TWI460199B - Flame retardant phosphor-containing epoxy resin composition and cured article thereof - Google Patents
Flame retardant phosphor-containing epoxy resin composition and cured article thereof Download PDFInfo
- Publication number
- TWI460199B TWI460199B TW099107407A TW99107407A TWI460199B TW I460199 B TWI460199 B TW I460199B TW 099107407 A TW099107407 A TW 099107407A TW 99107407 A TW99107407 A TW 99107407A TW I460199 B TWI460199 B TW I460199B
- Authority
- TW
- Taiwan
- Prior art keywords
- epoxy resin
- phosphorus
- weight
- containing epoxy
- flame
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
- H01L23/293—Organic, e.g. plastic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/30—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen
- C08G59/304—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen containing phosphorus
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
- C08G59/4014—Nitrogen containing compounds
- C08G59/4021—Ureas; Thioureas; Guanidines; Dicyandiamides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K21/00—Fireproofing materials
- C09K21/14—Macromolecular materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/0001—Technical content checked by a classifier
- H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/032—Organic insulating material consisting of one material
- H05K1/0326—Organic insulating material consisting of one material containing O
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Materials Engineering (AREA)
- Epoxy Resins (AREA)
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
- Reinforced Plastic Materials (AREA)
- Fireproofing Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Adhesive Tapes (AREA)
Description
本發明係關於要求難燃性之環氧樹脂組成物的發明,係有用於作為電子電路基板所用之覆銅積層板製造用之樹脂組成物、或電子零件所用之密封材、成形材、鑄模材、接著劑、電氣絕緣塗料等,尤其關於作為覆銅積層板製造用之樹脂組成物時不僅具有難燃效果,且亦可提供密著性、耐熱性及耐濕性優異之積層板的難燃性含磷環氧樹脂組成物。The present invention relates to a resin composition for producing a flame-retardant epoxy resin composition, a resin composition for producing a copper-clad laminate used for an electronic circuit board, or a sealing material, a molding material, and a mold material for use in an electronic component. In the case of a resin composition for the production of a copper clad laminate, it is not only a flame retardant effect, but also a flame retardant laminate which is excellent in adhesion, heat resistance and moisture resistance. A phosphorus-containing epoxy resin composition.
實際利用環氧樹脂之型態有液狀至固形狀、溶解於溶劑之清漆(varnish)狀等。液狀類型係廣泛利用於鑄模材料和接著劑用途等,固形類型係利用於密封材和粉體塗料等。此外,清漆類型係利用於含浸在玻璃基材和碳纖維等而使用之纖維補強塑膠材料和溶劑型塗料。尤其因其優異之密著性、電氣特性(絕緣性)而廣泛使用於電氣電子材料零件。The type of epoxy resin actually used has a liquid to solid shape, a varnish dissolved in a solvent, and the like. The liquid type is widely used for molding materials and adhesives, and the solid type is used for sealing materials and powder coatings. In addition, the varnish type is used for fiber-reinforced plastic materials and solvent-based coatings which are impregnated on glass substrates and carbon fibers. In particular, it is widely used in electrical and electronic materials because of its excellent adhesion and electrical properties (insulation).
由於此等電氣電子材料零件係如玻璃環氧積層板或IC密封材所代表般要求高之難燃性(UL:V-0),故通常是使用經鹵化之環氧樹脂。例如,在玻璃環氧積層板中,經難燃化之FR-4等級者一般係以經溴取代之環氧樹脂作為主原料成分,於其中混合各種環氧樹脂而成之環氧樹脂並調配環氧樹脂用硬化劑而使用。Halogenated epoxy resins are commonly used because such electrical and electronic material parts are highly flame-retardant (UL: V-0) as represented by glass epoxy laminates or IC sealants. For example, in a glass epoxy laminate, the flame-retarded FR-4 grade is generally made up of a bromine-substituted epoxy resin as a main raw material component, in which an epoxy resin of various epoxy resins is mixed and blended. The epoxy resin is used as a hardener.
然而,使用此等經鹵化之環氧樹脂,不但成為近年來以戴奧辛為代表之環境問題之一大要因,且在高溫環境下會因鹵素解離而對電性之長期可靠性造成不良影響,因此,強烈要求減少鹵素之使用量、或是希望研發出使用可替代鹵素之其他化合物的難燃劑或其他難燃處方。However, the use of such halogenated epoxy resins is not only one of the major causes of environmental problems represented by Dioxin in recent years, but also has a negative effect on the long-term reliability of electrical properties due to halogen dissociation in a high temperature environment. There is a strong demand to reduce the amount of halogen used, or to develop flame retardants or other flame retardant prescriptions that use other compounds that can replace halogens.
以往至今,就替代此等鹵素之難燃處方的技術而言,已檢討各種例如使用磷酸酯系化合物等作為添加系難燃劑之技術,但此等技術係皆會導致積層板之耐熱性和耐水性等之降低、難燃劑會隨著時間而溢出(bleedout)之問題、尤其是電積層板用途之密著性會急劇降低。於是,檢討各種使環氧樹脂與特定之磷化合物反應而提升積層板之性能的技術(專利文獻1至4)。然而,此等技術就耐熱性而言皆以FR-4等級為極限,難以提升至其以上之耐熱性。一般而言,若欲提升耐熱性,係採取使用甲酚酚醛(cresol novolac)環氧樹脂等多官能環氧樹脂之方法,但會招致難燃性降低和接著性降低。最近,為了對應無鉛焊接,為更加提高高溫時之可靠性而要求硬化物之吸水率下降和低彈性化等。在專利文獻5中雖藉由使具有萘芳烷基結構之環氧樹脂與特定之磷化合物反應而同時達成難燃性與耐熱性之提升,但仍招致接著性降低。如此,難以一邊藉由含磷環氧樹脂組成物來保持難燃性,一邊提升耐熱性並同時確保接著性。In the past, in order to replace the flame retardant formulation of such halogens, various techniques such as the use of a phosphate ester compound as an additive flame retardant have been reviewed, but these techniques all lead to heat resistance of the laminate. The decrease in water resistance and the like, the problem that the flame retardant will bleed out over time, and in particular, the adhesion of the use of the electric laminate will be drastically lowered. Then, various techniques for improving the performance of the laminated board by reacting an epoxy resin with a specific phosphorus compound are examined (Patent Documents 1 to 4). However, these techniques are based on the FR-4 rating in terms of heat resistance, and it is difficult to increase the heat resistance to the above. In general, in order to improve heat resistance, a method of using a polyfunctional epoxy resin such as cresol novolac epoxy resin is employed, but a decrease in flame retardancy and a decrease in adhesion are caused. Recently, in order to cope with lead-free soldering, in order to further improve the reliability at high temperatures, the water absorption rate of the cured product is lowered and the elasticity is lowered. In Patent Document 5, an epoxy resin having a naphthene aralkyl structure is reacted with a specific phosphorus compound to simultaneously achieve an improvement in flame retardancy and heat resistance, but the adhesion is lowered. Thus, it is difficult to maintain heat resistance while ensuring adhesion by maintaining the flame retardancy by the phosphorus-containing epoxy resin composition.
[專利文獻1]日本特開2001-288247號公報[Patent Document 1] Japanese Patent Laid-Open Publication No. 2001-288247
[專利文獻2]日本特開2002-249540號公報[Patent Document 2] Japanese Patent Laid-Open Publication No. 2002-249540
[專利文獻3]日本特開2001-123049號公報[Patent Document 3] Japanese Patent Laid-Open Publication No. 2001-123049
[專利文獻4]日本專利第3642403號公報[Patent Document 4] Japanese Patent No. 3642403
[專利文獻5]日本特開2008-214513號公報[Patent Document 5] Japanese Patent Laid-Open Publication No. 2008-214513
[專利文獻6]日本特開2008-150495號公報[Patent Document 6] Japanese Patent Laid-Open Publication No. 2008-150495
[專利文獻7]日本特開昭61-268691號公報[Patent Document 7] JP-A-61-268691
本發明欲解決之課題係提供一種耐熱性、耐濕性、難燃性優異之難燃性含磷環氧樹脂組成物,其係在不使用鹵素即賦予難燃性之含磷環氧樹脂中,因提高高溫時之可靠性,而不會招致接著性降低者。The problem to be solved by the present invention is to provide a flame-retardant phosphorus-containing epoxy resin composition excellent in heat resistance, moisture resistance, and flame retardancy, which is in a phosphorus-containing epoxy resin which imparts flame retardancy without using a halogen. , because the reliability at high temperatures is improved, and the decrease in adhesion is not caused.
亦即,本發明之要旨係一種難燃性含磷環氧樹脂組成物,其係含有含磷環氧樹脂(X)與硬化劑(Y)的難燃性含磷環氧樹脂組成物,其特徵為:前述含磷環氧樹脂(X)係藉由使含有50重量%至100重量%之骨架內具有硫原子之2官能環氧樹脂類的環氧樹脂類(a)、與相對於化學式(1)1莫耳以化學式(2)0.06莫耳以下之比率混合的磷化合物類(b)進行反應而得者,並且,該難燃性含磷環氧樹脂組成物中,相對於全部環氧樹脂成分,含磷率為0.5重量%至未達2.0重量%,再者,含硫率為2重量%至9重量%以下。That is, the gist of the present invention is a flame-retardant phosphorus-containing epoxy resin composition comprising a flame-retardant phosphorus-containing epoxy resin composition containing a phosphorus-containing epoxy resin (X) and a hardener (Y), The epoxy-containing epoxy resin (X) is an epoxy resin (a) having a bifunctional epoxy resin having a sulfur atom in a skeleton of 50% by weight to 100% by weight, and a chemical formula (1) The reaction of the phosphorus compound (b) in which the molar amount is mixed at a ratio of 0.06 mol or less in the chemical formula (2), and the flame-retardant phosphorus-containing epoxy resin composition is relative to the entire ring. The oxygen resin component has a phosphorus content of 0.5% by weight to less than 2.0% by weight, and further, the sulfur content is 2% by weight to 9% by weight or less.
