TW201910343A - Phosphorus-containing flame retardant and its composition, epoxy resin composition, thermoplastic resin composition and use obtained from condensation of cyanuric chloride with a phosphide or the like - Google Patents
Phosphorus-containing flame retardant and its composition, epoxy resin composition, thermoplastic resin composition and use obtained from condensation of cyanuric chloride with a phosphide or the like Download PDFInfo
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本發明提供一種含磷難燃劑，其係由三聚氯氰與膦化物等縮合所獲致，其係用於熱塑性樹脂、熱固性樹脂。及一種含磷難燃劑脂組成物，其係至少包含：(A)含不飽和基化合物；(B)含磷難燃劑，其係用於製造積層板、預浸漬片、半固化片、半導體構裝材、高頻基板等。及一種環氧樹脂組成物，其係至少包含：(A)含環氧官能基樹脂；(B)含磷難燃劑，其係於製造黏合片、純膠膜、覆蓋膜、軟硬結合板、防焊油墨、高頻軟性基板等。一種熱塑性樹脂組成物，其係至少包含：(A)熱塑性樹脂；(B)含磷難燃劑。 The present invention provides a phosphorus-containing flame retardant which is obtained by condensation of cyanuric chloride with a phosphide or the like, and is used for a thermoplastic resin or a thermosetting resin. And a phosphorus-containing flame retardant grease composition comprising : (A) an unsaturated group-containing compound; (B) a phosphorus-containing flame retardant, which is used for producing a laminate, a prepreg, a prepreg, a semiconductor structure Loading materials, high frequency substrates, etc. And an epoxy resin composition comprising at least : (A) an epoxy-containing resin; (B) a phosphorus-containing flame retardant, which is used in the manufacture of a bonding sheet, a pure film, a cover film, a soft and hard bonding board , solder resist ink, high frequency flexible substrate, etc. A thermoplastic resin composition comprising at least : (A) a thermoplastic resin; (B) a phosphorus-containing flame retardant.
溴系難燃劑燃燒產生戴奧辛的問題一直受到人們重視，近年來磷系難燃劑技術發展成為主流；三星手機***燃燒事件，使得廠商必須更嚴肅正視，電子產品難燃性不足對消費者生命財產與公共安全直接的危害；2017年4月瑞典政府所頒布之電子電氣產品化學品徵稅法案生效，意味著使用添加型磷系難燃劑可以減稅50%，使用反應型磷系難燃劑或添加型非鹵非磷系難燃劑可以減稅90%，因此可以理解為磷系難燃劑比溴系難燃劑更環保，反應型難燃劑比添加型難燃劑更環保。 The problem of burning dioxin in the combustion of brominated flame retardants has been paid attention to. In recent years, the development of phosphorus-based flame retardant technology has become the mainstream; the explosion of Samsung mobile phones has made manufacturers must take it more seriously, and the incompetence of electronic products is not enough for consumers. Direct damage to property and public safety; the taxation of the Electrical and Electronic Products Chemicals Act enacted by the Swedish government in April 2017, which means that the use of added phosphorus-based flame retardants can reduce taxes by 50%, using reactive phosphorus-based flame retardants The agent or the added non-halogen non-phosphorus flame retardant can reduce the tax by 90%, so it can be understood that the phosphorus-based flame retardant is more environmentally friendly than the bromine-based flame retardant, and the reactive flame retardant is more environmentally friendly than the added flame retardant.
資訊通信產品逐步走向高速高頻化，其相關電子材要求低介電常數與低介電損失外，亦同時要求難燃性，專利文獻TWI579337使用 三(三溴苯氧基)三嗪難燃劑，雖然可以達到不影響電性，但含溴難燃劑仍有環境衝擊顧慮；專利文獻TW201714951A使用對伸二甲苯基雙二苯基膦氧化物難燃劑，其雖表現極優異電性，但因磷含量較低使用量變大，因此如何提高磷含量及提高阻燃效果成為下階段難燃劑發展課題。 Information and communication products are gradually moving toward high-speed and high-frequency, and their related electronic materials require low dielectric constant and low dielectric loss, and also require flame retardancy. Patent document TWI579337 uses tris(tribromophenoxy)triazine flame retardant. Although it can be achieved without affecting the electrical properties, the bromine-containing flame retardant still has environmental impact concerns; the patent document TW201714951A uses a para-xylylene bisdiphenylphosphine oxide flame retardant, which exhibits excellent electrical properties, but The use of phosphorus is relatively low, so how to increase the phosphorus content and improve the flame retardant effect becomes the next stage of development of flame retardant.
1969年專利文獻FR1566675揭示一種三(三溴苯氧基)三嗪難燃劑，可用於苯乙稀系共聚物及其合金，具有良好的抗衝擊性、耐紫外線性、熱穩定性，5%熱分解溫度為385℃，550℃殘碳量約12%。 In 1969, the patent document FR1566675 discloses a tris(tribromophenoxy)triazine flame retardant which can be used for styrene copolymers and alloys thereof, and has good impact resistance, ultraviolet resistance and thermal stability, 5%. The thermal decomposition temperature is 385 °C , and the residual carbon content at 550 ° C is about 12%.
專利文獻CN101328153揭示一種三(三溴苯氧基)三嗪難燃劑製造方法，其採用水相合成法替代傳統溶劑相合成法；專利文獻TWI579337揭示一種三(三溴苯氧基)三嗪難燃劑，用於聚苯醚積層板除了維持原有介電損失(Df)外，比傳統十溴二苯乙烷有更佳抗撕裂強度效果。 Patent document CN101328153 discloses a method for producing tris(tribromophenoxy)triazine flame retardant, which uses an aqueous phase synthesis method instead of a conventional solvent phase synthesis method; patent document TWI579337 discloses a tris(tribromophenoxy)triazine which is difficult to disclose. The flammable agent for the polyphenylene ether laminate has better tear strength than the conventional decabromodiphenylethane except for maintaining the original dielectric loss (Df).
專利文獻CN101376665A揭示一種含三嗪結構氧杂膦菲阻燃性化合物，可用於熱塑性樹脂如：尼龍、ABS等及熱固性樹脂如：環氧樹脂、聚氨酯等，該難燃劑一個分子中含有三個-OH官能基及三個膦酸酯基，存在著吸水性及膦酸酯水解性問題，並不適用於低介電常數(Dk)及低介低損失(Df)要求之高速高頻電子材料。 Patent document CN101376665A discloses a flame retardant compound containing a triazine structure oxaphosphonium phenanthrene, which can be used for thermoplastic resins such as nylon, ABS, etc. and thermosetting resins such as epoxy resin, polyurethane, etc., and the flame retardant contains three molecules in one molecule. -OH functional group and three phosphonate groups, which have problems of water absorption and phosphonate hydrolysis, and are not suitable for high-speed high-frequency electronic materials with low dielectric constant (Dk) and low dielectric loss (Df) requirements. .
專利文獻CN103254233A揭示一種三嗪三苯次膦酸乙酯化合物，其具有磷氮協同阻燃之高效難燃劑，可用於PBT、PET、PVC、聚氨酯、環氧樹脂、不飽和樹脂等，該難燃劑一個分子中含有三個膦乙酸酯，高溫時容易分解，使得金屬模具表面污染，會對生產過程造成困擾，尚不能滿足產業殷切之需求。 Patent document CN103254233A discloses a triazine triphenylphosphinic acid ethyl ester compound which has a phosphorus-nitrogen synergistic flame retardant high-efficiency flame retardant and can be used for PBT, PET, PVC, polyurethane, epoxy resin, unsaturated resin, etc. The flammable agent contains three phosphine acetates in one molecule, which is easily decomposed at high temperature, which causes the surface of the metal mold to be contaminated, which may cause troubles in the production process, and cannot meet the demand of the industry.
本發明所欲解決之問題，其一在導入更環保之阻燃性氮元素，以磷氮協同阻燃性來提高含磷難燃劑之阻燃效果，因為氮含量與氧極限指數(LOI)、成碳率成正比，所以提高氮含量有助於降低磷之使用量，提供更友善環境之難燃劑；其二改善傳統磷系難燃劑仍存在吸水性高及易水解問題，對聚苯醚等樹脂之介電常數(Dk)與介電損失(Df)特性，不會有負面影響，在射出成型加工時亦不易污染金屬模具；其三導入不飽和官能基，經由自身聚合或與被阻燃樹脂共聚合，來提升阻燃效果，以降低磷使用量，避免難燃劑之移行性問題，或提難燃劑之高分子量以減低在被阻燃樹脂中之移行性；其四在不降低被阻燃樹脂之玻璃轉移溫度，強化被阻燃樹脂之機械與力學特性；因此本發明提供一種新型含磷難燃劑，可以廣泛用於熱塑性樹脂、熱固樹脂及次世代高速高頻電子材料，可以滿足產業之期待與需求。 The problem to be solved by the present invention is to introduce a more environmentally-friendly flame retardant nitrogen element and synergistic flame retardancy of phosphorus and nitrogen to improve the flame retardant effect of the phosphorus-containing flame retardant because of nitrogen content and oxygen limit index (LOI). The carbon ratio is proportional to the carbon ratio. Therefore, increasing the nitrogen content helps to reduce the amount of phosphorus used, and provides a more friendly environment for the flame retardant. Second, the improvement of the traditional phosphorus-based flame retardant still has the problem of high water absorption and easy hydrolysis. The dielectric constant (Dk) and dielectric loss (Df) characteristics of phenyl ether and other resins do not adversely affect the metal mold during injection molding; the third introduces unsaturated functional groups, which are self-polymerized or Copolymerized by a flame retardant resin to enhance the flame retardant effect, to reduce the amount of phosphorus used, to avoid the problem of migration of the flame retardant, or to increase the high molecular weight of the flame retardant to reduce the migration property in the flame retardant resin; The mechanical and mechanical properties of the flame retarded resin are strengthened without lowering the glass transition temperature of the flame retardant resin; therefore, the present invention provides a novel phosphorus-containing flame retardant which can be widely used for thermoplastic resins, thermosetting resins and high-speed high-generation Frequency electronic material Materials can meet the expectations and needs of the industry.
本發明解決問題之技術手段，在於提供一種含磷難燃劑，其化學結構如式(一)所示：
本發明提供一種含磷難燃劑組成物，其係至少包含：(A)含不飽和基化合物；(B)含磷難燃劑，其化學結構如式(一)所示：式(一)其中R2、R3為相同或不相同，且表示為：、、，所組成組群之一或多種；R1為選自：C1~C10之烴；R4為選自：氫、甲基；其中R5、R6、R7為相同或不相同，且表示為：C1~C5之烴、氫；R8為選自： 、，所組成組群之一或多種；n為選自0~50整數。 The present invention provides a phosphorus-containing flame retardant composition comprising at least : (A) an unsaturated group-containing compound; (B) a phosphorus-containing flame retardant, the chemical structure of which is represented by the formula (I): Formula (I) Where R2 and R3 are the same or different and are expressed as: , , One or more of the group consisting of; R1 is a hydrocarbon selected from: C1 to C10; R4 is selected from the group consisting of hydrogen and methyl; wherein R5, R6, and R7 are the same or different, and are represented as: C1~C5 Hydrocarbon, hydrogen; R8 is selected from: , One or more of the group consisting of; n is selected from 0 to 50 integers.
本發明提供一種環氧樹脂組成物，其係至少包含：(A)含二官能基以上之環氧樹脂；(B)含磷難燃劑，其化學結構如式(一)所示：式(一)其中R2、R3為相同或不相同，且表示為：、、，所組成組群之一或多種；R1為選自：C1~C10之烴；R4為選自：氫、甲基；其中R5、R6、R7為相同或不相同，且表示為：C1~C5之烴、氫；R8為選自：、，所組成組群之一或多種；n為選自0~50整數。 The present invention provides an epoxy resin composition comprising at least : (A) an epoxy resin having a difunctional group or more; (B) a phosphorus-containing flame retardant having a chemical structure as shown in the formula (I): One) Where R2 and R3 are the same or different and are expressed as: , , One or more of the group consisting of; R1 is a hydrocarbon selected from: C1 to C10; R4 is selected from the group consisting of hydrogen and methyl; wherein R5, R6, and R7 are the same or different, and are represented as: C1~C5 Hydrocarbon, hydrogen; R8 is selected from: , One or more of the group consisting of; n is selected from 0 to 50 integers.
本發明提供一種熱塑性樹脂組成物，其係至少包含：(A)熱塑性樹脂；(B)含磷難燃劑，其化學結構如式(一)所示：式(一)
本發明提供一種含磷難燃劑之用途，其係用於熱塑性樹、熱固性樹脂。本發明提供一種反應型難燃劑組成物之用途，其係用於製造積層板、預浸漬片、半固化片、半導體構裝材、高頻基板等。本發明提供一種環氧樹脂組成物之用途，其係於製造黏合片、純膠膜、覆蓋膜、軟硬結合板、防焊油墨、高頻軟性基板等。 The present invention provides a use of a phosphorus-containing flame retardant for use in thermoplastic trees and thermosetting resins. The present invention provides a use of a reactive flame retardant composition for producing a laminate, a prepreg, a prepreg, a semiconductor package, a high frequency substrate, and the like. The invention provides an epoxy resin composition for manufacturing an adhesive sheet, a pure rubber film, a cover film, a soft and hard bonding plate, a solder resist ink, a high frequency flexible substrate and the like.
