TW202006044A - Bleeding inhibitor, flame retardant for resins, resin composition and molded body of same - Google Patents
Bleeding inhibitor, flame retardant for resins, resin composition and molded body of same Download PDFInfo
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- TW202006044A TW202006044A TW108124488A TW108124488A TW202006044A TW 202006044 A TW202006044 A TW 202006044A TW 108124488 A TW108124488 A TW 108124488A TW 108124488 A TW108124488 A TW 108124488A TW 202006044 A TW202006044 A TW 202006044A
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- XSNXQJHWJPFJIX-UHFFFAOYSA-N c(cc1)cc(-c(cccc2)c2O2)c1Op21np2(Oc(cccc3)c3-c(cccc3)c3O2)np2(Oc(cccc3)c3-c3ccccc3O2)n1 Chemical compound c(cc1)cc(-c(cccc2)c2O2)c1Op21np2(Oc(cccc3)c3-c(cccc3)c3O2)np2(Oc(cccc3)c3-c3ccccc3O2)n1 XSNXQJHWJPFJIX-UHFFFAOYSA-N 0.000 description 1
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
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Abstract
Description
發明領域 本發明關於滲出抑制劑、樹脂用阻燃劑、樹脂組成物，及其成形體。Field of invention The present invention relates to an exudation inhibitor, a flame retardant for resin, a resin composition, and a molded body thereof.
發明背景 作為樹脂成形體的阻燃化方法，實行把阻燃劑添加於樹脂。就阻燃劑而言，有：鹵素系阻燃劑、磷系阻燃劑、金屬氫氧化物系阻燃劑等，出於安全性的考量，該等之中，經常使用磷系阻燃劑，例如：磷酸酯、磷酸醯胺、磷酸銨、膦氮烯等。Background of the invention As a method of flame retarding a resin molded body, a flame retardant is added to the resin. As for flame retardants, there are halogen-based flame retardants, phosphorus-based flame retardants, metal hydroxide-based flame retardants, etc. For safety reasons, among these, phosphorus-based flame retardants are often used , For example: phosphate ester, amide phosphate, ammonium phosphate, phosphazene, etc.
惟，當於樹脂大量地添加了磷系阻燃劑的情況，所獲得之成形體會因暴露於高溫狀態而在該成形體表面發生磷系阻燃劑溶出的現象(滲出)，且有發生阻燃性能降低，及與其它的成形體或者材料的接著性降低之虞。However, when a large amount of phosphorus-based flame retardant is added to the resin, the molded body obtained will be eluted (exuded) with phosphorus-based flame retardant on the surface of the molded body due to exposure to high temperature, and there will be resistance The flammability is lowered, and the adhesion with other molded bodies or materials may be lowered.
為解決上述滲出的問題，提案有例如：利用聚合物基材將膦氮烯予以微膠囊化的方法(專利文獻1)；使用含磷的環氧樹脂的方法(專利文獻2)；添加具有與樹脂的環氧基之反應性的膦氮烯化合物的方法(專利文獻3)等。惟，需要阻燃化的製品跨多類，而尋求在使用於該等之樹脂及阻燃劑的龐大組合上也可應用的方法。In order to solve the above-mentioned bleed-out problem, for example: a method of microencapsulating phosphazene using a polymer substrate (Patent Document 1); a method of using a phosphorus-containing epoxy resin (Patent Document 2); A method of a reactive phosphazene compound of an epoxy group of a resin (Patent Document 3) and the like. However, there are many types of products that need to be flame retarded, and they are seeking methods that can be applied to the huge combination of resins and flame retardants used in these.
[先行技術文獻] [專利文獻] 專利文獻1：日本特開2017-082229號公報 專利文獻2：日本特開2007-153998號公報 專利文獻3：日本特開2012-188633號公報[Advanced technical literature] [Patent Literature] Patent Document 1: Japanese Patent Application Publication No. 2017-082229 Patent Document 2: Japanese Patent Laid-Open No. 2007-153998 Patent Document 3: Japanese Patent Laid-Open No. 2012-188633
發明概要 發明欲解決之課題 本發明課題是在於提供一種磷系阻燃劑的滲出受到抑制之樹脂組成物及其成形體。Summary of the invention Problems to be solved by invention An object of the present invention is to provide a resin composition and a molded body thereof in which bleeding of a phosphorus-based flame retardant is suppressed.
又，本發明課題是在於提供一種能夠抑制磷系阻燃劑的滲出之滲出抑制劑。 用以解決課題之手段Moreover, the subject of this invention is providing the bleeding inhibitor which can suppress the bleeding of a phosphorus flame retardant. Means to solve the problem
本發明人等進行了各種探討的結果，發現：透過將式(1)所示之化合物摻合至包含樹脂與磷系阻燃劑的樹脂組成物中，在該樹脂組成物的成形體中磷系阻燃劑的滲出受到抑制，進而完成了本發明。As a result of various investigations conducted by the present inventors, it has been found that by blending the compound represented by formula (1) into a resin composition containing a resin and a phosphorus-based flame retardant, phosphorus in the molded body of the resin composition The bleed-out of the flame retardant was suppressed, and the present invention was completed.
即，本發明包含下述項1至18所示之滲出抑制劑、樹脂用阻燃劑、樹脂組成物及成形體等。That is, the present invention includes the bleeding inhibitors shown in the following items 1 to 18, flame retardants for resins, resin compositions, molded products, and the like.
(項1)一種滲出抑制劑，其係在含有樹脂及磷系阻燃劑之樹脂組成物中之磷系阻燃劑的滲出抑制劑，包含式(1)所示之化合物：(Item 1) An bleed inhibitor, which is a bleed inhibitor of a phosphorus-based flame retardant in a resin composition containing a resin and a phosphorus-based flame retardant, and includes the compound represented by formula (1):
[化學式1]
(項2)如項1之滲出抑制劑，其中前述磷系阻燃劑係選自於由磷酸酯、磷酸醯胺、磷酸銨，及膦氮烯所構成之群組中之至少1種。(Item 2) The bleeding inhibitor according to item 1, wherein the phosphorus-based flame retardant is at least one selected from the group consisting of phosphate esters, amide amine phosphates, ammonium phosphates, and phosphazenes.
(項3)如項1或者2之滲出抑制劑，其中前述樹脂係選自於由環氧樹脂、熱固性丙烯酸樹脂、苯二甲酸二烯丙酯樹脂、不飽和聚酯樹脂、苯乙烯系樹脂、聚酯樹脂、聚碳酸酯樹脂、聚苯醚(Polyphenylene ether)系樹脂，及聚醯胺樹脂所構成之群組中之至少1種。(Item 3) The bleed inhibitor according to item 1 or 2, wherein the aforementioned resin is selected from the group consisting of epoxy resin, thermosetting acrylic resin, diallyl phthalate resin, unsaturated polyester resin, styrene resin, At least one of the group consisting of polyester resin, polycarbonate resin, polyphenylene ether (Polyphenylene ether) resin, and polyamide resin.
(項4)一種樹脂用阻燃劑，包含如項1至3中任一項之滲出抑制劑及磷系阻燃劑。(Item 4) A flame retardant for resin, comprising the bleeding inhibitor according to any one of Items 1 to 3 and a phosphorus-based flame retardant.
(項5)如項4之樹脂用阻燃劑，其中當令前述滲出抑制劑中式(1)所示之化合物及前述磷系阻燃劑的合計質量為100質量份時，前述式(1)所示之化合物的比例為0.1至30質量份。(Item 5) The flame retardant for resin according to item 4, wherein when the total mass of the compound represented by formula (1) in the bleed inhibitor and the phosphorus-based flame retardant is 100 parts by mass, the formula (1) The ratio of the compound shown is 0.1 to 30 parts by mass.
(項6)如項4或者5之樹脂用阻燃劑，其中前述磷系阻燃劑是選自於由磷酸酯、磷酸醯胺、磷酸銨，及膦氮烯所構成之群組中之至少1種。(Item 6) The flame retardant for resin according to item 4 or 5, wherein the phosphorus-based flame retardant is at least one selected from the group consisting of phosphate ester, amide amine phosphate, ammonium phosphate, and phosphazene 1 kind.
(項7)如項4至6中任一項之樹脂用阻燃劑，其中前述樹脂是選自於由環氧樹脂、熱固性丙烯酸樹脂、苯二甲酸二烯丙酯樹脂、不飽和聚酯樹脂、苯乙烯系樹脂、聚酯樹脂、聚碳酸酯樹脂、聚苯醚系樹脂，及聚醯胺樹脂所構成之群組中之至少1種。(Item 7) The flame retardant for resin according to any one of items 4 to 6, wherein the resin is selected from the group consisting of epoxy resin, thermosetting acrylic resin, diallyl phthalate resin, unsaturated polyester resin , At least one of the group consisting of styrene resin, polyester resin, polycarbonate resin, polyphenylene ether resin, and polyamide resin.
(項8)一種樹脂組成物，包含樹脂、如項1至3中任一項之滲出抑制劑，及磷系阻燃劑。(Item 8) A resin composition comprising a resin, the bleeding inhibitor according to any one of Items 1 to 3, and a phosphorus-based flame retardant.
(項9)如項8之樹脂組成物，其中當令前述滲出抑制劑中式(1)所示之化合物及前述磷系阻燃劑的合計質量為100質量份時，前述式(1)所示之化合物的比例為0.1至30質量份。(Item 9) The resin composition according to item 8, wherein when the total mass of the compound represented by the formula (1) in the bleed inhibitor and the phosphorus-based flame retardant is 100 parts by mass, the formula (1) The ratio of the compound is 0.1 to 30 parts by mass.
(項10)如項8或者9之樹脂組成物，其中相對於100質量份前述樹脂，前述滲出抑制劑中式(1)所示之化合物及前述磷系阻燃劑的合計質量為10至50質量份。(Item 10) The resin composition according to item 8 or 9, wherein the total mass of the compound represented by formula (1) in the bleeding inhibitor and the phosphorus-based flame retardant is 10 to 50 parts by mass relative to 100 parts by mass of the resin Copies.
(項11)如項8至10中任一項之樹脂組成物，其中前述磷系阻燃劑是選自於由磷酸酯、磷酸醯胺、磷酸銨，及膦氮烯所構成之群組中之至少1種。(Item 11) The resin composition according to any one of items 8 to 10, wherein the phosphorus-based flame retardant is selected from the group consisting of phosphate ester, amide phosphate, ammonium phosphate, and phosphazene At least one of them.
(項12)一種樹脂組成物，包含樹脂，及如項4至7中任一項之樹脂用阻燃劑。(Item 12) A resin composition comprising a resin, and the flame retardant for resin according to any one of items 4 to 7.
(項13)如項12之樹脂組成物，其中相對於100質量份前述樹脂，含有10至50質量份前述樹脂用阻燃劑。(Item 13) The resin composition according to item 12, which contains 10 to 50 parts by mass of the flame retardant for the resin relative to 100 parts by mass of the resin.
(項14)如項8至13中任一項之樹脂組成物，其中前述樹脂是選自於由環氧樹脂、熱固性丙烯酸樹脂、苯二甲酸二烯丙酯樹脂、不飽和聚酯樹脂、苯乙烯系樹脂、聚酯樹脂、聚碳酸酯樹脂、聚苯醚系樹脂，及聚醯胺樹脂所構成之群組中之至少1種。(Item 14) The resin composition according to any one of items 8 to 13, wherein the resin is selected from the group consisting of epoxy resin, thermosetting acrylic resin, diallyl phthalate resin, unsaturated polyester resin, benzene At least one member selected from the group consisting of vinyl resins, polyester resins, polycarbonate resins, polyphenylene ether resins, and polyamide resins.
(項15)一種成形體，其係使用如項8至14中任一項之樹脂組成物所製作出。(Item 15) A molded body produced using the resin composition according to any one of items 8 to 14.
(項16)一種電氣或者電子零件，其係使用如項8至14中任一項之樹脂組成物所製作出。(Item 16) An electrical or electronic part manufactured by using the resin composition according to any one of items 8 to 14.
(項17)一種半導體元件用封裝材，包含如項8至14中任一項之樹脂組成物。(Item 17) A packaging material for a semiconductor element, comprising the resin composition according to any one of items 8 to 14.
(項18)一種基板材料，其係使用如項8至14中任一項之樹脂組成物所製作出。 發明效果(Item 18) A substrate material produced using the resin composition according to any one of items 8 to 14. Invention effect
本發明之樹脂組成物，由於含有含式(1)所示之化合物之滲出抑制劑與磷系阻燃劑，而在利用該樹脂組成物製作出成形體的情況下，能夠抑制該磷系阻燃劑的滲出。其結果，前述成形體能夠充分地發揮該磷系阻燃劑的阻燃性能，同時也不會對與其它的材料的接著性造成不利影響。因此，本發明之成形體能夠合適地使用於電氣、電子或者通信設備。The resin composition of the present invention contains an exudation inhibitor containing a compound represented by formula (1) and a phosphorus-based flame retardant, and when a molded body is produced from the resin composition, the phosphorus-based resistance can be suppressed Exudation of fuel. As a result, the molded body can fully exhibit the flame retardant performance of the phosphorus-based flame retardant without adversely affecting the adhesion with other materials. Therefore, the molded article of the present invention can be suitably used for electric, electronic, or communication equipment.
用以實施發明之形態Forms for carrying out the invention
以下，針對本發明詳細地進行說明。Hereinafter, the present invention will be described in detail.
(滲出抑制劑) 本發明之抑制摻合於樹脂之磷系阻燃劑之滲出的添加劑(以下稱「滲出抑制劑」)，包含式(1)所示之化合物。(Exudation inhibitor) The additive for suppressing the bleeding of the phosphorus flame retardant blended with the resin of the present invention (hereinafter referred to as "bleed inhibitor") includes the compound represented by formula (1).
[化學式2]
式(1)所示之化合物是公知的物質，已被報告有：作為鹵化銀照片感光材料(日本特開2002-169243號公報)、作為聚酯用的阻燃劑(美國專利3865783號公報)等的用途。The compound represented by formula (1) is a well-known substance and has been reported as: a silver halide photographic photosensitive material (Japanese Patent Laid-Open No. 2002-169243), and a flame retardant for polyester (US Patent No. 3865783) And other uses.
式(1)所示之化合物能夠使用公知的製造方法而製造。例如，如於下面的反應式-1所示般，能夠透過記載於美國專利3356769號公報的方法等，製造式(1)所示之化合物。The compound represented by formula (1) can be produced using a known production method. For example, as shown in the following reaction formula-1, the compound represented by the formula (1) can be produced by the method described in US Patent No. 3356769 or the like.
[化學式3]
式(2)所示之六氯環三膦氮烯是能夠透過公知的方法，即，透過基於五氯化磷與氯化銨的反應的製造方法而製造。又，亦能夠使用市售者。The hexachlorocyclotriphosphazene represented by formula (2) can be produced by a known method, that is, by a production method based on the reaction of phosphorus pentachloride and ammonium chloride. In addition, a marketer can also be used.
作為反應式-1中之鹼，可舉：鹼金屬鹽、胺化合物等，較佳為：氫氧化鋰、氫氧化鈉、氫氧化鉀、碳酸鋰、碳酸鈉、碳酸鉀等鹼金屬鹽。Examples of the base in Reaction Formula-1 include alkali metal salts and amine compounds, and preferably alkali metal salts such as lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium carbonate, sodium carbonate, and potassium carbonate.
式(1)所示之化合物，例如，能夠透過使六氯環三膦氮烯(2)與2,2’-聯苯酚(3)，在一氯苯等溶媒中進行反應而獲得。相對於1mol之六氯環三膦氮烯(2)，2,2’-聯苯酚(3)較佳為使用3mol左右。反應溫度較佳為20至140℃左右，反應時間較佳為0.5至20小時左右。The compound represented by formula (1) can be obtained, for example, by reacting hexachlorocyclotriphosphazene (2) with 2,2'-biphenol (3) in a solvent such as monochlorobenzene. The 2,2'-biphenol (3) is preferably used at about 3 mol with respect to 1 mol of hexachlorocyclotriphosphazene (2). The reaction temperature is preferably about 20 to 140°C, and the reaction time is preferably about 0.5 to 20 hours.
在本發明之滲出抑制劑來說，含有式(1)所示之化合物即可。The exudation inhibitor of the present invention may contain the compound represented by formula (1).
在本發明之樹脂組成物中，相對於100質量份樹脂，式(1)所示之化合物的摻合量通常為0.01至60質量份左右，較佳為0.1至55質量份左右，更佳為1至50質量份左右，進一步較佳為3至40質量份左右，特佳為5至30質量份左右。In the resin composition of the present invention, the compounding amount of the compound represented by formula (1) is usually about 0.01 to 60 parts by mass, preferably about 0.1 to 55 parts by mass, more preferably 100 parts by mass of the resin It is about 1 to 50 parts by mass, more preferably about 3 to 40 parts by mass, and particularly preferably about 5 to 30 parts by mass.
本發明之滲出抑制劑是包含：含有式(1)所示之化合物之，摻合了下述式(4)所示之混合物的態樣。意即，該混合物是含有在下述式(4)中，n為3的化合物(式(1)所示之化合物)，與n為3以外(4至15的整數)的化合物。The exudation inhibitor of the present invention includes a compound containing a compound represented by formula (1) and a mixture represented by the following formula (4). That is, the mixture is a compound containing a compound in which n is 3 (a compound represented by formula (1)) in the following formula (4), and n is other than 3 (an integer from 4 to 15).
在該混合物100質量%中，式(4)所示之混合物，例如較佳為含有：50至90質量%在式(4)中n為3的化合物(式(1)所示之化合物)、5至40質量%在式(4)中n為4的化合物、0至30質量%在式(4)中n為5的化合物，及0至20質量%在式(4)中n為6至15的化合物。In 100% by mass of the mixture, the mixture represented by the formula (4) preferably contains, for example, 50 to 90% by mass of the compound represented by the formula (4) where n is 3 (the compound represented by the formula (1)), 5 to 40 mass% of the compound where n is 4 in formula (4), 0 to 30 mass% of the compound where n is 5 in formula (4), and 0 to 20 mass% of n is 6 to in formula (4) 15 compounds.
當以式(4)所示之混合物的形態將式(1)所示之化合物摻合於本發明之樹脂組成物的情況，較佳為相對於100質量份樹脂，摻合式(4)所示之混合物，使得式(4)所示之混合物中n為3的化合物(式(1)所示之化合物)通常是0.01至60質量份左右，較佳為0.1至55質量份左右，更佳為1至50質量份左右，進一步較佳為3至40質量份左右，特佳使得成為為5至30質量份左右。When the compound represented by the formula (1) is blended with the resin composition of the present invention in the form of a mixture represented by the formula (4), it is preferable to blend the resin represented by the formula (4) with respect to 100 parts by mass of the resin Mixture, such that the compound represented by formula (4) where n is 3 (the compound represented by formula (1)) is usually about 0.01 to 60 parts by mass, preferably about 0.1 to 55 parts by mass, and more preferably It is about 1 to 50 parts by mass, more preferably about 3 to 40 parts by mass, and particularly preferably about 5 to 30 parts by mass.