若使用本發明之難燃性含磷環氧樹脂組成物,則難燃性、接著力、耐熱性皆優異。並且,可於含磷率為0.5重量%至未達2.0重量%獲得為難燃性且高耐熱性及尤其是與金屬之接著性優異的硬化物,藉由含有骨架內具有硫原子之2官能環氧樹脂作為必須成分,即更加提升該效果。When the flame retardant phosphorus-containing epoxy resin composition of the present invention is used, it is excellent in flame retardancy, adhesion, and heat resistance. Further, a cured product excellent in flame retardancy and high heat resistance and particularly excellent in adhesion to metals can be obtained at a phosphorus-containing ratio of 0.5% by weight to less than 2.0% by weight, by containing a 2-functional ring having a sulfur atom in the skeleton. Oxygen resin is an essential component, which further enhances the effect.
以下,針對本發明之實施型態而詳細說明。Hereinafter, the embodiment of the present invention will be described in detail.
本發明所使用之環氧樹脂類(a),係含有50重量%至100重量%之骨架內具有硫原子之2官能環氧樹脂類作為必須成分。此係由於若未達50重量%,則不僅未提升耐熱性,且亦招致難燃性降低,而無法獲得可使用於高耐熱用途的組成物之故。The epoxy resin (a) used in the present invention contains, as an essential component, 50% by weight to 100% by weight of a bifunctional epoxy resin having a sulfur atom in the skeleton. If it is less than 50% by weight, the heat resistance is not improved, and the flame retardancy is also lowered, and the composition which can be used for high heat resistance cannot be obtained.
骨架內具有硫原子之2官能環氧樹脂類只要是含有硫原子之2官能環氧樹脂即可,可為任何結構,但尤其是以含有硫原子之雙酚型環氧樹脂為特佳。具體上可列舉如EPOTOHTO TX-0908(東都化成股份公司製,取代雙酚S型環氧樹脂)等雙酚S型環氧樹脂或EPOTOHTO YSLV-120TE(東都化成股份公司製,二甲基二羥基二(第三丁基)二苯基硫醚型環氧樹脂)或EPOTOHTO YSLV-50TE(東都化成股份公司製,雙(二苯基硫醚)型環氧樹脂等二苯基硫醚(diphenyl sulfide)型環氧樹脂等,但不限定於此等,又亦可併用2種以上。The bifunctional epoxy resin having a sulfur atom in the skeleton may be any structure as long as it is a bifunctional epoxy resin containing a sulfur atom, but particularly preferably a bisphenol epoxy resin containing a sulfur atom. Specifically, bisphenol S type epoxy resin such as EPOTOHTO TX-0908 (made by Dongdu Chemical Co., Ltd., replacing bisphenol S type epoxy resin) or EPOTOHTO YSLV-120TE (made by Dongdu Chemical Co., Ltd., dimethyl dihydroxyl) Diphenyl sulfide (diphenyl sulfide) or EPOTOHTO YSLV-50TE (diphenyl sulfide, bis(diphenyl sulfide) epoxy resin (diphenyl sulfide) The epoxy resin or the like is not limited thereto, and two or more kinds thereof may be used in combination.
此外,雖亦可併用骨架內不具有硫原子之2官能環氧樹脂類作為2官能環氧樹脂類,但骨架內具有硫原子之2官能環氧樹脂類必須為環氧樹脂類(a)中之50重量%以上。Further, although a bifunctional epoxy resin having no sulfur atom in the skeleton may be used in combination as the bifunctional epoxy resin, the bifunctional epoxy resin having a sulfur atom in the skeleton must be an epoxy resin (a). 50% by weight or more.
為了提升接著性,前述骨架內具有硫原子之2官能環氧樹脂、以及視需要而併用之骨架內不具有硫原子之2官能環氧樹脂係必要的。其量係環氧樹脂類(a)中之50重量%以上,較佳為65重量%以上,更佳為80重量%以上。此係由於若未達50重量%,則接著性會急劇下降,而只能獲得缺乏實用性的組成物。In order to improve the adhesion, a bifunctional epoxy resin having a sulfur atom in the skeleton and a bifunctional epoxy resin having no sulfur atom in the skeleton which is used in combination as needed are necessary. The amount is 50% by weight or more, preferably 65% by weight or more, and more preferably 80% by weight or more based on the epoxy resin (a). In this case, if it is less than 50% by weight, the adhesion is drastically lowered, and only a composition lacking in practicality can be obtained.
可與骨架內具有硫原子之2官能環氧樹脂一起使用的骨架內不具有硫原子之2官能環氧樹脂,可列舉如氫醌(hydroquinone)型環氧樹脂、雙酚型環氧樹脂、聯酚(biphenol)型環氧樹脂、萘二醇型環氧樹脂等。具體上可列舉如EPOTOHTO YDC-1312、EPOTOHTO ZX-1027(東都化成股份公司製,氫醌型環氧樹脂)、EPOTOHTO ZX-1251(東都化成股份公司製,聯酚型環氧樹脂)、EPOTOHTO YD-127、EPOTOHTO YD-128、EPOTOHTO YD-8125、EPOTOHTO YD-825GS、EPOTOHTO YD-011、EPOTOHTO YD-900、EPOTOHTO YD-901(東都化成股份公司製,雙酚A型環氧樹脂)、EPOTOHTO YDF-170、EPOTOHTO YDF-8170、EPOTOHTO YDF-870GS、EPOTOHTO YDF-2001(東都化成股份公司製,雙酚P型環氧樹脂)、EPOTOHTO ZX-1201(東都化成股份公司製,雙酚茀型環氧樹脂)、EPOTOHTO ZX-1355、EPOTOHTO ZX-1711(東都化成股份公司製,萘二醇型環氧樹脂)等,但不限定於此等,又亦可併用2種以上。此外,從難燃性之觀點來看,以不具有烷基取代基之環氧樹脂為佳,此等中以萘二醇型環氧樹脂或聯苯型環氧樹脂或雙酚F型環氧樹脂為更佳。A bifunctional epoxy resin having no sulfur atom in the skeleton which can be used together with a bifunctional epoxy resin having a sulfur atom in the skeleton, and examples thereof include a hydroquinone type epoxy resin, a bisphenol type epoxy resin, and a combination. A phenolic epoxy resin or a naphthalenediol epoxy resin. Specifically, for example, EPOTOHTO YDC-1312, EPOTOHTO ZX-1027 (made by Dongdu Chemical Co., Ltd., hydroquinone type epoxy resin), EPOTOHTO ZX-1251 (made by Dongdu Chemical Co., Ltd., biphenol type epoxy resin), EPOTOHTO YD -127,EPOTOHTO YD-128,EPOTOHTO YD-8125,EPOTOHTO YD-825GS,EPOTOHTO YD-011,EPOTOHTO YD-900,EPOTOHTO YD-901 (made by Dongdu Chemical Co., Ltd., bisphenol A epoxy resin), EPOTOHTO YDF -170,EPOTOHTO YDF-8170,EPOTOHTO YDF-870GS,EPOTOHTO YDF-2001 (made by Dongdu Chemical Co., Ltd., bisphenol P type epoxy resin), EPOTOHTO ZX-1201 (made by Dongdu Chemical Co., Ltd., bisphenol oxime epoxy) Resin), EPOTOHTO ZX-1355, EPOTOHTO ZX-1711 (manufactured by Tosho Kasei Co., Ltd., naphthalene glycol type epoxy resin), etc., but not limited thereto, or two or more types may be used in combination. Further, from the viewpoint of flame retardancy, it is preferred to use an epoxy resin having no alkyl substituent, such as a naphthalenediol type epoxy resin or a biphenyl type epoxy resin or a bisphenol F type epoxy. The resin is better.
若使用50重量%以上的骨架內具有硫原子之2官能環氧樹脂,即可充分滿足耐熱性和接著性,但為了圖謀更進一步提升難燃性和耐熱性和接著性,亦可在未達50重量%之範圍含有骨架內具有硫原子之2官能環氧樹脂以外的環氧樹脂類。然而,從難燃性之觀點來看,脂肪族系環氧樹脂為不佳,雖然從提升接著性之觀點來看是以2官能環氧樹脂類為佳,但從提升耐熱性之觀點來看,以平均官能基數目為2.1以上之多官能環氧樹脂類為佳。When 50% by weight or more of a bifunctional epoxy resin having a sulfur atom in the skeleton is used, heat resistance and adhesion can be sufficiently satisfied, but in order to further improve flame retardancy, heat resistance and adhesion, it may not be reached. The range of 50% by weight includes an epoxy resin other than a bifunctional epoxy resin having a sulfur atom in the skeleton. However, from the viewpoint of flame retardancy, the aliphatic epoxy resin is not preferable, and it is preferable to use a bifunctional epoxy resin from the viewpoint of improving adhesion, but from the viewpoint of improving heat resistance A polyfunctional epoxy resin having an average number of functional groups of 2.1 or more is preferred.