對照先前技術之功效，其一在於本發明之含磷難燃劑導入更環保之阻燃性氮元素，以磷氮協同阻燃性來提高磷系難燃劑之阻燃效果，比先前技術之三(三溴苯氧基)三嗪溴系難燃劑更環保，比傳統之磷腈難燃劑、磷系難燃劑，有更優異之阻燃性及介電性、物理特性；其二在於本發明採用二烴基膦氧，其不具吸水性官能基與水解性，在介電常數(Dk)與介電損失(Df) 方面優於先前技術之膦酸酯及磷酸酯，亦不會污染金屬模具；其三可以導入不飽和官能基，經由自身聚合或與被阻燃樹脂共聚合，可以避免難燃劑之移行性，或提高難燃劑之分子量以降低在被阻燃樹脂之移行性，比先前技術之磷腈難燃劑、磷系難燃劑，更具環保性；其四在於本發明之磷系難燃劑採用盤狀剛性結構，分子更容易緊密堆疊而形成結晶，具有無機填充料之功能，可以強化被阻燃樹脂之機械與力學特性，亦不降低被阻燃樹脂之玻璃轉移溫度，有別於磷腈難燃劑為不同聚合度之混合物，存在著會使被阻燃樹脂之玻璃轉移溫度下降之缺點，因此本發明之磷系難燃劑可以解決先前技術存在的問題，也可以符合產業殷切期待與需求。 One of the effects of the prior art is that the phosphorus-containing flame retardant of the present invention introduces a more environmentally-friendly flame retardant nitrogen element, and the synergistic flame retardancy of phosphorus and nitrogen is used to improve the flame retardant effect of the phosphorus-based flame retardant, which is higher than the prior art. Tris(tribromophenoxy)triazine bromine-based flame retardant is more environmentally friendly, and has superior flame retardancy, dielectric properties and physical properties than conventional phosphazene flame retardants and phosphorus-based flame retardants; In the present invention, the dihydrocarbylphosphine oxide is used, which has no water-absorbent functional group and hydrolyzability, and is superior to the prior art phosphonates and phosphates in terms of dielectric constant (Dk) and dielectric loss (Df), and does not pollute. a metal mold; the third of which can introduce an unsaturated functional group, by self-polymerization or copolymerization with a flame-retardant resin, can avoid the migration of the flame retardant, or increase the molecular weight of the flame retardant to reduce the migration property of the flame-retardant resin. It is more environmentally friendly than the prior art phosphazene flame retardant and phosphorus flame retardant; the fourth is that the phosphorus-based flame retardant of the present invention adopts a disc-shaped rigid structure, and the molecules are more easily packed tightly to form crystals, and have inorganic The function of the filler can strengthen the flame retardant resin The mechanical and mechanical properties do not reduce the glass transition temperature of the flame retardant resin. Unlike the phosphazene flame retardant, which is a mixture of different degrees of polymerization, there is a disadvantage that the glass transition temperature of the flame retardant resin is lowered. The invented phosphorus-based flame retardant can solve the problems existing in the prior art, and can also meet the industry's earnest expectations and needs.
本發明在提供一種含磷難燃劑，其化學結構如式(一)所示：
本發明在提供一種含磷難燃劑，該含磷難燃劑分子中至少含有一盤狀剛性之三嗪環結構，分子更容易緊密堆疊而產生結晶，可以強化機械與力學特性，亦不會影響被阻燃樹脂之玻璃轉移溫度；磷難燃劑分子中最少含有一個磷原子及三個氮原子，磷氮共乘效應強化含磷難燃劑之阻燃性，可以含有或不含有不飽和官能基，含磷難燃劑其合成方式之一：為由三聚氯氰與膦化物縮合而得到含磷難燃劑，或由三聚氯氰與膦化物、烴基酚縮合反應而得到含磷難燃劑；含磷難燃劑其合成方式之二：為由三聚氯氰與膦化物、含磷雙酚縮合而得到高分子型含磷難燃劑，或由三聚氯氰與膦化物、烴基酚、含磷雙酚縮合反應而得到高分子型含磷難燃劑。 The invention provides a phosphorus-containing flame retardant, wherein the phosphorus-containing flame retardant molecule contains at least one disc-shaped rigid triazine ring structure, and the molecules are more easily packed in a tight manner to generate crystals, which can strengthen mechanical and mechanical properties, and does not Affecting the glass transition temperature of the flame retardant resin; the phosphorus flame retardant molecule contains at least one phosphorus atom and three nitrogen atoms, and the phosphorus-nitrogen synergistic effect enhances the flame retardancy of the phosphorus-containing flame retardant, and may or may not contain unsaturated One of the synthetic methods of functional group and phosphorus-containing flame retardant: obtaining a phosphorus-containing flame retardant by condensation of cyanuric chloride and a phosphinate, or obtaining a phosphorus-containing reaction by condensation reaction of cyanuric chloride with a phosphinate or a hydrocarbyl phenol Flame retardant; phosphorus-containing flame retardant is synthesized in the second way: it is obtained by condensation of cyanuric chloride with phosphonium and phosphorus-containing bisphenol to obtain polymer-type phosphorus-containing flame retardant, or cyanuric chloride and phosphide A hydrolyzable phenol or a phosphorus-containing bisphenol is condensed to obtain a polymer-type phosphorus-containing flame retardant.
本發明在提供一種含磷難燃劑，其含磷難燃劑合成所使用之膦化物包括包括：乙烯基苯基膦氧、丙烯基苯基膦氧、烯丙基苯基膦氧、丁 烯基苯基膦氧、戊烯基苯基膦氧、甲基苯基膦氧、乙基苯基膦氧、丙基苯基膦氧、丁基苯基膦氧、戊基苯基膦氧、二苯基膦氧、二甲基膦氧、二乙基膦氧、二丙基膦氧、二丁基膦氧、二戊基膦氧、二C1~C10烴基膦氧、甲基苯基甲氧基膦、乙基苯基甲氧基膦、丙基苯基甲氧基膦、丁基苯基甲氧基膦、戊基苯基甲氧基膦、二苯基甲氧基膦、二甲基甲氧基膦、二乙基甲氧基膦、二丙基甲氧基膦、二丁基甲氧基膦、二戊基甲氧基膦、二C1~C10烴基甲氧基膦、甲基苯基乙氧基膦、乙基苯基乙氧基膦、丙基苯基乙氧基膦、丁基苯基乙氧基膦、戊基苯基乙氧基膦、二苯基乙氧基膦、二甲基乙氧基膦、二乙基乙氧基膦、二丙基乙氧基膦、二丁基乙氧基膦、二戊基乙氧基膦、二C1~C10烴基乙氧基膦、、甲基苯基丙氧基膦、乙基苯基丙氧基膦、丙基苯基丙氧基膦、丁基苯基丙氧基膦、戊基苯基丙氧基膦、二苯基丙氧基膦、二甲基丙氧基膦、二乙基丙氧基膦、二丙基丙氧基膦、二丁基丙氧基膦、二戊基丙氧基膦、二C1~C10烴基丙氧基膦、甲基苯基丁氧基膦、乙基苯基丁氧基膦、丙基苯基丁氧基膦、丁基苯基丁氧基膦、戊基苯基丁氧基膦、二苯基丁氧基膦、二甲基丁氧基膦、二乙基丁氧基膦、二丙基丁氧基膦、二丁基丁氧基膦、二戊基丁氧基膦、二C1~C10烴基丁氧基膦、甲基苯基戊氧基膦、乙基苯基戊氧基膦、丙基苯基戊氧基膦、丁基苯基戊氧基膦、戊基苯基戊氧基膦、二苯基戊氧基膦、二甲基戊氧基膦、二乙基戊氧基膦、二丙基戊氧基膦、二丁基戊氧基膦、二戊基戊氧基膦、二C1~C10烴基戊氧基膦等。 The present invention provides a phosphorus-containing flame retardant, and the phosphonium compound used for the synthesis of the phosphorus-containing flame retardant comprises: vinylphenylphosphine oxide, propenylphenylphosphine oxide, allylphenylphosphine oxide, butene Phenylphosphine oxide, pentenylphenylphosphine oxide, methylphenylphosphine oxide, ethylphenylphosphine oxide, propylphenylphosphine oxide, butylphenylphosphine oxide, pentylphenylphosphine oxide, two Phenylphosphine oxide, dimethylphosphine oxide, diethylphosphine oxide, dipropylphosphine oxide, dibutylphosphine oxide, dipentylphosphine oxide, di-C1~C10 hydrocarbylphosphine oxide, methylphenylmethoxy Phosphine, ethylphenylmethoxyphosphine, propylphenylmethoxyphosphine, butylphenylmethoxyphosphine, pentylphenylmethoxyphosphine, diphenylmethoxyphosphine, dimethylmethyl Oxyphosphine, diethylmethoxyphosphine, dipropylmethoxyphosphine, dibutylmethoxyphosphine, dipentylmethoxyphosphine, di-C1~C10 hydrocarbyl methoxyphosphine, methylphenyl ethoxylate Phosphine, ethylphenylethoxyphosphine, propylphenylethoxyphosphine, butylphenylethoxyphosphine, pentylphenylethoxyphosphine, diphenylethoxyphosphine, dimethyl Ethoxy phosphine, diethyl ethoxy phosphine, dipropyl ethoxy phosphine, Dibutylethoxyphosphine, dipentylethoxyphosphine, di-C1~C10 hydrocarbyl ethoxyphosphine, methylphenylpropoxyphosphine, ethylphenylpropoxyphosphine, propylphenylpropyl Oxyphosphine, butyl phenyl propoxy phosphine, pentyl phenyl propoxy phosphine, diphenyl propoxy phosphine, dimethyl propoxy phosphine, diethyl propoxy phosphine, dipropyl propyl Oxyphosphine, dibutylpropoxyphosphine, dipentylpropoxyphosphine, di-C1~C10 hydrocarbyl propoxyphosphine, methylphenylbutoxyphosphine, ethylphenylbutoxyphosphine, propyl Phenylbutoxyphosphine, butylphenylbutoxyphosphine, pentylphenylbutoxyphosphine, diphenylbutoxyphosphine, dimethylbutoxyphosphine, diethylbutoxyphosphine, two Propylbutoxyphosphine, dibutylbutoxyphosphine, dipentylbutoxyphosphine, di-C1~C10 hydrocarbylbutoxyphosphine, methylphenylpentyloxyphosphine, ethylphenylpentyloxyphosphine , propylphenylpentyloxyphosphine, butylphenylpentyloxyphosphine, pentylphenylpentyloxyphosphine, diphenylpentyloxyphosphine, dimethylpentyloxyphosphine, diethylpentyloxy Phosphine, dipropyl pentyloxyphosphine, dibutyl pentyloxyphosphine, dipentyl pentyloxyphosphine, di-C1 to C10 hydrocarbyl pentoxide Phosphine.
本發明在提供一種含磷難燃劑，其中使用之烴基酚包括：鄰乙烯基苯酚、對乙烯基苯酚、間乙烯基苯酚、鄰丙烯基苯酚、對丙烯基苯酚、間丙烯基苯酚、鄰異烯丙基苯酚、對異烯丙基苯酚、間異烯丙基苯酚、鄰烯 丙基苯酚、對烯丙基苯酚、間烯丙基苯酚、2-乙烯基-5-甲基酚、3-乙烯基-5-甲基酚、4-乙烯基-5-甲基酚、2-丙烯基-5-甲基酚、3-丙烯基-5-甲基酚、4-丙烯基-5-甲基酚、2-烯丙基-5-甲基酚、3-烯丙基-5-甲基酚、4-烯丙基-5-甲基酚、2-異烯丙基-5-甲基酚、3-異烯丙基-5-甲基酚、4-異烯丙基-5-甲基酚、C1~C6烴基酚、甲基C1~C6烴基酚等。 The present invention provides a phosphorus-containing flame retardant, wherein the hydrocarbyl phenol used comprises: o-vinyl phenol, p-vinyl phenol, m-vinyl phenol, o-propenyl phenol, p-propenyl phenol, m-propenyl phenol, ortho- Allyl phenol, p-isoallyl phenol, m-isoallyl phenol, o-allyl phenol, p-allyl phenol, m-allyl phenol, 2-vinyl-5-methyl phenol, 3- Vinyl-5-methylphenol, 4-vinyl-5-methylphenol, 2-propenyl-5-methylphenol, 3-propenyl-5-methylphenol, 4-propenyl-5-A Phenol, 2-allyl-5-methylphenol, 3-allyl-5-methylphenol, 4-allyl-5-methylphenol, 2-isoallyl-5-methyl Phenol, 3-isoallyl-5-methylphenol, 4-isoallyl-5-methylphenol, C1~C6 hydrocarbyl phenol, methyl C1~C6 hydrocarbyl phenol, and the like.
本發明在提供一種含磷難燃劑，其中使用之含磷雙酚包括：2,5-二羥苯基二苯基氧化膦、2,5-二羥苯基苯基甲基氧化膦、2,5-二羥苯基苯基乙基氧化膦、2,5-二羥苯基苯基丙基氧化膦、2,5-二羥苯基苯基丁基氧化膦、、2,5-二羥苯基苯基戊基氧化膦、1,4-二羥萘基苯基甲基氧化膦、1,4-二羥萘基二苯基氧化膦、1,4-二羥萘基苯基乙基氧化膦、1,4-二羥萘基苯基丙基氧化膦、1,4-二羥萘基苯基丁基氧化膦、1,4-二羥萘基苯基戊基氧化膦、1,4-二羥萘基苯基烷基氧化膦等。 The present invention provides a phosphorus-containing flame retardant, wherein the phosphorus-containing bisphenol used comprises: 2,5-dihydroxyphenyldiphenylphosphine oxide, 2,5-dihydroxyphenylphenylmethylphosphine oxide, 2 , 5-dihydroxyphenyl phenylethylphosphine oxide, 2,5-dihydroxyphenylphenylpropylphosphine oxide, 2,5-dihydroxyphenylphenylbutylphosphine oxide, 2,5-di Hydroxyphenyl phenylpentyl phosphine oxide, 1,4-dihydroxynaphthylphenyl methyl phosphine oxide, 1,4-dihydroxynaphthyl diphenyl phosphine oxide, 1,4-dihydroxynaphthyl phenyl Phosphine oxide, 1,4-dihydroxynaphthylphenylpropylphosphine oxide, 1,4-dihydroxynaphthylphenylbutylphosphine oxide, 1,4-dihydroxynaphthylphenylpentylphosphine oxide, 1 , 4-dihydroxynaphthylphenyl alkyl phosphine oxide, and the like.
本發明在提供一種含磷難燃劑，其中合成含磷難燃劑之縮合反應可以使用或不使用鹼，該鹼包括：氫氧化鋰、氫氧化鉀、氫氧化鈉、氫氧化鈉、氫氧化鈣、甲醇鋰、甲醇鉀、甲醇鈉乙醇鋰、乙醇鉀、乙醇鈉、碳酸鋰、碳酸鉀、碳酸鈉、三甲胺三乙胺、三乙胺、三丙胺、三丁胺、吡啶、甲基吡啶、三級胺等，可以加入四級銨鹽或四級磷鹽之相轉移劑或不加相轉移劑。 The present invention provides a phosphorus-containing flame retardant, wherein a condensation reaction for synthesizing a phosphorus-containing flame retardant may or may not use a base, the base comprising: lithium hydroxide, potassium hydroxide, sodium hydroxide, sodium hydroxide, and hydroxide Calcium, lithium methoxide, potassium methoxide, sodium methoxide, lithium ethoxide, potassium ethoxide, sodium ethoxide, lithium carbonate, potassium carbonate, sodium carbonate, trimethylamine triethylamine, triethylamine, tripropylamine, tributylamine, pyridine, methylpyridine A tertiary amine or the like may be added with a phase transfer agent of a quaternary ammonium salt or a quaternary phosphonium salt or no phase transfer agent.