在上述式(1)所示之化合物的製造方法中，代替使用六氯環三膦氮烯，式(4)所示之混合物，例如，能夠藉由使式(5)所示之混合物與2,2’-聯苯酚在鹼存在下反應而製造。該混合物，含有：在下述式(5)中， n為3的化合物(式(2)所示之化合物)，與n為3以外(4至15的整數)的化合物。再者，式(5)所示之混合物，較佳為包含：50至90質量%在式(5)中m為3的化合物(式(2)所示之化合物)、5至40質量%在式(5)m為4的化合物、0至30質量%在式(5)中m=5的化合物，及0至20質量%在式(5)中m為6至15的化合物。式(5)所示之混合物能夠透過公知的方法而製造，例如，能夠按照記載於日本特開昭57-87427號公報、日本特公昭58-19604號公報、日本特公昭61-1363號公報、或者日本特公昭62-20124號公報等的方法而製造。In the method for producing the compound represented by the above formula (1), instead of using hexachlorocyclotriphosphazene, the mixture represented by the formula (4), for example, by using the mixture represented by the formula (5) and 2 , 2'-Biphenol is produced by reacting in the presence of alkali. This mixture contains: in the following formula (5), a compound in which n is 3 (a compound represented by formula (2)) and a compound in which n is other than 3 (an integer from 4 to 15). Furthermore, the mixture represented by the formula (5) preferably contains: 50 to 90% by mass of the compound in which m is 3 in the formula (5) (the compound represented by the formula (2)), and 5 to 40% by mass The compound of formula (5) m is 4, the compound of 0 to 30% by mass in formula (5) m=5, and the compound of 0 to 20% by mass of m in formula (5) is 6 to 15. The mixture represented by formula (5) can be produced by a known method, for example, it can be described in Japanese Patent Laid-Open No. 57-87427, Japanese Patent No. 58-19604, Japanese Patent No. 61-1363, Alternatively, it may be manufactured by methods such as Japanese Patent Publication No. 62-20124.
[化學式4]
(n表示3至15的整數)(n represents an integer from 3 to 15)
[化學式5]
本發明之滲出抑制劑能夠含有式(1)所示之化合物以外的滲出抑制劑。本發明之滲出抑制劑，較佳為由式(1)所示之化合物構成，更佳為僅由式(1)所示之化合物構成。The bleeding inhibitor of the present invention can contain a bleeding inhibitor other than the compound represented by formula (1). The bleeding inhibitor of the present invention is preferably composed of the compound represented by formula (1), and more preferably composed only of the compound represented by formula (1).
本發明之滲出抑制劑，透過被摻合於包含樹脂與磷系阻燃劑的樹脂組成物，而能夠防範在由該樹脂組成物所製作出之成形體中磷系阻燃劑的滲出。The bleeding inhibitor of the present invention can prevent the bleeding of the phosphorus-based flame retardant in the molded body produced from the resin composition by being blended with the resin composition containing the resin and the phosphorus-based flame retardant.
(磷系阻燃劑) 在本發明使用之磷系阻燃劑，是式(1)所示之化合物以外的磷系阻燃劑。作為這般的磷系阻燃劑，較佳可例示：磷酸酯、磷酸醯胺、多磷酸銨，及膦氮烯，該等之中又以已膦氮烯為較佳。(Phosphorus flame retardant) The phosphorus flame retardant used in the present invention is a phosphorus flame retardant other than the compound represented by formula (1). As such phosphorus-based flame retardants, preferably, phosphate esters, amide amine phosphates, ammonium polyphosphates, and phosphazenes, among these, phosphazenes are more preferred.
該等能夠單獨使用1種，或者能夠併用2種以上。One of these can be used alone, or two or more can be used in combination.
就磷酸酯而言，可舉：磷酸三甲酯、磷酸三乙酯、磷酸三苯酯、磷酸三甲苯酯(tricresyl phosphate)、磷酸三(二甲苯基)酯、磷酸甲苯酚基二苯酯等單體型磷酸酯系化合物；間苯二酚雙-磷酸二(二甲苯基)酯、間苯二酚雙-磷酸二苯酯、間苯二酚-雙2,6-二甲苯基磷酸酯、間苯二酚多(二-2,6-二甲苯基)磷酸酯、間苯二酚多苯基磷酸酯、雙酚A雙-磷酸二苯酯、雙酚A雙-磷酸二甲苯酚基酯、聯苯酚雙-磷酸二苯酯、聯苯酚雙-磷酸二(二甲苯基)酯等***與二價的苯酚系化合物；磷酸參(二氯丙基)酯、磷酸參(β-氯丙基)酯、磷酸參(氯乙基)酯、2,2-雙(氯甲基)三亞甲基雙(雙(2-氯乙基)磷酸酯、聚氧伸烷基雙二氯烷基磷酸酯等含鹵素磷酸酯系化合物；及為與苯酚(或者烷基苯酚)之反應產物的芳香族縮合磷酸酯系化合物等。Examples of phosphate esters include trimethyl phosphate, triethyl phosphate, triphenyl phosphate, tricresyl phosphate, tri(xylyl) phosphate, and cresyl diphenyl phosphate. Monomer type phosphate ester compound; resorcinol bis-bis(xylyl) phosphate, resorcinol bis-diphenyl phosphate, resorcinol-bis 2,6-xylyl phosphate, Resorcinol poly(di-2,6-xylyl) phosphate, resorcinol polyphenyl phosphate, bisphenol A bis-diphenyl phosphate, bisphenol A bis-xylyl phosphate , Bisphenol bis-diphenyl phosphate, diphenol bis-diphenyl bis(xylyl) phosphate and other divalent phenol compounds; ginseng (dichloropropyl) phosphate, ginseng phosphate (β- Chloropropyl), ginseng (chloroethyl) phosphate, 2,2-bis (chloromethyl) trimethylene bis (bis (2-chloroethyl) phosphate, polyoxyalkylene bis dichloroane Halogen-containing phosphate-based compounds such as phosphoric acid esters; and aromatic condensed phosphate-based compounds that are reaction products with phenol (or alkylphenol).
就磷酸醯胺而言，可舉：苯胺基二苯基磷酸酯、二-鄰甲苯酚基苯基胺基磷酸酯、環己基胺基二苯基磷酸酯、磷胺酸(phosphoramidic acid)-1,4-伸苯基雙-肆(2,6-二甲基苯基)酯等。As for the amide phosphate, anilino diphenyl phosphate, di-o-cresyl phenyl amino phosphate, cyclohexyl amino diphenyl phosphate, phosphoramidic acid-1 , 4-Phenylbis-bis(2,6-dimethylphenyl) ester, etc.
就磷酸銨而言，可舉：磷酸一銨、磷酸二銨、磷酸三銨、多磷酸銨、多磷酸黑色素等。Examples of the ammonium phosphate include monoammonium phosphate, diammonium phosphate, triammonium phosphate, ammonium polyphosphate, and polyphosphate melanin.
就膦氮烯而言，未被特別限制，可舉習知公知的膦氮烯。作為膦氮烯，例如，可舉：式(6)所示之環狀膦氮烯、式(7)所示之鏈狀膦氮烯、選自具有烷氧基、芳烷氧基(aralkyloxy)、或者芳氧基作為取代基之環狀膦氮烯及鏈狀膦氮烯之至少一種膦氮烯，透過選自鄰伸苯基、間伸苯基、對伸苯基及式(8)所示之雙伸苯基之至少一種交聯基所交聯而成的交聯膦氮烯(惟，該交聯基是介隔於環狀膦氮烯及鏈狀膦氮烯之取代基的烷氧基、芳烷氧基，或者芳氧基的烷基、芳烷基，或者芳基部分脫離而成之2個氧原子之間，且以上述環狀膦氮烯及/或鏈狀膦氮烯中全部苯基的總數為基準，在被交聯而成的化合物中苯基的含有比例是50至99.9%，並且在分子內不具有游離之羥基)等。The phosphazene is not particularly limited, and conventionally known phosphazenes may be mentioned. As the phosphazene, for example, a cyclic phosphazene represented by the formula (6), a chain phosphazene represented by the formula (7), selected from an alkoxy group and an aralkyloxy group , Or at least one phosphazene of cyclic phosphazene and chain phosphazene as aryloxy as a substituent, selected from the group consisting of o-phenylene, m-phenylene, p-phenylene and formula (8) The cross-linked phosphazenes formed by crosslinking of at least one cross-linking group of bis-phenylene shown (however, the cross-linking group is an alkane interposed by the substituents of cyclic phosphazene and chain phosphazene Oxygen, aralkyloxy, or aryloxy alkyl, aralkyl, or aryl groups partially separated between two oxygen atoms, and with the above cyclic phosphazene and/or chain phosphine nitrogen Based on the total number of all phenyl groups in the olefin, the content of phenyl groups in the cross-linked compound is 50 to 99.9%, and it does not have free hydroxyl groups in the molecule.
[化學式6]
[式中，R1 及R2 相同或者不同，表示可能有取代基的烷基、可能有取代基的烷氧基、可能有取代基的芳烷基、可能有取代基的芳烷氧基、可能有取代基的芳基、可能有取代基的芳氧基、或者可能有取代基的胺基；m1表示3至25的整數。][In the formula, R 1 and R 2 are the same or different, and represent an alkyl group that may have a substituent, an alkoxy group that may have a substituent, an aralkyl group that may have a substituent, an aralkoxy group that may have a substituent, An aryl group that may have a substituent, an aryloxy group that may have a substituent, or an amine group that may have a substituent; m1 represents an integer of 3 to 25. ]
[化學式7]
[式中，R3 及R4 相同或者不同，表示可能有取代基的烷基、可能有取代基的烷氧基、可能有取代基的芳烷基、可能有取代基的芳烷氧基、可能有取代基的芳基、或者可能有取代基的芳氧基。X1表示-N=P(R5 )3 。Y1表示-P(R6 )4 。R5 及R6 相同或者不同，表示可能有取代基的烷基、可能有取代基的烷氧基、可能有取代基的芳烷基、可能有取代基的芳烷氧基、可能有取代基的芳基、或者可能有取代基的芳氧基。n1表示3至10000的整數。][In the formula, R 3 and R 4 are the same or different, and represent an alkyl group that may have a substituent, an alkoxy group that may have a substituent, an aralkyl group that may have a substituent, an aralkoxy group that may have a substituent, An aryl group which may have a substituent, or an aryloxy group which may have a substituent. X1 represents -N=P(R 5 ) 3 . Y1 represents -P(R 6 ) 4 . R 5 and R 6 are the same or different and represent an alkyl group that may have a substituent, an alkoxy group that may have a substituent, an aralkyl group that may have a substituent, an aralkoxy group that may have a substituent, or a substituent Aryl groups, or aryloxy groups which may have substituents. n1 represents an integer of 3 to 10000. ]
[化學式8]
[式中，Z表示-C(CH3 )2 -、-CH2 -、-SO2 -、-S-或者-O-，a表示0或者1。][In the formula, Z represents -C(CH 3 ) 2 -, -CH 2 -, -SO 2 -, -S-, or -O-, and a represents 0 or 1. ]
在本說明書中，就「烷基」而言，無特別限定，例如可舉：直鏈狀、分枝鏈狀或者環狀的烷基，具體地，例如可舉：甲基、乙基、正丙基、異丙基、正丁基、異丁基、二級丁基、三級丁基、1-乙基丙基等碳數1至4之直鏈狀或者分枝鏈狀的烷基，進一步可舉：加上了正戊基、異戊基、新戊基、正己基、異己基、3-甲基戊基、正庚基、正辛基、正壬基、正癸基、正十一烷基、正十二烷基、5-丙基壬基、正十三烷基、正十四烷基、正十五烷基、十六烷基、十七烷基、十八烷基等之碳數1至18之直鏈狀或者分枝鏈狀烷基；又可舉：環丙基、環丁基、環戊基、環己基、環庚基、環辛基等碳數3至8環狀烷基等。In this specification, "alkyl" is not particularly limited, and examples include linear, branched, or cyclic alkyl groups, and specific examples include methyl, ethyl, and n-alkyl. Straight or branched chain alkyl groups with 1 to 4 carbon atoms, such as propyl, isopropyl, n-butyl, isobutyl, secondary butyl, tertiary butyl, 1-ethylpropyl, Further examples: added n-pentyl, isopentyl, neopentyl, n-hexyl, isohexyl, 3-methylpentyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-ten Monoalkyl, n-dodecyl, 5-propylnonyl, n-tridecyl, n-tetradecyl, n-pentadecyl, hexadecyl, heptadecyl, octadecyl, etc. Straight-chain or branched-chain alkyl having 1 to 18 carbon atoms; another example: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, etc. Cyclic alkyl, etc.
在本說明書中，就「烷氧基」而言，無特別限定，例如可舉：直鏈狀、分枝鏈狀或者環狀的烷氧基；具體地例如可舉：甲氧基、乙氧基、正丙氧基、異丙氧基、正丁氧基、三級丁氧基、正戊氧基、新戊氧基、正己氧基之直鏈狀或者分枝鏈狀的烷氧基；環丙氧基、環丁氧基、環戊氧基、環己氧基、環庚氧基、環辛氧基等環狀烷氧基等。In this specification, "alkoxy" is not particularly limited, and examples include linear, branched, or cyclic alkoxy; specific examples include methoxy and ethoxy. Straight-chain or branched-chain alkoxy groups of the group, n-propoxy, isopropoxy, n-butoxy, tertiary butoxy, n-pentyloxy, neopentyloxy, n-hexyloxy; Cyclic alkoxy groups such as cyclopropoxy, cyclobutoxy, cyclopentyloxy, cyclohexyloxy, cycloheptyloxy, cyclooctyloxy, etc.
在本說明書中，就「芳烷基」而言，無特別限定，例如可舉：苄基、苯乙基、三苯甲基等。In the present specification, "aralkyl" is not particularly limited, and examples thereof include benzyl, phenethyl, and trityl.
在本說明書中，就「芳烷氧基」而言，無特別限定，例如可舉：苄氧基、苯乙氧基(phenethyloxy group)、三苯甲基氧基等。In the present specification, "aralkoxy" is not particularly limited, and examples thereof include benzyloxy, phenethyloxy group, trityloxy, and the like.
在本說明書中，就「芳基」而言，無特別限定，例如可舉：苯基、聯苯基、萘基等。In the present specification, "aryl" is not particularly limited, and examples include phenyl, biphenyl, and naphthyl.
在本說明書中，「就芳氧基」而言，無特別限定，例如可舉：苯氧基、聯苯基氧基、萘氧基等。In this specification, "aryloxy" is not particularly limited, and examples thereof include phenoxy, biphenyloxy, and naphthoxy.
在本說明書中，就「胺基」而言，不僅是-NH2 所示之胺基，亦包含例如：甲基胺基、乙基胺基、正丙基胺基、正丁基胺基、異丁基胺基、二級丁基胺基、三級丁基胺基、1-乙基丙基胺基、正戊基胺基、新戊基胺基、正己基胺基、異己基胺基、3-甲基戊基胺基等直鏈狀或者分枝鏈狀的單烷基胺基；二甲基胺基、乙基甲基胺基、二乙基胺基等具有2個直鏈狀或者分枝鏈狀的烷基之二烷基胺基等取代胺基。In this specification, the term "amino group" is not only an amine group represented by -NH 2 but also includes, for example, methylamino group, ethylamino group, n-propylamino group, n-butylamino group, Isobutylamino, secondary butylamino, tertiary butylamino, 1-ethylpropylamino, n-pentylamino, neopentylamino, n-hexylamino, isohexylamino , 3-methylpentylamino and other linear or branched-chain monoalkylamine groups; dimethylamino, ethylmethylamino, diethylamino, etc. have two linear Or substituted amine groups such as branched chain alkyl dialkylamine groups.
可能有取代基的烷基、可能有取代基的烷氧基、可能有取代基的芳烷基、可能有取代基的芳烷氧基、可能有取代基的芳基、可能有取代基的芳氧基，及可能有取代基的胺基之取代基，能夠在可取代的任意位置被取代。Alkyl groups with possible substituents, alkoxy groups with possible substituents, aralkyl groups with possible substituents, aralkoxy groups with possible substituents, aryl groups with possible substituents, aryl groups with possible substituents The oxygen group, and the substituent of the amine group which may have a substituent, can be substituted at any position which can be substituted.
就該取代基的種類而言，無特別限定，例如，可舉：鹵素原子、羥基、胺基、胺基烷基、烷氧基羰基、醯基、醯氧基、醯胺基、羧基、羧基烷基、甲醯基、腈基、硝基、烷基、羥烷基、烯基、烷氧基、烯氧基、芳氧基、硫醇基、烷硫基、芳硫基等。The type of the substituent is not particularly limited, and examples thereof include halogen atom, hydroxyl group, amino group, aminoalkyl group, alkoxycarbonyl group, acyl group, acyloxy group, acylamino group, carboxyl group, and carboxyl group Alkyl, formyl, nitrile, nitro, alkyl, hydroxyalkyl, alkenyl, alkoxy, alkenyloxy, aryloxy, thiol, alkylthio, arylthio, etc.
在本說明書中，就「鹵素原子」而言，可舉：氟原子、氯原子、溴原子，及碘原子。In this specification, the "halogen atom" includes fluorine atom, chlorine atom, bromine atom, and iodine atom.
在本說明書中，就「胺基烷基」而言，無特別限定，例如可舉：胺基甲基、甲基胺基甲基、乙基胺基甲基、二甲基胺基甲基、乙基甲基胺基甲基、二乙基胺基甲基、2-胺基乙基、2-(甲基胺基)乙基、2-(乙基胺基)乙基、2-(二甲基胺基)乙基、2-(乙基甲基胺基)乙基、2-(二乙基胺基)乙基、3-胺基丙基、3-(甲基胺基)丙基、3-(乙基胺基)丙基、3-(二甲基胺基)丙基、3-(乙基甲基胺基)丙基、3-(二乙基胺基)丙基等胺基烷基、單烷基取代胺基烷基或者二烷基取代胺基烷基等。In this specification, "aminoalkyl" is not particularly limited, and examples include aminomethyl, methylaminomethyl, ethylaminomethyl, and dimethylaminomethyl. Ethylmethylaminomethyl, diethylaminomethyl, 2-aminoethyl, 2-(methylamino)ethyl, 2-(ethylamino)ethyl, 2-(di Methylamino)ethyl, 2-(ethylmethylamino)ethyl, 2-(diethylamino)ethyl, 3-aminopropyl, 3-(methylamino)propyl , 3-(ethylamino)propyl, 3-(dimethylamino)propyl, 3-(ethylmethylamino)propyl, 3-(diethylamino)propyl and other amines Alkyl group, monoalkyl substituted aminoalkyl group, dialkyl substituted aminoalkyl group, etc.
在本說明書中，就「烷氧基羰基」而言，無特別限定，例如可舉：甲氧羰基、乙氧羰基等。In the present specification, the "alkoxycarbonyl group" is not particularly limited, and examples thereof include a methoxycarbonyl group and an ethoxycarbonyl group.
在本說明書中，就「醯基」而言，無特別限定，例如可舉：乙醯基、丙醯基、三甲基乙醯基等碳數1至4之直鏈狀或者分枝鏈狀烷基羰基。In this specification, the "acyl group" is not particularly limited, and examples thereof include straight-chain or branched chains having 1 to 4 carbon atoms, such as acetyl group, propyl group, and trimethyl acetyl group. Alkylcarbonyl.
在本說明書中，就「醯氧基」而言，無特別限定，例如可舉：乙醯氧基、丙醯氧基、正丁醯氧基等。In the present specification, "acyloxy" is not particularly limited, and examples thereof include acetyloxy, propyloxy, n-butyloxy, and the like.