平均官能基數目為2.1以上之多官能環氧樹脂類,可列舉如酚酚醛(phenol novolac)型環氧樹脂、甲酚酚醛型環氧樹脂、芳烷基型環氧樹脂等。具體例可列舉如EPOTOHTO YDPN-638(東都化成股份公司製,酚酚醛型環氧樹脂)、EPOTOHTO YDCN-701、EPOTOHTO YDCN-702、EPOTOHTO YDCN-703、EPOTOHTO YDCN-704(東都化成股份公司製,鄰甲酚酚醛型環氧樹脂)、EPOTOHTO ESN-175(東都化成股份公司製,β-萘醇芳烷基型環氧樹脂)、EPOTOHTO ESN-475V、EPOTOHTO ESN-485(東都化成股份公司製,α-萘醇芳烷基型環氧樹脂)、EPOTOHTO ESN-355、EPOTOHTO ESN-375(東都化成股份公司製,二萘醇芳烷基型環氧樹脂)、EPPN-501H、EPPN-502(日本化藥股份公司製,多官能環氧樹脂)、NC-3000(日本化藥股份公司製,聯苯芳烷基型環氧樹脂)等,但不限定於此等,又亦可併用2種以上。此外,從難燃性之觀點來看,以不具有烷基取代基之環氧樹脂為佳,此等中以酚酚醛型環氧樹脂或萘醇芳烷基型環氧樹脂為更佳。Examples of the polyfunctional epoxy resin having an average number of functional groups of 2.1 or more include a phenol novolac type epoxy resin, a cresol novolac type epoxy resin, and an aralkyl type epoxy resin. Specific examples include, for example, EPOTOHTO YDPN-638 (made by Dongdu Chemical Co., Ltd., phenol novolak type epoxy resin), EPOTOHTO YDCN-701, EPOTOHTO YDCN-702, EPOTOHTO YDCN-703, and EPOTOHTO YDCN-704 (made by Dongdu Chemical Co., Ltd.). O-cresol novolac type epoxy resin), EPOTOHTO ESN-175 (made by Dongdu Chemical Co., Ltd., β-naphthyl aralkyl type epoxy resin), EPOTOHTO ESN-475V, EPOTOHTO ESN-485 (made by Dongdu Chemical Co., Ltd.) Α-naphthyl aralkyl type epoxy resin), EPOTOHTO ESN-355, EPOTOHTO ESN-375 (made by Dongdu Chemical Co., Ltd., dinaphthyl aralkyl type epoxy resin), EPPN-501H, EPPN-502 (Japan Chemicals Co., Ltd., polyfunctional epoxy resin), NC-3000 (manufactured by Nippon Kayaku Co., Ltd., biphenyl aralkyl type epoxy resin), etc., but not limited thereto, or two or more types may be used in combination. . Further, from the viewpoint of flame retardancy, an epoxy resin having no alkyl substituent is preferred, and among these, a phenol novolak type epoxy resin or a naphthol aralkyl type epoxy resin is more preferable.
在專利文獻1中,雖然揭示由含有最多為45重量%之骨架內具有硫原子之2官能環氧樹脂的環氧樹脂所獲得的含磷環氧樹脂,但由於其為未達50重量%,而使耐熱性不充分。在專利文獻5中揭示由萘醇芳烷基型環氧樹脂所獲得的含磷環氧樹脂,雖然其耐熱性充分,但由於未使用骨架內具有硫原子之2官能環氧樹脂類,故其接著性不佳。In Patent Document 1, although a phosphorus-containing epoxy resin obtained from an epoxy resin containing up to 45% by weight of a bifunctional epoxy resin having a sulfur atom in a skeleton is disclosed, since it is less than 50% by weight, The heat resistance is not sufficient. Patent Document 5 discloses that a phosphorus-containing epoxy resin obtained from a naphthyl aralkyl type epoxy resin has sufficient heat resistance, but since a bifunctional epoxy resin having a sulfur atom in a skeleton is not used, Then the sex is not good.
本發明所用之磷化合物類(b)必須為相對於化學式(1)所示化合物1莫耳,以0.06莫耳以下之比率混合化學式(2)所示化合物的磷化合物類。The phosphorus compound (b) used in the present invention is required to be a phosphorus compound in which a compound represented by the chemical formula (2) is mixed at a ratio of 0.06 mol or less to the compound 1 of the formula (1).
化學式(1)所示化合物之代表例,係化學式(2)所示之化合物9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物(9,10-Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide)與1,4-萘醌反應而獲得的磷化合物。A representative example of the compound of the formula (1) is a compound of the formula (2), 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (9,10-Dihydro-9) -oxa-10-phosphaphenanthrene-10-oxide) A phosphorus compound obtained by reaction with 1,4-naphthoquinone.
就磷化合物類(b)而言,可將預先合成之化學式(1)所示化合物與化學式(2)所示化合物混合使用,亦可在與環氧樹脂類(a)反應前,相對於化學式(2)所示化合物1莫耳,以0.94莫耳至1.00莫耳之範圍使1,4-萘醌反應。當在與環氧樹脂類(a)反應前使化學式(2)所示化合物與1,4-萘醌反應時,相對於化學式(2)所示化合物1莫耳,以使用未達1.00莫耳之1,4-萘醌為佳。此時,化學式(2)所示化合物與1,4-萘醌之反應會依理論進行,而獲得化學式(1)所示化合物,所得之含磷環氧樹脂(X)中不會殘存原料之1,4-萘醌。相對於化學式(2)所示化合物1莫耳,若使用1.00莫耳以上之1,4-萘醌,則所得之含磷環氧樹脂(X)中會殘存原料之1,4-萘醌,而使硬化物之耐濕性惡化,故較不佳。In the case of the phosphorus compound (b), the compound represented by the chemical formula (1) synthesized in advance may be used in combination with the compound represented by the chemical formula (2), or may be used before the reaction with the epoxy resin (a), relative to the chemical formula. (2) The compound 1 shown is a molar reaction of 1,4-naphthoquinone in a range of from 0.94 mol to 1.00 mol. When the compound of the formula (2) is reacted with 1,4-naphthoquinone before the reaction with the epoxy resin (a), the compound of the formula (2) is 1 mol, and the use is less than 1.00 mol. The 1,4-naphthoquinone is preferred. At this time, the reaction of the compound of the formula (2) with 1,4-naphthoquinone is carried out according to the theory, and the compound of the formula (1) is obtained, and the obtained phosphorus-containing epoxy resin (X) does not remain in the raw material. 1,4-naphthoquinone. The 1,4-naphthoquinone which remains in the phosphorus-containing epoxy resin (X) obtained by using 1,4-naphthoquinone of 1.00 mol or more with respect to the compound 1 molar represented by the chemical formula (2), However, the moisture resistance of the cured product is deteriorated, which is not preferable.
當化學式(2)所示化合物超過0.06莫耳時,由於容易調整含磷率,故對於提升難燃性和降低黏度為有效果,但多發生1官能之化學式(2)所示化合物與環氧基之反應,降低環氧基數目,而導致硬化物之接著性降低和耐熱性降低和耐濕性降低,使高耐熱用途之電氣絕緣可靠性明顯下降。未使用化學式(2)所示化合物時,必須預先製造化學式(1)所示化合物。該化合物之製造需要許多步驟,生產性不佳,於工業上為不具利益。並且,在與環氧樹脂類(b)之反應中,最終之含磷環氧樹脂組成物中的含磷率若設為高值,則所得之含磷環氧樹脂之分子量增大,樹脂黏度會過度上升,而與玻璃布之含浸性明顯惡化,不僅在工業上成為不具利益,且所得之積層板之物性,尤其是焊接耐熱性惡化,彈性模數(elastic modulus)亦有變高之傾向,積層板容易變得又硬又脆而不佳。因此,相對於化學式(1)所示化合物1莫耳,化學式(2)所示化合物之莫耳比為0.06莫耳以下,較佳為0.01莫耳至0.05莫耳。When the compound represented by the chemical formula (2) exceeds 0.06 mol, since the phosphorus content is easily adjusted, it is effective for improving flame retardancy and lowering the viscosity, but a compound having a monofunctional chemical formula (2) and an epoxy are often generated. The reaction of the base lowers the number of epoxy groups, resulting in a decrease in the adhesion of the cured product, a decrease in heat resistance and a decrease in moisture resistance, and a significant decrease in electrical insulation reliability for high heat-resistant applications. When the compound represented by the chemical formula (2) is not used, the compound represented by the chemical formula (1) must be produced in advance. The manufacture of this compound requires many steps, is not productive, and is not of industrial interest. Further, in the reaction with the epoxy resin (b), if the phosphorus content in the final phosphorus-containing epoxy resin composition is set to a high value, the molecular weight of the resulting phosphorus-containing epoxy resin is increased, and the resin viscosity is increased. It will rise excessively, and the impregnation with the glass cloth will be significantly deteriorated. Not only will it be unprofitable in the industry, but the physical properties of the laminated sheets obtained, especially the weld heat resistance, and the elastic modulus tend to become higher. The laminate is easy to become hard and brittle. Therefore, the molar ratio of the compound represented by the chemical formula (2) to the compound of the formula (1) is 0.06 mol or less, preferably 0.01 mol to 0.05 mol.
專利文獻4中,雖暗示由雙酚S型環氧樹脂所獲得之含磷環氧樹脂,但並無揭示於實施例,亦未考慮到殘存之化學式(2)所示化合物。於其實施例中雖例示雙酚A或雙酚F,但相對於化學式(1)所示化合物1莫耳,係以化學式(2)所示化合物0.92莫耳進行反應,故化學式(2)所示化合物會殘存許多,因而使耐熱性不佳,在高耐熱用途之電氣絕緣可靠性上有問題。In Patent Document 4, a phosphorus-containing epoxy resin obtained from a bisphenol S-type epoxy resin is suggested, but it is not disclosed in the examples, and the compound represented by the chemical formula (2) remaining is not considered. In the examples, bisphenol A or bisphenol F is exemplified, but the compound 1 of the formula (1) is reacted with 0.92 mole of the compound represented by the formula (2), so the chemical formula (2) The compound is left to be present in a large amount, so that heat resistance is poor, and there is a problem in electrical insulation reliability for high heat-resistant use.