本發明合成一種含磷難燃劑，其中合成含磷難燃劑使用之溶劑至少包括含選自：N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基-2吡咯啶酮、二甲基亞碸、二甲基磷醯胺、甲乙基酮、甲基異丁基酮、二異丁基酮、甲基異戊基酮、環戊酮、環己酮、、四氫呋喃、四甲脲、二咢烷、γ- 丁內酯、氯仿、二氯甲烷、二乙二醇單己基醚、丙二醇單甲基醚、丙二醇單乙基醚、丙二醇單丙基醚、乙酸正丁酯、二乙二醇單丁基醚乙酸酯、甲苯、二甲苯、氯化苯等。 The invention synthesizes a phosphorus-containing flame retardant, wherein the solvent used for synthesizing the phosphorus-containing flame retardant comprises at least one selected from the group consisting of: N,N -dimethylformamide, N,N -dimethylacetamide, N- Methyl-2-pyrrolidone, dimethyl hydrazine, dimethylphosphoniumamine, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, methyl isoamyl ketone, cyclopentanone, ring Hexanone, tetrahydrofuran, tetramethylurea, dioxane, γ-butyrolactone, chloroform, dichloromethane, diethylene glycol monohexyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl Ether, n-butyl acetate, diethylene glycol monobutyl ether acetate, toluene, xylene, chlorinated benzene, and the like.
本發明在提供一種含磷難燃劑組成物，其係至少包含：(A)含不飽和基化合物；(B)含磷難燃劑，其化學結構如式(一)所示：
本發明提供一種含磷難燃劑組成物，其中含不飽和基化合物包括：含不飽和基聚苯醚、含不飽和基聚醯亞胺、馬來醯亞胺樹脂、雙馬來醯亞胺、雙馬來醯亞胺寡聚物、雙衣康醯亞胺樹脂、雙衣康醯亞胺、雙衣康 醯亞胺寡聚物、氰酸酯樹脂、異氰酸酯樹脂、乙烯基樹脂、不飽和聚酯樹脂、含丙烯酸酯化合物、含甲基丙烯酸酯化合物、含馬來醯亞胺化合物、含衣康醯亞胺化合物、含乙烯基化合物、含丙烯基化合物、含烯丙基化合物、含異烯丙基化合物、含氰酸酯基化合物、含異氰酸酯化合物、含四氫鄰苯醯亞胺化合物、含乙烯基聚苯醚、含烯丙基聚苯醚、含苯乙烯聚苯醚、含丙烯酸酯之聚苯醚、含甲基丙烯酸酯之聚苯醚、含氰酸酯基聚苯醚、含馬林醯亞胺基聚苯醚、含衣康醯亞胺基聚苯醚、含四氫鄰苯醯亞胺基聚苯醚、含異氰酸酯基聚苯醚、三烯丙基三聚氰酸酯、三烯丙基三聚異氰酸酯、含C=C不飽和基聚苯醚、含C=N不飽合基聚苯醚、聚丁二烯樹脂、改質聚丁二烯樹脂、聚丁二烯苯乙烯、改質聚丁二烯苯乙烯、丁二烯共聚物、含C=C鍵化合物、含C=C聚醯亞胺、含C=N鍵化合物，所組成組群之一或多種。 The present invention provides a phosphorus-containing flame retardant composition, wherein the unsaturated group-containing compound comprises: an unsaturated polyphenylene ether, an unsaturated polyalkyleneimine, a maleimide resin, a bismaleimide , bismaleimide oligomer, double coat quinone imine resin, double coat quinone imine, double coat quinone imine oligomer, cyanate resin, isocyanate resin, vinyl resin, unsaturated Polyester resin, acrylate-containing compound, methacrylate-containing compound, maleimide-containing compound, itaconide-containing compound, vinyl-containing compound, propylene-containing compound, allyl-containing compound, and different Allyl compound, cyanate-containing compound, isocyanate-containing compound, tetrahydroorthophenylimine-containing compound, vinyl-containing polyphenylene ether, allyl polyphenylene ether, styrene-containing polyphenylene ether, acrylic acid Polyphenylene ether of ester, polyphenylene ether containing methacrylate, polyphenylene ether containing polycyanate, polyphenylene ether containing mercapto imine, polyphenylene ether containing isoprene, tetrahydrogen O-phenylenimine polyphenylene ether, isocyanate-containing polyphenylene ether, triallyl Cyanurate, triallyl isocyanurate, C=C unsaturated polyphenylene ether, C=N unsaturated polyphenylene ether, polybutadiene resin, modified polybutadiene resin Polybutadiene styrene, modified polybutadiene styrene, butadiene copolymer, compound containing C=C bond, C=C polyimine, compound containing C=N bond, group One or more.
本發明提供一種含磷難燃劑組成物，其進一步可再含有硬化促進劑，其係包括：偶氮二異丁腈、偶氮二(2-異丙基)丁腈、偶氮二異庚腈、過氧化二苯甲醯、過氧化乙醯異丁醯、過氧化二乙醯、過氧化(2,4-二氯苯甲醯)、過氧化(2-二甲基苯甲醯)、過氧化十二醯、過氧化二碳酸二異丙酯、過氧化雙(3,5,5-三甲基己醯)、過氧化環己酮、過氧化甲乙酮、過氧化二碳酸二環己丙酯、過氧化二碳酸二環己酯、過氧化二碳酸二(4-叔丁基環己酯)、過氧化二碳酸二(2-乙基己基)酯、過氧化二碳酸雙(2-苯基乙氧基)酯、過氧化二碳酸雙十六烷基酯、過氧化苯甲酸特丁酯、過氧化苯乙酸特丁酯、過氧乙酸、過氧化特戊酸叔丁酯、過氧化特戊酸叔己酯、過氧化新癸酸異丙苯酯、過氧化苯甲酸叔丁酯、叔丁基過氧化氫、叔丁基過氧化苯甲酸酯、叔丁基過氧化特戊酸酯、異丙苯過氧化氫、對孟烷過氧化氫、過氧化二特丁基、過氧化二 異丙苯、過氧化二叔丁基、過氧化氫、過硫酸銨、過硫酸鉀、過氧化物-烷基金屬、氧-烷基金屬、脂肪酸鋅，所組成組群之一或多種。 The present invention provides a phosphorus-containing flame retardant composition, which may further comprise a hardening accelerator, which comprises: azobisisobutyronitrile, azobis(2-isopropyl)butyronitrile, azobisglyoxime Nitrile, benzamidine peroxide, isobutyl sulfonium peroxide, diethyl hydrazine peroxide, peroxidized (2,4-dichlorobenzhydrazide), peroxy (2-dimethylbenzhydrazide), Twisted dodecyl peroxide, diisopropyl peroxydicarbonate, bis(3,5,5-trimethylhexyl) peroxide, cyclohexanone peroxide, methyl ethyl ketone peroxide, dicyclohexyl peroxydicarbonate Ester, dicyclohexyl peroxydicarbonate, di(4-tert-butylcyclohexyl)dicarbonate, di(2-ethylhexyl)peroxydicarbonate, bis(2-benzenedicarbonate) Ethyloxy)ester, dihexadecyl peroxydicarbonate, tert-butyl peroxybenzoate, tert-butyl peroxybenzoate, peroxyacetic acid, t-butyl peroxypivalate, peroxide Tert-hexyl valerate, cumene peroxy neodecanoate, tert-butyl peroxybenzoate, t-butyl hydroperoxide, t-butyl peroxybenzoate, t-butyl peroxypivalate Cumene peroxidation Hydrogen, para-hydrogen peroxide, di-tert-butyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, hydrogen peroxide, ammonium persulfate, potassium persulfate, peroxide-alkyl metal, One or more of the group consisting of oxy-alkyl metal and zinc fatty acid.
本發明提供一種含磷難燃劑組成物，其中含不飽和基樹脂之氰酸酯樹脂在熱和催化劑作用下生成三嗪環高度交聯密度網狀結構大分子、更容易與含磷難燃劑之三嗪環結構，緊密堆疊而產生結晶；含磷難燃劑之不飽和官能基與氰酸酯或其他含不飽和基樹脂可以進一步共聚合，因此更可以強化機械與力學特性及難燃性，具有超低熱膨脹性、超低吸濕性、高接著性、超低介電等特性。 The invention provides a phosphorus-containing flame retardant composition, wherein a cyanate resin containing an unsaturated group resin forms a triazine ring highly crosslinked density network structure macromolecule under the action of heat and a catalyst, and is more resistant to flame retardation with phosphorus. The triazine ring structure of the agent is closely packed to produce crystallization; the unsaturated functional group of the phosphorus-containing flame retardant can be further copolymerized with the cyanate ester or other unsaturated group-containing resin, thereby further strengthening mechanical and mechanical properties and being flame retardant. Properties, with ultra-low thermal expansion, ultra-low hygroscopicity, high adhesion, ultra-low dielectric and other characteristics.
本發明提供一種環氧樹脂組成物，其係至少包含：(A)含二官能基以上之環氧樹脂；(B)含磷難燃劑，其化學結構如式(一)所示：
本發明提供一種環氧樹脂組成物，其含環氧官能基樹脂包括：雙酚A型縮水甘油醚、雙酚F型縮水甘油醚、雙酚S型縮水甘油醚、氫化雙酚A型縮水甘油醚、氫化雙酚A型縮水甘油醚、鄰苯二甲酸縮水甘油酯、海因環氧樹脂、醯亞胺環氧樹脂、雙(2,3環氧基環戊基)醚、3,4環氧基-6-甲基環己基甲酸、3,4-環氧基-6-甲基環己基甲酯、乙烯基環己烯二環氧化合物、3,4環氧基環己基甲酸、3,4-環氧基環己基甲酯、二異戊二烯二環氧化物、二丁二烯二環氧化物、己二酸二(3,4環氧基-6-甲基環己基甲酯)、二縮水甘油醚、聚乙醇二縮水甘油醚、乙醇二縮水甘油醚、聚丙醇二縮水甘油醚、丙醇二縮水甘油醚、聚丁醇二縮水甘油醚、丁醇二縮水甘油醚、二縮水甘油基苯胺、對苯二甲酸二縮水甘油酯、內次甲基四氫鄰苯二甲酸二縮水甘油酯、鄰苯二甲酸二縮水甘油酯、四氫鄰苯二甲酸二縮水甘油酯、間苯二甲酸二縮水甘油酯、4,5環氧環己烷1,2-二甲酸二縮水甘油酯、鄰苯二辛酸二環氧丙酯、二氧化戊烯、二氧化雙環戊二烯多元醇醚、酚醛型環氧樹脂、甲酚醛型環氧樹脂、聯苯型環氧樹脂、DCPD型環氧樹脂、雙酚A醛型環氧樹脂、四苯基縮水甘油醚基乙烷、三苯基縮水甘油醚基甲烷、三縮水甘油基對胺基苯酚、三縮水甘油基三聚異氰酸酯、四縮水甘油基二胺基二苯基甲烷、四縮水甘油基二甲苯二胺、四縮水甘油基1,3-雙氨基甲基環己烷 三甲醇基丙烷三縮水 甘油醚、丙三醇三縮水甘油醚、丁基縮水甘油醚、苯基縮水甘油醚、苄基縮水甘油醚、烯丙基縮水甘油醚、含一個以上環氧基化合物，所組成組群之一或多種。 The present invention provides an epoxy resin composition comprising an epoxy functional group resin comprising: bisphenol A glycidyl ether, bisphenol F glycidyl ether, bisphenol S glycidyl ether, hydrogenated bisphenol A glycidyl Ether, hydrogenated bisphenol A glycidyl ether, glycidyl phthalate, hydantoin epoxy resin, quinone imine epoxy resin, bis(2,3 epoxycyclopentyl) ether, 3,4 ring Oxy-6-methylcyclohexylcarboxylic acid, 3,4-epoxy-6-methylcyclohexylmethyl ester, vinylcyclohexene diepoxide, 3,4 epoxycyclohexylcarboxylic acid, 3, 4-epoxycyclohexylmethyl ester, diisoprene diepoxide, dibutadiene diepoxide, bis(3,4 epoxy-6-methylcyclohexylmethyl) adipate , diglycidyl ether, polyglycol diglycidyl ether, ethanol diglycidyl ether, polyglycol diglycidyl ether, propanol diglycidyl ether, polybutanol diglycidyl ether, butanol diglycidyl ether, condensed water Glyceryl aniline, diglycidyl terephthalate, sec-methyltetrahydrophthalic acid diglycidyl ester, diglycidyl phthalate, tetrahydroortylene Acid diglycidyl ester, diglycidyl isophthalate, 4,5 epoxy cyclohexane 1,2-dicarboxylic acid diglycidyl ester, diglycidyl phthalate, pentylene oxide, two Oxidized dicyclopentadiene polyol ether, phenolic epoxy resin, cresol novolac epoxy resin, biphenyl type epoxy resin, DCPD type epoxy resin, bisphenol A aldehyde type epoxy resin, tetraphenyl glycidyl ether Ethylene, triphenyl glycidyl ether methane, triglycidyl p-aminophenol, triglycidyl trimeric isocyanate, tetraglycidyl diaminodiphenylmethane, tetraglycidyl xylylenediamine , tetraglycidyl 1,3-diaminomethylcyclohexane trimethylolpropane triglycidyl ether, glycerol triglycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, benzyl glycidyl ether And one or more of the group consisting of allyl glycidyl ether and one or more epoxy compounds.
本發明提供一種環氧樹脂組成物，其進一步可再含有硬化促進劑，其係包括：一級胺、二級胺、三級胺、四級胺鹽、三級磷、四級磷鹽，所組成組群之一或多種。 The present invention provides an epoxy resin composition, which further comprises a hardening accelerator, which comprises: a primary amine, a secondary amine, a tertiary amine, a quaternary amine salt, a tertiary phosphorus, a quaternary phosphorus salt, and is composed of One or more of the groups.
