。The following materials were used for the respective components used in the examples and comparative examples.
(I)聚碳酸酯樹脂(A成分)(I) Polycarbonate resin (component A)
(i)製備例8中合成之聚碳酸酯(以下稱為PC-1)(i) Polycarbonate synthesized in Preparation Example 8 (hereinafter referred to as PC-1)
(ii)製備例9中合成之聚碳酸酯(以下稱為PC-2)(ii) Polycarbonate synthesized in Preparation Example 9 (hereinafter referred to as PC-2)
(iii)製備例10中合成之聚碳酸酯(以下稱為PC-3)(iii) Polycarbonate synthesized in Preparation Example 10 (hereinafter referred to as PC-3)
(II)有機磷化合物(B成分)(II) Organic phosphorus compound (component B)
(i)製備例1中合成之2,4,8,10-四氧雜-3,9-二磷雜螺[5.5]十一烷、3,9-二苄基-3,9-二氧化物{式(1-a)的磷系化合物(以下稱為FR-1)}(i) 2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-dibenzyl-3,9-dioxide synthesized in Preparation Example 1. A compound of the formula (1-a) (hereinafter referred to as FR-1)
(ii)製備例2中合成之2,4,8,10-四氧雜-3,9-二磷雜螺[5.5]十一烷、3,9-二苄基-3,9-二氧化物{式(1-a)的磷系化合物(以下稱為FR-2)}(ii) 2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-dibenzyl-3,9-dioxide synthesized in Preparation Example 2. a phosphorus compound of the formula (1-a) (hereinafter referred to as FR-2)}
(iii)製備例3中合成之2,4,8,10-四氧雜-3,9-二磷雜螺[5.5]十一烷、3,9-二α-甲苄基-3,9-二氧化物{式(1-b)的磷系化合物(以下稱為FR-3)}(iii) 2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-diα-methylbenzyl-3,9 synthesized in Preparation Example 3. - dioxide {phosphorus compound of formula (1-b) (hereinafter referred to as FR-3)}
(iv)製備例4中合成之2,4,8,10-四氧雜-3,9-二磷雜螺[5.5]十一烷、3,9-二(2-苯乙基)-3,9-二氧化物{式(1-c)的磷系化合物(以下稱為FR-4)}(iv) 2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis(2-phenylethyl)-3 synthesized in Preparation Example 4. , 9-dioxide {phosphorous compound of formula (1-c) (hereinafter referred to as FR-4)}
(v)製備例5中合成之2,4,8,10-四氧雜-3,9-二磷雜螺[5.5]十一烷、3,9-二(2-苯乙基)-3,9-二氧化物{式(1-c)的磷系化合物(以下稱為FR-5)}(v) 2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis(2-phenylethyl)-3 synthesized in Preparation Example 5. , 9-dioxide {phosphorus compound of formula (1-c) (hereinafter referred to as FR-5)}
(vi)製備例6中合成之2,4,8,10-四氧雜-3,9-二磷雜螺[5.5]十一烷、3,9-雙(二苯甲基)-3,9-二氧化物{式(1-d)的磷系化合物(以下稱為FR-6)}(vi) 2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis(diphenylmethyl)-3 synthesized in Preparation Example 6, 9-dioxide {phosphorus compound of formula (1-d) (hereinafter referred to as FR-6)}
(vii)製備例7中合成之2,4,8,10-四氧雜-3,9-二磷雜螺[5.5]十一烷、3,9-雙(二苯甲基)-3,9-二氧化物{式(1-d)的磷系化合物(以下稱為FR-7)}(vii) 2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis(diphenylmethyl)-3 synthesized in Preparation Example 7, 9-dioxide {phosphorus compound of formula (1-d) (hereinafter referred to as FR-7)}
(III)其他有機磷化合物(III) Other organophosphorus compounds
(i)使用磷酸三苯酯(Daihachi Chemical Industry CO.,LTD製TPP)(以下稱為TPP)(i) Use of triphenyl phosphate (TPP manufactured by Daihachi Chemical Industry Co., Ltd.) (hereinafter referred to as TPP)
(ii)使用間苯二酚[(2,6-二甲基苯基)磷酸酯](Daihachi Chemical Industry CO.,LTD製PX-200)(以下稱為PX-200)(ii) Resorcinol [(2,6-dimethylphenyl) phosphate] (PX-200 manufactured by Daihachi Chemical Industry Co., Ltd.) (hereinafter referred to as PX-200)
實施例1~22及比較例1~9Examples 1 to 22 and Comparative Examples 1 to 9
以表1~3記載的量(重量分)用大杯來混合表1~3記載的各成分,用15mmΦ雙軸擠壓機(Technovel Corporation製,KZW15)進行製粒化。用130℃的熱風乾燥機對製得之顆粒進行4小時乾燥。用射出成形機((株)日本製鋼所製J75EIII)將乾燥之顆粒加以成形。使用成形板將評價結果示於表1~3中。The components described in Tables 1 to 3 were mixed in a large cup in the amounts (weight fractions) shown in Tables 1 to 3, and granulated by a 15 mm Φ biaxial extruder (KZW15, manufactured by Technovel Corporation). The obtained granules were dried by a hot air dryer at 130 ° C for 4 hours. The dried pellets were molded by an injection molding machine (J75EIII, manufactured by Nippon Steel Co., Ltd.). The evaluation results are shown in Tables 1 to 3 using a forming plate.