當本發明所用之環氧樹脂類(a)與磷化合物類(b)反應時,亦可使用磷化合物類(b)以外之2官能以上之酚化合物類。2官能以上之酚化合物類可列舉如雙酚A、雙酚S、雙酚F、萘二醇、聯酚、酚酚醛樹脂、甲酚酚醛樹脂、乙二醛四酚樹脂、雙酚A酚醛樹脂、酚芳烷基樹脂、萘醇(naphthol)芳烷基樹脂、聯酚芳烷基樹脂等。尤其是從難燃性之觀點來看,以不具有烷基取代基之酚化合物為佳,此等中尤以雙酚S或萘二醇或聯酚為特佳。使用2官能以上之酚化合物類之目的,係為了在使環氧樹脂類(a)與磷化合物類(b)反應時,調整含磷率或含硫率或軟化點或環氧當量,或是調整積層板之彈性模數。When the epoxy resin (a) used in the present invention is reacted with the phosphorus compound (b), a phenol compound having two or more functional groups other than the phosphorus compound (b) may be used. Examples of the phenolic compound having two or more functional groups include bisphenol A, bisphenol S, bisphenol F, naphthalenediol, biphenol, phenol novolac resin, cresol novolac resin, glyoxal tetraphenol resin, and bisphenol A phenol resin. , phenol aralkyl resin, naphthol aralkyl resin, biphenol aralkyl resin, and the like. In particular, from the viewpoint of flame retardancy, a phenol compound having no alkyl substituent is preferred, and among these, bisphenol S or naphthalenediol or biphenol is particularly preferred. The purpose of using a bifunctional or higher phenolic compound is to adjust the phosphorus content or sulfur content or softening point or epoxy equivalent when reacting the epoxy resin (a) with the phosphorus compound (b), or Adjust the elastic modulus of the laminate.
此外,本發明所用之環氧樹脂類(a)與磷化合物類(b)與視需要而使用之2官能以上之酚化合物類的反應可依公知方法進行,反應溫度可為100℃至200℃,更佳為在120℃至180℃於攪拌下進行。反應時間可進行環氧當量之測定而決定。環氧當量之測定可依據JIS K-7236之方法測定。由於環氧樹脂類(a)與磷化合物類(b)與酚化合物進行反應,而使環氧當量變大,可依據與理論環氧當量之比較而決定反應終點。Further, the reaction of the epoxy resin (a) and the phosphorus compound (b) used in the present invention with a difunctional or higher phenol compound used as needed may be carried out by a known method, and the reaction temperature may be from 100 ° C to 200 ° C. More preferably, it is carried out under stirring at 120 ° C to 180 ° C. The reaction time can be determined by measuring the epoxy equivalent. The measurement of the epoxy equivalent can be carried out in accordance with the method of JIS K-7236. Since the epoxy resin (a) and the phosphorus compound (b) react with the phenol compound to increase the epoxy equivalent, the reaction end point can be determined in accordance with the comparison with the theoretical epoxy equivalent.
又,反應速度慢時,可視需要而使用觸媒以改善生產性。具體而言,可使用苄基二甲基胺等三級胺類、氯化四甲基銨等四級銨鹽類、三苯基膦、三(2,6-二甲氧基苯基)膦等膦類、溴化乙基三苯基鏻等鏻鹽類、2-甲基咪唑、2-乙基-4-甲基咪唑等咪唑類等各種觸媒。Further, when the reaction rate is slow, a catalyst may be used as needed to improve productivity. Specifically, a tertiary amine such as benzyldimethylamine, a quaternary ammonium salt such as tetramethylammonium chloride, triphenylphosphine or tris(2,6-dimethoxyphenyl)phosphine can be used. Various catalysts such as phosphines, sulfonium salts such as ethyltriphenylphosphonium bromide, and imidazoles such as 2-methylimidazole and 2-ethyl-4-methylimidazole.
本發明之難燃性含磷環氧樹脂組成物中,相對於全部環氧樹脂成分之含磷率必須為0.5重量%至未達2.0重量%。若未達0.5重量%則無法賦予充分之難燃性。若為2.0重量%以上,則會因含磷環氧樹脂中之磷成分之影響,而使硬化物之耐濕性降低,並使高耐熱用途之可靠性明顯下降。In the flame-retardant phosphorus-containing epoxy resin composition of the present invention, the phosphorus content must be from 0.5% by weight to less than 2.0% by weight based on the total epoxy resin component. If it is less than 0.5% by weight, sufficient flame retardancy cannot be imparted. When it is 2.0% by weight or more, the moisture resistance of the cured product is lowered by the influence of the phosphorus component in the phosphorus-containing epoxy resin, and the reliability of the high heat-resistant use is remarkably lowered.
難燃性含磷環氧樹脂組成物中,由於將相對於全部環氧樹脂成分之含磷率調整為0.5重量%至未達2.0重量%的必要性,故相對於含磷環氧樹脂(X)100重量份,可調配不含磷之環氧樹脂0重量份至50重量份。若調配50重量份以上時,則必須提高含磷環氧樹脂(X)之含磷率以使難燃性不受損,在此情形下,難燃性含磷環氧樹脂組成物之耐熱性會大幅降低。從難燃性之觀點來看,不含磷之環氧樹脂係以脂肪族系環氧樹脂為不佳,從耐熱性之觀點來看,以平均官能基數目為2.1以上之多官能環氧樹脂類為佳,且以前述環氧樹脂類為佳。尤其是當使用平均官能基數目為2.1以上之多官能環氧樹脂類作為不含磷之環氧樹脂類時,若為50重量份以下,即可無損耐熱性、難燃性而獲得本發明之難燃性含磷環氧樹脂組成物。更佳係相對於含磷環氧樹脂(X)100重量份,不含磷之環氧樹脂為0重量份至25重量份。In the flame-retardant phosphorus-containing epoxy resin composition, since the phosphorus content of the entire epoxy resin component is adjusted to 0.5% by weight to less than 2.0% by weight, it is relative to the phosphorus-containing epoxy resin (X). 100 parts by weight, 0 parts by weight to 50 parts by weight of the epoxy resin containing no phosphorus. When 50 parts by weight or more is blended, the phosphorus content of the phosphorus-containing epoxy resin (X) must be increased so that the flame retardancy is not impaired, and in this case, the heat resistance of the flame-retardant phosphorus-containing epoxy resin composition Will be greatly reduced. From the viewpoint of flame retardancy, the epoxy resin containing no phosphorus is poor in aliphatic epoxy resin, and from the viewpoint of heat resistance, the polyfunctional epoxy resin having an average number of functional groups of 2.1 or more The class is preferred, and the above epoxy resins are preferred. In particular, when a polyfunctional epoxy resin having an average number of functional groups of 2.1 or more is used as the epoxy resin containing no phosphorus, if it is 50 parts by weight or less, the present invention can be obtained without impairing heat resistance and flame retardancy. A flame retardant phosphorus-containing epoxy resin composition. More preferably, the epoxy resin containing no phosphorus is from 0 part by weight to 25 parts by weight relative to 100 parts by weight of the phosphorus-containing epoxy resin (X).
本發明之含磷環氧樹脂(X)之含磷率只要是在0.5重量%至3.5重量%之範圍內即可,以0.8重量%至3.0重量%為佳,以1.2重量%至2.7重量%為更佳,以1.5重量%至2.3重量%為特佳。含磷率若未達0.5重量%,則會難以確保難燃性。若超過3.5重量%,則樹脂黏度會明顯變高而難以合成,且因樹脂之分子量增大,而對耐熱性造成不良影響,對於玻璃布之含浸性亦惡化,不僅在工業上不具利益,所得硬化物之物性,尤其是耐濕性和焊接耐熱性會惡化。此外,當未使用含磷環氧樹脂(X)以外之環氧樹脂時,含磷環氧樹脂(X)之含磷率必須為0.5重量%至未達2.0重量%。The phosphorus-containing ratio of the phosphorus-containing epoxy resin (X) of the present invention may be in the range of 0.5% by weight to 3.5% by weight, preferably 0.8% by weight to 3.0% by weight, and 1.2% by weight to 2.7% by weight. More preferably, it is particularly preferably from 1.5% by weight to 2.3% by weight. If the phosphorus content is less than 0.5% by weight, it is difficult to ensure flame retardancy. When it exceeds 3.5% by weight, the resin viscosity becomes high and it is difficult to synthesize, and the molecular weight of the resin increases, which adversely affects heat resistance, and the impregnation property of the glass cloth is also deteriorated, which is not industrially advantageous. The physical properties of the cured product, especially moisture resistance and solder heat resistance, are deteriorated. Further, when an epoxy resin other than the phosphorus-containing epoxy resin (X) is not used, the phosphorus-containing epoxy resin (X) must have a phosphorus content of 0.5% by weight to less than 2.0% by weight.