在本說明書中，就「醯胺基」而言，無特別限定，例如可舉：乙醯胺基、苯甲醯胺基等羧酸醯胺基；硫代乙醯胺基、硫代苯甲醯胺基等硫代醯胺基；N-甲基乙醯胺基、N-苄基乙醯胺基等N-取代醯胺基等。In this specification, the "acylamino group" is not particularly limited, and examples thereof include: carboxylic acid amido groups such as acetamido groups and benzamide groups; thioacetamido groups and thiobenzyl groups Thioamido such as acylamino; N-substituted acylamino such as N-methylacetamido and N-benzylacetamido.
在本說明書中，就「羧基烷基」而言，無特別限定，例如可舉：羧甲基、2-羧乙基、3-羧丙基、4-羧丁基、5-羧戊基、6-羧己基等羧基烷基。In this specification, "carboxyalkyl" is not particularly limited, and examples include carboxymethyl, 2-carboxyethyl, 3-carboxypropyl, 4-carboxybutyl, 5-carboxypentyl, 6-carboxyhexyl and other carboxyalkyl groups.
在本說明書中，就「羥烷基」而言，無特別限定，例如可舉：羥甲基、2-羥乙基、3-羥丙基、4-羥丁基等羥烷基。In the present specification, "hydroxyalkyl" is not particularly limited, and examples thereof include hydroxyalkyl such as hydroxymethyl, 2-hydroxyethyl, 3-hydroxypropyl, and 4-hydroxybutyl.
在本說明書中，就「烯基」而言，無特別限定，例如可舉：乙烯基、1-丙烯基、烯丙基、異丙烯基、2-丁烯基、3-丁烯基、1-甲基-2-丙烯基、1,3-丁二烯基、1-戊烯基、2-戊烯基、3-戊烯基、4-戊烯基、1,1-二甲基-2-丙烯基、1-乙基-2-丙烯基、1-甲基-2-丁烯基、1-甲基-3-丁烯基、1-己烯基、2-己烯基、3-己烯基、4-己烯基、5-己烯基、1,1-二甲基-2-丁烯基、1,1-二甲基-3-丁烯基等在任意位置至少具有1個雙鍵之碳數2至6之直鏈狀或者分枝鏈狀烯基。In this specification, "alkenyl" is not particularly limited, and examples include vinyl, 1-propenyl, allyl, isopropenyl, 2-butenyl, 3-butenyl, and 1 -Methyl-2-propenyl, 1,3-butadienyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1,1-dimethyl- 2-propenyl, 1-ethyl-2-propenyl, 1-methyl-2-butenyl, 1-methyl-3-butenyl, 1-hexenyl, 2-hexenyl, 3 -Hexenyl, 4-hexenyl, 5-hexenyl, 1,1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl, etc. have at least any position A double-bond straight or branched chain alkenyl group with 2 to 6 carbon atoms.
在本說明書中，就「烯氧基」而言，無特別限定，例如可舉：乙烯氧基、1-丙烯氧基、烯丙氧基、異丙烯氧基、2-丁烯氧基、3-丁烯氧基、1-甲基-2-丙烯氧基、1,3-丁二烯氧基、1-戊烯氧基、2-戊烯氧基、3-戊烯氧基、4-戊烯氧基、1,1-二甲基-2-丙烯氧基、1-乙基-2-丙烯氧基、1-甲基-2-丁烯氧基、1-甲基-3-丁烯氧基、1-己烯氧基、2-己烯氧基、3-己烯氧基、4-己烯氧基、5-己烯氧基、1,1-二甲基-2-丁烯氧基、1,1-二甲基-3-丁烯氧基等在任意位置具有至少1個雙鍵之碳數2至6之直鏈狀或者分枝鏈狀烯氧基。In this specification, "alkenyloxy" is not particularly limited, and examples thereof include ethyleneoxy, 1-propenyloxy, allyloxy, isopropenyloxy, 2-butenyloxy, 3 -Butenyloxy, 1-methyl-2-propenyloxy, 1,3-butadienyloxy, 1-pentenyloxy, 2-pentenyloxy, 3-pentenyloxy, 4- Pentenyloxy, 1,1-dimethyl-2-propenyloxy, 1-ethyl-2-propenyloxy, 1-methyl-2-butenyloxy, 1-methyl-3-butene Alkenyloxy, 1-hexeneoxy, 2-hexeneoxy, 3-hexeneoxy, 4-hexeneoxy, 5-hexeneoxy, 1,1-dimethyl-2-butene Alkenyloxy, 1,1-dimethyl-3-butenyloxy, etc. have a straight or branched chain alkenyloxy group having at least one double bond and a carbon number of 2 to 6 at any position.
在本說明書中，就「烷硫基」而言，無特別限定，例如可舉：直鏈狀、分枝鏈狀或者環狀的烷硫基；具體地說例如可舉：甲硫基、2-乙硫基、3-丙硫基、異丙硫基、4-丁硫基、三級丁硫基、5-戊硫基、新戊硫基、6-己硫基之直鏈狀或者分枝鏈狀的烷硫基；環丙硫基、環丁硫基、環戊硫基、環己硫基、環庚硫基、環辛硫基等環狀烷硫基等。In the present specification, "alkylthio" is not particularly limited, and examples include linear, branched, or cyclic alkylthio; specific examples include methylthio and 2 -Ethylthio, 3-propylthio, isopropylthio, 4-butylthio, tertiary butylthio, 5-pentylthio, neopentylthio, 6-hexylthio linear or divided Branched chain alkylthio groups; cyclopropylthio, cyclobutylthio, cyclopentylthio, cyclohexylthio, cycloheptylthio, cyclooctylthio and other cyclic alkylthio groups.
在本說明書中，就「芳硫基」而言，無特別限定，例如可舉：苯硫基、聯苯硫基、萘硫基等。In the present specification, the "arylthio group" is not particularly limited, and examples thereof include a phenylthio group, a biphenylthio group, and a naphthylthio group.
就式(6)所示之環狀膦氮烯之具體例而言，例如可舉：1,1,3,3,5,5-六(甲氧基)環三膦氮烯、1,1,3,3,5,5-六(乙氧基)環三膦氮烯、1,1,3,3,5,5-六(正丙氧基)環三膦氮烯、1,1,3,3,5,5-六(異丙氧基)環三膦氮烯、1,1,3,3,5,5-六(正丁氧基)環三膦氮烯、1,1,3,3,5,5-六(異丁氧基)環三膦氮烯、1,1,3,3,5,5-六(苯氧基)環三膦氮烯、1,1,3,3,5,5-六(對甲苯氧基)環三膦氮烯、1,1,3,3,5,5-六(間甲苯氧基)環三膦氮烯、1,1,3,3,5,5-六(鄰甲苯氧基)環三膦氮烯、1,1,3,3,5,5-六(4-乙基苯氧基)環三膦氮烯、1,1,3,3,5,5-六(4-正丙基苯氧基)環三膦氮烯、1,1,3,3,5,5-六(4-異丙基苯氧基)環三膦氮烯、1,1,3,3,5,5-六(4-三級丁基苯氧基)環三膦氮烯、1,1,3,3,5,5-六(4-三級辛基苯氧基)環三膦氮烯、1,1,3,3,5,5-六(2,3-二甲基苯氧基)環三膦氮烯、1,1,3,3,5,5-六(2,4-二甲基苯氧基)環三膦氮烯、1,1,3,3,5,5-六(2,5-二甲基苯氧基)環三膦氮烯、1,1,3,3,5,5-六(2,6-二甲基苯氧基)環三膦氮烯、1,3,5-參(甲氧基)-1,3,5-參(苯氧基)環三膦氮烯、1,3,5-參(乙氧基)-1,3,5-參(苯氧基)環三膦氮烯、1,3,5-參(正丙氧基)-1,3,5-參(苯氧基)環三膦氮烯、1,3,5-參(異丙氧基)-1,3,5-參(苯氧基)環三膦氮烯、1,3,5-參(正丁氧基)-1,3,5-參(苯氧基)環三膦氮烯、1,3,5-參(異丁氧基)-1,3,5-參(苯氧基)環三膦氮烯、1,3,5-參(甲氧基)-1,3,5-參(對甲苯氧基)環三膦氮烯、1,3,5-參(甲氧基)-1,3,5-參(間甲苯氧基)環三膦氮烯、1,3,5-參(甲氧基)-1,3,5-參(鄰甲苯氧基)環三膦氮烯、1,3,5-參(乙氧基)-1,3,5-參(對甲苯氧基)環三膦氮烯、1,3,5-參(乙氧基)-1,3,5-參(間甲苯氧基)環三膦氮烯、1,3,5-參(乙氧基)-1,3,5-參(鄰甲苯氧基)環三膦氮烯、1,3,5-參(正丙氧基)-1,3,5-參(對甲苯氧基)環三膦氮烯、1,3,5-參(正丙氧基)-1,3,5-參(間甲苯氧基)環三膦氮烯、1,3,5-參(正丙氧基)-1,3,5-參(鄰甲苯氧基)環三膦氮烯、1,3,5-參(異丙氧基)-1,3,5-參(對甲苯氧基)環三膦氮烯、1,3,5-參(正丁氧基)-1,3,5-參(對甲苯氧基)環三膦氮烯、1,3,5-參(異丁氧基)-1,3,5-參(對甲苯氧基)環三膦氮烯、1,3,5-參(甲氧基)-1,3,5-參(4-三級丁基苯氧基)環三膦氮烯、1,3,5-參(甲氧基)-1,3,5-參(4-三級辛基苯氧基)環三膦氮烯、1,3,5-參(正丙氧基)-1,3,5-參(4-三級丁基苯氧基)環三膦氮烯、1,3,5-參(正丙氧基)-1,3,5-參(4-三級辛基苯氧基)環三膦氮烯、1,1,3,3,5,5-六(鄰胺基苯氧基)環三膦氮烯、1,1,3,3,5,5-六(間胺基苯氧基)環三膦氮烯、1,1,3,3,5,5-六(對胺基苯氧基)環三膦氮烯、1,3,5-參(苯氧基)-1,3,5-參(鄰胺基苯氧基)環三膦氮烯、1,3,5-參(苯氧基)-1,3,5-參(間胺基苯氧基)環三膦氮烯、1,3,5-參(苯氧基)-1,3,5-參(對胺基苯氧基)環三膦氮烯、1,1,3,3-四(鄰胺基苯氧基)-5,5-二苯氧基環三膦氮烯、1,1,3,3-四(間胺基苯氧基)-5,5-二苯氧基環三膦氮烯、1,1,3,3-四(對胺基苯氧基)-5,5-二苯氧基環三膦氮烯、1,1,3,3-四(苯氧基)-5,5-二(鄰胺基苯氧基)環三膦氮烯、1,1,3,3-四(苯氧基)-5,5-二(間胺基苯氧基)環三膦氮烯、1,1,3,3-四(苯氧基)-5,5-二(對胺基苯氧基)環三膦氮烯、1,1,3,3,5,5-六(鄰羥基苯氧基)環三膦氮烯、1,1,3,3,5,5-六(間羥基苯氧基)環三膦氮烯、1,1,3,3,5,5-六(對羥基苯氧基)環三膦氮烯、1,3,5-參(苯氧基)-1,3,5-參(鄰羥基苯氧基)環膦氮烯、1,3,5-參(苯氧基)-1,3,5-參(間羥基苯氧基)環膦氮烯、1,3,5-參(苯氧基)-1,3,5-參(對羥基苯氧基)環膦氮烯、1,1,3,3,5,5-六(鄰烯丙基苯氧基)環三膦氮烯、1,1,3,3,5,5-六(間烯丙基苯氧基)環三膦氮烯、1,1,3,3,5,5-六(對烯丙基苯氧基)環三膦氮烯、1,3,5-參(鄰烯丙基苯氧基)-1,3,5-參(苯氧基)-環三膦氮烯、1,3,5-參(間烯丙基苯氧基)-1,3,5-參(苯氧基)-環三膦氮烯、1,3,5-參(對烯丙基苯氧基)-1,3,5-參(苯氧基)-環三膦氮烯、1,1,3,3,5,5-六胺基環三膦氮烯、1,3,5-參(苯氧基)-1,3,5-參(胺基)環三膦氮烯、1,1,3,3-四胺基-5,5-二苯氧基環三膦氮烯、1,1,3,3-四苯氧基-5,5-二胺基環三膦氮烯等。Specific examples of the cyclic phosphazenes represented by formula (6) include, for example: 1,1,3,3,5,5-hexa(methoxy)cyclotriphosphazene, 1,1 ,3,3,5,5-hexa(ethoxy)cyclotriphosphazene, 1,1,3,3,5,5-hexa(n-propoxy)cyclotriphosphazene, 1,1, 3,3,5,5-hexa(isopropoxy)cyclotriphosphazene, 1,1,3,3,5,5-hexa(n-butoxy)cyclotriphosphazene, 1,1, 3,3,5,5-hexa(isobutoxy)cyclotriphosphazene, 1,1,3,3,5,5-hexa(phenoxy)cyclotriphosphazene, 1,1,3 ,3,5,5-hexa(p-tolyloxy)cyclotriphosphazene, 1,1,3,3,5,5-hexa(m-tolyloxy)cyclotriphosphazene, 1,1,3 ,3,5,5-hexa(o-tolyloxy)cyclotriphosphazene, 1,1,3,3,5,5-hexa(4-ethylphenoxy)cyclotriphosphazene, 1, 1,3,3,5,5-hexa(4-n-propylphenoxy)cyclotriphosphazene, 1,1,3,3,5,5-hexa(4-isopropylphenoxy) Cyclotriphosphazene, 1,1,3,3,5,5-hexa(4-tert-butylphenoxy)cyclotriphosphazene, 1,1,3,3,5,5-hexa( 4-tertiary octylphenoxy) cyclotriphosphazene, 1,1,3,3,5,5-hexa(2,3-dimethylphenoxy)cyclotriphosphazene, 1,1 ,3,3,5,5-hexa(2,4-dimethylphenoxy)cyclotriphosphazene, 1,1,3,3,5,5-hexa(2,5-dimethylbenzene Oxy)cyclotriphosphazene, 1,1,3,3,5,5-hexa(2,6-dimethylphenoxy)cyclotriphosphazene, 1,3,5-ginseng (methoxy Group)-1,3,5-Shen(phenoxy)cyclotriphosphazene, 1,3,5-Shen(ethoxy)-1,3,5-Shen(phenoxy)cyclotriphosphine nitrogen Ene, 1,3,5-ginseng (n-propoxy)-1,3,5-ginseng (phenoxy)cyclotriphosphazene, 1,3,5-ginseng (isopropoxy)-1, 3,5-Shen(phenoxy)cyclotriphosphazene, 1,3,5-Shen(n-butoxy)-1,3,5-Shen(phenoxy)cyclotriphosphazene, 1, 3,5-ginseng (isobutoxy)-1,3,5-ginseng (phenoxy)cyclotriphosphazene, 1,3,5-ginseng (methoxy)-1,3,5-ginseng (P-tolyloxy)cyclotriphosphazene, 1,3,5-ginseng (methoxy)-1,3,5- ginseng (m-tolyloxy)cyclotriphosphazene, 1,3,5- Ginseng (methoxy)-1,3,5-gins (o-tolyloxy)cyclotriphosphazene, 1,3,5-ginseng (ethoxy)-1,3,5-ginseng (p-tolueneoxy) Group) Cyclotriphosphazene, 1,3,5-ginseng (ethoxy)-1,3,5- gins (m-tolyloxy) cyclotriphosphazene, 1,3,5-ginseng (ethoxy Group)-1,3,5-Shen(o-tolyloxy)cyclotriphosphazene, 1,3,5-Shen(n-propoxy)-1,3,5-Shen(p-tolyloxy) ring Triphosphazene, 1,3,5-ginseng (n-propoxy)-1,3,5-ginseng (m-tolyloxy)cyclotriphosphazene , 1,3,5-ginseng (n-propoxy)-1,3,5-ginseng (o-tolyloxy)cyclotriphosphazene, 1,3,5-ginseng (isopropoxy)-1, 3,5-ginseng (p-tolyloxy)cyclotriphosphazene, 1,3,5-ginseng (n-butoxy)-1,3,5-shen (p-toluyloxy)cyclotriphosphazene, 1,3,5-ginseng (isobutoxy)-1,3,5-ginseng (p-tolyloxy)cyclotriphosphazene, 1,3,5-ginseng (methoxy)-1,3, 5-ginseng (4-tert-butylphenoxy) cyclotriphosphazene, 1,3,5-ginseng (methoxy)-1,3,5-ginseng (4-tert-octylphenoxy) ) Cyclotriphosphazene, 1,3,5-ginseng (n-propoxy)-1,3,5- ginseng (4-tertiary butylphenoxy) cyclotriphosphazene, 1,3,5 -Shen(n-propoxy)-1,3,5-Shen(4-tert-octylphenoxy)cyclotriphosphazene, 1,1,3,3,5,5-hexa(o-amino (Phenoxy) cyclotriphosphazene, 1,1,3,3,5,5-hexa(m-aminophenoxy)cyclotriphosphazene, 1,1,3,3,5,5-hexa (P-Aminophenoxy) cyclotriphosphazene, 1,3,5-Shen(phenoxy)-1,3,5-span (o-aminophenoxy)cyclotriphosphazene, 1, 3,5-ginseng (phenoxy)-1,3,5-ginseng (m-aminophenoxy) cyclotriphosphazene, 1,3,5-ginseng (phenoxy)-1,3,5 -Shen(p-aminophenoxy)cyclotriphosphazene, 1,1,3,3-tetra(o-aminophenoxy)-5,5-diphenoxycyclotriphosphazene, 1, 1,3,3-tetrakis(m-aminophenoxy)-5,5-diphenoxycyclotriphosphazene, 1,1,3,3-tetrakis(p-aminophenoxy)-5, 5-diphenoxycyclotriphosphazene, 1,1,3,3-tetra(phenoxy)-5,5-bis(o-aminophenoxy)cyclotriphosphazene, 1,1, 3,3-tetra(phenoxy)-5,5-bis(m-aminophenoxy)cyclotriphosphazene, 1,1,3,3-tetra(phenoxy)-5,5-bis (P-aminophenoxy) cyclotriphosphazene, 1,1,3,3,5,5-hexa(o-hydroxyphenoxy)cyclotriphosphazene, 1,1,3,3,5, 5-hexa(m-hydroxyphenoxy)cyclotriphosphazene, 1,1,3,3,5,5-hexa(p-hydroxyphenoxy)cyclotriphosphazene, 1,3,5-ginseng ( Phenoxy)-1,3,5-Shen (o-hydroxyphenoxy) cyclophosphazene, 1,3,5-Shen (phenoxy)-1,3,5-Shen (m-hydroxyphenoxy) ) Cyclophosphazene, 1,3,5-Shen (phenoxy)-1,3,5-Shen (p-hydroxyphenoxy) cyclophosphazene, 1,1,3,3,5,5- Hexa(o-allylphenoxy)cyclotriphosphazene, 1,1,3,3,5,5-hexa(m-allylphenoxy)cyclotriphosphazene, 1,1,3, 3,5,5-hexa(p-allylphenoxy)cyclotriphosphazene, 1,3,5-ginseng (o-allylphenoxy)-1,3,5-ginseng (phenoxy )-Cyclotriphosphazene, 1,3,5-Shen(m-allylphenoxy)-1,3,5-Shen(phenoxy)-cyclotri Phosphazene, 1,3,5-Shen (p-allylphenoxy)-1,3,5-Shen (phenoxy)-cyclotriphosphazene, 1,1,3,3,5, 5-Hexaaminocyclotriphosphazene, 1,3,5-Phenoxy (phenoxy)-1,3,5-paraben (amino)cyclotriphosphazene, 1,1,3,3-Tetra Amino-5,5-diphenoxycyclotriphosphazene, 1,1,3,3-tetraphenoxy-5,5-diaminocyclotriphosphazene, etc.