本發明提供一種環氧樹脂組成物，可以加入或不加入共固化物包括：烯丙基縮水甘油醚、丙烯酸縮水甘油酯、甲基丙烯酸縮水甘油酯、二烯丙基雙酚A、二丙烯基雙酚A、烯丙基酚、乙烯酚、丙烯基酚、烯丙酚基縮水甘油醚、羥苯馬來醯亞胺、羧苯馬來醯亞胺、含不飽和基端酸酐聚醯亞胺、含不飽和基酚醛樹脂、含不飽和基苯并惡嗪、氰酸酯、異氰酸酯、酚醛樹脂、苯并惡嗪、雙馬來醯亞胺、馬來酸酐苯乙烯共聚物、聚苯醚所組成組群之一或多種。加入共固化劑目的，在於使環氧樹脂與含不飽和基難燃劑或含不飽合基化合物間產生鍵結，常用於半導體封裝材、軟性基板材料、高頻基板材料等電子相關材料中。 The present invention provides an epoxy resin composition with or without co-cured materials including: allyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, diallyl bisphenol A, dipropylene Bisphenol A, allyl phenol, vinyl phenol, propylene phenol, allyl phenol glycidyl ether, hydroxybenzene maleimide, carboxybenzene maleimide, unsaturated hydroxy terminated imine , unsaturated phenolic resin, unsaturated benzoxazine, cyanate, isocyanate, phenolic resin, benzoxazine, bismaleimide, maleic anhydride styrene copolymer, polyphenylene ether Form one or more of the groups. The purpose of adding a co-curing agent is to bond the epoxy resin to the unsaturated-containing flame retardant or the unsaturated-containing compound, and is commonly used in electronic related materials such as semiconductor packaging materials, flexible substrate materials, and high-frequency substrate materials. .
本發明提供一種熱塑性樹脂組成物，其係至少包含：(A)熱塑性樹脂；(B)含磷難燃劑，其化學結構如式(一)所示：
本發明提供一種熱塑性樹脂組成物，其熱塑性樹脂包括：ABS、PC、PS、PC/ABS、PC/PBT、PPE/HIPS、PP、PE、PET、PBT、PA、聚芳酯、聚氨酯、聚氨酯、聚苯醚、液晶高分子樹脂、聚醯亞胺樹脂、聚苯硫醚樹脂、聚碸樹脂、聚醚碸樹脂、聚醚醚酮樹脂，所組成組群之一或多種。 The present invention provides a thermoplastic resin composition comprising: ABS, PC, PS, PC/ABS, PC/PBT, PPE/HIPS, PP, PE, PET, PBT, PA, polyarylate, polyurethane, polyurethane, One or more of a group consisting of polyphenylene ether, liquid crystal polymer resin, polyimide resin, polyphenylene sulfide resin, polyfluorene resin, polyether oxime resin, and polyether ether ketone resin.
本發明提供一種含磷型難燃劑之用途，其係用於熱塑性樹脂、熱固性樹脂，其中熱塑性樹脂包括：，其熱塑性樹脂包括：ABS、PC、PS、PC/ABS、PC/PBT、PPE/HIPS、PP、PE、PET、PBT、PA、聚芳酯、聚氨酯、聚氨酯、聚苯醚、液晶高分子樹脂、聚醯亞胺樹脂、聚苯硫醚樹脂、聚碸樹脂、聚醚碸樹脂、聚醚醚酮樹脂等，所組成組群之一或多種；其中熱固性樹脂包括：環氧樹脂、DAP、不飽和聚酯樹脂、乙烯基樹脂、BT樹脂、BMI樹脂、氰酸酯樹脂、異氰酸酯樹脂、含不飽和基聚苯醚、含不飽和基聚醯亞胺樹脂、含酸酐聚醯亞胺樹脂、含酸聚醯亞胺樹脂、聚馬來酸酐苯乙烯、酚醛樹脂、苯并噁嗪樹脂、含不飽和基樹脂等，所組成組群之一或多種。 The invention provides a use of a phosphorus-containing flame retardant for a thermoplastic resin or a thermosetting resin, wherein the thermoplastic resin comprises: the thermoplastic resin comprises: ABS, PC, PS, PC/ABS, PC/PBT, PPE/ HIPS, PP, PE, PET, PBT, PA, polyarylate, polyurethane, polyurethane, polyphenylene ether, liquid crystal polymer resin, polyimide resin, polyphenylene sulfide resin, polyfluorene resin, polyether resin, One or more groups of polyetheretherketone resins, etc.; wherein the thermosetting resin includes: epoxy resin, DAP, unsaturated polyester resin, vinyl resin, BT resin, BMI resin, cyanate resin, isocyanate resin , unsaturated polyphenylene ether, unsaturated polyalkyleneimide resin, anhydride-containing polyimine resin, acid-containing polyimide resin, polymaleic anhydride styrene, phenolic resin, benzoxazine resin One or more of the group consisting of unsaturated resin and the like.
本發明在提供一種含磷難燃劑組成物之用途，其係於製造積層板、預浸漬片、半固化片、半導體構裝材、高頻基板等。 The present invention provides a use of a phosphorus-containing flame retardant composition for producing a laminate, a prepreg, a prepreg, a semiconductor package, a high frequency substrate, and the like.
本發明在提供一種環氧樹脂組成物之用途，其係於製造黏合片、純膠膜、覆蓋膜、軟硬結合板、防焊油墨、高頻軟性基板等。 The present invention provides an epoxy resin composition for producing an adhesive sheet, a pure rubber film, a cover film, a soft and hard bonding plate, a solder resist ink, a high frequency flexible substrate, and the like.
實施例1 Example 1
將三聚氯氰18.4g(0.1mole)、甲苯200g加入裝有機械攪拌、冷凝管、滴液漏斗、溫度計、通入氮氣之四口反應瓶中，攪拌溶解，緩慢滴入二苯基乙氧基膦23.0g(0.1mole)，溫度控制在15~20℃，加料完畢後持續反應1小時，再滴入二苯基乙氧基膦23.0g(0.1mole)，溫度控制在30~40℃，加料完畢後持續反應1小時，再滴入二苯基乙氧基膦29.9g(0.13mole)，溫度控制在75~85℃，加料完畢後持續反應5小時，後減壓蒸餾去除甲苯及二苯基乙氧基膦，冷卻至50℃，加乙酸乙酯150g攪拌溶解30分鐘，滴加環己烷175g使其結晶析出，過濾，真空乾燥後得到產物2,4,6-三(二苯基膦醯基)1,3,5-三嗪(簡稱：PT-P)，HPLC分析收率88.6%，以HPLC分析其純度為99.5%，以消化法檢測其磷含量為13.5%，氮含量為8.2%。 18.4g (0.1mole) of cyanuric chloride and 200g of toluene were added to a four-reaction reaction flask equipped with mechanical stirring, condenser, dropping funnel, thermometer and nitrogen gas, stirred and dissolved, and slowly dropped into diphenyl ethoxylate. 23.0g (0.1mole) of phosphine, the temperature is controlled at 15~20 °C, the reaction is continued for 1 hour after the addition, and then 23.0g (0.1mole) of diphenylethoxyphosphine is added dropwise, and the temperature is controlled at 30~40°C. After the addition was completed, the reaction was continued for 1 hour, and then 29.9 g (0.13 mole) of diphenylethoxyphosphine was added dropwise thereto, and the temperature was controlled at 75 to 85 ° C. After the completion of the addition, the reaction was continued for 5 hours, and then toluene and diphenyl were distilled off under reduced pressure. The ethoxyphosphine was cooled to 50 ° C, and 150 g of ethyl acetate was added and stirred for 30 minutes. 175 g of cyclohexane was added dropwise to crystallize it, which was filtered and dried in vacuo to give the product 2,4,6-tris(diphenyl). Phosphonium)1,3,5-triazine (abbreviation: PT-P), HPLC analysis yield 88.6%, its purity was 99.5% by HPLC analysis, its phosphorus content was 13.5% by digestion, and the nitrogen content was 8.2%.
PT-P其化學反應如下式所示：
實施例2 Example 2
將甲基苯基氧化膦43.4g(0.31mole)、甲醇鈉19.4g(0.36mole)、二異丁酮200g加入裝有機械攪拌、冷凝管、溫度計、通入氮氣之四口反應瓶中，攪拌溶解，分批加入將三聚氯氰18.4g(0.1mole)，溫度控制在15~20℃，加料完畢後持續反應1小時，升溫至30~60℃反應1小時，升溫至75~85℃反應5小時，後加入水500g使其結晶析出，以蒸餾水洗淨過濾三次，再以甲醇洗淨過濾二 次後真空乾燥，得到產物2,4,6-三(苯基甲基膦醯基)1,3,5-三嗪(簡稱：PT-M)，收率75.6%，以HPLC分析其純度為99.7%，以消化法檢測其磷含量為18.8%，氮含量為8.5%。 43.4 g (0.31 mole) of methylphenylphosphine oxide, 19.4 g (0.36 mole) of sodium methoxide, and 200 g of diisobutyl ketone were placed in a four-neck reaction flask equipped with mechanical stirring, a condenser, a thermometer, and nitrogen gas, and stirred. Dissolve, add 18.4g (0.1mole) of cyanuric chloride in batches, control the temperature at 15~20°C, continue to react for 1 hour after the addition, heat up to 30~60°C for 1 hour, and increase the temperature to 75~85°C. After 5 hours, 500 g of water was added to precipitate crystals, washed three times with distilled water, washed twice with methanol, and then vacuum dried to obtain the product 2,4,6-tris(phenylmethylphosphonium) 1 3,5-triazine (abbreviation: PT-M), the yield was 75.6%, the purity was 99.7% by HPLC analysis, and the phosphorus content was 18.8% and the nitrogen content was 8.5% by the digestion method.
PT-M其化學反應如下式所示：
實施例3 Example 3
將烯丙基苯基氧化膦51.2g(0.31mole)、甲醇鈉19.4g(0.36mole)、二異丁酮200g加入裝有機械攪拌、冷凝管、溫度計、通入氮氣之四口反應瓶中，攪拌溶解，分批加入將三聚氯氰18.4g(0.1mole)，溫度控制在15~20℃，加料完畢後持續反應1小時，升溫至30~40℃反應1小時，升溫至75~85℃反應5小時，後加入水500g使其結晶析出，以蒸餾水洗淨過濾三次，再以甲醇洗淨過濾二次後真空乾燥，得到產物2,4,6-三(苯基烯丙基膦醯基)1,3,5-三嗪(簡稱：PT-3A)，收率70.2%，以HPLC分析其純度為99.6%，以消化法檢測其磷含量為16.2%，氮含量為7.3%。 51.2 g (0.31 mole) of allyl phenylphosphine oxide, 19.4 g (0.36 mole) of sodium methoxide, and 200 g of diisobutyl ketone were placed in a four-reaction reaction flask equipped with a mechanical stirring, a condenser, a thermometer, and a nitrogen gas. Stir and dissolve, add 18.4g (0.1mole) of cyanuric chloride in batches, control the temperature at 15~20 °C, continue to react for 1 hour after the addition, heat up to 30~40 °C for 1 hour, heat up to 75~85 °C After reacting for 5 hours, 500 g of water was added thereto to cause crystallization, and the mixture was washed three times with distilled water, washed twice with methanol, and then vacuum dried to give the product 2,4,6-tris(phenylallylphosphinyl). 1,3,5-triazine (abbreviation: PT-3A), the yield was 70.2%, the purity was 99.6% by HPLC analysis, the phosphorus content was 16.2% by the digestion method, and the nitrogen content was 7.3%.
PT-3A其化學反應如下式所示：
實施例4 Example 4
將甲基苯基氧化膦28.0g(0.2mole)、甲醇鈉19.4g(0.36mole)、二異丁酮200g加入裝有機械攪拌、冷凝管、溫度計、通入氮氣之四口反應瓶中，攪拌溶解，分批加入將三聚氯氰18.4g(0.1mole)，溫度控制在15~20℃，加料完畢後持續反應1小時，升溫至30~40℃反應1小時，加入對乙烯基酚12.6g(0.105mole)升溫至75~85℃反應5小時，後加入水500g使其結晶析出，以蒸餾水洗淨過濾三次，再以甲醇洗淨過濾二次後真空乾燥，得到產物2,4-二(甲基苯基膦醯基)6-乙烯苯氧基1,3,5-三嗪(簡稱：PT-1V)，收率75.3%，以HPLC分析其純度為99.4%，以消化法檢測其磷含量為13.1%，氮含量為8.9%。 28.0g (0.2mole) of methylphenylphosphine oxide, 19.4g (0.36mole) of sodium methoxide, and 200g of diisobutyl ketone were added to a four-reaction reaction flask equipped with mechanical stirring, a condenser, a thermometer, and nitrogen gas, and stirred. Dissolve, add 18.4g (0.1mole) of cyanuric chloride in batches, control the temperature at 15~20 °C, continue to react for 1 hour after the addition, heat up to 30~40 °C for 1 hour, add p-vinylphenol 12.6g (0.105 mole), the temperature was raised to 75-85 ° C for 5 hours, and then 500 g of water was added to cause crystallization, and the mixture was washed three times with distilled water, washed twice with methanol, and then vacuum dried to obtain the product 2,4-di ( Methylphenylphosphonium)6-vinylphenoxy 1,3,5-triazine (abbreviation: PT-1V), yield 75.3%, its purity was 99.4% by HPLC, and its phosphorus was detected by digestion. The content was 13.1% and the nitrogen content was 8.9%.
PT-1V其化學反應如下式所示：
實施例5 Example 5
將甲基苯基氧化膦28.0g(0.2mole)、甲醇鈉19.4g(0.36mole)、二異丁酮200g加入裝有機械攪拌、冷凝管、溫度計、通入氮氣之四口反應瓶中，攪拌溶解，分批加入將三聚氯氰18.4g(0.1mole)，溫度控制在15~20℃，加料完畢後持續反應1小時，升溫至30~40℃反應1小時，加入對2-烯丙基5-甲基酚15.5g(0.105mole)乙烯基酚12.6g(0.105mole)升溫至75~85℃反應5小時，後加入水500g使其結晶析出，以蒸餾水洗淨過濾三次，再以甲醇洗淨過濾二次後真空乾燥，得到產物2,4-二(甲基苯基膦醯基)6-(2-烯丙基5-甲基苯氧 基)1,3,5-三嗪(簡稱：PT-1V)，收率71.7%，以HPLC分析其純度為99.6%，以消化法檢測其磷含量為12.3%，氮含量為8.4%。 28.0g (0.2mole) of methylphenylphosphine oxide, 19.4g (0.36mole) of sodium methoxide, and 200g of diisobutyl ketone were added to a four-reaction reaction flask equipped with mechanical stirring, a condenser, a thermometer, and nitrogen gas, and stirred. Dissolve, add 18.4g (0.1mole) of cyanuric chloride in batches, control the temperature at 15~20 °C, continue to react for 1 hour after the addition, heat up to 30~40 °C for 1 hour, add 2-allyl 5-methylphenol 15.5 g (0.105 mole) of vinyl phenol 12.6 g (0.105 mole) was heated to 75-85 ° C for 5 hours, then 500 g of water was added to crystallize it, washed with distilled water three times, and then washed with methanol. After net filtration and vacuum drying, the product 2,4-bis(methylphenylphosphino)6-(2-allyl-5-methylphenoxy)1,3,5-triazine (abbreviation) : PT-1V), the yield was 71.7%, the purity was 99.6% by HPLC analysis, the phosphorus content was 12.3% by the digestion method, and the nitrogen content was 8.4%.