本發明之難燃性含磷環氧樹脂組成物中,相對於全部環氧樹脂成分之含硫率必須為2重量%至9重量%以下。若未達2重量%,則無法賦予充分之耐熱性。若超過9重量%,則因含磷環氧樹脂中之硫成分之影響,而使所得硬化物之物性,尤其是耐濕性或焊接耐熱性會惡化,使高耐熱用途之可靠性明顯下降。較佳為3重量%至8重量%,更佳為4重量%至7重量%。此外,當未使用含磷環氧樹脂(X)以外之環氧樹脂時,含磷環氧樹脂(X)之含硫率必須為2重量%至9重量%以下。In the flame-retardant phosphorus-containing epoxy resin composition of the present invention, the sulfur content of the epoxy resin component must be 2% by weight to 9% by weight or less. If it is less than 2% by weight, sufficient heat resistance cannot be imparted. When it exceeds 9% by weight, the physical properties of the obtained cured product, particularly moisture resistance or solder heat resistance, are deteriorated by the influence of the sulfur component in the phosphorus-containing epoxy resin, and the reliability of the high heat-resistant use is remarkably lowered. It is preferably from 3% by weight to 8% by weight, more preferably from 4% by weight to 7% by weight. Further, when an epoxy resin other than the phosphorus-containing epoxy resin (X) is not used, the sulfur content of the phosphorus-containing epoxy resin (X) must be 2% by weight to 9% by weight or less.
本發明之含磷環氧樹脂(X)之環氧當量較佳為200g/eq至900g/eq,更佳為250g/eq至800g/eq,特佳為300g/eq至600g/eq。當環氧當量未達200g/eq時,接著性不佳,當超過900g/eq時,會對耐熱性造成不良影響,故以調整成200g/eq至900g/eq為佳。The epoxy equivalent of the phosphorus-containing epoxy resin (X) of the present invention is preferably from 200 g/eq to 900 g/eq, more preferably from 250 g/eq to 800 g/eq, particularly preferably from 300 g/eq to 600 g/eq. When the epoxy equivalent is less than 200 g/eq, the adhesion is poor, and when it exceeds 900 g/eq, the heat resistance is adversely affected, so it is preferably adjusted to 200 g/eq to 900 g/eq.
本發明之硬化劑(Y)可列舉如酚酚醛樹脂、烷基酚酚醛樹脂、芳烷基酚酚醛樹脂、含有三環之酚酚醛樹脂、聯苯芳烷基酚樹脂、芳烷基萘二醇樹脂、三苯基甲烷、四苯基乙烷等多元酚類、己二醯肼(adipic dihydrazide)、癸二醯肼等醯肼類、咪唑化合物類及其鹽類、雙氰胺(dicyandiamide)、胺基苯甲酸酯類、二伸乙基三胺、三伸乙基四胺、四伸乙基五胺、間苯二甲胺(m-xylylenediamine)、異佛爾酮二胺等脂肪族胺類、二胺基二苯基甲烷、二胺基二苯基碸、二胺基乙基苯等芳香族胺類、酞酸酐、苯偏三酸酐(trimellitic anhydride)、苯均四酸酐(pyromellitic dianhydride)、馬來酸酐、四氫酞酸酐、甲基四氫酞酸酐、六氫酞酸酐、甲基六氫酞酸酐、甲基納迪克酸酐(methylnadic acid anhydride)等酸酐類等公知之慣用硬化劑,但不限定於此等。此等硬化劑可僅使用1種,亦可併用2種以上。相對於所使用之環氧樹脂中之環氧基1當量,此等硬化劑之使用量係以0.3當量至1.5當量之範圍為佳,以0.4當量至1.2當量為更佳。The hardener (Y) of the present invention may, for example, be a phenol novolac resin, an alkylphenol novolac resin, an aralkylphenol novolac resin, or a third Phenolic phenolic resin, biphenyl aralkyl phenol resin, aralkyl naphthalenediol resin, polyphenols such as triphenylmethane and tetraphenylethane, adipic dihydrazide, bismuth dioxime Isoindoles, imidazole compounds and their salts, dicyandiamide, aminobenzoic acid esters, di-ethyltriamine, tri-ethylidene tetraamine, tetraethylidene pentaamine, m-benzene An aliphatic amine such as m-xylylenediamine or isophorone diamine, an aromatic amine such as diaminodiphenylmethane, diaminodiphenylanthracene or diaminoethylbenzene; Anhydride, trimellitic anhydride, pyromellitic dianhydride, maleic anhydride, tetrahydrofurfuric anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl hexahydrophthalic anhydride, methyl A known conventional curing agent such as an acid anhydride such as methylnadic acid anhydride, but is not limited thereto. These hardeners may be used alone or in combination of two or more. These hardeners are preferably used in an amount of from 0.3 to 1.5 equivalents, more preferably from 0.4 to 1.2 equivalents, per equivalent of the epoxy group in the epoxy resin to be used.
此外,本發明之難燃性含磷環氧樹脂組成物亦可視需要而併用膦類、咪唑化合物類、四級鏻鹽類、三級胺類、四級銨鹽類、三氟化硼錯合物類、3-(3,4-二氯二苯基)-1,1-二甲基脲、3-(4-氯苯基)-1,1-二甲基脲、3-苯基-1,1-二甲基脲等硬化促進劑。此等硬化促進劑雖依併用之環氧樹脂、使用之環氧樹脂硬化劑之種類、成型方法、硬化溫度、要求特性而異,但相對於環氧樹脂100重量份,以0.01重量份至20重量份之範圍為佳,以0.1重量份至10重量份為更佳。In addition, the flame-retardant phosphorus-containing epoxy resin composition of the present invention may also be combined with a phosphine, an imidazole compound, a quaternary phosphonium salt, a tertiary amine, a quaternary ammonium salt, and a boron trifluoride as needed. Species, 3-(3,4-dichlorodiphenyl)-1,1-dimethylurea, 3-(4-chlorophenyl)-1,1-dimethylurea, 3-phenyl- A hardening accelerator such as 1,1-dimethylurea. These hardening accelerators vary depending on the epoxy resin to be used, the type of the epoxy resin hardener to be used, the molding method, the curing temperature, and the required characteristics, but are 0.01 parts by weight to 20 parts by weight based on 100 parts by weight of the epoxy resin. The range of parts by weight is preferably from 0.1 part by weight to 10 parts by weight.
本發明之難燃性含磷環氧樹脂組成物亦可在不損及特性之範圍內調配環氧樹脂以外之其他熱硬化性樹脂、熱塑性樹脂。例如可列舉如酚樹脂、丙烯酸系樹脂、石油樹脂、茚樹脂、茚香豆酮(indene coumarone)樹脂、苯氧基樹脂、氰酸酯(cyanate)樹脂、聚胺甲酸乙酯(polyurethane)、聚酯、聚醯胺、聚醯亞胺、聚醯胺醯亞胺、聚醚醯亞胺、雙馬來醯亞胺三樹脂、聚醚碸、聚碸、聚醚醚酮、聚苯硫醚(polyphenylene sulfide)、聚乙烯醇縮甲醛(polyvinylformal)等,但不限定於此等。The flame-retardant phosphorus-containing epoxy resin composition of the present invention may be formulated with a thermosetting resin or a thermoplastic resin other than the epoxy resin within a range that does not impair the properties. For example, a phenol resin, an acrylic resin, a petroleum resin, an anthraquinone resin, an indene coumarone resin, a phenoxy resin, a cyanate resin, a polyurethane, and a poly Ester, polyamide, polyimine, polyamidimide, polyetherimide, bismaleimide Resin, polyether oxime, polyfluorene ether, polyetheretherketone, polyphenylene sulfide, polyvinylformal, etc., but are not limited thereto.
本發明之難燃性含磷環氧樹脂組成物可視需要調配無機填充劑、有機填充劑。填充劑之例可列舉如熔融二氧化矽、結晶二氧化矽、氧化鋁、氮化矽、氫氧化鋁、滑石、雲母、碳酸鈣、矽酸鈣、氫氧化鈣、碳酸鎂、碳酸鋇、硫酸鋇、氮化硼、碳、玻璃纖維、碳纖維、氧化鋁纖維、二氧化矽氧化鋁纖維、碳化矽纖維、聚酯纖維、纖維素纖維、芳綸(aramid)纖維等。此等填充劑較佳為環氧樹脂全量中之1重量%至95重量%。The flame retardant phosphorus-containing epoxy resin composition of the present invention may be formulated with an inorganic filler or an organic filler as needed. Examples of the filler include, for example, molten cerium oxide, crystalline cerium oxide, aluminum oxide, cerium nitride, aluminum hydroxide, talc, mica, calcium carbonate, calcium citrate, calcium hydroxide, magnesium carbonate, barium carbonate, sulfuric acid. Niobium, boron nitride, carbon, glass fiber, carbon fiber, alumina fiber, cerium oxide alumina fiber, strontium carbide fiber, polyester fiber, cellulose fiber, aramid fiber, and the like. These fillers are preferably from 1% by weight to 95% by weight of the total amount of the epoxy resin.
本發明之難燃性含磷環氧樹脂組成物可視需要再調配矽烷耦合劑、抗氧化劑、離型劑、消泡劑、乳化劑、搖變性賦予劑、平滑劑、難燃劑、顏料等各種添加劑。此等添加劑較佳為環氧樹脂組成物全量中之0.01重量%至20重量%。The flame-retardant phosphorus-containing epoxy resin composition of the present invention may be further formulated with a decane coupling agent, an antioxidant, a release agent, an antifoaming agent, an emulsifier, a shake imparting agent, a smoothing agent, a flame retardant, a pigment, and the like as needed. additive. These additives are preferably from 0.01% by weight to 20% by weight based on the total amount of the epoxy resin composition.