就式(7)所示之鏈狀膦氮烯的具體例而言，可舉：1,1,3,3,5,5-六(甲氧基)三膦氮烯、1,1,3,3,5,5-六(乙氧基)三膦氮烯、1,1,3,3,5,5-六(正丙氧基)三膦氮烯、1,1,3,3,5,5-六(異丙氧基)三膦氮烯、1,1,3,3,5,5-六(正丁氧基)三膦氮烯、1,1,3,3,5,5-六(異丁氧基)三膦氮烯、1,1,3,3,5,5-六(苯氧基)三膦氮烯、1,1,3,3,5,5-六(對甲苯氧基)三膦氮烯、1,1,3,3,5,5-六(間甲苯氧基)三膦氮烯、1,1,3,3,5,5-六(鄰甲苯氧基)三膦氮烯、1,1,3,3,5,5-六(對大茴香基氧基)三膦氮烯、1,1,3,3,5,5-六(間大茴香基氧基)三膦氮烯、1,1,3,3,5,5-六(鄰大茴香基氧基)三膦氮烯、1,1,3,3,5,5-六(4-乙基苯氧基)三膦氮烯、1,1,3,3,5,5-六(4-正丙基苯氧基)三膦氮烯、1,1,3,3,5,5-六(4-異丙基苯氧基)三膦氮烯、1,1,3,3,5,5-六(4-三級丁基苯氧基)三膦氮烯、1,1,3,3,5,5-六(4-三級辛基苯氧基)三膦氮烯、1,1,3,3,5,5-六(2,3-二甲基苯氧基)三膦氮烯、1,1,3,3,5,5-六(2,4-二甲基苯氧基)三膦氮烯、1,1,3,3,5,5-六(2,5-二甲基苯氧基)三膦氮烯、1,1,3,3,5,5-六(2,6-二甲基苯氧基)三膦氮烯、1,1,3,3,5,5-六胺基三膦氮烯，1,1,3,3,5,5-六(4-苯基苯氧基)三膦氮烯、1,3,5-參(甲氧基)-1,3,5-參(苯氧基)三膦氮烯、1,3,5-參(乙氧基)-1,3,5-參(苯氧基)三膦氮烯、1,3,5-參(正丙氧基)-1,3,5-參(苯氧基)三膦氮烯、1,3,5-參(異丙氧基)-1,3,5-參(苯氧基)三膦氮烯、1,3,5-參(正丁氧基)-1,3,5-參(苯氧基)三膦氮烯、1,3,5-參(異丁氧基)-1,3,5-參(苯氧基)三膦氮烯、1,3,5-參(甲氧基)-1,3,5-參(對甲苯氧基)三膦氮烯、1,3,5-參(甲氧基)-1,3,5-參(間甲苯氧基)三膦氮烯、1,3,5-參(甲氧基)-1,3,5-參(鄰甲苯氧基)三膦氮烯、1,3,5-參(甲氧基)-1,3,5-參(對大茴香基氧基)三膦氮烯、1,3,5-參(甲氧基)-1,3,5-參(間大茴香基氧基)三膦氮烯、1,3,5-參(甲氧基)-1,3,5-參(鄰大茴香基氧基)三膦氮烯、1,3,5-參(乙氧基)-1,3,5-參(對甲苯氧基)三膦氮烯、1,3,5-參(乙氧基)-1,3,5-參(間甲苯氧基)三膦氮烯、1,3,5-參(乙氧基)-1,3,5-參(鄰甲苯氧基)三膦氮烯、1,3,5-參(乙氧基)-1,3,5-參(對大茴香基氧基)三膦氮烯、1,3,5-參(乙氧基)-1,3,5-參(間大茴香基氧基)三膦氮烯、1,3,5-參(乙氧基)-1,3,5-參(鄰大茴香基氧基)三膦氮烯、1,3,5-參(正丙氧基)-1,3,5-參(對甲苯氧基)三膦氮烯、1,3,5-參(正丙氧基-1,3,5-參(間甲苯氧基)三膦氮烯、1,3,5-參(正丙氧基)-1,3,5-參(鄰甲苯氧基)三膦氮烯、1,3,5-參(正丙氧基)-1,3,5-參(對大茴香基氧基)三膦氮烯、1,3,5-參(正丙氧基)-1,3,5-參(間大茴香基氧基)三膦氮烯、1,3,5-參(正丙氧基)-1,3,5-參(鄰大茴香基氧基)三膦氮烯、1,3,5-參(異丙氧基)-1,3,5-參(對甲苯氧基)三膦氮烯、1,3,5-參(正丁氧基)-1,3,5-參(對甲苯氧基)三膦氮烯、1,3,5-參(異丁氧基)-1,3,5-參(對甲苯氧基)三膦氮烯、1,3,5-參(甲氧基)-1,3,5-參(4-三級丁基苯氧基)三膦氮烯、1,3,5-參(甲氧基)-1,3,5-參(4-三級辛基苯氧基)三膦氮烯、1,3,5-參(正丙氧基)-1,3,5-參(4-三級丁基苯氧基)三膦氮烯、1,3,5-參(正丙氧基)-1,3,5-參(4-三級辛基苯氧基)三膦氮烯、1,3,5-參(甲氧基)-1,3,5-參(4-苯基苯氧基)三膦氮烯、1,3,5-參(乙氧基)-1,3,5-參(4-苯基苯氧基)三膦氮烯、1,3,5-參(正丙氧基)-1,3,5-參(4-苯基苯氧基)三膦氮烯、1,3,5-參(異丙氧基)-1,3,5-參(4-苯基苯氧基)三膦氮烯、1,3,5-參(正丁氧基)-1,3,5-參(4-苯基苯氧基)三膦氮烯、1,3,5-參(異丁氧基)-1,3,5-參(4-苯基苯氧基)三膦氮烯、1,1-二胺基-3,3,5,5-肆(甲氧基)三膦氮烯、1,1-二胺基-3,3,5,5-肆(乙氧基)三膦氮烯、1,1-二胺基-3,3,5,5-肆(正丙氧基)三膦氮烯、1,1-二胺基-3,3,5,5-肆(異丙氧基)三膦氮烯、1,1-二胺基-3,3,5,5-肆(正丁氧基)三膦氮烯、1,1-二胺基-3,3,5,5-肆(異丁氧基)三膦氮烯、1,1-二胺基-3,3,5,5-肆(苯氧基)三膦氮烯、1,1-二胺基-3,3,5,5-肆(對甲苯氧基)三膦氮烯、1,1-二胺基-3,3,5,5-肆(間甲苯氧基)三膦氮烯、1,1-二胺基-3,3,5,5-肆(鄰甲苯氧基)三膦氮烯、1,1-二胺基-3,3,5,5-肆(對大茴香基氧基)三膦氮烯、1,1-二胺基-3,3,5,5-肆(間大茴香基氧基)三膦氮烯、1,1-二胺基-3,3,5,5-肆(鄰大茴香基氧基)三膦氮烯、1,1-二胺基-3,3,5,5-肆(4-苯基苯氧基)三膦氮烯等。Specific examples of the chain phosphazenes represented by formula (7) include: 1,1,3,3,5,5-hexa(methoxy)triphosphazene, 1,1,3 ,3,5,5-hexa(ethoxy)triphosphazene, 1,1,3,3,5,5-hexa(n-propoxy)triphosphazene, 1,1,3,3, 5,5-hexa(isopropoxy)triphosphazene, 1,1,3,3,5,5-hexa(n-butoxy)triphosphazene, 1,1,3,3,5, 5-hexa(isobutoxy)triphosphazene, 1,1,3,3,5,5-hexa(phenoxy)triphosphazene, 1,1,3,3,5,5-hexa (P-tolyloxy)triphosphazene, 1,1,3,3,5,5-hexa(m-tolyloxy)triphosphazene, 1,1,3,3,5,5-hexa(o Tolyloxy) triphosphazene, 1,1,3,3,5,5-hexa (p-aniselyloxy) triphosphazene, 1,1,3,3,5,5-hexa (between Anisyloxy)triphosphazene, 1,1,3,3,5,5-hexa(o-anisyloxy)triphosphazene, 1,1,3,3,5,5-hexa (4-ethylphenoxy) triphosphazene, 1,1,3,3,5,5-hexa(4-n-propylphenoxy)triphosphazene, 1,1,3,3, 5,5-hexa(4-isopropylphenoxy)triphosphazene, 1,1,3,3,5,5-hexa(4-tert-butylphenoxy)triphosphazene, 1 ,1,3,3,5,5-hexa(4-tert-octylphenoxy)triphosphazene, 1,1,3,3,5,5-hexa(2,3-dimethylbenzene Oxy)triphosphazene, 1,1,3,3,5,5-hexa(2,4-dimethylphenoxy)triphosphazene, 1,1,3,3,5,5- Hexa(2,5-dimethylphenoxy)triphosphazene, 1,1,3,3,5,5-hexa(2,6-dimethylphenoxy)triphosphazene, 1, 1,3,3,5,5-hexaaminotriphosphazene, 1,1,3,3,5,5-hexa(4-phenylphenoxy)triphosphazene, 1,3,5 -Shen(methoxy)-1,3,5-Shen(phenoxy)triphosphazene, 1,3,5-Shen(ethoxy)-1,3,5-Shen(phenoxy) Triphosphazene, 1,3,5-ginseng (n-propoxy)-1,3,5-ginseng (phenoxy) triphosphazene, 1,3,5-ginseng (isopropoxy)- 1,3,5-ginseng (phenoxy) triphosphazene, 1,3,5-ginseng (n-butoxy)-1,3,5-ginseng (phenoxy) triphosphazene, 1, 3,5-ginseng (isobutoxy)-1,3,5-ginseng (phenoxy) triphosphazene, 1,3,5-ginseng (methoxy)-1,3,5-ginseng ( P-tolyloxy) triphosphazene, 1,3,5-ginseng (methoxy)-1,3,5-gins (m-tolyloxy) triphosphazene, 1,3,5-ginseng (methine Oxy)-1,3,5-ginseng (o-tolyloxy) triphosphazene, 1,3,5-ginseng (methoxy)-1,3,5-ginseng (p-anisyloxy) Triphosphazene, 1,3,5-ginseng (methoxy)-1,3,5-ginseng (m-anisyloxy) triphosphazene, 1,3,5-ginseng (methoxy)-1,3,5-ginseng (o-anisyloxy) triphosphazene, 1,3,5-ginseng (ethoxy)-1,3, 5-Phenoxy(p-tolyloxy)triphosphazene, 1,3,5-Phenoxy(ethoxy)-1,3,5-Phenyl(m-tolyloxy)triphosphazene, 1,3,5 -Ginseng (ethoxy)-1,3,5-gins (o-tolyloxy) triphosphazene, 1,3,5-ginseng (ethoxy)-1,3,5-ginseng (p-Anise) Yloxy)triphosphazene, 1,3,5-ginseng (ethoxy)-1,3,5-ginseng (m-anisyloxy) triphosphazene, 1,3,5-ginseng ( Ethoxy)-1,3,5-ginseng (o-anisyloxy) triphosphazene, 1,3,5-ginseng (n-propoxy)-1,3,5-ginseng (p-tolyloxy Group) triphosphazene, 1,3,5-ginseng (n-propoxy-1,3,5-gins (m-tolyloxy) triphosphazene, 1,3,5-ginseng (n-propoxy )-1,3,5-ginseng (o-tolyloxy) triphosphazene, 1,3,5-ginseng (n-propoxy)-1,3,5-ginseng (p-anisyloxy) tri Phosphazene, 1,3,5-ginseng (n-propoxy)-1,3,5-ginseng (m-anisyloxy) triphosphazene, 1,3,5-ginseng (n-propoxy) )-1,3,5-ginseng (o-anisyloxy) triphosphazene, 1,3,5-ginseng (isopropoxy)-1,3,5-ginseng (p-tolyloxy) Phosphazene, 1,3,5-ginseng (n-butoxy)-1,3,5-ginseng (p-tolyloxy) triphosphazene, 1,3,5-ginseng (isobutoxy)- 1,3,5-ginseng (p-tolyloxy) triphosphazene, 1,3,5-ginseng (methoxy)-1,3,5-ginseng (4-tertiary butylphenoxy) tri Phosphazene, 1,3,5-ginseng (methoxy)-1,3,5-ginseng (4-tert-octylphenoxy) triphosphazene, 1,3,5-ginseng (n-propyl Oxy)-1,3,5-ginseng (4-tert-butylphenoxy) triphosphazene, 1,3,5-ginseng (n-propoxy)-1,3,5-ginseng (4 -Tertiary octylphenoxy)triphosphazene, 1,3,5-ginseng (methoxy)-1,3,5-ginseng (4-phenylphenoxy)triphosphazene, 1, 3,5-ginseng (ethoxy)-1,3,5-ginseng (4-phenylphenoxy) triphosphazene, 1,3,5-ginseng (n-propoxy)-1,3, 5-Shen(4-phenylphenoxy)triphosphazene, 1,3,5-Shen(isopropoxy)-1,3,5-Shen(4-phenylphenoxy)triphosphazene Ene, 1,3,5-ginseng (n-butoxy)-1,3,5-ginseng (4-phenylphenoxy) triphosphazene, 1,3,5-ginseng (isobutoxy) -1,3,5-ginseng (4-phenylphenoxy) triphosphazene, 1,1-diamino-3,3,5,5-(methoxy)triphosphazene, 1 ,1-diamino-3,3,5,5-an (ethoxy) triphosphazene, 1,1-diamino-3,3,5,5-an (n-propoxy) tri Phosphazene, 1,1-diamino-3,3,5,5-(isopropoxy)triphosphazene, 1, 1-diamino-3,3,5,5-an (n-butoxy) triphosphazene, 1,1-diamino-3,3,5,5-an (isobutoxy) tri Phosphazene, 1,1-diamino-3,3,5,5-(phenoxy)triphosphazene, 1,1-diamino-3,3,5,5-(for (Tolyloxy)triphosphazene, 1,1-diamino-3,3,5,5-(m-tolyloxy)triphosphazene, 1,1-diamino-3,3,5 ,5-sulfan (o-tolyloxy) triphosphazene, 1,1-diamino-3,3,5,5-sulfan (p-anisyloxy) triphosphazene, 1,1-bis Amino-3,3,5,5-an (m-anisyloxy) triphosphazene, 1,1-diamino-3,3,5,5-an (o-anisyloxy) Triphosphazene, 1,1-diamino-3,3,5,5-(4-phenylphenoxy)triphosphazene, etc.
就交聯膦氮烯的具體例而言，可舉：具有根據4,4’-磺醯基二伸苯基之交聯結構的苯氧基膦氮烯、具有根據2,2-(4,4’-二伸苯基)異亞丙基之交聯結構的苯氧基膦氮烯、具有根據4,4’-氧基二伸苯基之交聯結構的苯氧基膦氮烯、具有4,4’-硫基二伸苯基的苯氧基膦氮烯、具有根據4,4’-二伸苯基之交聯結構的苯氧基膦氮烯等。Specific examples of the cross-linked phosphazenes include phenoxyphosphazenes having a cross-linked structure according to 4,4′-sulfonyldiphenylene, and having 2,2-(4, 4'-diphenylene) isopropylidene cross-linked phenoxyphosphazene, phenoxyphosphazene having a cross-linked structure according to 4,4'-oxydiphenylene, 4,4'-thiodiphenylene phenoxyphosphazene, phenoxyphosphazene having a cross-linked structure according to 4,4'-diphenylene, etc.
令人驚訝的是，本發明藉由將式(1)所示之化合物摻合於樹脂，能夠抑制不具有會與樹脂進行反應之基(以下有時稱為「反應性基」。)之磷系阻燃劑的滲出。此事，因不會發生樹脂與磷系阻燃劑的反應，因此不會損及樹脂本來的性質或者性能，且進一步還能夠擴大磷系阻燃劑的選項，因而非常地有用。就不具有反應性基的磷系阻燃劑而言，例如可舉：於分子內不具有羥基、胺基、羧基、烯基、環氧基等官能基的磷系阻燃劑。再者，即便是具有該等官能基的磷系阻燃劑，若是不會發生與使用之樹脂的反應者的話，是包含於在本說明書中所稱之不具有反應性基的磷系阻燃劑。Surprisingly, by blending the compound represented by formula (1) into a resin, the present invention can suppress phosphorus that does not have a group that will react with the resin (hereinafter sometimes referred to as "reactive group"). Department of flame retardant exudation. In this case, since the reaction between the resin and the phosphorus-based flame retardant does not occur, the original properties or performance of the resin is not impaired, and the options of the phosphorus-based flame retardant can be further expanded, which is very useful. Examples of the phosphorus-based flame retardant that does not have a reactive group include phosphorus-based flame retardants that do not have functional groups such as hydroxyl groups, amine groups, carboxyl groups, alkenyl groups, and epoxy groups in the molecule. In addition, even if the phosphorus-based flame retardant having these functional groups does not occur with a resin used, it is included in the phosphorus-based flame retardant which does not have a reactive group in this specification Agent.
就不具有反應性基的磷系阻燃劑而言，可舉：不具有反應性基的磷酸酯、不具有反應性基的磷酸醯胺、不具有反應性基的多磷酸銨，及不具有反應性基的膦氮烯。在不具有反應性基的磷酸酯之中來說，較佳為：間苯二酚多(二-2,6-二甲苯基)磷酸酯、間苯二酚多苯基磷酸酯，及間苯二酚-雙2,6-二甲苯基磷酸酯。在不具有反應性基的磷酸醯胺之中來說，較佳為磷胺酸(phosphoramidic acid)-1,4-伸苯基雙-肆(2,6-二甲基苯基)酯。在不具有反應性基的多磷酸銨之中來說，較佳為多磷酸黑色素。在不具有反應性基的膦氮烯之中來說，較佳為下面的式(9)所示之環狀膦氮烯及式(10)所示之鏈狀膦氮烯，更佳為式(9)所示之環狀膦氮烯。Examples of phosphorus-based flame retardants that do not have reactive groups include: phosphate esters without reactive groups, amide phosphate without reactive groups, ammonium polyphosphate without reactive groups, and non-reactive groups Reactive phosphazene. Among the phosphate esters having no reactive groups, preferred are: resorcinol poly(di-2,6-xylyl) phosphate, resorcinol polyphenyl phosphate, and m-benzene Diphenol-bis 2,6-xylyl phosphate. Among the amide phosphates which do not have reactive groups, phosphoramidic acid-1,4-phenylenebis-bis(2,6-dimethylphenyl) ester is preferred. Among the ammonium polyphosphates having no reactive groups, melanin polyphosphate is preferred. Among the phosphazenes that do not have a reactive group, cyclic phosphazenes represented by the following formula (9) and chain phosphazenes represented by the formula (10) are preferred, and the most preferred is the formula (9) The cyclic phosphazene shown.