PT-1A其化學反應如下式所示：
實施例6 Example 6
甲基苯基氧化膦22.4g(0.16mole)、甲醇鈉21.6g(0.4mole)異丁酮300g入裝有機械攪拌、冷凝管、溫度、通入氮氣之四口反應瓶中，攪拌溶解，分批加入將三聚氯氰22.08g(0.12mole)，溫度控制在15~20℃，加料完畢後持續反應1小時，升溫至30~40℃反應1小時，加入2,5-二羥苯基二苯基氧化膦31.0g(0.10mole)升溫至75~85℃反應5小時，後加入水500g使其結晶析出，以蒸餾水洗淨過濾三次，再以甲醇洗淨過濾二次後真空乾燥，得到高分子型含磷難燃劑簡稱：PT-1V)，收率91.7%，以HPLC分析其純度為99.5%，以消化法檢測其磷含量為12.9%，氮含量為8.1%。 Methylphenylphosphine oxide 22.4g (0.16mole), sodium methoxide 21.6g (0.4mole) isobutyl ketone 300g into a four-reaction reaction flask equipped with mechanical stirring, condensation tube, temperature, nitrogen gas, stirring and dissolving The batch was added with 22.08g (0.12mole) of cyanuric chloride, the temperature was controlled at 15~20°C, the reaction was continued for 1 hour after the completion of the addition, the temperature was raised to 30~40°C for 1 hour, and 2,5-dihydroxyphenyl group was added. 31.0 g (0.10 mole) of phenylphosphine oxide was heated to 75-85 ° C for 5 hours, and then 500 g of water was added thereto to cause crystal precipitation, washed three times with distilled water, washed twice with methanol, and then vacuum dried to obtain high. The molecular type phosphorus-containing flame retardant is abbreviated as: PT-1V), the yield is 91.7%, the purity is 99.5% by HPLC analysis, the phosphorus content is 12.9% by the digestion method, and the nitrogen content is 8.1%.
PT-1P其化學反應如下式所示：
實施例7 Example 7
甲基苯基氧化膦22.4g(0.16mole)、甲醇鈉21.6g(0.4mole)異丁酮300g入裝有機械攪拌、冷凝管、溫度、通入氮氣之四口反應瓶中，攪拌溶解，分批加入將三聚氯氰22.08g(0.12mole)，溫度控制在15~20℃，加料完畢後持續反應1小時，升溫至30~40℃反應1小時，加入1,4-二羥萘基苯基甲基氧化膦29.8g(0.10mole)升溫至75~85℃反應5小時，後加入水500g使其結晶析出，以蒸餾水洗淨過濾三次，再以甲醇洗淨過濾二次後真空乾燥，得到高分子型含磷難燃劑簡稱：PT-1V)，收率90.5%，以HPLC分析其純度為99.3%，以消化法檢測其磷含量為13.2%，氮含量為6.2%。 Methylphenylphosphine oxide 22.4g (0.16mole), sodium methoxide 21.6g (0.4mole) isobutyl ketone 300g into a four-reaction reaction flask equipped with mechanical stirring, condensation tube, temperature, nitrogen gas, stirring and dissolving 22.08g (0.12mole) of cyanuric chloride was added in batches, the temperature was controlled at 15~20°C, the reaction was continued for 1 hour after the addition, and the temperature was raised to 30~40°C for 1 hour, and 1,4-dihydroxynaphthylbenzene was added. 29.8 g (0.10 mole) of methyl phosphine oxide was heated to 75-85 ° C for 5 hours, and then 500 g of water was added to precipitate crystals, which were washed three times with distilled water, washed twice with methanol, and vacuum dried. The polymer type phosphorus-containing flame retardant is abbreviated as: PT-1V), the yield is 90.5%, the purity is 99.3% by HPLC analysis, the phosphorus content is 13.2% by the digestion method, and the nitrogen content is 6.2%.
PT-2P其化學反應如下式所示：
實施例8 Example 8
將含磷難燃劑PN-M取15重量份、苯乙烯基聚苯醚(OPE-St-2200/MGC製)50重量份、3,3',5,5'-四甲基聯苯二乙烯苯醚(TMBPV/晉一製)50重量份、過氧化二異丙苯(DCP)0.01重量份，溶於丁酮80重量份中做成膠液，經220℃ 3小時固化製成試片，測量其玻璃轉移溫度(Tg)、介電損失(Df)、介電常數(Dk)、難燃性(UL-94)、熱膨脹係數(α1)、模量，其數據如表一所示。 15 parts by weight of phosphine-containing flame retardant PN-M, 50 parts by weight of styryl polyphenylene ether (OPE-St-2200/MGC), 3,3',5,5'-tetramethylbiphenyl 50 parts by weight of vinyl phenyl ether (TMBPV/Jinyi), 0.01 parts by weight of dicumyl peroxide (DCP), dissolved in 80 parts by weight of methyl ethyl ketone to make a glue solution, and cured at 220 ° C for 3 hours to prepare a test piece. , measuring its glass transition temperature (Tg), dielectric loss (Df), dielectric constant (Dk), flame retardancy (UL-94), thermal expansion coefficient ( α 1), modulus, as shown in Table 1. .
實施例9 Example 9
將含磷難燃劑PN-M取22重量份、苯乙烯基聚苯醚(OPE-St-2200/MGC製)50重量份、3,3',5,5'-四甲基聯苯二乙烯苯醚(TMBPV/晉一製)50重量份、 過氧化二異丙苯(DCP)0.01重量份，溶於丁酮80重量份中做成膠液，經220℃ 3小時固化製成試片，測量其玻璃轉移溫度(Tg)、介電損失(Df)、介電常數(Dk)、難燃性(UL-94)、熱膨脹係數(α1)、模量，其數據如表一所示。 22 parts by weight of phosphorus-containing flame retardant PN-M, 50 parts by weight of styryl polyphenylene ether (OPE-St-2200/MGC), 3,3',5,5'-tetramethylbiphenyl 50 parts by weight of vinyl phenyl ether (TMBPV/Jinyi), 0.01 parts by weight of dicumyl peroxide (DCP), dissolved in 80 parts by weight of methyl ethyl ketone to make a glue solution, and cured at 220 ° C for 3 hours to prepare a test piece. , measuring its glass transition temperature (Tg), dielectric loss (Df), dielectric constant (Dk), flame retardancy (UL-94), thermal expansion coefficient ( α 1), modulus, as shown in Table 1. .
實施例10 Example 10
將含磷難燃劑PN-3A取17重量份、苯乙烯基聚苯醚(OPE-St-2200/MGC製)50重量份、3,3',5,5'-四甲基聯苯二乙烯苯醚(TMBPV/晉一製)50重量份、過氧化二異丙苯(DCP)0.01重量份，溶於丁酮80重量份中做成膠液，經220℃ 3小時固化製成試片，測量其玻璃轉移溫度(Tg)、介電損失(Df)、介電常數(Dk)、難燃性(UL-94)、熱膨脹係數(α1)、模量，其數據如表一所示。 17 parts by weight of phosphorus-containing flame retardant PN-3A, 50 parts by weight of styryl polyphenylene ether (OPE-St-2200/MGC), 3,3',5,5'-tetramethylbiphenyl 50 parts by weight of vinyl phenyl ether (TMBPV/Jinyi), 0.01 parts by weight of dicumyl peroxide (DCP), dissolved in 80 parts by weight of methyl ethyl ketone to make a glue solution, and cured at 220 ° C for 3 hours to prepare a test piece. , measuring its glass transition temperature (Tg), dielectric loss (Df), dielectric constant (Dk), flame retardancy (UL-94), thermal expansion coefficient ( α 1), modulus, as shown in Table 1. .
實施例11 Example 11
將含磷難燃劑PN-1A取13重量份、苯乙烯基聚苯醚(OPE-St-2200/MGC製)50重量份、3,3',5,5'-四甲基聯苯二乙烯苯醚(TMBPV/晉一製)50重量份、過氧化二異丙苯(DCP)0.01重量份，溶於丁酮80重量份中做成膠液，經220℃ 3小時固化製成試片，測量其玻璃轉移溫度(Tg)、介電損失(Df)、介電常數(Dk)、難燃性(UL-94)、熱膨脹係數(α1)、模量，其數據如表一所示。 13 parts by weight of phosphorus-containing flame retardant PN-1A, 50 parts by weight of styryl polyphenylene ether (made by OPE-St-2200 / MGC ), 3,3',5,5'-tetramethylbiphenyl 50 parts by weight of vinyl phenyl ether (TMBPV/Jinyi), 0.01 parts by weight of dicumyl peroxide (DCP), dissolved in 80 parts by weight of methyl ethyl ketone to make a glue solution, and cured at 220 ° C for 3 hours to prepare a test piece. , measuring its glass transition temperature (Tg), dielectric loss (Df), dielectric constant (Dk), flame retardancy (UL-94), thermal expansion coefficient ( α 1), modulus, as shown in Table 1. .
實施例12 Example 12
將含磷難燃劑PN-1V取12重量份、苯乙烯基聚苯醚(OPE-St-2200/MGC製)50重量份、3,3',5,5'-四甲基聯苯二乙烯苯醚(TMBPV/晉一製)50重量份、過氧化二異丙苯(DCP)0.01重量份，溶於丁酮80重量份中做成膠液，經220℃ 3小時固化製成試片，測量其玻璃轉移溫度(Tg)、介電損失(Df)、介電常數(Dk)、難燃性(UL-94)、熱膨脹係數(α1)、模量，其數據如表一所示。 12 parts by weight of phosphorus-containing flame retardant PN-1V, 50 parts by weight of styryl polyphenylene ether (made by OPE-St-2200 / MGC ), 3,3',5,5'-tetramethylbiphenyl 50 parts by weight of vinyl phenyl ether (TMBPV/Jinyi), 0.01 parts by weight of dicumyl peroxide (DCP), dissolved in 80 parts by weight of methyl ethyl ketone to make a glue solution, and cured at 220 ° C for 3 hours to prepare a test piece. , measuring its glass transition temperature (Tg), dielectric loss (Df), dielectric constant (Dk), flame retardancy (UL-94), thermal expansion coefficient ( α 1), modulus, as shown in Table 1. .
實施例13 Example 13
將含磷難燃劑PN-3A取15重量份、3,3',5,5'-四甲基聯苯二乙烯苯醚(TMBPV/晉一製)100重量份、過氧化二異丙苯(DCP)0.01重量份，溶於丁酮80重量份中做成膠液，經220℃ 3小時固化製成試片，測量其玻璃轉移溫度(Tg)、介電損失(Df)、介電常數(Dk)、難燃性(UL-94)、熱膨脹係數(α1)、模量，其數據如表一所示。 15 parts by weight of phosphorus-containing flame retardant P N-3A , 100 parts by weight of 3,3',5,5'-tetramethylbiphenyldiphenyl phenyl ether (TMBPV/Jinyi), diisopropyl peroxide 0.01 parts by weight of benzene (DCP), dissolved in 80 parts by weight of methyl ethyl ketone to make a glue, cured at 220 ° C for 3 hours to prepare a test piece, measuring its glass transition temperature (Tg), dielectric loss (Df), dielectric Constant (Dk), flame retardancy (UL-94), coefficient of thermal expansion ( α 1), modulus, and the data are shown in Table 1.
實施例14 Example 14
將含磷難燃劑PN-M取15重量份、苯乙烯基聚苯醚(OPE-St-2200/MGC製)50重量份、三烯丙基三聚異氰酸酯(TAIC)40重量份、聚丁二烯(Ricon130/Cray Valley製)10重量份、過氧化二異丙苯(DCP)0.01重量份，溶於丁酮80重量份中做成膠液，經220℃ 3小時固化製成試片，測量其玻璃轉移溫度(Tg)、介電損失(Df)、介電常數(Dk)、難燃性(UL-94)、熱膨脹係數(α1)、模量，其數據如表一所示。 Phosphorus-containing flame retardant PN-M 15 parts by weight taken, styryl polyphenylene ether (OPE-St-2200 / MGC, Ltd.) 50 parts by weight, 40 parts by weight of triallyl isocyanate (of TAIC), polybutadiene 10 parts by weight of diene ( manufactured by Ricon 130 / Cray Valley ), 0.01 parts by weight of dicumyl peroxide (DCP), dissolved in 80 parts by weight of methyl ethyl ketone to form a glue, and cured at 220 ° C for 3 hours to prepare a test piece. The glass transition temperature (Tg), dielectric loss (Df), dielectric constant (Dk), flame retardancy (UL-94), coefficient of thermal expansion ( α 1), and modulus were measured, and the data are shown in Table 1.
比較例1 Comparative example 1
將難燃劑三(三溴苯基)三嗪(FR-245/ICL製)取25重量份、苯乙烯基聚苯醚(OPE-St-2200/MGC製)50重量份、三烯丙基三聚異氰酸酯(TAIC)40重量份、聚丁二烯(Ricon130/Cray Valley製)10重量份、過氧化二異丙苯(DCP)0.01重量份，溶於丁酮80重量份中做成膠液，經220℃ 3小時固化製成試片，測量其玻璃轉移溫度(Tg)、介電損失(Df)、介電常數(Dk)、難燃性(UL-94)、熱膨脹係數(α1)、模量，其數據如表一所示。 25 parts by weight of a flame retardant tris(tribromophenyl)triazine (manufactured by FR-245/ICL), 50 parts by weight of styryl polyphenylene ether (made by OPE-St-2200 / MGC ), triallyl group 80 parts by weight of trimerized polyisocyanates (of TAIC) 40 parts by weight of polybutadiene (Ricon130 / Cray Valley Ltd.) 10 parts by weight of dicumyl peroxide (DCP) 0.01 parts by weight, was dissolved in methyl ethyl ketone to make glue The test piece was cured by curing at 220 ° C for 3 hours, and its glass transition temperature (Tg), dielectric loss (Df), dielectric constant (Dk), flame retardancy (UL-94), and thermal expansion coefficient ( α 1) were measured. Modulus, the data is shown in Table 1.