本發明之難燃性含磷環氧樹脂組成物可藉由以公知方法調配必須成分之含磷環氧樹脂(X)、硬化劑(Y)、視需要之硬化促進劑、各種填充劑、各種添加劑等並均一混合而獲得。The flame-retardant phosphorus-containing epoxy resin composition of the present invention can be prepared by a known method of preparing a phosphorus-containing epoxy resin (X), a hardener (Y), a hardening accelerator as needed, various fillers, and various various components. Additives and the like are obtained by uniformly mixing.
本發明之難燃性含磷環氧樹脂組成物可依據公知方法而成型、硬化並容易地製成硬化物。成型方法、硬化方法可採用與公知之環氧樹脂組成物同樣的方法。The flame-retardant phosphorus-containing epoxy resin composition of the present invention can be molded, hardened, and easily formed into a cured product in accordance with a known method. The molding method and the hardening method can be the same as those of the known epoxy resin composition.
本發明之難燃性含磷環氧樹脂組成物可採取密封材、接著層、成型物、積層物、薄膜等形態。The flame-retardant phosphorus-containing epoxy resin composition of the present invention may be in the form of a sealing material, an adhesive layer, a molded article, a laminate, or a film.
將使用本發明之難燃性含磷環氧樹脂組成物而獲得之積層板之特性予以評估的結果,可獲得高耐熱性、低吸水率、且高溫時之可靠性高之硬化物。可知該難燃性含磷環氧樹脂組成物及其硬化物係有用於作為電子電路基板所用之覆銅積層板之製造用樹脂組成物、或電子零件所用之密封材、成形材、鑄模材、接著劑、薄膜材、電氣絕緣塗料用材料等。As a result of evaluating the characteristics of the laminate obtained by using the flame-retardant phosphorus-containing epoxy resin composition of the present invention, a cured product having high heat resistance, low water absorption, and high reliability at high temperatures can be obtained. It is understood that the flame-retardant phosphorus-containing epoxy resin composition and the cured product thereof are a resin composition for manufacturing a copper-clad laminate used for an electronic circuit board, or a sealing material, a molding material, a mold material for an electronic component, Subsequent materials, film materials, materials for electrical insulating coatings, and the like.
以下,基於合成例、實施例及比較例而具體說明本發明,但本發明之技術範圍不僅限於實施例。又,合成例、實施例及比較例之各成分之調配份數只要未特別聲明,即表示重量份。Hereinafter, the present invention will be specifically described based on Synthesis Examples, Examples, and Comparative Examples, but the technical scope of the present invention is not limited to the examples. In addition, the number of the components of the synthesis examples, the examples, and the comparative examples is a part by weight unless otherwise specified.
此外,本發明係使用以下之分析方法。Further, the present invention uses the following analytical methods.
環氧當量:依據JIS K-7236記載之方法。亦即,將試料溶解於氯仿10mL中,分別添加乙酸酐20mL、20%之溴化四乙基銨乙酸溶液10mL,使用電位差滴定裝置並以0.1mol/L過氯酸乙酸標準液進行滴定。Epoxy equivalent: According to the method described in JIS K-7236. That is, the sample was dissolved in 10 mL of chloroform, and 10 mL of acetic anhydride 20 mL and 20% of a tetraethylammonium bromide solution were added thereto, and titrated with a 0.1 mol/L perchloric acid acetic acid standard solution using a potentiometric titration apparatus.
軟化點:依據JIS K-7234記載之環球法。亦即,將試料予以熔融脫泡並注入環中,於甘油浴測定。Softening point: The ringing method according to JIS K-7234. That is, the sample was melted and defoamed and injected into a ring, and measured in a glycerin bath.
含磷率:依據硝酸-過氯酸分解法。亦即,將硫酸、硝酸、過氯酸添加於試料並進行熱分解,使所有磷成為正磷酸後,於硫酸酸性溶液中與0.25%釩酸銨溶液及5%鉬酸銨溶液反應,所產生之磷-釩鉬酸錯合物之發色係測定波長420nm時之吸光度,以校準曲線求得含磷率。Phosphorus content: based on the nitric acid-perchloric acid decomposition method. That is, sulfuric acid, nitric acid, and perchloric acid are added to the sample and thermally decomposed to make all the phosphorus become orthophosphoric acid, and then reacted with a 0.25% ammonium vanadate solution and a 5% ammonium molybdate solution in an acidic sulfuric acid solution to produce The chromonic color of the phosphorus-vanadium molybdate complex was measured for the absorbance at a wavelength of 420 nm, and the phosphorus content was determined by a calibration curve.
含硫率:依據JIS K-6233-1記載的依據氧瓶燃燒法(oxygen flask combustion method)之方法。亦即,於燃燒瓶中將試料完全分解,並於溶液中以硫酸離子之形式予以捕捉吸收後,使用離子層析儀測定。Sulfur content: A method according to the oxygen flask combustion method described in JIS K-6233-1. That is, the sample was completely decomposed in a combustion flask, and captured and absorbed in the form of sulfate ions in the solution, and then measured using an ion chromatograph.
銅箔剝離強度:依據JIS C-6481 5.7記載之方法。亦即,在銅箔與絕緣板之間,朝直角方向以50mm/分鐘之速度進行剝離而測定。Copper foil peeling strength: According to the method described in JIS C-6481 5.7. That is, the copper foil and the insulating sheet were peeled off at a speed of 50 mm/min in a right angle direction and measured.
層間剝離強度:依據以JIS C-6481 5.7為準之方法。亦即,在1片預浸片(prepreg)與其餘3片之間,朝直角方向以50mm/分鐘之速度進行剝離而測定。Interlaminar peel strength: According to JIS C-6481 5.7. That is, the peeling was performed at a speed of 50 mm/min in a right angle direction between one prepreg and the other three sheets.
難燃性:依據UL(Underwriters Laboratories)規格、UL94垂直試驗法而進行測定,以作為同規格之判定基準之V-0、V-1、V-2、NG(無難燃性)之4水準判定(越為後者,難燃性越差)。Flame retardancy: It is measured according to the UL (Underwriters Laboratories) specification and the UL94 vertical test method, and is determined as the 4 level of V-0, V-1, V-2, and NG (non-flammability) based on the same specifications. (The more the latter, the worse the flame retardancy).
玻璃轉移溫度:依據TMA法。亦即,使用SII NanoTechnology股份公司製之TMA/SS120U作為分析裝置,依據熱機械分析(TMA)以10℃/分鐘之升溫速度進行測定。Glass transfer temperature: according to the TMA method. That is, TMA/SS120U manufactured by SII NanoTechnology Co., Ltd. was used as an analysis device, and the measurement was performed at a temperature increase rate of 10 ° C/min in accordance with thermomechanical analysis (TMA).
線熱膨脹係數:依據TMA法。亦即,使用SII NanoTechnology股份公司製之TMA/SS120U作為分析裝置,依據熱機械分析(TMA)以10℃/分鐘之升溫速度進行測定而求得之50℃至150℃之位移。Linear thermal expansion coefficient: according to the TMA method. That is, the TMA/SS120U manufactured by SII NanoTechnology Co., Ltd. was used as an analysis device, and the displacement at 50 ° C to 150 ° C was determined by thermomechanical analysis (TMA) at a temperature increase rate of 10 ° C /min.
吸水率:依據以JIS C-6481 5.13為準之方法。亦即,使用已裁切為50mm×50mm之試驗片,測定於50℃之烤爐中乾燥24小時後之乾燥重量,繼而測定於100℃煮沸2小時後之重量,基於從乾燥重量增加之份量而測定吸濕率。Water absorption rate: According to JIS C-6481 5.13. That is, using a test piece which has been cut into 50 mm × 50 mm, the dry weight after drying in an oven at 50 ° C for 24 hours is measured, and then the weight after boiling at 100 ° C for 2 hours is measured, based on the amount of increase from the dry weight. The moisture absorption rate was measured.
焊接耐熱性:依據以JIS C-6481 5.5為準之方法。亦即,使用已裁切為25mm×25mm之試驗片,將於100℃煮沸2小時後之試驗片以n=5而浸於288℃之焊浴中20秒,當5片皆未發生膨脹和剝離時為○,即使僅有1片發生該等現象亦為×。Solder heat resistance: According to JIS C-6481 5.5. That is, using a test piece which has been cut into 25 mm × 25 mm, the test piece which is boiled at 100 ° C for 2 hours is immersed in a solder bath of 288 ° C for 20 seconds at n = 5, when none of the five pieces expands and When peeling, it is ○, and even if only one sheet occurs, it is also ×.