[化學式9]
[式中，R7 及R8 相同或者不同，表示可能有取代基的烷基、可能有取代基的烷氧基、可能有取代基的芳烷基、可能有取代基的芳烷氧基、可能有取代基的芳基、或者可能有取代基的芳氧基。於此處，前述取代基並非為反應性基。m1是與前述相同。][In the formula, R 7 and R 8 are the same or different, and represent an alkyl group that may have a substituent, an alkoxy group that may have a substituent, an aralkyl group that may have a substituent, an aralkoxy group that may have a substituent, An aryl group which may have a substituent, or an aryloxy group which may have a substituent. Here, the aforementioned substituent is not a reactive group. m1 is the same as described above. ]
[化學式10]
[式中，R9 及R10 相同或者不同，表示可能有取代基的烷基、可能有取代基的烷氧基、可能有取代基的芳烷基、可能有取代基的芳烷氧基、可能有取代基的芳基、或者可能有取代基的芳氧基。X2 表示-N=P(R11 )3 。Y2 表示-P(R12 )4 。R11 及R12 相同或者不同，表示可能有取代基的烷基、可能有取代基的烷氧基、可能有取代基的芳烷基、可能有取代基的芳烷氧基、可能有取代基的芳基、或者可能有取代基的芳氧基。於此處，前述取代基並非為反應性基。n1是與前述相同。][In the formula, R 9 and R 10 are the same or different, and represent an alkyl group that may have a substituent, an alkoxy group that may have a substituent, an aralkyl group that may have a substituent, an aralkoxy group that may have a substituent, An aryl group which may have a substituent, or an aryloxy group which may have a substituent. X 2 represents -N=P(R 11 ) 3 . Y 2 represents -P(R 12 ) 4 . R 11 and R 12 are the same or different, and may represent an alkyl group that may have a substituent, an alkoxy group that may have a substituent, an aralkyl group that may have a substituent, an aralkoxy group that may have a substituent, or a substituent Aryl groups, or aryloxy groups which may have substituents. Here, the aforementioned substituent is not a reactive group. n1 is the same as described above. ]
就式(9)所示之環狀膦氮烯而言，較佳為R7 及R8 相同或者不同，是烷氧基、或者芳氧基的膦氮烯，更佳是芳氧基的膦氮烯。As for the cyclic phosphazene represented by the formula (9), it is preferable that R 7 and R 8 are the same or different, and they are alkoxy or aryloxy phosphazenes, more preferably aryloxy phosphines Nitrene.
就式(9)所示之環狀膦氮烯而言，較佳為m1為3至15的膦氮烯，更佳為m1為3至5的膦氮烯，進一步較佳為m1為3或者4的膦氮烯，特佳為m1為3的膦氮烯。As for the cyclic phosphazene represented by the formula (9), the phosphazene having m1 of 3 to 15 is preferred, the phosphazene having m1 of 3 to 5 is more preferred, and the m1 is 3 or 3 The phosphazene of 4 is particularly preferably a phosphazene with m1 of 3.
就式(9)所示之環狀膦氮烯而言，特佳為1,1,3,3,5,5-六(苯氧基)環三膦氮烯。As for the cyclic phosphazene represented by the formula (9), particularly preferred is 1,1,3,3,5,5-hexa(phenoxy)cyclotriphosphazene.
(樹脂用阻燃劑) 本發明之滲出抑制劑亦能夠以包含磷系阻燃劑之樹脂用阻燃劑的形態而使用。即，本發明之樹脂用阻燃劑，包含前述滲出抑制劑及磷系阻燃劑。就所應用之樹脂而言可舉：環氧樹脂、熱固性丙烯酸樹脂、苯二甲酸二烯丙酯樹脂、不飽和聚酯樹脂、苯乙烯系樹脂、聚酯樹脂、聚碳酸酯樹脂、聚苯醚系樹脂，及聚醯胺樹脂。(Flame retardant for resin) The bleeding inhibitor of the present invention can also be used in the form of a flame retardant for resin containing a phosphorus-based flame retardant. That is, the flame retardant for resin of the present invention includes the aforementioned bleeding inhibitor and phosphorus-based flame retardant. Examples of the resin used include epoxy resin, thermosetting acrylic resin, diallyl phthalate resin, unsaturated polyester resin, styrene resin, polyester resin, polycarbonate resin, polyphenylene ether Resin, and polyamide resin.
在本發明之樹脂用阻燃劑中，把滲出抑制劑中式(1)所示之化合物及磷系阻燃劑的合計質量令為100質量份時，式(1)所示之化合物的比例，通常為0.1至30質量份左右，較佳為1至28質量份左右，進一步較佳為2至25質量份，特佳為3至20質量份。當要添加本發明之樹脂用阻燃劑之樹脂為熱固性樹脂的情況，通常為0.1至30質量份左右，較佳為1至20質量份，進一步較佳為2至15質量份，特佳為7至12質量份。當要添加本發明之樹脂用阻燃劑之樹脂為熱塑性樹脂的情況，通常為0.1至30質量份左右，較佳為5至28質量份，進一步較佳為7至25質量份，特佳為9至20質量份。透過以上述範圍含有式(1)所示之化合物，能夠不使樹脂性質變化地，使抑制滲出的效果充分地發揮。In the flame retardant for resin of the present invention, when the total mass of the compound represented by formula (1) and the phosphorus-based flame retardant in the bleeding inhibitor is 100 parts by mass, the ratio of the compound represented by formula (1), It is usually about 0.1 to 30 parts by mass, preferably about 1 to 28 parts by mass, further preferably 2 to 25 parts by mass, and particularly preferably 3 to 20 parts by mass. When the resin to which the flame retardant for resin of the present invention is added is a thermosetting resin, it is usually about 0.1 to 30 parts by mass, preferably 1 to 20 parts by mass, further preferably 2 to 15 parts by mass, particularly preferably 7 to 12 parts by mass. When the resin to which the flame retardant for resin of the present invention is added is a thermoplastic resin, it is usually about 0.1 to 30 parts by mass, preferably 5 to 28 parts by mass, further preferably 7 to 25 parts by mass, particularly preferably 9 to 20 parts by mass. By containing the compound represented by the formula (1) in the above range, the effect of suppressing bleeding can be sufficiently exhibited without changing the resin properties.
本發明之樹脂用阻燃劑，能夠在滲出抑制劑及磷系阻燃劑等被混合過的狀態下使用。此情況時，能夠將滲出抑制劑及磷系阻燃劑等秤量指定量或者適量並以公知的方法進行混合。混合能夠使用，例如：旋轉球磨機、振動球磨機、行星式磨機、油漆攪拌器(paint shaker)、搖擺式磨機、搖擺式混合機、珠磨機、攪拌機等，以濕式及乾式之哪一者進行。The flame retardant for resin of the present invention can be used in a state in which an exudation inhibitor, a phosphorus flame retardant, and the like are mixed. In this case, it is possible to mix a specified amount or an appropriate amount by weighing, such as an exudation inhibitor and a phosphorus-based flame retardant, in a known method. Mixing can be used, for example: rotary ball mill, vibrating ball mill, planetary mill, paint shaker, rocking mill, rocking mixer, bead mill, blender, etc., whether wet or dry者进行。 The person carries on.
(樹脂) 就構成本發明之樹脂組成物的樹脂，或者被應用樹脂用阻燃劑的樹脂而言，未被特別限制，能夠使用透過習知公知的方法所得者、或者使用市售品。具體地，可舉：熱固性樹脂，及熱塑性樹脂。再者，在本發明中，橡膠及彈性體視為包含於「樹脂」者。又，亦可將熱固性樹脂與熱塑性樹脂併用。(Resin) The resin constituting the resin composition of the present invention or the resin to which the flame retardant for resin is applied is not particularly limited, and those obtained by a conventionally known method or commercially available products can be used. Specific examples include thermosetting resins and thermoplastic resins. In addition, in the present invention, rubber and elastomer are regarded as included in "resin". Moreover, thermosetting resin and thermoplastic resin can also be used together.
就熱固性樹脂而言，例如可舉：環氧樹脂、苯酚樹脂、三聚氰胺樹脂、脲樹脂、矽酮樹脂、聚胺基甲酸酯樹脂、不飽和聚酯樹脂、苯二甲酸二烯丙酯樹脂、熱固性丙烯酸樹脂、熱固性聚亞醯胺樹脂、聚羰二醯亞胺樹脂、天然橡膠、異戊二烯橡膠、苯乙烯丁二烯橡膠、丁二烯橡膠、丁基橡膠、乙烯丙烯二烯橡膠、丙烯腈丁二烯橡膠、苯乙烯異戊二烯丁二烯橡膠、氯丁二烯橡膠等。該等之中可單獨使用1種，或者可組合2種以上而使用。Examples of thermosetting resins include epoxy resin, phenol resin, melamine resin, urea resin, silicone resin, polyurethane resin, unsaturated polyester resin, diallyl phthalate resin, Thermosetting acrylic resin, thermosetting polyimide resin, polycarbodiimide resin, natural rubber, isoprene rubber, styrene butadiene rubber, butadiene rubber, butyl rubber, ethylene propylene diene rubber, Acrylonitrile butadiene rubber, styrene isoprene butadiene rubber, chloroprene rubber, etc. Among these, one kind may be used alone, or two or more kinds may be used in combination.
就熱塑性樹脂而言，例如可舉：聚烯烴樹脂(聚乙烯樹脂、聚丙烯樹脂、聚異戊二烯樹脂、聚丁烯樹脂、環狀聚烯烴(COP)樹脂、環狀烯烴/共聚物(COC)樹脂等)、氯化聚烯烴樹脂(聚氯乙烯樹脂、聚偏二氯乙烯等)、苯乙烯系樹脂(聚苯乙烯樹脂、耐衝撃性聚苯乙烯(HIPS)樹脂、間規聚苯乙烯(SPS)樹脂、丙烯腈-丁二烯-苯乙烯共聚物(ABS樹脂)、丙烯腈-苯乙烯共聚物(AS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-丙烯酸橡膠-苯乙烯共聚物(AAS樹脂)等)、聚甲基丙烯酸甲酯(PMMA)、聚乙烯醇、聚酯樹脂(聚對苯二甲酸乙二酯樹脂、聚對苯二甲酸丁二酯樹脂、聚對苯二甲酸亞甲酯樹脂、聚萘二甲酸乙二酯樹脂、聚對苯二甲酸環己烷二亞甲酯(Polycyclohexylenedimethylene terephthalate)樹脂、聚乳酸樹脂等)、脂肪族聚醯胺樹脂(聚醯胺6樹脂、聚醯胺66樹脂、聚醯胺11樹脂、聚醯胺12樹脂、聚醯胺46樹脂、聚醯胺6樹脂與聚醯胺66樹脂的共聚物(聚醯胺6/66樹脂)、聚醯胺6樹脂與聚醯胺12樹脂的共聚物(聚醯胺6/12樹脂)等)、半芳香族聚醯胺樹脂(聚醯胺MXD6樹脂、聚醯胺6T樹脂、聚醯胺9T樹脂、聚醯胺10T樹脂等由具有芳香環的結構單位與不具有芳香環之結構單位構成的樹脂)、聚縮醛(POM)樹脂、聚碳酸酯樹脂、聚苯醚系樹脂、聚碸系樹脂、聚醚碸樹脂、聚苯硫醚樹脂(polyphenylenesulfide resin)、聚醚腈樹脂、聚硫醚碸樹脂(polythioether sulfone resin)、聚芳酯樹脂、聚醯胺醯亞胺樹脂、聚醚醯亞胺樹脂、聚醚芳香族酮樹脂(聚醚酮樹脂、聚醚酮酮樹脂、聚醚醚酮酮樹脂、聚醚醚酮樹脂等)、熱塑性聚亞醯胺(TPI)樹脂、液晶聚合物(LCP)樹脂(液晶聚酯樹脂等)、聚醯胺系熱塑性彈性體、聚酯系熱塑性彈性體、聚苯并咪唑樹脂等。該等之中能夠單獨使用1種，或者組合2種以上而使用。Examples of thermoplastic resins include polyolefin resins (polyethylene resins, polypropylene resins, polyisoprene resins, polybutene resins, cyclic polyolefin (COP) resins, and cyclic olefin/copolymers ( COC resin, etc.), chlorinated polyolefin resin (polyvinyl chloride resin, polyvinylidene chloride, etc.), styrene resin (polystyrene resin, impact-resistant polystyrene (HIPS) resin, syndiotactic polyphenylene) Ethylene (SPS) resin, acrylonitrile-butadiene-styrene copolymer (ABS resin), acrylonitrile-styrene copolymer (AS resin), methyl methacrylate-butadiene-styrene copolymer (MBS Resin), methyl methacrylate-acrylonitrile-butadiene-styrene copolymer (MABS resin), acrylonitrile-acrylic rubber-styrene copolymer (AAS resin), etc.), polymethyl methacrylate (PMMA ), polyvinyl alcohol, polyester resin (polyethylene terephthalate resin, polybutylene terephthalate resin, polymethylene terephthalate resin, polyethylene naphthalate resin, poly Polycyclohexylene dimethylene terephthalate resin, polylactic acid resin, etc.), aliphatic polyamide resin (polyamide 6 resin, polyamide 66 resin, polyamide 11 resin, polyamide) Amine 12 resin, Polyamide 46 resin, Copolymer of Polyamide 6 resin and Polyamide 66 resin (Polyamide 6/66 resin), Copolymer of Polyamide 6 resin and Polyamide 12 resin (Polyamide (Amide 6/12 resin), etc.), semi-aromatic polyamide resin (polyamide MXD6 resin, polyamide 6T resin, polyamide 9T resin, polyamide 10T resin, etc. (Resin composed of structural units that do not have an aromatic ring), polyacetal (POM) resin, polycarbonate resin, polyphenylene ether-based resin, polyphenol resin, polyether resin, polyphenylenesulfide resin , Polyether nitrile resin, polythioether sulfone resin, polyarylate resin, polyamidoamide resin, polyether amide resin, polyether aromatic ketone resin (polyether ketone resin, poly (Ether ketone ketone resin, polyether ether ketone ketone resin, polyether ether ketone resin, etc.), thermoplastic polyimide (TPI) resin, liquid crystal polymer (LCP) resin (liquid crystal polyester resin, etc.), polyamido-based thermoplastic Elastomers, polyester thermoplastic elastomers, polybenzimidazole resins, etc. Among these, one type can be used alone, or two or more types can be used in combination.
該等樹脂之中，較佳亦為選自環氧樹脂、苯二甲酸二烯丙酯樹脂、不飽和聚酯樹脂、苯乙烯系樹脂、聚酯樹脂、聚碳酸酯樹脂、聚苯醚系樹脂，及聚醯胺樹脂選之至少1種或者2種以上，其中，特佳為環氧樹脂。Among these resins, preferably also selected from epoxy resins, diallyl phthalate resins, unsaturated polyester resins, styrene resins, polyester resins, polycarbonate resins, polyphenylene ether resins , And at least one type or two or more types of polyamide resins are selected, among which the most preferred is epoxy resin.
在本說明書中，環氧樹脂是環氧化合物與硬化劑的反應物。In this specification, epoxy resin is a reactant of an epoxy compound and a hardener.
就環氧化合物而言，例如可舉：透過苯酚類與醛類的反應物，和表氯醇或者2-甲基表氯醇等表氯醇類與的反應可獲得之酚醛清漆型(novolac type)環氧化合物；透過苯酚類與表氯醇類的反應可獲得之苯酚型環氧化合物；透過三羥甲基丙烷、低聚丙二醇、氫化雙酚-A等醇與表氯醇類的反應可獲得之脂肪族環氧化合物；透過六氫苯二甲酸、四氫苯二甲酸或者苯二甲酸，與表氯醇類的反應可獲得之縮水甘油酯系環氧化合物；透過二胺基二苯基甲烷、胺基苯酚等胺與表氯醇類的反應可獲得之縮水甘油基胺系環氧化合物；透過異三聚氰酸等多胺與表氯醇類的反應可獲得之雜環式環氧化合物；及該等的改性環氧化合物等。Examples of epoxy compounds include novolac type which can be obtained by reacting phenols and aldehydes with epichlorohydrin or 2-methylepichlorohydrin and other epichlorohydrins. ) Epoxy compounds; phenol epoxy compounds available through the reaction of phenols and epichlorohydrins; through the reaction of trimethylolpropane, oligopropylene glycol, hydrogenated bisphenol-A and other alcohols with epichlorohydrin Aliphatic epoxy compound obtained; glycidyl ester epoxy compound obtained through reaction of hexahydrophthalic acid, tetrahydrophthalic acid or phthalic acid with epichlorohydrin; through diaminodiphenyl Glycidylamine-based epoxy compounds obtained by the reaction of amines such as methane, aminophenol, and epichlorohydrin; heterocyclic epoxy obtained by the reaction of polyamines such as isocyanuric acid and epichlorohydrin Compounds; and such modified epoxy compounds.
作為前述酚醛清漆型環氧化合物，可舉：苯酚酚醛清漆型環氧化合物、溴化苯酚酚醛清漆型環氧化合物、鄰甲酚酚醛清漆型環氧化合物及萘酚酚醛清漆型環氧化合物等。Examples of the novolak-type epoxy compounds include phenol novolak-type epoxy compounds, brominated phenol novolak-type epoxy compounds, o-cresol novolak-type epoxy compounds, and naphthol novolak-type epoxy compounds.
作為前述苯酚型環氧化合物，可舉：雙酚-A型環氧化合物、溴化雙酚-A型環氧化合物、雙酚-F型環氧化合物、雙酚-AD型環氧化合物、雙酚-S型環氧化合物、烷基取代聯苯酚型環氧化合物、參(羥基苯基)甲烷型環氧化合物等。Examples of the phenol epoxy compound include bisphenol-A epoxy compound, brominated bisphenol-A epoxy compound, bisphenol-F epoxy compound, bisphenol-AD epoxy compound, and bisphenol Phenol-S type epoxy compound, alkyl substituted biphenol type epoxy compound, ginseng (hydroxyphenyl) methane type epoxy compound, etc.
該等之中，較佳亦為：苯酚酚醛清漆型環氧化合物、鄰甲酚酚醛清漆型環氧化合物、雙酚-A型環氧化合物、雙酚-F型環氧化合物，及苯酚型環氧化合物。該等化合物，能夠單獨使用1種，或者混合2種以上而使用。Among these, preferred are also: phenol novolac epoxy compound, o-cresol novolac epoxy compound, bisphenol-A epoxy compound, bisphenol-F epoxy compound, and phenol ring Oxygen compounds. These compounds can be used alone or in combination of two or more.
在組成物中製造環氧樹脂亦是可能的。例如，透過將環氧化合物與硬化劑添加於組成物，進行加熱，藉此使樹脂化，而可獲得環氧樹脂。It is also possible to produce epoxy resin in the composition. For example, epoxy resin and epoxy resin can be obtained by adding an epoxy compound and a hardener to the composition and heating to thereby resinize.
又，藉著將單官能性環氧化合物、2官能性環氧化合物或者3官能性以上之多官能性環氧化合物添加於上述環氧化合物，能夠將環氧樹脂改性。Furthermore, by adding a monofunctional epoxy compound, a bifunctional epoxy compound, or a polyfunctional epoxy compound having a trifunctionality or more to the epoxy compound, the epoxy resin can be modified.