本發明之難燃性樹脂組成物及由其形成之成形品,與過去使用源自植物的原料之樹脂組成物比較得出以下優點。The flame-retardant resin composition of the present invention and the molded article formed therefrom have the following advantages as compared with the resin composition of the plant-derived raw material in the past.
(i)實質不使用含鹵素的難燃劑且具有高度的難燃性。(i) Substantially no halogen-containing flame retardant is used and has a high degree of flame retardancy.
(i i)作為難燃劑之有機磷化合物,因為相對於使用源自植物的原料之樹脂具有優良的難燃效果,故即使比較少的使用量亦達成V-2水準。(i i) The organophosphorus compound as a flame retardant has an excellent flame retardant effect with respect to a resin using a plant-derived raw material, so that the V-2 level is achieved even with a relatively small amount of use.
(i i i)起因於作為難燃劑使用之有機磷化合物的結構及特性,使用源自植物的原料之樹脂在樹脂成形時或成形品的使用時,幾乎不會引起使用源自植物的原料之樹脂熱劣化,熱安定性優良。因此本發明之難燃性樹脂組成物,難燃性、機械強度及熱安定性每一種都是平衡的,較優良。(iii) The structure and characteristics of the organophosphorus compound used as a flame retardant, the resin using the plant-derived raw material hardly causes the use of the plant-derived raw material at the time of resin molding or the use of the molded article. Thermal deterioration and excellent thermal stability. Therefore, the flame retardant resin composition of the present invention is balanced and excellent in each of flame retardancy, mechanical strength and thermal stability.
(i v)作為難燃劑之有機磷化合物,是無色的而且相對於使用源自植物的原料之樹脂是相溶性的,故可以製得透明性優良的成形品。(i v) The organophosphorus compound as a flame retardant is colorless and compatible with a resin using a plant-derived raw material, so that a molded article excellent in transparency can be obtained.
因為本發明之難燃性樹脂組成物,實質不含鹵素,具有非常高的難燃性能,故作為成形家電製品部件、電氣‧電子產品、汽車部件、機械‧機構部件、化妝品容器等之各種成形品的材料是有用的。Since the flame-retardant resin composition of the present invention contains substantially no halogen and has a very high flame retardancy, it is variously formed as a component of a molded home appliance, an electric appliance, an electronic component, an automobile component, a machine, a mechanical component, a cosmetic container, and the like. The material of the product is useful.
Claims (15)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
TW098143102A TWI448543B (en) | 2009-12-16 | 2009-12-16 | A flame retardant resin composition and a molded article derived |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
TW098143102A TWI448543B (en) | 2009-12-16 | 2009-12-16 | A flame retardant resin composition and a molded article derived |
Publications (2)
Publication Number | Publication Date |
---|---|
TW201122087A TW201122087A (en) | 2011-07-01 |
TWI448543B true TWI448543B (en) | 2014-08-11 |
Family
ID=45045908
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
TW098143102A TWI448543B (en) | 2009-12-16 | 2009-12-16 | A flame retardant resin composition and a molded article derived |
Country Status (1)
Country | Link |
---|---|
TW (1) | TWI448543B (en) |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2004018764A (en) * | 2002-06-19 | 2004-01-22 | Teijin Chem Ltd | Flame-retardant resin composition and molding prepared therefrom |
TW200909517A (en) * | 2007-06-01 | 2009-03-01 | Teijin Ltd | Flame retardancy polycarbonate composition |
-
2009
- 2009-12-16 TW TW098143102A patent/TWI448543B/en active
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2004018764A (en) * | 2002-06-19 | 2004-01-22 | Teijin Chem Ltd | Flame-retardant resin composition and molding prepared therefrom |
TW200909517A (en) * | 2007-06-01 | 2009-03-01 | Teijin Ltd | Flame retardancy polycarbonate composition |
Also Published As
Publication number | Publication date |
---|---|
TW201122087A (en) | 2011-07-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5371974B2 (en) | Flame retardant resin composition and molded product therefrom | |
TWI475070B (en) | A flame retardant resin composition and a molded product derived | |
TWI464212B (en) | A flame retardant resin composition, and a molded product derived from the resin composition | |
EP2634217A1 (en) | Flame-retardant resin composition and molded article produced from same | |
JP5378712B2 (en) | Flame retardant resin composition and molded product therefrom | |
TWI684622B (en) | Flame retardant resin composition and its molded product | |
TWI448543B (en) | A flame retardant resin composition and a molded article derived | |
US8618196B2 (en) | Flame retardant resin composition and molded article thereof | |
JP5346708B2 (en) | Flame retardant resin composition and molded product therefrom |