在備有攪拌裝置、溫度計、冷卻管、氮氣導入裝置的4口玻璃製可分離式燒瓶中,饋入作為化學式(2)所示磷化合物之HCA(三光股份公司製,含磷率:14.2重量%)64.0g與甲苯150g,一邊於氮氣環境下攪拌,一邊加熱使完全溶解。然後,一邊注意因反應熱所致之升溫,一邊分次投入作為醌類之1,4-萘醌(川崎化成工業股份公司製,3%含水品)45.9g。此時之1,4-萘醌與HCA之莫耳比為1,4-萘醌/HCA=0.95。加熱反應後,饋入作為骨架內具有硫原子之2官能環氧樹脂的EPOTOHTO TX-0908(東都化成股份公司製,環氧當量:219g/eq)317.1g、以及作為平均官能基數目為2.1以上之多官能環氧樹脂的EPOTOHTO YDPN-638(東都化成股份公司製,酚酚醛型環氧樹脂,環氧當量:176g/eq)74.4g,一邊導入氮氣一邊進行攪拌,加熱至130℃並將甲苯去除至系統外。然後,添加作為觸媒之三苯基膦(北興化學工業股份公司製,製品名:TPP)0.11g,一邊使反應溫度保持於160℃至165℃一邊反應4小時,獲得含磷環氧樹脂A。所得之含磷環氧樹脂A之環氧當量為392g/eq,含磷率為1.8重量%,含硫率為5.2重量%,軟化點為83℃。In a four-port separable flask equipped with a stirring device, a thermometer, a cooling tube, and a nitrogen gas introduction device, HCA (phosphorus compound of the chemical formula (2) was fed (manufactured by Sanko Co., Ltd., phosphorus content: 14.2 weight) %) 64.0 g and 150 g of toluene were heated while stirring under a nitrogen atmosphere to completely dissolve. Then, 45.9 g of 1,4-naphthoquinone (manufactured by Kawasaki Kasei Kogyo Co., Ltd., 3% hydrated product) as an anthracene was placed in a divided manner. At this time, the molar ratio of 1,4-naphthoquinone to HCA was 1,4-naphthoquinone/HCA=0.95. After the heating reaction, EPOTOHTO TX-0908 (epoxy equivalent: 219 g/eq) manufactured by Epoxy Chemical Co., Ltd. having a sulfur atom in the skeleton was fed, and 317.1 g of epoxy functional equivalent: 219 g/eq, and the number of average functional groups was 2.1 or more. EPOTOHTO YDPN-638 (manufactured by Toshiro Kasei Co., Ltd., phenol novolac type epoxy resin, epoxy equivalent: 176 g/eq) of 74.4 g of polyfunctional epoxy resin, stirred while introducing nitrogen gas, heated to 130 ° C and toluene Remove to the outside of the system. Then, 0.11 g of triphenylphosphine (manufactured by Kitagawa Chemical Co., Ltd., product name: TPP) as a catalyst was added, and the reaction temperature was maintained at 160 ° C to 165 ° C for 4 hours to obtain a phosphorus-containing epoxy resin A. . The obtained phosphorus-containing epoxy resin A had an epoxy equivalent of 392 g/eq, a phosphorus content of 1.8% by weight, a sulfur content of 5.2% by weight, and a softening point of 83 °C.
在備有攪拌裝置、溫度計、冷卻管、氮氣導入裝置的4口玻璃製可分離式燒瓶中,饋入作為化學式(2)所示磷化合物之HCA(如前述)45.5g與甲苯110g,一邊於氮氣環境下攪拌,一邊加熱使完全溶解。然後,一邊注意因反應熱所致之升溫,一邊分次投入作為醌類之1,4-萘醌(如前述)33.6g。此時之1,4-萘醌與HCA之莫耳比為1,4-萘醌/HCA=0.98。加熱反應後,饋入作為骨架內具有硫原子之2官能環氧樹脂的EPOTOHTO TX-0908(如前述)420.7g,一邊導入氮氣一邊進行攪拌,加熱至130℃並將甲苯去除至系統外。然後,添加作為觸媒之三苯基膦(如前述)0.08g,一邊使反應溫度保持於160℃至165℃一邊反應4小時,獲得含磷環氧樹脂B。所得之含磷環氧樹脂B之環氧當量為338g/eq,含磷率為1.3重量%,含硫率為7.0重量%,軟化點為76℃。In a four-port separable flask equipped with a stirring device, a thermometer, a cooling tube, and a nitrogen gas introduction device, 45.5 g of HCA (as described above) and 110 g of toluene were fed as a phosphorus compound represented by the chemical formula (2). Stir under a nitrogen atmosphere and heat to dissolve completely. Then, while paying attention to the temperature rise due to the heat of reaction, 33.6 g of 1,4-naphthoquinone (as described above) as an anthracene was introduced in portions. At this time, the molar ratio of 1,4-naphthoquinone to HCA was 1,4-naphthoquinone/HCA=0.98. After heating the reaction, 420.7 g of EPOTOHTO TX-0908 (as described above) which is a bifunctional epoxy resin having a sulfur atom in the skeleton was fed, and while stirring with nitrogen gas, the mixture was heated to 130 ° C and the toluene was removed to the outside of the system. Then, 0.08 g of triphenylphosphine (as described above) as a catalyst was added, and the reaction temperature was maintained at 160 ° C to 165 ° C for 4 hours to obtain a phosphorus-containing epoxy resin B. The obtained phosphorus-containing epoxy resin B had an epoxy equivalent of 338 g/eq, a phosphorus content of 1.3% by weight, a sulfur content of 7.0% by weight, and a softening point of 76 °C.
在備有攪拌裝置、溫度計、冷卻管、氮氣導入裝置的4口玻璃製可分離式燒瓶中,饋入作為化學式(2)所示磷化合物之HCA(如前述)64.5g與甲苯150g,一邊於氮氣環境下攪拌,一邊加熱使完全溶解。然後,一邊注意因反應熱所致之升溫,一邊分次投入作為醌類之1,4-萘醌(如前述)47.2g。此時之1,4-萘醌與HCA之莫耳比為1,4-萘醌/HCA=0.97。加熱反應後,饋入作為骨架內具有硫原子之2官能環氧樹脂的EPOTOHTO TX-0908(如前述)350.0g,一邊導入氮氣一邊進行攪拌,加熱至130℃並將甲苯去除至系統外。然後,添加作為觸媒之三苯基膦(如前述)0.11g,一邊使反應溫度保持於160℃至165℃一邊反應4小時,獲得含磷環氧樹脂C。所得之含磷環氧樹脂C之環氧當量為751g/eq,含磷率為2.0重量%,含硫率為6.3重量%,軟化點為120℃。In a four-port separable flask equipped with a stirring device, a thermometer, a cooling tube, and a nitrogen gas introduction device, 64.5 g of HCA (as described above) and 150 g of toluene were fed as a phosphorus compound represented by the chemical formula (2). Stir under a nitrogen atmosphere and heat to dissolve completely. Then, while paying attention to the temperature rise due to the heat of reaction, 47.2 g of 1,4-naphthoquinone (as described above) as an anthracene was introduced in a divided manner. At this time, the molar ratio of 1,4-naphthoquinone to HCA was 1,4-naphthoquinone/HCA=0.97. After heating the reaction, 350.0 g of EPOTOHTO TX-0908 (as described above) having a bifunctional epoxy resin having a sulfur atom in the skeleton was fed, and while stirring with nitrogen gas, the mixture was heated to 130 ° C and the toluene was removed to the outside of the system. Then, 0.11 g of triphenylphosphine (as described above) as a catalyst was added, and the reaction temperature was maintained at 160 ° C to 165 ° C for 4 hours to obtain a phosphorus-containing epoxy resin C. The obtained phosphorus-containing epoxy resin C had an epoxy equivalent of 751 g/eq, a phosphorus content of 2.0% by weight, a sulfur content of 6.3% by weight, and a softening point of 120 °C.
在備有攪拌裝置、溫度計、冷卻管、氮氣導入裝置的4口玻璃製可分離式燒瓶中,饋入作為化學式(2)所示磷化合物之HCA(如前述)75.0g與甲苯175g,一邊於氮氣環境下攪拌,一邊加熱使完全溶解。然後,一邊注意因反應熱所致之升溫,一邊分次投入作為醌類之1,4-萘醌(如前述)55.9g。此時之1,4-萘醌與HCA之莫耳比為1,4-萘醌/HCA=0.99。加熱反應後,饋入作為骨架內具有硫原子之2官能環氧樹脂的EPOTOHTO TX-0908(如前述)320.0g、作為平均官能基數目為2.1以上之多官能環氧樹脂的EPOTOHTO ESN-485(東都化成股份公司製,α-萘醇芳烷基型環氧樹脂,環氧當量:269g/eq)30.0g、以及作為2官能以上之酚化合物的4,4’-聯酚(新日鐵化學股份公司製,羥基當量:93g/eq)18.0g,一邊導入氮氣一邊進行攪拌,加熱至130℃並將甲苯去除至系統外。然後,添加作為觸媒之三苯基膦(如前述)0.15g,一邊使反應溫度保持於160℃至165℃一邊反應4小時,獲得含磷環氧樹脂D。所得之含磷環氧樹脂D之環氧當量為723g/eq,含磷率為2.1重量%,含硫率為5.3重量%,軟化點為125℃。In a four-port separable flask equipped with a stirring device, a thermometer, a cooling tube, and a nitrogen gas introduction device, 75.0 g of HCA (as described above) and 175 g of toluene were fed as a phosphorus compound represented by the chemical formula (2). Stir under a nitrogen atmosphere and heat to dissolve completely. Then, while paying attention to the temperature rise due to the heat of reaction, 55.9 g of 1,4-naphthoquinone (as described above) as an anthracene was introduced in portions. At this time, the molar ratio of 1,4-naphthoquinone to HCA was 1,4-naphthoquinone/HCA=0.99. After heating the reaction, 320.0 g of EPOTOHTO TX-0908 (as described above) as a bifunctional epoxy resin having a sulfur atom in the skeleton, and EPOTOHTO ESN-485 as a polyfunctional epoxy resin having an average number of functional groups of 2.1 or more were fed ( Manufactured by Dongdu Chemical Co., Ltd., α-naphthyl aralkyl type epoxy resin, epoxy equivalent: 269 g/eq) 30.0 g, and 4,4'-biphenol as a bisphenol or higher phenol compound (Nippon Steel Chemical Co., Ltd. The company's product, hydroxyl equivalent: 93 g/eq), 18.0 g, was stirred while introducing nitrogen gas, heated to 130 ° C, and toluene was removed to the outside of the system. Then, 0.15 g of triphenylphosphine (as described above) as a catalyst was added, and the reaction temperature was maintained at 160 ° C to 165 ° C for 4 hours to obtain a phosphorus-containing epoxy resin D. The obtained phosphorus-containing epoxy resin D had an epoxy equivalent of 723 g/eq, a phosphorus content of 2.1% by weight, a sulfur content of 5.3% by weight, and a softening point of 125 °C.