比較例2 Comparative example 2
將磷腈難燃劑(SPB100/大塚製)取22重量份、苯乙烯基聚苯醚(OPE-St-2200/MGC製)50重量份、3,3',5,5'-四甲基聯苯二乙烯苯醚(TMBPV/晉一製)50重 量份、過氧化二異丙苯(DCP)0.01重量份，溶於丁酮80重量份中做成膠液，經220℃ 3小時固化製成試片，測量其玻璃轉移溫度(Tg)、介電損失(Df)、介電常數(Dk)、難燃性(UL-94)、熱膨脹係數(α1)、模量，其數據如表一所示。 22 parts by weight of phosphazene flame retardant ( SPB100 / manufactured by Otsuka Co., Ltd.), 50 parts by weight of styryl polyphenylene ether (made by OPE-St-2200 / MGC ), 3,3', 5,5'-tetramethyl 50 parts by weight of biphenyl divinyl phenyl ether (TMBPV/Jinyi), 0.01 parts by weight of dicumyl peroxide (DCP), dissolved in 80 parts by weight of methyl ethyl ketone to form a glue, cured at 220 ° C for 3 hours Test piece, measure its glass transition temperature (Tg), dielectric loss (Df), dielectric constant (Dk), flame retardancy (UL-94), thermal expansion coefficient ( α 1), modulus, and its data is shown in the table. One is shown.
實施例15 Example 15
將含磷難燃劑PN-M取15重量份、雙酚A二氰酸酯(BA-23S/Lonza製)37重量份、苯乙烯馬來酸酐共聚物(SMA1000/Cray Valley製)18重量份、N-苯基酚酞型苯并惡嗪(N-40/晉一製)18重量份、雙(3-乙基-5-甲基-4-馬来醯亞胺基苯)甲烷(BMI-70/KI製)18重量份、聯苯芳烷基型環氧樹脂(NC-3000L/日本化藥製)9重量份、辛酸鋅0.003重量份、三苯基磷(TPP)0.03重量份， 溶於丁酮80重量份中做成膠液，將膠液含浸塗布於2116玻璃纖維布上，並於175℃下乾燥2~15分鐘，藉此做出半固化狀態之半固化片，然後將四片半固化片層合，上下二側各一張0.5盎司銅箔，接著進行熱壓，條件為以1~3℃/分鐘升溫速度至220℃，在該溫度下以8~15公斤/平方公分之壓力熱壓180分鐘，藉此獲得積層板，測量其玻璃轉移溫度(Tg)、介電損失(Df)、介電常數(Dk)、難燃性(UL-94)、撕裂強度，其數據如表二所示。 Phosphorus-containing flame retardant PN-M taken 15 parts by weight, 37 parts by weight of a bisphenol A dicyanate (BA-23S / Lonza Ltd.), 18 parts by weight of styrene-maleic anhydride copolymer (SMA1000 / Cray Valley Ltd.) , N -phenylphenolphthalein type benzoxazine ( N - 40 /Jinyi) 18 parts by weight, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane (BMI- 70 parts by weight of KI) 18 parts by weight of a biphenyl aralkyl type epoxy resin (manufactured by NC - 3000L / manufactured by Nippon Kasei Co., Ltd.) 9 parts by weight, 0.003 parts by weight of zinc octoate, and 0.03 parts by weight of triphenylphosphine ( TPP ). The glue was made into 80 parts by weight of methyl ethyl ketone, and the glue was impregnated and coated on 2116 glass fiber cloth, and dried at 175 ° C for 2 to 15 minutes, thereby forming a semi-cured prepreg, and then four prepregs. Lamination, 0.5 ounces of copper foil on each of the upper and lower sides, followed by hot pressing, at a temperature of 1 to 3 ° C / min to 220 ° C, at this temperature with a pressure of 8 ~ 15 kg / cm ^ 2 180 minutes, thereby obtaining a laminate, measuring its glass transition temperature (Tg), dielectric loss (Df), dielectric constant (Dk), flame retardancy (UL-94), tear strength, as shown in Table 2 Shown.
實施例16 Example 16
將含磷難燃劑PN-P取22重量份、雙酚A二氰酸酯(BA-23S/Lonza製)37重量份、苯乙烯馬來酸酐共聚物(SMA1000/Cray Valley製)18重量份、N-苯基酚酞型苯并惡嗪(N-40/晉一製)18重量份、雙(3-乙基-5-甲基-4-馬来醯亞胺基苯)甲烷(BMI-70/KI製)18重量份、聯苯芳烷基型環氧樹脂(NC-3000L/日本化藥製)9重量份、辛酸鋅0.003重量份、三苯基磷(TPP)0.03重量份，溶於丁酮80重量份中做成膠液，將膠液含浸塗布於2116玻璃纖維布上，並於175℃下乾燥2~15分鐘，藉此做出半固化狀態之半固化片，然後將四片半固化片層合，上下二側各一張0.5盎司銅箔，接著進行熱壓，條件為以1~3℃/分鐘升溫速度至220℃，在該溫度下以8~15公斤/平方公分之壓力熱壓180分鐘，藉此獲得積層板，測量其玻璃轉移溫度(Tg)、介電損失(Df)、介電常數(Dk)、難燃性(UL-94)、撕裂強度，其數據如表二所示。 Phosphorus-containing flame retardant PN-P takes 22 parts by weight, 37 parts by weight of a bisphenol A dicyanate (BA-23S / Lonza Ltd.), 18 parts by weight of styrene-maleic anhydride copolymer (SMA1000 / Cray Valley Ltd.) , N -phenylphenolphthalein type benzoxazine ( N - 40 /Jinyi) 18 parts by weight, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane (BMI- 70 parts by weight of KI) 18 parts by weight of a biphenyl aralkyl type epoxy resin (manufactured by NC-3000L / manufactured by Nippon Kasei Co., Ltd.) 9 parts by weight, 0.003 parts by weight of zinc octoate, and 0.03 parts by weight of triphenylphosphine ( TPP ). The glue was made into 80 parts by weight of methyl ethyl ketone, and the glue was impregnated and coated on 2116 glass fiber cloth, and dried at 175 ° C for 2 to 15 minutes, thereby forming a semi-cured prepreg, and then four prepregs. Lamination, 0.5 ounces of copper foil on each of the upper and lower sides, followed by hot pressing, at a temperature of 1 to 3 ° C / min to 220 ° C, at this temperature with a pressure of 8 ~ 15 kg / cm ^ 2 180 minutes, thereby obtaining a laminate, measuring its glass transition temperature (Tg), dielectric loss (Df), dielectric constant (Dk), flame retardancy (UL-94), tear strength, as shown in Table 2 Shown.
實施例17 Example 17
將含磷難燃劑PN-3A取17重量份、雙酚A二氰酸酯(BA-23S/Lonza製)37重量份、苯乙烯馬來酸酐共聚物(SMA1000/Cray Valley製)18重量份、N-苯基酚酞型苯并惡嗪(N-40/晉一製)18重量份、雙(3-乙基-5-甲基-4-馬来醯 亞胺基苯)甲烷(BMI-70/KI製)18重量份、聯苯芳烷基型環氧樹脂(NC-3000L/日本化藥製)9重量份、辛酸鋅0.003重量份、三苯基磷(TPP)0.03重量份，溶於丁酮80重量份中做成膠液，將膠液含浸塗布於2116玻璃纖維布上，並於175℃下乾燥2~15分鐘，藉此做出半固化狀態之半固化片，然後將四片半固化片層合，上下二側各一張0.5盎司銅箔，接著進行熱壓，條件為以1~3℃/分鐘升溫速度至220℃，在該溫度下以8~15公斤/平方公分之壓力熱壓180分鐘，藉此獲得積層板，測量其玻璃轉移溫度(Tg)、介電損失(Df)、介電常數(Dk)、難燃性(UL-94)、撕裂強度，其數據如表二所示。 Phosphorus-containing flame retardant PN-3A taken 17 parts by weight, 37 parts by weight of a bisphenol A dicyanate (BA-23S / Lonza Ltd.), 18 parts by weight of styrene-maleic anhydride copolymer (SMA1000 / Cray Valley Ltd.) , N -phenylphenolphthalein type benzoxazine ( N - 40 /Jinyi) 18 parts by weight, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane (BMI- 70 parts by weight of KI) 18 parts by weight of a biphenyl aralkyl type epoxy resin (manufactured by NC-3000L / manufactured by Nippon Kasei Co., Ltd.) 9 parts by weight, 0.003 parts by weight of zinc octoate, and 0.03 parts by weight of triphenylphosphine ( TPP ). The glue was made into 80 parts by weight of methyl ethyl ketone, and the glue was impregnated and coated on 2116 glass fiber cloth, and dried at 175 ° C for 2 to 15 minutes, thereby forming a semi-cured prepreg, and then four prepregs. Lamination, 0.5 ounces of copper foil on each of the upper and lower sides, followed by hot pressing, at a temperature of 1 to 3 ° C / min to 220 ° C, at this temperature with a pressure of 8 ~ 15 kg / cm ^ 2 180 minutes, thereby obtaining a laminate, measuring its glass transition temperature (Tg), dielectric loss (Df), dielectric constant (Dk), flame retardancy (UL-94), tear strength, as shown in Table 2 Shown.
實施例18 Example 18
將含磷難燃劑PN-1A取22重量份、雙酚A二氰酸酯(BA-23S/Lonza製)37重量份、苯乙烯馬來酸酐共聚物(SMA1000/Cray Valley製)18重量份、N-苯基酚酞型苯并惡嗪(N-40/晉一製)18重量份、雙(3-乙基-5-甲基-4-馬来醯亞胺基苯)甲烷(BMI-70/KI製)18重量份、聯苯芳烷基型環氧樹脂(NC-3000L/日本化藥製)9重量份、辛酸鋅0.003重量份、三苯基磷(TPP)0.03重量份，溶於丁酮80重量份中做成膠液，將膠液含浸塗布於2116玻璃纖維布上，並於175℃下乾燥2~15分鐘，藉此做出半固化狀態之半固化片，然後將四片半固化片層合，上下二側各一張0.5盎司銅箔，接著進行熱壓，條件為以1~3℃/分鐘升溫速度至220℃，在該溫度下以8~15公斤/平方公分之壓力熱壓180分鐘，藉此獲得積層板，測量其玻璃轉移溫度(Tg)、介電損失(Df)、介電常數(Dk)、難燃性(UL-94)、撕裂強度，其數據如表二所示。 Phosphorus-containing flame retardant PN-1A taken 22 parts by weight, 37 parts by weight of a bisphenol A dicyanate (BA-23S / Lonza Ltd.), 18 parts by weight of styrene-maleic anhydride copolymer (SMA1000 / Cray Valley Ltd.) , N -phenylphenolphthalein type benzoxazine ( N - 40 /Jinyi) 18 parts by weight, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane (BMI- 70 parts by weight of KI) 18 parts by weight of a biphenyl aralkyl type epoxy resin (manufactured by NC-3000L / manufactured by Nippon Kasei Co., Ltd.) 9 parts by weight, 0.003 parts by weight of zinc octoate, and 0.03 parts by weight of triphenylphosphine ( TPP ). The glue was made into 80 parts by weight of methyl ethyl ketone, and the glue was impregnated and coated on 2116 glass fiber cloth, and dried at 175 ° C for 2 to 15 minutes, thereby forming a semi-cured prepreg, and then four prepregs. Lamination, 0.5 ounces of copper foil on each of the upper and lower sides, followed by hot pressing, at a temperature of 1 to 3 ° C / min to 220 ° C, at this temperature with a pressure of 8 ~ 15 kg / cm ^ 2 180 minutes, thereby obtaining a laminate, measuring its glass transition temperature (Tg), dielectric loss (Df), dielectric constant (Dk), flame retardancy (UL-94), tear strength, as shown in Table 2 Shown.
實施例19 Example 19
將含磷難燃劑PN-1V取22重量份、雙酚A二氰酸酯(BA-23S/Lonza製)37 重量份、苯乙烯馬來酸酐共聚物(SMA1000/Cray Valley製)18重量份、N-苯基酚酞型苯并惡嗪(N-40/晉一製)18重量份、雙(3-乙基-5-甲基-4-馬来醯亞胺基苯)甲烷(BMI-70/KI製)18重量份、聯苯芳烷基型環氧樹脂(NC-3000L/日本化藥製)9重量份、辛酸鋅0.003重量份、三苯基磷(TPP)0.03重量份，溶於丁酮80重量份中做成膠液，將膠液含浸塗布於2116玻璃纖維布上，並於175℃下乾燥2~15分鐘，藉此做出半固化狀態之半固化片，然後將四片半固化片層合，上下二側各一張0.5盎司銅箔，接著進行熱壓，條件為以1~3℃/分鐘升溫速度至220℃，在該溫度下以8~15公斤/平方公分之壓力熱壓180分鐘，藉此獲得積層板，測量其玻璃轉移溫度(Tg)、介電損失(Df)、介電常數(Dk)、難燃性(UL-94)、撕裂強度，其數據如表二所示。 Phosphorus-containing flame retardant PN-1V taken 22 parts by weight, 37 parts by weight of a bisphenol A dicyanate (BA-23S / Lonza Ltd.), 18 parts by weight of styrene-maleic anhydride copolymer (SMA1000 / Cray Valley Ltd.) , N -phenylphenolphthalein type benzoxazine ( N-40 / Jinyi) 18 parts by weight, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane (BMI- 70 parts by weight of KI) 18 parts by weight of a biphenyl aralkyl type epoxy resin (manufactured by NC-3000L / manufactured by Nippon Kasei Co., Ltd.) 9 parts by weight, 0.003 parts by weight of zinc octoate, and 0.03 parts by weight of triphenylphosphine ( TPP ). The glue was made into 80 parts by weight of methyl ethyl ketone, and the glue was impregnated and coated on 2116 glass fiber cloth, and dried at 175 ° C for 2 to 15 minutes, thereby forming a semi-cured prepreg, and then four prepregs. Lamination, 0.5 ounces of copper foil on each of the upper and lower sides, followed by hot pressing, at a temperature of 1 to 3 ° C / min to 220 ° C, at this temperature with a pressure of 8 ~ 15 kg / cm ^ 2 180 minutes, thereby obtaining a laminate, measuring its glass transition temperature (Tg), dielectric loss (Df), dielectric constant (Dk), flame retardancy (UL-94), tear strength, as shown in Table 2 Shown.