作為單官能性環氧化合物的具體例，例如，可舉：丁基縮水甘油醚、苯基縮水甘油醚、甲苯酚基縮水甘油醚、烯丙基縮水甘油醚、醇的縮水甘油醚等。Specific examples of the monofunctional epoxy compound include, for example, butyl glycidyl ether, phenyl glycidyl ether, cresyl glycidyl ether, allyl glycidyl ether, and alcohol glycidyl ether.
作為2官能性之環氧化合物的具體例，例如，可舉：乙二醇二縮水甘油醚、丙二醇二縮水甘油醚、三丙二醇二縮水甘油醚、1,6-己二醇二縮水甘油醚、雙酚A的二縮水甘油醚、丁二烯二環氧化物、3,4-環氧基環己基甲基-(3,4-環氧基)環己烷羧酸酯、二氧化乙烯基環己烷、4,4’-二(1,2-環氧基乙基)二苯基醚、4,4’-(1,2-環氧基乙基)聯苯、2,2-雙(3,4-環氧基環己基)丙烷、雷瑣辛(resorcin)的縮水甘油醚、藤黃酸(phloroglucin)的二縮水甘油醚、甲基藤黃酸(methyl phloroglucin)的二縮水甘油醚、雙(2,3’-環氧基環戊基)醚、2-(3,4-環氧基)環己烷-5,5-螺(3,4-環氧基)環己烷-間二
作為3官能性以上之多官能性環氧化合物之具體例，例如，可舉：對胺基苯酚的三縮水甘油醚、聚烯丙基縮水甘油醚、1,3,5-三(1,2-環氧基乙基)苯、2,2’,4,4’-四縮水甘油氧基二苯甲酮、苯酚甲醛酚醛清漆的聚縮水甘油醚、三羥甲基丙烷的三縮水甘油醚、三羥甲基丙烷的三縮水甘油醚等。Specific examples of polyfunctional epoxy compounds having 3 or more functionalities include, for example, triglycidyl ether of p-aminophenol, polyallyl glycidyl ether, 1,3,5-tris(1,2 -Epoxyethyl)benzene, 2,2',4,4'-tetraglycidoxybenzophenone, polyglycidyl ether of phenol formaldehyde novolak, triglycidyl ether of trimethylolpropane, Triglycidyl ether of trimethylolpropane, etc.
該等單官能性環氧化合物、2官能性環氧化合物或者3官能性以上之多官能性環氧化合物，分別能夠單獨使用1種，或者併用2種以上。These monofunctional epoxy compounds, bifunctional epoxy compounds, or polyfunctional epoxy compounds with three or more functionalities can be used alone or in combination of two or more.
就硬化劑而言，能夠廣泛使用在此領域公知者。作為硬化劑，例如，可舉：二氰二胺(dicyandiamide)(DICY)化合物、酚醛清漆型苯酚樹脂、胺基改性酚醛清漆型苯酚樹脂、聚乙烯基苯酚樹脂、有機酸醯肼、二胺基馬來腈化合物、三聚氰胺化合物、胺醯亞胺、多胺鹽、分子篩、胺化合物、酸酐、聚醯胺、咪唑、光或者紫外線硬化劑等。As for the hardener, those known in this field can be widely used. Examples of the curing agent include dicyandiamide (DICY) compounds, novolak-type phenol resins, amine-modified novolak-type phenol resins, polyvinyl phenol resins, organic acid hydrazides, and diamines. Basic maleimide compounds, melamine compounds, amide imines, polyamine salts, molecular sieves, amine compounds, acid anhydrides, polyamides, imidazoles, light or ultraviolet hardeners, etc.
該等之中，因使用包含下述之組成物所製作出之成形體，抑制磷系阻燃劑溶出的效果特別高，因此較佳為胺化合物：經利用胺化合物使硬化而得之環氧樹脂與本發明之滲出抑制劑與磷系阻燃劑。作為胺化合物的具體例，例如可舉：二胺基二苯基碸、間苯二甲胺(m-xylylenediamine)、N-胺基乙基哌
該等硬化劑能夠單獨使用1種或者混合2種以上而使用。These hardeners can be used alone or in combination of two or more.
硬化劑的摻合量是能夠依環氧化合物的環氧當量、硬化劑的活性氫當量或者胺當量(胺系硬化劑的活性氫的當量)等，基於環氧化合物及硬化劑的官能基數而適宜調整。The blending amount of the hardener can be based on the epoxy equivalent of the epoxy compound, the active hydrogen equivalent of the hardener or the amine equivalent (the equivalent of active hydrogen of the amine hardener), etc., based on the number of functional groups of the epoxy compound and the hardener Suitable for adjustment.
又，為了使容易促進硬化，亦可添加硬化助劑。就硬化助劑而言，能夠廣泛使用此領域公知者。作為硬化助劑，例如可舉：三級胺、咪唑、芳香族胺及三苯基膦等。該等硬化助劑，能夠單獨使用1種或者混合2種以上而使用。硬化助劑的摻合量未被特別限制，通常，相對於100質量份環氧樹脂，是10質量份以下，較佳為5質量份以下，更佳為1質量份以下。硬化助劑摻合量的下限値未被特別限定，例如相對於100質量份環氧樹脂，較佳令為0.01質量份，更佳令為0.1質量份。In addition, in order to facilitate curing, a curing aid may be added. As for the hardening aid, those known in this field can be widely used. Examples of the curing aid include tertiary amine, imidazole, aromatic amine, triphenylphosphine and the like. These hardening aids can be used alone or in combination of two or more. The blending amount of the curing aid is not particularly limited, but it is usually 10 parts by mass or less, preferably 5 parts by mass or less, and more preferably 1 part by mass or less with respect to 100 parts by mass of the epoxy resin. The lower limit value of the blending amount of the hardening aid is not particularly limited. For example, with respect to 100 parts by mass of epoxy resin, it is preferably 0.01 part by mass, and more preferably 0.1 part by mass.
(樹脂組成物) 本發明之樹脂組成物，包含：上述之樹脂、滲出抑制劑，及磷系阻燃劑。(Resin composition) The resin composition of the present invention includes the above-mentioned resin, an exudation inhibitor, and a phosphorus-based flame retardant.
在本發明之樹脂組成物中，當把滲出抑制劑中式(1)所示之化合物與磷系阻燃劑的合計質量令為100質量份時，式(1)所示之化合物的比例，通常為0.1至30質量份左右，較佳為1至28質量份左右，進一步較佳為2至25質量份，特佳為3至20質量份。當本發明之樹脂組成物的樹脂為熱固性樹脂的情況，通常為0.1至30質量份左右，較佳為1至20質量份，進一步較佳為2至15質量份，特佳為7至12質量份。當本發明之樹脂組成物的樹脂為熱塑性樹脂的情況，通常為0.1至30質量份左右，較佳為5至28質量份，進一步較佳為7至25質量份，特佳為9至20質量份。樹脂組成物透過以上述範圍含有式(1)所示之化合物，而樹脂的性質不會變化，且滲出受到抑制。In the resin composition of the present invention, when the total mass of the compound represented by formula (1) and the phosphorus-based flame retardant in the bleeding inhibitor is 100 parts by mass, the ratio of the compound represented by formula (1) is usually It is about 0.1 to 30 parts by mass, preferably about 1 to 28 parts by mass, further preferably 2 to 25 parts by mass, and particularly preferably 3 to 20 parts by mass. When the resin of the resin composition of the present invention is a thermosetting resin, it is usually about 0.1 to 30 parts by mass, preferably 1 to 20 parts by mass, further preferably 2 to 15 parts by mass, and particularly preferably 7 to 12 parts by mass Copies. When the resin of the resin composition of the present invention is a thermoplastic resin, it is usually about 0.1 to 30 parts by mass, preferably 5 to 28 parts by mass, further preferably 7 to 25 parts by mass, particularly preferably 9 to 20 parts by mass Copies. When the resin composition contains the compound represented by the formula (1) in the above range, the properties of the resin do not change, and bleeding is suppressed.
在本發明之樹脂組成物中，相對於100質量份樹脂，滲出抑制劑中式(1)所示之化合物與磷系阻燃劑的合計質量，通常為1至70質量份左右，較佳為5至50質量份左右，進一步較佳為10至45質量份左右。當本發明之樹脂組成物的樹脂為熱固性樹脂的情況，通常為10至50質量份左右，較佳為11至48質量份左右，更佳為13至45質量份左右，進一步較佳為15至40質量份左右，特佳為20至35質量份左右。當本發明之樹脂組成物的樹脂為熱塑性樹脂的情況，通常為6至30質量份左右，較佳為8至25質量份左右，進一步較佳為10至20質量份左右。In the resin composition of the present invention, the total mass of the compound represented by formula (1) in the bleed inhibitor and the phosphorus-based flame retardant is usually about 1 to 70 parts by mass, preferably 5 parts per 100 parts by mass of the resin. It is about 50 parts by mass, more preferably about 10 to 45 parts by mass. When the resin of the resin composition of the present invention is a thermosetting resin, it is usually about 10 to 50 parts by mass, preferably about 11 to 48 parts by mass, more preferably about 13 to 45 parts by mass, and still more preferably 15 to About 40 parts by mass, particularly preferably about 20 to 35 parts by mass. When the resin of the resin composition of the present invention is a thermoplastic resin, it is usually about 6 to 30 parts by mass, preferably about 8 to 25 parts by mass, and more preferably about 10 to 20 parts by mass.
相對於100質量份樹脂之，本發明之滲出抑制劑中式(1)所示之化合物的摻合量，是能夠從當把上述本發明之滲出抑制劑中式(1)所示之化合物及磷系阻燃劑的合計質量令為100質量份時式(1)所示之化合物的比例，及相對於100質量份樹脂之，本發明之滲出抑制劑中式(1)所示之化合物與磷系阻燃劑的合計質量之範圍，進行適宜調整。The compounding amount of the compound represented by the formula (1) in the bleed inhibitor of the present invention is equivalent to the compound represented by the formula (1) in the bleed inhibitor of the present invention and phosphorus based on 100 parts by mass of the resin. The ratio of the compound represented by formula (1) when the total mass of the flame retardant is 100 parts by mass, and the compound represented by formula (1) in the bleeding inhibitor of the present invention and the phosphorus-based resistance relative to 100 parts by mass of the resin The range of the total mass of the fuel is appropriately adjusted.
例如，在本發明之樹脂組成物中，本發明之滲出抑制劑中式(1)所示之化合物的摻合量，相對於100質量份樹脂，通常為0.01至60質量份左右，較佳為0.1至55質量份左右，更佳為1至50質量份左右，進一步較佳為3至40質量份左右，特佳可令為5至30質量份左右，進一步具體地，當本發明之滲出抑制劑中式(1)所示之化合物與磷系阻燃劑的合計質量為20質量份的情況，相對於100質量份樹脂之，本發明之滲出抑制劑中式(1)所示之化合物的摻合量，通常為0.02至6質量份左右，較佳為0.2至4質量份左右，進一步較佳為0.4至3質量份左右，特佳為0.6至2.4質量份左右；當本發明之滲出抑制劑中之式(1)所示之化合物與磷系阻燃劑的合計質量為30質量份的情況，相對於100質量份樹脂之，本發明之滲出抑制劑中式(1)所示之化合物的摻合量，通常為0.03至9質量份左右，較佳為0.3至6質量份左右，進一步較佳為0.6至4.5質量份左右，特佳為0.9至3.6質量份左右；當本發明之滲出抑制劑中式(1)所示之化合物與磷系阻燃劑的合計質量為45質量份的情況，相對於100質量份樹脂之，本發明之滲出抑制劑中式(1)所示之化合物的摻合量，通常為0.045至13.5質量份左右，較佳為0.45至9質量份左右，進一步較佳為0.9至6.75質量份左右，特佳可令為1.35至5.4質量份左右。For example, in the resin composition of the present invention, the compounding amount of the compound represented by formula (1) in the bleed inhibitor of the present invention is usually about 0.01 to 60 parts by mass, preferably 0.1 relative to 100 parts by mass of the resin To about 55 parts by mass, more preferably about 1 to 50 parts by mass, further preferably about 3 to 40 parts by mass, particularly preferably about 5 to 30 parts by mass, further specifically, when the bleed inhibitor of the present invention When the total mass of the compound represented by the formula (1) and the phosphorus-based flame retardant is 20 parts by mass, the compounding amount of the compound represented by the formula (1) in the bleeding inhibitor of the present invention relative to 100 parts by mass of the resin , Usually about 0.02 to 6 parts by mass, preferably about 0.2 to 4 parts by mass, further preferably about 0.4 to 3 parts by mass, particularly preferably about 0.6 to 2.4 parts by mass; When the total mass of the compound represented by the formula (1) and the phosphorus-based flame retardant is 30 parts by mass, the blending amount of the compound represented by the formula (1) in the bleeding inhibitor of the present invention relative to 100 parts by mass of the resin , Usually about 0.03 to 9 parts by mass, preferably about 0.3 to 6 parts by mass, more preferably about 0.6 to 4.5 parts by mass, particularly preferably about 0.9 to 3.6 parts by mass; when the exudation inhibitor of the present invention is ( 1) When the total mass of the compound shown and the phosphorus-based flame retardant is 45 parts by mass, the blending amount of the compound represented by the formula (1) in the bleeding inhibitor of the present invention is usually about 100 parts by mass of the resin. It is about 0.045 to 13.5 parts by mass, preferably about 0.45 to 9 parts by mass, further preferably about 0.9 to 6.75 parts by mass, particularly preferably about 1.35 to 5.4 parts by mass.
或者，本發明之樹脂組成物，是包含：上述之樹脂，及包含上述滲出抑制劑及磷系阻燃劑而成之本發明之樹脂用阻燃劑。Alternatively, the resin composition of the present invention includes the above-mentioned resin and the flame retardant for resin of the present invention including the above-mentioned bleeding inhibitor and phosphorus-based flame retardant.
在本發明之樹脂組成物中，相對於100質量份樹脂，樹脂用阻燃劑通常含有1至70質量份左右，較佳含有5至50質量份左右，進一步較佳含有10至45質量份左右。當要添加本發明之樹脂用添加劑之樹脂為熱固性樹脂的情況，通常含有10至50質量份左右，較佳含有11至48質量份左右，更佳含有13至45質量份左右，進一步較佳含有15至40質量份左右，特佳含有20至35質量份左右。當要添加本發明之樹脂用添加劑之樹脂為熱塑性樹脂的情況，通常含有6至30質量份左右，較佳含有8至25質量份左右，進一步較佳含有10至20質量份左右。In the resin composition of the present invention, the flame retardant for resin generally contains about 1 to 70 parts by mass, preferably about 5 to 50 parts by mass, and more preferably about 10 to 45 parts by mass relative to 100 parts by mass of the resin. . When the resin to which the resin additive of the present invention is added is a thermosetting resin, it generally contains about 10 to 50 parts by mass, preferably about 11 to 48 parts by mass, more preferably about 13 to 45 parts by mass, and further preferably contains About 15 to 40 parts by mass, particularly good contains about 20 to 35 parts by mass. When the resin to which the resin additive of the present invention is added is a thermoplastic resin, it usually contains about 6 to 30 parts by mass, preferably about 8 to 25 parts by mass, and more preferably about 10 to 20 parts by mass.
前述樹脂用阻燃劑，包含前述滲出抑制劑及磷系阻燃劑。於前述樹脂用阻燃劑所含之滲出抑制劑中式(1)所示之化合物與磷系阻燃劑的比例是與前述同樣的。The flame retardant for resin includes the bleeding inhibitor and the phosphorus flame retardant. The ratio of the compound represented by formula (1) to the phosphorus-based flame retardant in the bleeding inhibitor contained in the flame retardant for resin is the same as described above.
(其它的添加劑) 在本發明之樹脂組成物來說，出於使其之阻燃性能、特別是防止滴垂(dripping)(燃燒時的滴下所致之延燒)性能更進一步提升的目的，因應需要，能夠摻合氟樹脂、無機填充材等。該等可以單獨摻合任一者，或者可同時地摻合雙方。(Other additives) For the resin composition of the present invention, for the purpose of further improving the flame retardant performance, especially the performance of preventing dripping (due burning due to dripping during combustion), it can be blended as needed Fluorine resin, inorganic filler, etc. These can be blended either individually, or both can be blended simultaneously.
就氟樹脂而言，能夠使用公知者。作為氟樹脂，例如，可舉：聚四氟乙烯(PTFE)、四氟乙烯-六氟丙烯共聚物(FEP)、四氟乙烯-全氟烷基乙烯基醚共聚物(PFA)、四氟乙烯-乙烯共聚物(ETFE)、聚(三氟氯乙烯)(CTFE)、聚偏氟乙烯(polyvinylidenefluoride)(PVdF)等。該等之中，較佳亦為PTFE。氟樹脂能夠單獨使用1種，或者能夠併用2種以上。As for the fluororesin, known ones can be used. Examples of the fluororesin include polytetrafluoroethylene (PTFE), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), and tetrafluoroethylene -Ethylene copolymer (ETFE), poly(chlorotrifluoroethylene) (CTFE), polyvinylidene fluoride (PVdF), etc. Among these, PTFE is also preferable. One type of fluororesin can be used alone, or two or more types can be used in combination.
氟樹脂的摻合量未被特別限制，相對於100質量份樹脂，通常為0.01至2.5質量份左右，較佳為0.1至1.2質量份左右。The blending amount of the fluororesin is not particularly limited, and it is usually about 0.01 to 2.5 parts by mass, preferably about 0.1 to 1.2 parts by mass with respect to 100 parts by mass of the resin.
無機填充材會使得防止滴垂的效果增強，同時亦能夠使得樹脂組成物的機械強度、電性能(例如：絕緣性、導電性、異向導電性、介電性、耐濕性等)、熱性能(例如：耐熱性、焊接耐熱性、熱傳導性、低熱收縮性、低熱膨脹性、低應力性、耐熱衝撃性、耐熱循環性、耐回焊裂紋性、保存穩定性、溫度循環性等)、作業性或者成形性(流動性、硬化性、接著性、黏著性、壓接性、密接性、底膠填充性、無空泡性、耐磨耗性、潤滑性、離型性、高彈性、低彈性、可撓性、彎曲性等)提升。The inorganic filler will enhance the effect of preventing dripping, and at the same time, the mechanical strength, electrical properties (for example: insulation, conductivity, anisotropic conductivity, dielectric properties, moisture resistance, etc.), heat Performance (for example: heat resistance, welding heat resistance, thermal conductivity, low heat shrinkage, low thermal expansion, low stress, heat shock resistance, heat cycle resistance, reflow crack resistance, storage stability, temperature cycle, etc.), Workability or formability (fluidity, hardenability, adhesiveness, adhesiveness, crimpability, adhesiveness, primer filling, no cavitation, wear resistance, lubricity, mold release, high elasticity, Low elasticity, flexibility, flexibility, etc.) improved.
就無機填充材而言，無特別限制，能夠使用公知的無機填充材。作為無機填充材，例如，可舉：雲母、高嶺土、滑石、熔融氧化矽、結晶氧化矽、氧化鋁、黏土、硫酸鋇、碳酸鋇、碳酸鈣、硫酸鈣、氫氧化鋁、氫氧化鎂、矽酸鈣、氧化鈦、氧化鋅、硼酸鋅、氮化鋁、氮化硼、氮化矽、玻璃珠、玻璃氣球、玻璃碎片、玻璃纖維、纖維狀鈦酸鹼金屬鹽(鈦酸鉀纖維、鈦酸鈉纖維等)、纖維狀硼酸鹽(硼酸鋁纖維、硼酸鎂纖維、硼酸鋅纖維等)、氧化鋅纖維、氧化鈦纖維、氧化鎂纖維、石膏纖維、矽酸鋁纖維、矽酸鈣纖維、碳化矽纖維、碳化鈦纖維、氮化矽纖維、氮化鈦纖維、碳纖維、碳化矽纖維、氧化鋁纖維、氧化鋁-氧化矽纖維、氧化鋯纖維、石英纖維、薄片狀鈦酸鹽、薄片狀氧化鈦等。The inorganic filler is not particularly limited, and a well-known inorganic filler can be used. Examples of inorganic fillers include mica, kaolin, talc, fused silica, crystalline silica, alumina, clay, barium sulfate, barium carbonate, calcium carbonate, calcium sulfate, aluminum hydroxide, magnesium hydroxide, and silicon Calcium acid, titanium oxide, zinc oxide, zinc borate, aluminum nitride, boron nitride, silicon nitride, glass beads, glass balloons, glass fragments, glass fiber, fibrous alkali metal titanate (potassium titanate fiber, titanium Sodium fiber, etc.), fibrous borate (aluminum borate fiber, magnesium borate fiber, zinc borate fiber, etc.), zinc oxide fiber, titanium oxide fiber, magnesium oxide fiber, gypsum fiber, aluminum silicate fiber, calcium silicate fiber, Silicon carbide fiber, titanium carbide fiber, silicon nitride fiber, titanium nitride fiber, carbon fiber, silicon carbide fiber, alumina fiber, alumina-silica fiber, zirconia fiber, quartz fiber, lamellar titanate, lamellar Titanium oxide, etc.
該等之中，就作為用以使機械強度提升之無機填充材而言，較佳為纖維狀物、薄片狀，或者板狀等具有形狀異向性者，特佳為：纖維狀鈦酸鹼金屬鹽、矽灰石纖維、硬矽鈣石纖維、鹼性硫酸鎂纖維、纖維狀硼酸鹽、氧化鋅纖維、矽酸鈣纖維、薄片狀鈦酸鹽、薄片狀氧化鈦、雲母、雲母、絹雲母、伊萊石、滑石、高嶺石、蒙脫石、水鋁石、膨潤石、蛭石等。又，就用以使電性能、熱性能、作業性或者成形性等提升的無機填充材而言，較佳為：熔融氧化矽、結晶氧化矽、氧化鋁、滑石、氮化鋁、氮化硼、氮化矽、氧化鈦、硫酸鋇等球狀物或者粉末狀物；特佳為：熔融氧化矽、結晶氧化矽、氧化鋁、氮化鋁等球狀物或者粉末狀物。Among these, as the inorganic filler for improving the mechanical strength, fibrous, sheet-like, or plate-like materials having shape anisotropy are preferred, and fibrous alkali titanate is particularly preferred: Metal salt, wollastonite fiber, xonotlite fiber, basic magnesium sulfate fiber, fibrous borate, zinc oxide fiber, calcium silicate fiber, flaky titanate, flaky titanium oxide, mica, mica, silk Mica, illite, talc, kaolinite, montmorillonite, diaspore, bentonite, vermiculite, etc. Moreover, as for the inorganic filler for improving electrical performance, thermal performance, workability or formability, it is preferably: fused silica, crystalline silica, alumina, talc, aluminum nitride, boron nitride , Silicon nitride, titanium oxide, barium sulfate and other spherical or powder; particularly preferably: molten silica, crystalline silica, alumina, aluminum nitride and other spherical or powder.
該等無機填充材，能夠單獨使用1種，或者能夠併用2種以上。One type of these inorganic fillers can be used alone, or two or more types can be used in combination.
又，出於抑制樹脂成分劣化的目的，亦能夠使用已經使用表面處理用之矽烷耦合劑、鈦耦合劑等被覆過無機填充材之表面而得者。In addition, for the purpose of suppressing the deterioration of the resin component, it is also possible to use a silane coupling agent for surface treatment, a titanium coupling agent, or the like that covers the surface of the inorganic filler.
相對於100質量份樹脂，無機填充材的摻合量，通常為0.01至90質量份左右，較佳為1至80質量份左右。The blending amount of the inorganic filler with respect to 100 parts by mass of the resin is usually about 0.01 to 90 parts by mass, preferably about 1 to 80 parts by mass.
在不損及該較佳特性的範圍，在本發明之樹脂組成物而言，能夠摻合其它的添加劑。作為其它的添加劑可舉各種阻燃劑等。就阻燃劑而言未被特別限制，能夠使用公知者。例如可舉：無機系阻燃劑等。該等可單獨使用1種，或者可併用2種以上。The resin composition of the present invention can be blended with other additives as long as the preferable characteristics are not impaired. Examples of other additives include various flame retardants. The flame retardant is not particularly limited, and known ones can be used. Examples include inorganic flame retardants. One of these may be used alone, or two or more may be used in combination.
進一步，在不損及該較佳特性的範圍，在本發明之樹脂組成物來說，能夠摻合一般的樹脂添加劑。就該樹脂添加劑而言，無特別限制，例如，可舉：紫外線吸收劑(二苯甲酮系、苯并***系、氰基丙烯酸酯系、三
該等其它添加劑，亦可包含於本發明之滲出抑制劑，或者樹脂用阻燃劑。These other additives may also be included in the exudation inhibitor of the present invention, or a flame retardant for resin.
(樹脂組成物的製造方法) 本發明之樹脂組成物適能夠透過將各種原材料秤量指定量或者適量，並利用公知的方法進行混合或者混煉而獲得。例如，將能夠透過使用1軸擠出機、2軸擠出機等擠出機、班布里混合機、加壓捏合機、2輥機、3輥機等混煉機等，將粉末、珠、碎片或者丸粒狀的各成分的混合物，進行混煉，而獲得本發明之樹脂組成物。又，在需要摻合液體的情況來說，能夠使用公知的液體注入裝置，並利用上述之擠出機或者混煉機等進行混煉。亦可預先利用混合機(滾動機(tumbler)、亨歇爾混合機等)將各種原材料進行預備混合再使用。(Manufacturing method of resin composition) The resin composition of the present invention can be obtained by weighing various raw materials by a specified amount or an appropriate amount, and mixing or kneading by a known method. For example, by using an extruder such as a 1-axis extruder or a 2-axis extruder, a Banbury mixer, a pressure kneader, a 2-roller, a 3-roller, etc., the powder and beads , Chips or pellets of each component mixture, and kneaded to obtain the resin composition of the present invention. In addition, when a liquid needs to be blended, a well-known liquid injection device can be used, and kneading can be performed using the above-mentioned extruder or kneader. It is also possible to preliminarily mix various raw materials with a mixer (tumbler, Henschel mixer, etc.) before use.
又，本發明之樹脂組成物能夠透過調整高濃度地包含有所期望之成分(例如本發明之滲出抑制劑及磷系阻燃劑，或者本發明之樹脂用阻燃劑)的母料(masterbatch)樹脂組成物，並依需要將其它的成分進行混合或者混煉而獲得。In addition, the resin composition of the present invention can be adjusted to contain a desired concentration (such as the bleeding inhibitor and phosphorus flame retardant of the present invention, or the flame retardant for resin of the present invention) at a high concentration by adjusting the masterbatch ) The resin composition is obtained by mixing or kneading other components as necessary.
(成形體) 本發明之樹脂組成物，例如，能夠透過鑄塑成形、射出成形、壓縮成形、轉注成形、***成形、RIM成形、擠出成形、吹脹成形、吹製成形等公知的成形方法，作成單一層或者多層的樹脂板、片材、薄膜、纖維、圓棒、方棒、球狀、方狀、管子、管、異形品等任意形狀的成形體。(Molded body) The resin composition of the present invention can be formed into a single layer by known molding methods such as casting molding, injection molding, compression molding, injection molding, insert molding, RIM molding, extrusion molding, inflation molding, blow molding, etc. Or a multilayered resin plate, sheet, film, fiber, round bar, square bar, ball, square, tube, tube, shaped product, or any other shaped shaped body.
本發明之樹脂組成物，能夠應用在樹脂成分可使用的所有領域。作為可使用的領域，例如可舉：電氣、電子或者通信設備、精密設備、汽車等運輸設備、纖維製品、各種製造機械類、食品包裝薄膜、容器、農林水產領域、建設用資材、醫療用品、家具類的構成零件等。The resin composition of the present invention can be applied to all fields where the resin component can be used. As applicable fields, for example, electrical, electronic or communication equipment, precision equipment, transportation equipment such as automobiles, fiber products, various manufacturing machinery, food packaging films, containers, agriculture, forestry and fisheries fields, construction materials, medical supplies, Components such as furniture.
特別是，當使用了環氧樹脂作為樹脂成分的情況，由本發明之樹脂組成物所製作之成形體，在電氣、電子或者通信設備的用途為較佳。就電氣、電子或者通信設備而言，例如可舉：構成印表機、電腦、文字處理機、鍵盤、小型資訊終端機(PDA)、電話機、行動終端(行動電話、智慧型手機、平板電腦型終端等)、傳真、影印機、電子收銀機(ECR)、電子計算器、電子筆記本、電子字典等OA機器、洗衣機、冰箱、電鍋、吸塵器、微波爐、照明器具、空調、熨斗、暖爐桌(kotatsu)等家電製品、電視、調諧器、VTR、攝影機、攝錄影機、數位相機、收錄音機、錄音機、MD播放器、CD播放器、DVD播放器、LD播放器、HDD(硬式磁碟機)、揚聲器、汽車導航、液晶顯示器、EL顯示器、電漿顯示器等AV製品等的外殼、機構零件或者結構零件之一部分或者全部的材料、構成電線、纜繩等的被覆電阻、用以收納恆溫器、溫度保險絲等電氣元件的殼體、馬達用培林、分隔件、點式印表機用線導等滑動零件的一部分或者全部的材料等。In particular, when epoxy resin is used as the resin component, the molded body produced from the resin composition of the present invention is preferably used in electrical, electronic, or communication equipment. For electrical, electronic or communication equipment, for example: printer, computer, word processor, keyboard, small information terminal (PDA), telephone, mobile terminal (mobile phone, smart phone, tablet computer type) Terminals, etc.), faxes, photocopiers, electronic cash registers (ECR), electronic calculators, electronic notebooks, electronic dictionaries and other OA machines, washing machines, refrigerators, electric cookers, vacuum cleaners, microwave ovens, lighting appliances, air conditioners, irons, stove tables (kotatsu) and other home appliances, TVs, tuners, VTRs, cameras, camcorders, digital cameras, radio cassette recorders, recorders, MD players, CD players, DVD players, LD players, HDD (hard disk drives) Machine), speakers, car navigation, liquid crystal displays, EL displays, plasma displays, and other AV products such as housings, mechanism parts or structural parts, part or all of the materials, coating resistors constituting wires, cables, etc., for storing thermostats , Part of or all the materials of sliding parts such as housings of electrical components such as temperature fuses, motor bearings, separators, wire guides for dot printers, etc.
本發明之成形體在電氣、電子或者通信設備之中，特佳的用途亦為：在被使用於該等之電氣或者電子零件的用途，例如，各種半導體元件的封裝材、配線板的基板材料等的用途。在將半導體元件等予以封裝之際來說，能夠廣泛採用習知公知的方法。例如，將半導體晶片、電晶體、二極體、發光二極體(LED)、閘流體等主動元件、電容器、電阻體、線圈等被動元件等半導體元件安裝於引線框、配線完畢的帶載體、配線板、玻璃、矽晶元等支持構件，並連接至預先形成好的電路圖案，利用本發明之樹脂組成物的溶液或者糊劑將需要的部分進行封裝，藉此能夠製造電子零件。The molded article of the present invention is particularly suitable for use in electrical, electronic, or communication equipment as well as for use in such electrical or electronic parts, for example, packaging materials for various semiconductor elements and substrate materials for wiring boards And other uses. When packaging semiconductor elements and the like, conventionally known methods can be widely used. For example, semiconductor elements such as semiconductor chips, transistors, diodes, light emitting diodes (LEDs), thyristors and other active components, capacitors, resistors, coils and other passive components are mounted on the lead frame, the wired carrier, A supporting member such as a wiring board, glass, silicon wafer, etc. is connected to a circuit pattern formed in advance, and the required part is encapsulated with the solution or paste of the resin composition of the present invention, thereby making it possible to manufacture electronic parts.
就安裝方法而言無特別限制，例如，能夠採用：引線框架包裝、面安裝包裝[SOP(small outline package)、SOJ(small outline j-leaded package)、QFP(quad flat package)、BGA(ball grid array)等]、CSP(chip size/scale package)等方法。There is no particular restriction on the installation method, for example, lead frame packaging, surface mounting package [SOP (small outline package), SOJ (small outline j-leaded package), QFP (quad flat package), BGA (ball grid) array) etc., CSP (chip size/scale package) and other methods.
與電路圖案的連接方法亦未被特別限制，例如，可採用：線接式、TAB(tape automated bonding)連接、倒裝(flipchip)連接等公知的方法。The connection method to the circuit pattern is also not particularly limited. For example, a well-known method such as wire bonding, TAB (tape automated bonding) connection, and flip chip connection can be adopted.
就封裝方法而言，低壓轉注成形法(low pressure transfer molding)是最一般的，亦可使用注射成形法、壓縮成形法、鑄塑法等。此際，能夠因應要安裝元件之支持構件的種類、要進行安裝之元件的種類、安裝方法、連接方法、封裝方法等各種條件，適宜變更本發明之樹脂組成物的組成。又，為了將半導體元件、焊球、引線框、散熱器、加強板等零件安裝至支持構件，亦能夠將本發明之樹脂組成物作為接著劑使用。In terms of packaging methods, low pressure transfer molding (low pressure transfer molding) is the most common, and injection molding, compression molding, casting, etc. can also be used. At this time, the composition of the resin composition of the present invention can be appropriately changed in accordance with various conditions such as the type of support member to which the component is mounted, the type of the component to be mounted, the mounting method, the connection method, and the packaging method. In addition, in order to mount components such as semiconductor elements, solder balls, lead frames, heat sinks, and reinforcing plates to the support member, the resin composition of the present invention can also be used as an adhesive.
進一步亦能夠將本發明之樹脂組成物預先成形為薄膜狀，並將此薄膜，作為例如二次安裝用封裝材而使用。就利用這般的方法所製造之電子零件而言，例如，可舉：利用本發明之樹脂組成物，把已利用凸塊而連接在帶載體的半導體晶片進行封裝而得之TCP(tape carrier package)。又，可舉：利用本發明之樹脂組成物，把已利用線接式、倒裝晶片接合法(flip chip bonding)、焊接等，而連接至配線板或者已形成在玻璃上的配線的半導體晶片、積體電路、大規模積體電路、電晶體、二極體、閘流體等主動元件及/或電容器、電阻體、線圈等被動元件，進行封裝而成之COB模組、拼合積體電路(hybrid integrated circuit)、多晶片模組等。Furthermore, the resin composition of the present invention can be formed into a film in advance, and this film can be used as, for example, a packaging material for secondary mounting. For electronic parts manufactured by such a method, for example, a TCP (tape carrier carrier) package obtained by packaging a semiconductor wafer with a carrier that has been bumped and connected to a carrier using the resin composition of the present invention ). In addition, it is possible to use the resin composition of the present invention to connect a semiconductor wafer that has been connected to a wiring board or wiring formed on glass by wire bonding, flip chip bonding, soldering, or the like , Integrated circuits, large-scale integrated circuits, transistors, diodes, thyristors and other active components and/or passive components such as capacitors, resistors, coils, etc., packaged COB module, assembled integrated circuit ( hybrid integrated circuit), multi-chip modules, etc.
當把本發明之樹脂組成物作為配線板用的基板材料使用的情況，亦是能夠與習知的方法同樣地實施即可。例如，利用使紙、玻璃纖維布、芳綸纖維(aramid fiber)布等基材含浸本發明之樹脂組成物，並在90至220℃左右的溫度下使乾燥1至5分鐘左右的方法等使之半硬化，藉此製造預浸體，並將該預浸體作為配線板用的基板材料即可。又，亦能夠將本發明之樹脂組成物成形為薄膜狀，並將此薄膜作為配線板用的基板材料而使用。此時，若摻合導電性物質或者介電性物質的話，亦能夠作成導電性層、異向導電性層、導電率控制層、介電性層、異向介電性層、介電率控制層等機能性膜。When the resin composition of the present invention is used as a substrate material for a wiring board, it can be implemented in the same manner as the conventional method. For example, a method of impregnating the resin composition of the present invention with a substrate such as paper, glass fiber cloth, aramid fiber cloth, etc., and drying at a temperature of about 90 to 220°C for about 1 to 5 minutes, etc. The half is hardened to manufacture a prepreg and use the prepreg as a substrate material for a wiring board. Also, the resin composition of the present invention can be formed into a film shape, and this film can be used as a substrate material for a wiring board. At this time, if a conductive substance or a dielectric substance is blended, a conductive layer, an anisotropic conductive layer, a conductivity control layer, a dielectric layer, an anisotropic dielectric layer, and a dielectric control can also be made Functional film.
進一步，亦能夠作為樹脂製凸塊或者作為形成在通孔內側的導電性層而使用。在將預浸體或者薄膜進行積層而製造配線板之際，亦能夠將本發明之樹脂組成物作為接著劑使用。此時，亦是與進行薄膜化的情況同樣地，可含有導電性無機物質、介電性無機物質等。Furthermore, it can also be used as a resin bump or as a conductive layer formed inside a through hole. The resin composition of the present invention can also be used as an adhesive when a prepreg or a film is laminated to manufacture a wiring board. At this time, as in the case of thinning, a conductive inorganic substance, a dielectric inorganic substance, etc. may be contained.
在本發明來說，可僅以使得基材含浸本發明之樹脂組成物而成之預浸體及/或本發明之樹脂組成物予以成形而成的薄膜來製造配線板，亦可將習知的配線板用預浸體及/或薄膜與該等一起併用。就配線板而言，未被特別限制，例如，可為剛硬型或者可撓型之物，形狀亦能夠從片材狀或者薄膜狀到板狀適宜選擇。例如，可舉：敷金屬箔積層板、印刷配線板、接合片材、附載體之樹脂薄膜等。In the context of the present invention, the wiring board may be manufactured only from a film formed by impregnating the base material with the resin composition of the present invention and/or the resin composition of the present invention, or it may be known The prepreg and/or film for wiring board are used together with these. The wiring board is not particularly limited. For example, it may be a rigid type or a flexible type, and the shape can be appropriately selected from a sheet shape or a film shape to a plate shape. For example, a metal-clad laminate, a printed wiring board, a bonding sheet, a resin film with a carrier, etc. can be mentioned.