實施例20 Example 20
將含磷難燃劑PN-P取7重量份、雙酚A二氰酸酯(BA-23S/Lonza製)37重量份、苯乙烯馬來酸酐共聚物(SMA1000/Cray Valley製)9重量份、N-苯基酚酞型苯并惡嗪(N-40/晉一製)18重量份、雙(3-乙基-5-甲基-4-馬来醯亞胺基苯)甲烷(BMI-70/KI製)27重量份、N-苯基酚酞型環氧樹脂(PPPBP-E/日本化藥製)9重量份、辛酸鋅0.003重量份、三苯基磷(TPP)0.03重量份，溶於丁酮80重量份中做成膠液，將膠液含浸塗布於2116玻璃纖維布上，並於175℃下乾燥2~15分鐘，藉此做出半固化狀態之半固化片，然後將四片半固化片層合，上下二側各一張0.5盎司銅箔，接著進行熱壓，條件為以1~3℃/分鐘升溫速度至220℃，在該溫度下以8~15公斤/平方公分之壓力熱壓180分鐘，藉此獲得積層板，測量其玻璃轉移溫度(Tg)、介電損失(Df)、介電常數(Dk)、難燃性(UL-94)、撕裂強度，其數據如表二所示。 7 parts by weight of phosphine - containing flame retardant PN-P , 37 parts by weight of bisphenol A dicyanate ( BA-23S / manufactured by Lonza ), and 9 parts by weight of styrene maleic anhydride copolymer ( manufactured by SMA1000 / Cray Valley ) , N -phenylphenolphthalein type benzoxazine ( N-40 / Jinyi) 18 parts by weight, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane (BMI- 70 / KI, Ltd.) 27 parts by weight, N - phenyl phenolphthalein type epoxy resin (PPPBP-E / Nippon Kayaku Ltd.) 9 parts by weight, 0.003 parts by weight zinc octoate, triphenylphosphine (TPP) 0.03 parts by weight of solvent The glue was made into 80 parts by weight of methyl ethyl ketone, and the glue was impregnated and coated on 2116 glass fiber cloth, and dried at 175 ° C for 2 to 15 minutes, thereby forming a semi-cured prepreg, and then four prepregs. Lamination, 0.5 ounces of copper foil on each of the upper and lower sides, followed by hot pressing, at a temperature of 1 to 3 ° C / min to 220 ° C, at this temperature with a pressure of 8 ~ 15 kg / cm ^ 2 180 minutes, thereby obtaining a laminate, measuring its glass transition temperature (Tg), dielectric loss (Df), dielectric constant (Dk), flame retardancy (UL-94), tear strength, as shown in Table 2 Shown.
比較例3 Comparative example 3
將磷腈難燃劑(SPB100/大塚製)取7重量份、雙酚A二氰酸酯(BA-23S/Lonza製)37重量份、苯乙烯馬來酸酐共聚物(SMA1000/Cray Valley製)9重量份、N-苯基酚酞型苯并惡嗪(N-40/晉一製)18重量份、雙(3-乙基-5-甲基-4-馬来醯亞胺基苯)甲烷(BMI-70/KI製)27重量份、N-苯基酚酞型環氧樹脂(PPPBP-E/日本化藥製)9重量份、辛酸鋅0.003重量份、三苯基磷(TPP)0.03重量份，溶於丁酮80重量份中做成膠液，將膠液含浸塗布於2116玻璃纖維布上，並於175℃下乾燥2~15分鐘，藉此做出半固化狀態之半固化片，然後將四片半固化片層合，上下二側各一張0.5盎司銅箔，接著進行熱壓，條件為以1~3℃/分鐘升溫速度至220℃，在該溫度下以8~15公斤/平方公分之壓力熱壓180分鐘，藉此獲得積層板，測量其玻璃轉移溫度(Tg)、介電損失(Df)、介電常數(Dk)、難燃性(UL-94)、撕裂強度，其數據如表二所示。 7 parts by weight of a phosphazene flame retardant ( manufactured by SPB100 / manufactured by Otsuka Co., Ltd.), bisphenol A dicyanate (manufactured by BA-23S / Lonza ), 37 parts by weight, and a styrene maleic anhydride copolymer ( manufactured by SMA1000 / Cray Valley ) 9 parts by weight, N -phenylphenolphthalein type benzoxazine ( N-40 / Jinyi) 18 parts by weight, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane (BMI-70/KI) 27 parts by weight, N -phenylphenolphthalein type epoxy resin (made by PPPBP-E / manufactured by Nippon Kasei Co., Ltd.) 9 parts by weight, 0.003 parts by weight of zinc octoate, and triphenylphosphine ( TPP ) 0.03 by weight a solution, dissolved in 80 parts by weight of methyl ethyl ketone to make a glue, impregnating the glue on 2116 glass fiber cloth, and drying at 175 ° C for 2 to 15 minutes, thereby making a semi-cured prepreg, and then Four prepregs are laminated, one 0.5 ounce copper foil on each of the upper and lower sides, followed by hot pressing at a temperature of 1 to 3 ° C / min to 220 ° C, at this temperature of 8 to 15 kg / cm ^ 2 Pressure hot pressing for 180 minutes, thereby obtaining a laminate, measuring its glass transition temperature (Tg), dielectric loss (Df), dielectric constant (Dk), flame retardancy (UL-94), tear strength, data As shown in Table 2.
比較例4 Comparative example 4
將磷腈難燃劑(SPB100/大塚製)取22重量份、雙酚A二氰酸酯(BA-23S/Lonza製)37重量份、苯乙烯馬來酸酐共聚物(SMA1000/Cray Valley製)18重量份、N-苯基酚酞型苯并惡嗪(N-40/晉一製)18重量份、雙(3-乙基-5-甲基-4-馬来醯亞胺基苯)甲烷(BMI-70/KI製)18重量份、聯苯芳烷基型環氧樹脂(NC-3000L/日本化藥製)9重量份、辛酸鋅0.003重量份、三苯基磷(TPP)0.03重量份，溶於丁酮80重量份中做成膠液，將膠液含浸塗布於2116玻璃纖維布上，並於175℃下乾燥2~15分鐘，藉此做出半固化狀態之半固化片，然後將四片半固化片層合，上下二側各一張0.5盎司銅箔，接著進行熱壓，條件為以1~3℃/分鐘升溫速度至220℃，在該溫度下以8~15公斤/平 方公分之壓力熱壓180分鐘，藉此獲得積層板，測量其玻璃轉移溫度(Tg)、介電損失(Df)、介電常數(Dk)、難燃性(UL-94)、撕裂強度，其數據如表二所示。 The phosphazene flame-retardant (SPB100 / Otsuka) taking 22 parts by weight, 37 parts by weight of a bisphenol A dicyanate (BA-23S / Lonza Ltd.), styrene-maleic anhydride copolymer (SMA1000 / Cray Valley Ltd.) 18 parts by weight of N -phenylphenolphthalein type benzoxazine ( N-40 / Jinyi) 18 parts by weight of bis(3-ethyl-5-methyl-4-maleimidophenyl)methane (BMI-70/KI) 18 parts by weight, biphenyl aralkyl type epoxy resin (manufactured by NC-3000L / manufactured by Nippon Kasei Co., Ltd.) 9 parts by weight, 0.003 parts by weight of zinc octoate, and triphenylphosphine ( TPP ) 0.03 by weight a solution, dissolved in 80 parts by weight of methyl ethyl ketone to make a glue, impregnating the glue on 2116 glass fiber cloth, and drying at 175 ° C for 2 to 15 minutes, thereby making a semi-cured prepreg, and then Four prepregs are laminated, one 0.5 ounce copper foil on each of the upper and lower sides, followed by hot pressing at a temperature of 1 to 3 ° C / min to 220 ° C, at this temperature of 8 to 15 kg / cm ^ 2 Pressure hot pressing for 180 minutes, thereby obtaining a laminate, measuring its glass transition temperature (Tg), dielectric loss (Df), dielectric constant (Dk), flame retardancy (UL-94), tear strength, data As shown in Table 2.
比較例5 Comparative Example 5
將難燃劑三(三溴苯基)三嗪(FR-245/ICL製)取25重量份、雙酚A二氰酸酯(BA-23S/Lonza製)37重量份、苯乙烯馬來酸酐共聚物(SMA1000/Cray Valley製)18重量份、N-苯基酚酞型苯并惡嗪(N-40/晉一製)18重量份、雙(3-乙基-5-甲基-4-馬来醯亞胺基苯)甲烷(BMI-70/KI製)18重量份、聯苯芳烷基型環氧樹脂(NC-3000L/日本化藥製)9重量份、辛酸鋅0.003重量份、三苯基磷(TPP)0.03重量份，溶於丁酮80重量份中做成膠液，將膠液含浸塗布於2116玻璃纖維布上，並於175℃下乾燥2~15分鐘，藉此做出半固化狀態之半固化片，然後將四片半固化片層合，上下二側各一張0.5盎司銅箔，接著進行熱壓，條件為以1~3℃/分鐘升溫速度至220℃，在該溫度下以8~15公斤/平方公分之壓力熱壓180分鐘，藉此獲得積層板，測量其玻璃轉移溫度(Tg)、介電損失(Df)、介電常數(Dk)、難燃性(UL-94)、撕裂強度，其數據如表二所示。 25 parts by weight of a flame retardant tris(tribromophenyl)triazine (manufactured by FR-245/ICL), bisphenol A dicyanate (manufactured by BA-23S / Lonza ), 37 parts by weight, styrene maleic anhydride Copolymer ( manufactured by SMA1000 / Cray Valley ) 18 parts by weight, N -phenylphenolphthalein type benzoxazine (N-40/Jinyi) 18 parts by weight, bis(3-ethyl-5-methyl-4- 18 parts by weight of a p-phenylene aralkyl type epoxy resin (manufactured by NC-3000L / manufactured by Nippon Kasei Co., Ltd.), 9 parts by weight, and 0.003 parts by weight of zinc octoate, 0.03 parts by weight of triphenylphosphine ( TPP ), dissolved in 80 parts by weight of methyl ethyl ketone to make a glue, impregnating the glue on 2116 glass fiber cloth, and drying at 175 ° C for 2 to 15 minutes, thereby doing A semi-cured prepreg is prepared, and then four prepregs are laminated, one 0.5 ounce copper foil on each of the upper and lower sides, followed by hot pressing under the condition of a temperature increase of 1 to 3 ° C / minute to 220 ° C, at this temperature The laminate was heat-pressed at a pressure of 8 to 15 kg/cm 2 for 180 minutes to measure the glass transition temperature (Tg), dielectric loss (Df), dielectric constant (Dk), and flame retardancy (UL- 94), tear strength, the data is shown in Table 2 Shows.
實施例21 Example 21
將含磷難燃劑PN-M/15重量份、PET/100重量份，放入內徑20mm之雙螺旋擠出機中，於250℃混合並經一衝模擠壓後冷卻切成小粒，再於70℃下減壓乾燥，再將其射出成型為試片，測試其難燃性、熱變形溫度(HDT)、金屬腐蝕性，其數據如表三所示。 Pf-containing flame retardant PN-M / 15 parts by weight, PET / 100 parts by weight, placed in a double screw extruder with an inner diameter of 20 mm, mixed at 250 ° C and extruded through a die, cooled and cut into small pieces, and then It was dried under reduced pressure at 70 ° C, and then injection molded into a test piece to test its flame retardancy, heat distortion temperature (HDT), and metal corrosion. The data are shown in Table 3.
實施例22 Example 22
將含磷難燃劑PN-P/20重量份、PBT(聚酯樹脂)/100重量份，放入內徑20mm之雙螺旋擠出機中，於250℃混合並經一衝模擠壓後冷卻切成小粒，再於70 ℃下減壓乾燥，再將其射出成型為試片，測試其難燃性、熱變形溫度(HDT)、金屬腐蝕性，其數據如表三所示。 The phosphorus-containing flame retardant PN-P / 20 parts by weight, PBT (polyester resin) / 100 parts by weight, placed in a double screw extruder with an inner diameter of 20 mm, mixed at 250 ° C and cooled by a die extrusion The pellets were cut into small pellets, dried at 70 ° C under reduced pressure, and then fired into test pieces to test their flame retardancy, heat distortion temperature (HDT), and metal corrosion. The data are shown in Table 3.
實施例23 Example 23
將含磷難燃劑PN-1P/20重量份、PBT(聚酯樹脂)/100重量份，放入內徑20mm之雙螺旋擠出機中，於250℃混合並經一衝模擠壓後冷卻切成小粒，再於70℃下減壓乾燥，再將其射出成型為試片，測試其難燃性、熱變形溫度(HDT)、金屬腐蝕性，其數據如表三所示。 The phosphorus-containing flame retardant PN-1P / 20 parts by weight, PBT (polyester resin) / 100 parts by weight, placed in a double screw extruder with an inner diameter of 20 mm, mixed at 250 ° C and cooled by a die extrusion The pellets were cut into small pellets, dried at 70 ° C under reduced pressure, and then fired into test pieces to test their flame retardancy, heat distortion temperature (HDT), and metal corrosion. The data are shown in Table 3.
比較例6 Comparative Example 6
將磷系難燃劑FCX-210(帝人製)/15重量份、PBT(聚酯樹脂)/100重量份，放入內徑20mm之雙螺旋擠出機中，於250℃混合並經一衝模擠壓後冷卻切成小粒，再於70℃下減壓乾燥，再將其射出成型為試片，測試其難燃性、熱變形溫度(HDT)、金屬腐蝕性，其數據如表三所示。 Phosphorus-based flame retardant FCX-210 (manufactured by Teijin) / 15 parts by weight, PBT (polyester resin) / 100 parts by weight, placed in a double screw extruder with an inner diameter of 20 mm, mixed at 250 ° C and passed through a die After extrusion, it was cooled and cut into small pellets, dried at 70 ° C under reduced pressure, and then injection molded into test pieces to test its flame retardancy, heat distortion temperature (HDT), and metal corrosion. The data is shown in Table 3. .
比較例7 Comparative Example 7
將磷酸酯難燃劑PX-200(大八化學製)20重量份、PBT(聚酯樹脂)/100重量份，放入內徑20mm之雙螺旋擠出機中，於250℃混合並經一衝模擠壓後冷卻切成小粒，再於70℃下減壓乾燥，再將其射出成型為試片，測試其難燃性、熱變形溫度(HDT)、金屬腐蝕性，其數據如表三所示。 20 parts by weight of phosphate flame retardant PX-200 (made by Daiha Chemical Co., Ltd.), PBT (polyester resin) / 100 parts by weight, placed in a double screw extruder with an inner diameter of 20 mm, mixed at 250 ° C and passed through a After extrusion, the die was cooled and cut into small pellets, dried at 70 ° C under reduced pressure, and then injection molded into test pieces to test its flame retardancy, heat distortion temperature (HDT), and metal corrosion. The data are shown in Table 3. Show.
實施例24 Example 24
將含磷難燃劑PN-M/9重量份、PA66(聚醯胺樹脂)/100重量份，放入內徑20mm之雙螺旋擠出機中，於250℃混合並經一衝模擠壓後冷卻切成小粒，再於70℃下減壓乾燥，再將其射出成型為試片，測試其難燃性、熱變形溫度(HDT)、金屬腐蝕性，其數據如表三所示。 The phosphorus-containing flame retardant PN-M / 9 parts by weight, PA66 (polyamide resin) / 100 parts by weight, placed in a double screw extruder with an inner diameter of 20 mm, mixed at 250 ° C and pressed through a die After cooling, it was cut into small particles, dried at 70 ° C under reduced pressure, and then injection molded into test pieces to test its flame retardancy, heat distortion temperature (HDT), and metal corrosion. The data are shown in Table 3.
實施例25 Example 25
將含磷難燃劑PN-P/9重量份、PA66(聚醯胺樹脂)/100重量份，放入內徑20mm之雙螺旋擠出機中，於250℃混合並經一衝模擠壓後冷卻切成小粒，再於70℃下減壓乾燥，再將其射出成型為試片，測試其難燃性、熱變形溫度(HDT)、金屬腐蝕性，其數據如表三所示。 The phosphorus-containing flame retardant PN-P/9 parts by weight, PA66 (polyamide resin) / 100 parts by weight, placed in a double screw extruder with an inner diameter of 20 mm, mixed at 250 ° C and pressed through a die After cooling, it was cut into small particles, dried at 70 ° C under reduced pressure, and then injection molded into test pieces to test its flame retardancy, heat distortion temperature (HDT), and metal corrosion. The data are shown in Table 3.
實施例26 Example 26
將含磷難燃劑PT-2P/9重量份、PA66(聚醯胺樹脂)/100重量份，放入內徑20mm之雙螺旋擠出機中，於250℃混合並經一衝模擠壓後冷卻切成小粒，再於70℃下減壓乾燥，再將其射出成型為試片，測試其難燃性、熱變形溫度(HDT)、金屬腐蝕性，其數據如表三所示。 The phosphorus-containing flame retardant PT-2P/9 parts by weight, PA66 (polyamide resin) / 100 parts by weight, placed in a double screw extruder with an inner diameter of 20 mm, mixed at 250 ° C and pressed through a die After cooling, it was cut into small particles, dried at 70 ° C under reduced pressure, and then injection molded into test pieces to test its flame retardancy, heat distortion temperature (HDT), and metal corrosion. The data are shown in Table 3.
比較例8 Comparative Example 8
將磷系難燃劑FCX-210(帝人製)/9重量份、PA66(聚醯胺樹脂)/100重量份，放入內徑20mm之雙螺旋擠出機中，於250℃混合並經一衝模擠壓後冷卻切成小粒，再於70℃下減壓乾燥，再將其射出成型為試片，測試其難燃性、熱變形溫度(HDT)、金屬腐蝕性，其數據如表三所示。 Phosphorus flame retardant FCX-210 (manufactured by Teijin) / 9 parts by weight, PA66 (polyamide resin) / 100 parts by weight, placed in a double screw extruder with an inner diameter of 20 mm, mixed at 250 ° C and passed through a After extrusion, the die was cooled and cut into small pellets, dried at 70 ° C under reduced pressure, and then injection molded into test pieces to test its flame retardancy, heat distortion temperature (HDT), and metal corrosion. The data are shown in Table 3. Show.
比較例9 Comparative Example 9
將磷酸酯難燃劑PX-200(大八化學製)/9重量份、PA66(聚醯胺樹脂)/100重量份，放入內徑20mm之雙螺旋擠出機中，於250℃混合並經一衝模擠壓後冷卻切成小粒，再於70℃下減壓乾燥，再將其射出成型為試片，測試其難燃性、熱變形溫度(HDT)、金屬腐蝕性，其數據如表三所示。 Phosphate flame retardant PX-200 (made by Daiha Chemical) / 9 parts by weight, PA66 (polyamide resin) / 100 parts by weight, placed in a double screw extruder with an inner diameter of 20 mm, mixed at 250 ° C and After being squeezed by a die, it is cooled and cut into small particles, and then dried under reduced pressure at 70 ° C, and then injection molded into test pieces to test its flame retardancy, heat distortion temperature (HDT), and metal corrosion. Three are shown.
玻璃轉移溫度(Tg)：將積層板去除銅箔後以，TA公司製TMA測定。 Glass transition temperature (Tg): After removing the copper foil from the laminate, it was measured by TMA manufactured by TA.
介電常數(Dk)：將積層板去除銅箔後，以Agilent公司製LCR Meter在1GHz頻率下測定。 Dielectric constant (Dk): After removing the copper foil from the laminate, it was measured at a frequency of 1 GHz using an LCR Meter manufactured by Agilent.
介電損失(Df)：將積層板去除銅箔後，以Agilent公司製共振腔/網路分析儀在1GHz頻率下測定。 Dielectric loss (Df): After removing the copper foil from the laminate, it was measured at a frequency of 1 GHz using a cavity/network analyzer manufactured by Agilent.
難燃性UL-94：依UL-94標準，使用垂直燃燒法測定阻燃性，試片大小為長127mm，寬12.5mm，厚0.8mm。 Flame-retardant UL-94: The flame retardancy was measured by the vertical burning method according to the UL-94 standard. The test piece was 127 mm long, 12.5 mm wide, and 0.8 mm thick.
氧極限指數(LOI)：依ASTM D2863-77標準測試，表示物質燃燒的難易程度，其值愈高表示愈難燃，LOI在27以上代表難燃。 Oxygen Limit Index (LOI): Tested according to ASTM D2863-77, indicating the difficulty of burning a substance. The higher the value, the more difficult it is to burn. The LOI above 27 indicates that it is difficult to burn.
撕裂強度：銅箔層對積層板之附著力，以1/8英吋寬之銅箔自板面上垂直撕起所需之力的大小。 Tear strength: The adhesion of the copper foil layer to the laminate, the force required to tear the copper foil vertically from the panel surface by 1/8 inch wide.
熱膨脹係數(α1)：以TA公司製TMA測定，玻璃轉移溫度前之熱膨脹係數。 Thermal expansion coefficient ( α 1): The coefficient of thermal expansion before the glass transition temperature measured by TMA manufactured by TA Corporation.
模量：以TA公司製DMA測定。 Modulus: DMA measurement by TA company.
熱變形溫度(HDT)：依JIS6810標準測定，試片大小為長127mm，寬12.7mm，厚3.2mm。 Heat distortion temperature (HDT): measured according to JIS6810 standard, the test piece size is 127mm long, 12.7mm wide and 3.2mm thick.
金屬腐蝕性：以2g樹脂粒試樣，置於SKD-11潔淨鋼板上，覆蓋上倒置之培養皿，以280℃烘烤1小時，後觀察金屬表面腐蝕性，無腐蝕以O表示，輕微腐蝕以△表示，明顯腐蝕以X表示。 Corrosion of metal: 2g resin pellet sample, placed on SKD-11 clean steel plate, covered with inverted petri dish, baked at 280 °C for 1 hour, after observing the corrosion of metal surface, no corrosion is indicated by O, slightly corroded Expressed by Δ, the apparent corrosion is indicated by X.
FCX-210為：
PX-200為：
SPB100為：
FR-245為：
由表一之實施例8~12與比較例2可知，含磷難燃劑與聚苯醚/TMBPV之樹脂混合物固化後之難燃性、玻璃轉移溫度、Dk、Df、熱膨脹性(α 1)、模量表現都優於SPB-100；實施例13中發現使用PN-3A含磷難燃劑與TMBPV固化可以達成前所未有之超低熱膨脹性(α 1)；實施例14與比較例1可知，含磷難燃劑與聚苯醚/TMBPV之樹脂混合物固化後之難燃性、玻璃轉移溫度、Dk、Df、熱膨脹性(α 1)、模量表現都優於溴系難燃劑FR-245。 From Examples 8 to 12 and Comparative Example 2 of Table 1, it is known that the flame retardancy, glass transition temperature, Dk, Df, and thermal expansion ( α 1) of the resin mixture containing the phosphorus-containing flame retardant and the polyphenylene ether/TMBPV are cured. The modulus performance is better than SPB-100; in Example 13, it is found that the use of PN-3A phosphorus-containing flame retardant and TMBPV curing can achieve unprecedented ultra-low thermal expansion ( α 1); Example 14 and Comparative Example 1 show that The flame retardancy, glass transition temperature, Dk, Df, thermal expansion ( α 1) and modulus of the mixture of phosphorus-containing flame retardant and polyphenylene ether/TMBPV are better than those of bromine-based flame retardant FR-245. .
由表二之實施例15~17與比較例4可知，含磷難燃劑與氰酸酯/苯乙烯馬來酸酐共聚物/雙馬來醯亞胺/苯并惡嗪/環氧樹脂之樹脂混合物固化後之難燃性、玻璃轉移溫度、Dk、Df、撕裂強度表現都優於SPB-100；實施例15~19與比較例5可知，含磷難燃劑與氰酸酯/苯乙烯馬來酸乾共聚物/雙馬來醯亞胺/苯并惡嗪/環氧樹脂之樹脂混合物固化後之Dk、Df表現都優於溴系難燃劑FR-245；實施例20與比較例3可知，含磷難燃劑與氰酸酯/苯乙烯馬來酸乾共聚物/雙馬來醯亞胺/苯并惡嗪/環氧樹脂之樹脂混合物固化後之玻璃轉移溫度、Dk表現都優於SPB-100。 From Examples 15 to 17 and Comparative Example 4 of Table 2, the phosphorus-containing flame retardant and the cyanate/styrene maleic anhydride copolymer/bismaleimide/benzoxazine/epoxy resin were known. The flame retardancy, glass transition temperature, Dk, Df, and tear strength of the mixture after curing were better than SPB-100; Examples 15-19 and Comparative Example 5 showed that the phosphorus-containing flame retardant and cyanate/styrene Dk, Df after curing of maleic acid dry copolymer / bismaleimide / benzoxazine / epoxy resin mixture is better than bromine flame retardant FR-245; Example 20 and comparative examples 3 It can be seen that the glass transition temperature and Dk performance of the phosphorus-containing flame retardant and the cyanate/styrene maleic acid dry copolymer/bismaleimide/benzoxazine/epoxy resin mixture are cured. Better than SPB-100.
由表三之實施例21與比較例6可知，含磷難燃劑與PBT樹脂混合成型後之LOI、HDI、金屬腐蝕性表現都優於FCX-210；實施例22~23與比較例7可知，含磷難燃劑與PBT樹脂混合成型後之難燃性、LOI、HDI、金屬腐蝕性都優於PX-200；實施例24~26與比較例8~9可知，含磷難燃劑與PA66樹脂混合成型後之難燃性、LOI、HDI、金屬腐蝕性都優於PX-200、FCX-210。 It can be seen from Example 21 and Comparative Example 6 in Table 3 that the LOI, HDI, and metal corrosive properties of the phosphorus-containing flame retardant and the PBT resin are better than that of the FCX-210; the examples 22 to 23 and the comparative example 7 show that The flame retardancy, LOI, HDI and metal corrosivity of the phosphorus-containing flame retardant and PBT resin are better than PX-200; in Examples 24-26 and Comparative Examples 8-9, the phosphorus-containing flame retardant and PA66 resin is better than PX-200 and FCX-210 in flame retardancy, LOI, HDI and metal corrosion after mixing.
由表四可知由實施例1~7合成之含磷難燃劑，其氮含量高於傳統磷系難燃劑PX-200、FCX-210，因磷氮共乘效應強化含磷難燃劑之阻燃性，有助於降低磷之使用量，提供更友善環境之難燃劑。 It can be seen from Table 4 that the phosphorus-containing flame retardant synthesized from Examples 1 to 7 has higher nitrogen content than the conventional phosphorus-based flame retardants PX-200 and FCX-210, and strengthens the phosphorus-containing flame retardant due to the phosphorus-nitrogen synergistic effect. Flame retardant, which helps reduce the amount of phosphorus used and provides a more environmentally friendly flame retardant.
本發明提供一種含磷難燃劑係用於熱塑性樹脂、熱固性樹脂；一種反應型難燃劑組成物之用途，其係用於製造積層板、預浸漬片、半固化片、半導體構裝材、高頻基板等；一種環氧樹脂組成物之用途，其係於製造黏合片、純膠膜、覆蓋膜、軟硬結合板、防焊油墨、高頻軟性基板等。一種熱塑性樹脂組成物具有優秀之特性；因此本發明之磷系難燃劑可以解決先前技術存在的問題，也可以符合產業殷切期待與需求。 The present invention provides a phosphorus-containing flame retardant for use in a thermoplastic resin, a thermosetting resin, and a reactive flame retardant composition for producing a laminate, a prepreg, a prepreg, a semiconductor component, and a high frequency. A substrate or the like; the use of an epoxy resin composition for producing an adhesive sheet, a pure adhesive film, a cover film, a soft and hard bonding plate, a solder resist ink, a high frequency flexible substrate, and the like. A thermoplastic resin composition has excellent characteristics; therefore, the phosphorus-based flame retardant of the present invention can solve the problems of the prior art, and can also meet the industry's earnest expectations and needs.
本發明已經配合上述具體實施例、比較例描述，熟悉本項技藝人士將可基於以上描述作出多種變化，不因此而限制本發明之申請專利範圍。 The present invention has been described in connection with the foregoing specific embodiments and comparative examples, and those skilled in the art can make various changes based on the above description, and do not limit the scope of the patent application of the present invention.
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