作為敷金屬箔積層板，更具體地，可舉：敷銅積層板、複合敷銅積層板、可撓式敷銅積層板等。該等敷金屬箔積層板能夠與習知的方法同樣地製作。例如，將上述預浸體重疊1片或者多片，並於其單面或者兩面配置厚度2至70μm左右的金屬(銅、鋁等)箔，使用多級壓製機(multistage press)、連續成形機等，以溫度180至350℃左右、加熱時間100至300分鐘左右，及面壓20至100kg/cm2 左右進行積層成形，藉此能夠製作敷金屬箔積層板。As a metal-clad laminate, more specifically, a copper-clad laminate, a composite copper-clad laminate, a flexible copper-clad laminate, etc. are mentioned. These metal-clad laminates can be produced in the same manner as conventional methods. For example, one or more sheets of the above prepregs are stacked, and a metal (copper, aluminum, etc.) foil with a thickness of about 2 to 70 μm is arranged on one or both sides of the prepreg, and a multistage press or continuous forming machine is used. In this way, metal foil-clad laminates can be produced by performing layer forming at a temperature of about 180 to 350° C., a heating time of about 100 to 300 minutes, and a surface pressure of about 20 to 100 kg/cm 2 .
作為印刷配線板，更具體地，可舉：增層型多層印刷配線板、可撓性印刷配線板等。該等印刷配線板能夠與習知的方法同樣地製作。例如，對敷金屬箔積層板的表面施行蝕刻處理，並形成內層電路而藉此製作内裝基板，在內層電路的表面重疊數片預浸體，並於其外側積層外裝電路用的金屬箔，藉由進行加熱及加壓而進行一體成型而獲得多層的積層體。在所獲得之多層的積層體鑽孔，並使內層電路與外層電路用的金屬箔導通於該孔的壁面而形成鍍覆金屬皮膜。進一步，對外層電路用的金屬箔施行蝕刻處理，形成外層電路，藉此可製作印刷配線板。As the printed wiring board, more specifically, a multi-layer multilayer printed wiring board, a flexible printed wiring board, etc. may be mentioned. These printed wiring boards can be produced in the same manner as the conventional methods. For example, an etching process is performed on the surface of a metal-clad laminate to form an inner layer circuit, thereby forming an inner substrate, a plurality of prepregs are superimposed on the surface of the inner layer circuit, and an outer circuit is laminated on the outer side The metal foil is integrally formed by heating and pressing to obtain a multilayer laminate. The obtained multilayer laminate is drilled, and the metal foils for the inner layer circuit and the outer layer circuit are led to the wall surface of the hole to form a plated metal film. Furthermore, the metal foil for the outer layer circuit is etched to form an outer layer circuit, thereby making it possible to produce a printed wiring board.
接合片材是能夠與習知的方法同樣地製作。例如，使用輥塗布機、缺角輪塗布機(comma coater)等，把使本發明之樹脂組成物溶解於溶劑而得之溶液，塗布於聚乙烯薄膜、聚丙烯薄膜等可剝離的塑料薄膜的支撑材，並將其在40至160℃左右進行1至20分鐘左右加熱處理，並利用輥等進行壓接，藉此能夠製作接合片材。The joined sheet can be produced in the same manner as the conventional method. For example, using a roll coater, a comma coater, etc., a solution obtained by dissolving the resin composition of the present invention in a solvent is applied to a peelable plastic film such as polyethylene film or polypropylene film. The support material is heat-treated at about 40 to 160° C. for about 1 to 20 minutes, and is pressure-bonded with a roller or the like, whereby a joined sheet can be produced.
附載體之樹脂薄膜，能夠與習知的方法同樣地製作。例如，利用棒式塗佈(bar coater)、刮刀等，把使得本發明之樹脂組成物溶解於溶劑而得之溶液，塗布於聚乙烯薄膜、聚丙烯薄膜等可剝離的塑料薄膜的支撑材，並在80至200℃左右的溫度下進行1至180分鐘左右乾燥，藉此能夠製作附載體之樹脂薄膜。The resin film with a carrier can be produced in the same manner as the conventional method. For example, a solution obtained by dissolving the resin composition of the present invention in a solvent is applied to a support material of a peelable plastic film such as a polyethylene film or a polypropylene film using a bar coater, a spatula, etc., And it is dried at a temperature of about 80 to 200°C for about 1 to 180 minutes, whereby a resin film with a carrier can be produced.
就其它的用途而言，可舉：精密設備、運輸設備、製造設備、家庭用品、土木建設資材等。就精密設備的具體例而言，可舉：構成鐘錶、顯微鏡、相機等之外殼、機構零件或者結構零件之一部分或者全部的材料。就運輸設備的具體例而言，可舉：構成遊艇、舟艇等船舶、電車、汽車、腳踏車、機車、飛機等的車體、機構零件或者結構零件(框架、管子、軸(shaft)、敞篷車頂部(convertible top)、門貼板、遮陽板、輪蓋、吊環、吊環帶等)之一部分或者全部的材料；構成各種運輸設備的內飾零件(臂靠、安裝架(package tray)、遮陽板、墊罩(mattress covers)等)之一部分或者全部的材料。就製造設備的具體例而言，可舉：構成機械手、輥、輥軸、分隔件、絕緣子、墊圈、止推墊圈(thrust washer)、齒輪、繞線圈(bobbin)、活塞(piston)構件、汽缸構件、皮帶輪(pulley)、泵構件、軸承、軸構件、板片彈簧、蜂窩結構材、掩蔽模(masking jig)、分電盤、防水墊(water proof pan)等機構零件或者結構零件之一部分或者全部的材料；構成水槽、淨化槽、旋轉槽等工業用槽類或者管子類、樹脂型、安全帽等之一部分或者全部的材料。就家庭用品的具體例而言，可舉：構成羽毛球或者網球之球拍框、高爾夫球桿的桿或者頭、曲棍球的球棍、滑雪之雪杖或者板、滑雪板、滑板、釣魚桿、球棒、帳篷的支柱等運動或者休閒用品、浴缸、洗臉盆、便器、該等的附屬品等衛生設備、片材、水桶、軟管等之一部分或者全部的材料、被設於家具之頂板或者桌子等表面的耐熱積層體材料、家具、櫥櫃等的裝飾材料等。就土木建築資材的具體例而言，可舉：各種建造物的內外飾材、屋頂材、地板材、壁紙、窗玻璃、窗玻璃的密封材、混凝土結構建築物(混凝土製橋墩、混凝土製支柱等)或者混凝土結構物(混凝土製柱、壁面、道路等)的強化材、污水管等管路補修材等。 較佳實施例之詳細說明 實施例For other uses, it can include: precision equipment, transportation equipment, manufacturing equipment, household goods, civil construction materials, etc. Specific examples of precision equipment include materials that form part or all of cases, mechanism parts, or structural parts of watches, microscopes, cameras, and the like. Specific examples of transportation equipment include: bodies, mechanism parts or structural parts (frames, pipes, shafts, convertibles) constituting ships, trams, automobiles, bicycles, locomotives, airplanes, and other ships, yachts, boats, etc. Part or all of the materials of the top (convertible top), door panels, sun visors, wheel covers, rings, eye straps, etc.; interior parts (arm rests, package trays, sun visors) that constitute various transportation equipment , Mat covers (mattress covers), etc.) part or all of the material. Specific examples of manufacturing equipment include: manipulators, rollers, roller shafts, separators, insulators, washers, thrust washer (thrust washer), gears, bobbin, piston (piston) members, Cylinder components, pulleys, pump components, bearings, shaft components, leaf springs, honeycomb structural materials, masking jigs, distributor plates, water proof pans, etc. Or all the materials; part or all of the materials that constitute industrial tanks or pipes such as water tanks, purification tanks, rotary tanks, resin types, safety helmets, etc. Specific examples of household items include: rackets for badminton or tennis, golf clubs or heads, hockey sticks, ski poles or boards, snowboards, skateboards, fishing rods, clubs, Part or all of the sanitary equipment, sheets, buckets, hoses, and other sanitary equipment, sheets, buckets, hoses, etc., such as sports or leisure products such as tent pillars, bathtubs, washbasins, toilets, and other accessories, are installed on the surface of furniture tops or tables, etc. Heat-resistant laminate materials, decorative materials for furniture, cabinets, etc. Specific examples of civil construction materials include internal and external decorative materials for various structures, roofing materials, floor boards, wallpaper, window glass, sealing materials for window glass, concrete structures (concrete bridge piers, concrete pillars) Etc.) or reinforced materials of concrete structures (concrete columns, walls, roads, etc.), pipeline repair materials such as sewage pipes, etc. Detailed description of the preferred embodiment Examples
於以下透過實施例及比較例具體地說明本發明，但本發明並非因該等而受到任何限定。In the following, the present invention will be described in detail through examples and comparative examples, but the present invention is not limited in any way by these.
製造六氯環三膦氮烯 將500ml一氯苯、873.6g五氯化磷及224.3g氯化銨置入於已裝有回流冷卻裝置的1L燒瓶，並使回流了5小時。回流結束後，停止加熱，並進行過濾、蒸餾，藉此獲得了483g六氯環三膦氮烯並使用於以下的製造例。Manufacturing hexachlorocyclotriphosphazene 500 ml of monochlorobenzene, 873.6 g of phosphorus pentachloride, and 224.3 g of ammonium chloride were placed in a 1 L flask equipped with a reflux cooling device, and refluxed for 5 hours. After the reflux was completed, heating was stopped, and filtration and distillation were carried out, whereby 483 g of hexachlorocyclotriphosphazene was obtained and used in the following production example.
製造例1：製造式(1)所示之化合物 將2,2’-聯苯酚(491.1g，2.6mol)與包含26.8質量%六氯環三膦氮烯的一氯苯溶液(1064.7g，2.5mol)、48%氫氧化鈉水溶液(441.6g，5.3mol)，與一氯苯(2.3L)，置入於已裝有迪安斯達克裝置(Dean-Stark apparatus)的5L燒瓶，流動氮氣，並使加熱回流了12小時。回流結束後，停止加熱，將去離子水(1.2L)添加於殘留的反應混合物，並攪拌了2小時。分離取得析出於反應器內的結晶，並利用去離子水及甲醇進行洗淨，並使乾燥，藉此獲得了白色固體(413.88g)。Production Example 1: Production of a compound represented by formula (1) 2,2'-biphenol (491.1g, 2.6mol) and a monochlorobenzene solution (1064.7g, 2.5mol) containing 26.8% by mass of hexachlorocyclotriphosphazene, and 48% aqueous sodium hydroxide solution (441.6g, 5.3 mol), together with monochlorobenzene (2.3 L), was placed in a 5 L flask already equipped with a Dean-Stark apparatus, nitrogen was flowed, and the heating was refluxed for 12 hours. After the reflux was completed, the heating was stopped, deionized water (1.2 L) was added to the remaining reaction mixture, and stirred for 2 hours. The crystals deposited in the reactor were separated, washed with deionized water and methanol, and dried to obtain a white solid (413.88 g).
實施例1至6及比較例1至3：製作樹脂成形體 量取記載於表1之各成分的量，並一邊在100℃進行加溫一邊進行混合使成為均勻。其後，在120℃下加熱1小時、在150℃下加熱1小時，進一步在200℃下加熱2小時，使硬化，並使所獲得之硬化物冷卻至室溫而製作了環氧樹脂成形體。Examples 1 to 6 and Comparative Examples 1 to 3: Production of resin molded bodies The amount of each component described in Table 1 was measured and mixed while heating at 100°C to make it uniform. Then, it heated at 120 degreeC for 1 hour, 150 degreeC for 1 hour, and further heated at 200 degreeC for 2 hours, hardened it, and cooled the obtained hardened|cured material to room temperature, and produced the epoxy resin molded body. .
惟，所謂表1內之「式(1)所示之化合物的含有比例[質量份]」，是表示把式(1)所示之化合物及磷系阻燃劑的合計質量令為100質量份時式(1)所示之化合物的含有比例。However, the "content ratio [parts by mass] of the compound represented by formula (1)" in Table 1 means that the total mass of the compound represented by formula (1) and the phosphorus-based flame retardant is set to 100 parts by mass The content ratio of the compound represented by Formula (1).
(溶出試驗) 測定了在實施例1至6及比較例1至3製作出之環氧樹脂成形體的質量。其後，在200℃下加熱2小時，並將已冷卻至室溫之樹脂組成物的表面以帶有丙酮的拭淨紙(Kimwipes)(註冊商標)擦拭附著於成形體表面之阻燃劑的溶出份，使成形體表面充分乾燥之後，從以下之式算出了溶出度。將其結果顯示於表1。(Dissolution test) The mass of the epoxy resin molded bodies produced in Examples 1 to 6 and Comparative Examples 1 to 3 was measured. After that, it was heated at 200° C. for 2 hours, and the surface of the resin composition that had been cooled to room temperature was wiped with acetone wiped paper (Kimwipes) (registered trademark) on the flame retardant attached to the surface of the molded body After the elution fraction was sufficiently dried on the surface of the molded body, the elution degree was calculated from the following formula. The results are shown in Table 1.
溶出度[%] = A/B × 100 A=(加熱前之成形體質量)-(加熱後經以丙酮擦拭後之成形體質量) B=(加熱前之成形體質量)Dissolution [%] = A/B × 100 A=(Quality of shaped body before heating)-(Quality of shaped body after heating and wiped with acetone) B=(Quality of molded body before heating)
[表1]
※1：雙酚F型環氧化合物；三菱化學股份有限公司製，Epikote 806 ※2：二胺基二苯基碸；和光純藥工業股份有限公司製 ※3：在製造例1製造出的化合物 ※4：1,1,3,3,5,5-六(苯氧基)環三膦氮烯；和光純藥工業股份有限公司製 ※5：間苯二酚多(二-2,6-二甲苯基)磷酸酯；大八化學工業股份有限公司製，PX-200 ※6：間苯二酚多苯基磷酸酯；股份有限公司ADEKA公司製，FP-700※1: Bisphenol F epoxy compound; manufactured by Mitsubishi Chemical Corporation, Epikote 806 ※2: Diaminodiphenyl sulfone; manufactured by Wako Pure Chemical Industries, Ltd. ※3: Compound produced in Production Example 1 ※4: 1,1,3,3,5,5-hexa(phenoxy)cyclotriphosphazene; manufactured by Wako Pure Chemical Industries, Ltd. ※5: Resorcinol poly(di-2,6-xylyl) phosphate; manufactured by Daba Chemical Industry Co., Ltd., PX-200 ※6: Resorcinol polyphenyl phosphate; manufactured by ADEKA Corporation, FP-700
實施例7至10及比較例4至5：製作樹脂成形體 利用雙軸擠出機以表2所示之摻合比例，將各成分進行熔融混煉，並分別製造出丸粒。再者，雙軸擠出機的料筒溫度為240℃。Examples 7 to 10 and Comparative Examples 4 to 5: Production of resin molded bodies Using a twin-screw extruder at the blending ratio shown in Table 2, the components were melt-kneaded, and pellets were produced separately. Furthermore, the barrel temperature of the twin-screw extruder was 240°C.
利用射出成形機將所獲得之丸粒成形為UL試驗片(長度127mm、寬度12.7mm、厚度1.6mm)，作為評價樣本。再者，以射出成形機的料筒溫度為260℃、模具溫度為85℃進行了成形。The obtained pellets were molded into an UL test piece (length 127 mm, width 12.7 mm, thickness 1.6 mm) using an injection molding machine as an evaluation sample. In addition, the molding was performed with the cylinder temperature of the injection molding machine being 260°C and the mold temperature being 85°C.
惟，所謂表2內之「式(1)所示之化合物的含有比例[質量份]」，是表示把式(1)所示之化合物及磷系阻燃劑的合計質量令為100質量份時式(1)所示之化合物的含有比例。However, the "content ratio [parts by mass] of the compound represented by formula (1)" in Table 2 means that the total mass of the compound represented by formula (1) and the phosphorus-based flame retardant is set to 100 parts by mass The content ratio of the compound represented by Formula (1).
(溶出試驗) 把所獲得之UL試驗片(成形體)在85℃下480小時，在空氣中的烘箱中進行了加熱。量測加熱後成形體的質量，以帶丙酮的拭淨紙(Kimwipes)(註冊商標)擦拭附著於成形體表面的溶出份，並使成形體表面充分乾燥之後，再次測定成形體的質量，從以下之式算出了溶出度。將其結果顯示於表2。(Dissolution test) The obtained UL test piece (molded body) was heated at 85°C for 480 hours in an air oven. After measuring the mass of the molded body after heating, wipe the dissolution amount adhering to the surface of the molded body with acetone wiped paper (Kimwipes) (registered trademark), and allow the surface of the molded body to dry sufficiently, then measure the quality of the molded body again, from The dissolution rate was calculated by the following formula. The results are shown in Table 2.
溶出度[%] = A/B × 100 A=(以丙酮擦拭前之成形體質量)-(以丙酮擦拭後之成形體質量) B=(以丙酮擦拭前之成形體質量)Dissolution [%] = A/B × 100 A=(Quality of molded body before wiping with acetone)-(Quality of molded body after wiping with acetone) B=(Quality of molded body before wiping with acetone)
[表2]
※7：聚對苯二甲酸丁二酯樹脂；POLYPLASTICS公司製，DURANEX 2002 ※8：聚四氟乙烯樹脂；AGC旭硝子公司製，CD145E [產業上之可利用性]※7: Polybutylene terephthalate resin; manufactured by POLYPLASTICS, DURANEX 2002 ※8: PTFE resin; AGC Asahi Glass Co., Ltd., CD145E [Industry availability]
本發明能夠提供一種磷系阻燃劑不會滲出之阻燃性樹脂組成物及其成形體。The present invention can provide a flame-retardant resin composition that does not bleed out with a phosphorus-based flame retardant and its molded body.
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| US3356769A (en) * | 1964-07-13 | 1967-12-05 | American Cyanamid Co | Phosphonitrilic halide derivatives and adducts thereof |
| US3865783A (en) * | 1972-05-18 | 1975-02-11 | Akzona Inc | Flame-retardant polyester |
| JP2006176596A (en) * | 2004-12-21 | 2006-07-06 | Daicel Chem Ind Ltd | Cellulose ester-based resin composition |
| JP2011233883A (en) * | 2010-04-09 | 2011-11-17 | Kyocera Chemical Corp | Dry film for coverlay, coverlay, flexible printed wiring board and method for manufacturing flexible printed wiring board |
| JP2012188633A (en) * | 2011-03-14 | 2012-10-04 | Panasonic Corp | Thermosetting resin composition, resin sheet with metal foil, and flexible printed wiring board |
| JP5561215B2 (en) * | 2011-03-17 | 2014-07-30 | 東洋インキＳｃホールディングス株式会社 | Flame retardant resin composition |
| WO2014021101A1 (en) * | 2012-07-30 | 2014-02-06 | 東レ株式会社 | Flame-retardant thermoplastic polyester resin composition and molded article |
| JP6231013B2 (en) * | 2012-11-28 | 2017-11-15 | ウィンテックポリマー株式会社 | Flame retardant polybutylene terephthalate resin composition and molded article thereof |
| CN103896985B (en) * | 2013-05-06 | 2016-09-21 | 深圳华力兴新材料股份有限公司 | The synthetic method of hexachlorocyclotriph,sphazene and synthesizer, and the preparation method of terphenyl basic ring phosphonitrile |
| JP6472350B2 (en) * | 2015-07-27 | 2019-02-20 | 大日精化工業株式会社 | Flame retardant masterbatch |
-
2019
- 2019-07-11 TW TW108124488A patent/TW202006044A/en unknown
- 2019-07-11 WO PCT/JP2019/027446 patent/WO2020013263A1/en active Application Filing
- 2019-07-11 JP JP2020530249A patent/JPWO2020013263A1/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2020013263A1 (en) | 2021-08-05 |
| WO2020013263A1 (en) | 2020-01-16 |
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