在備有攪拌裝置、溫度計、冷卻管、氮氣導入裝置的4口玻璃製可分離式燒瓶中,饋入作為骨架內具有硫原子之2官能環氧樹脂的2,4-雙酚S型環氧樹脂(依專利文獻6之實施例1記載之方法所預先合成者,環氧當量:220g/eq)340.0g、作為化學式(1)所示磷化合物之9,10-二氫-9-氧雜-10-(2,7-二羥基萘基)-10-磷雜菲-10-氧化物(依專利文獻7之實施例1記載之方法所預先合成者,以下簡稱為HCA-NQ)64.8g、作為化學式(2)所示磷化合物之HCA(如前述)1.1g、以及作為2官能以上之酚化合物的4,4’-雙酚S(日華化學股份公司製之BPS-P(T),羥基當量:125g/eq)25.0g,一邊於氮氣環境下攪拌,一邊加熱至130℃。此時,相對於化學式(1)所示磷化合物1莫耳,化學式(2)所示磷化合物為0.03莫耳。然後,添加作為觸媒之三苯基膦(如前述)0.09g,一邊使反應溫度保持於160℃至165℃一邊反應4小時,獲得含磷環氧樹脂E。所得之含磷環氧樹脂E之環氧當量為441g/eq,含磷率為1.2重量%,含硫率為7.8重量%,軟化點為104℃。In a 4-port separable flask equipped with a stirring device, a thermometer, a cooling tube, and a nitrogen gas introduction device, a 2,4-bisphenol S-type epoxy which is a bifunctional epoxy resin having a sulfur atom in the skeleton is fed. Resin (pre-synthesized according to the method described in Example 1 of Patent Document 6, epoxy equivalent: 220 g/eq) 340.0 g, and 9,10-dihydro-9-oxa compound as a phosphorus compound represented by Chemical Formula (1) -10-(2,7-dihydroxynaphthyl)-10-phosphaphenanthrene-10-oxide (previously synthesized according to the method described in Example 1 of Patent Document 7, hereinafter abbreviated as HCA-NQ) 64.8 g , Hg (as described above) of the phosphorus compound of the chemical formula (2) (1.1 g), and 4,4'-bisphenol S (a BPS-P (T) manufactured by Rihua Chemical Co., Ltd.) The hydroxyl group equivalent: 125 g/eq) 25.0 g was heated to 130 ° C while stirring under a nitrogen atmosphere. At this time, the phosphorus compound represented by the chemical formula (2) was 0.03 mol based on the phosphorus compound 1 mol represented by the chemical formula (1). Then, 0.09 g of triphenylphosphine (as described above) as a catalyst was added, and the reaction temperature was maintained at 160 ° C to 165 ° C for 4 hours to obtain a phosphorus-containing epoxy resin E. The obtained phosphorus-containing epoxy resin E had an epoxy equivalent of 441 g/eq, a phosphorus content of 1.2% by weight, a sulfur content of 7.8% by weight, and a softening point of 104 °C.
在備有攪拌裝置、溫度計、冷卻管、氮氣導入裝置的4口玻璃製可分離式燒瓶中,饋入作為骨架內具有硫原子之2官能環氧樹脂的EPOTOHTO YSLV-50TE(東都化成股份公司製,環氧當量:172g/eq)400.0g、作為化學式(1)所示磷化合物之HCA-NQ(如前述)62.0g、以及作為2官能以上之酚化合物的4,4’-聯酚(如前述)40.0g,一邊於氮氣環境下攪拌,一邊加熱至130℃。此時,不使用化學式(2)所示磷化合物。然後,添加作為觸媒之三苯基膦(如前述)0.1g,一邊使反應溫度保持於160℃至165℃一邊反應4小時,獲得含磷環氧樹脂F。所得之含磷環氧樹脂F之環氧當量為333g/eq,含磷率為1.0重量%,含硫率為7.7重量%,軟化點為96℃。In a 4-port separable flask equipped with a stirring device, a thermometer, a cooling tube, and a nitrogen gas introduction device, EPOTOHTO YSLV-50TE (manufactured by Tohto Kasei Co., Ltd.), which is a bifunctional epoxy resin having a sulfur atom in the skeleton, is fed. , epoxy equivalent: 172 g/eq) 400.0 g, HCA-NQ (as described above) of the phosphorus compound represented by the chemical formula (1), 62.0 g, and 4,4'-biphenol as a bifunctional or higher phenol compound (for example) 40.0 g of the above) was heated to 130 ° C while stirring under a nitrogen atmosphere. At this time, the phosphorus compound represented by the chemical formula (2) is not used. Then, 0.1 g of triphenylphosphine (as described above) as a catalyst was added, and the reaction temperature was maintained at 160 ° C to 165 ° C for 4 hours to obtain a phosphorus-containing epoxy resin F. The obtained phosphorus-containing epoxy resin F had an epoxy equivalent of 333 g/eq, a phosphorus content of 1.0% by weight, a sulfur content of 7.7% by weight, and a softening point of 96 °C.
在備有攪拌裝置、溫度計、冷卻管、氮氣導入裝置的4口玻璃製可分離式燒瓶中,饋入作為化學式(2)所示磷化合物之HCA(如前述)75.0g與甲苯175g,一邊於氮氣環境下攪拌,一邊加熱使完全溶解。然後,一邊注意因反應熱所致之升溫,一邊分次投入作為醌類之1,4-萘醌(如前述)55.9g。此時之1,4-萘醌與HCA之莫耳比為1,4-萘醌/HCA=0.99。加熱反應後,饋入作為骨架內具有硫原子之2官能環氧樹脂的EPOTOHTO TX-0908(如前述)180.0g、以及作為2官能環氧樹脂的EPOTOHTO ZX-1711(東都化成股份公司製,2,5-萘二醇型環氧樹脂,環氧當量:146g/eq)175.0g,一邊導入氮氣一邊進行攪拌,加熱至130℃並將甲苯去除至系統外。然後,添加作為觸媒之三苯基膦(如前述)0.13g,一邊使反應溫度保持於160℃至165℃一邊反應4小時,獲得含磷環氧樹脂G。所得之含磷環氧樹脂G之環氧當量為371g/eq,含磷率為2.2重量%,含硫率為3.0重量%,軟化點為110℃。In a four-port separable flask equipped with a stirring device, a thermometer, a cooling tube, and a nitrogen gas introduction device, 75.0 g of HCA (as described above) and 175 g of toluene were fed as a phosphorus compound represented by the chemical formula (2). Stir under a nitrogen atmosphere and heat to dissolve completely. Then, while paying attention to the temperature rise due to the heat of reaction, 55.9 g of 1,4-naphthoquinone (as described above) as an anthracene was introduced in portions. At this time, the molar ratio of 1,4-naphthoquinone to HCA was 1,4-naphthoquinone/HCA=0.99. After heating the reaction, 180.0 g of EPOTOHTO TX-0908 (as described above) having a bifunctional epoxy resin having a sulfur atom in the skeleton, and EPOTOHTO ZX-1711 as a bifunctional epoxy resin (manufactured by Tohto Kasei Co., Ltd., 2 5-pentanediol type epoxy resin, epoxy equivalent: 146 g/eq) 175.0 g, stirred while introducing nitrogen gas, heated to 130 ° C, and toluene was removed to the outside of the system. Then, 0.13 g of triphenylphosphine (as described above) as a catalyst was added, and the reaction temperature was maintained at 160 ° C to 165 ° C for 4 hours to obtain a phosphorus-containing epoxy resin G. The obtained phosphorus-containing epoxy resin G had an epoxy equivalent of 371 g/eq, a phosphorus content of 2.2% by weight, a sulfur content of 3.0% by weight, and a softening point of 110 °C.
在備有攪拌裝置、溫度計、冷卻管、氮氣導入裝置的4口玻璃製可分離式燒瓶中,饋入作為化學式(2)所示磷化合物之HCA(如前述)103.6g與甲苯240g,一邊於氮氣環境下攪拌,一邊加熱使完全溶解。然後,一邊注意因反應熱所致之升溫,一邊分次投入作為醌類之1,4-萘醌(如前述)53.4g。此時之1,4-萘醌與HCA之莫耳比為1,4-萘醌/HCA=0.68。加熱反應後,饋入作為骨架內具有硫原子之2官能環氧樹脂的EPOTOHTO TX-0908(如前述)226.4g、以及作為平均官能基數目為2.1以上之多官能環氧樹脂的EPOTOHTO YDPN-638(如前述)117.3g,一邊導入氮氣一邊進行攪拌,加熱至130℃並將甲苯去除至系統外。然後,添加作為觸媒之三苯基膦(如前述)0.16g,一邊使反應溫度保持於160℃至165℃一邊反應4小時,獲得含磷環氧樹脂H。所得之含磷環氧樹脂H之環氧當量為563g/eq,含磷率為2.9重量%,含硫率為3.7重量%,軟化點為110℃。In a four-port separable flask equipped with a stirring device, a thermometer, a cooling tube, and a nitrogen gas introduction device, 103.6 g of HCA (as described above) and 240 g of toluene were fed as a phosphorus compound represented by the chemical formula (2). Stir under a nitrogen atmosphere and heat to dissolve completely. Then, while paying attention to the temperature rise due to the heat of reaction, 53.4 g of 1,4-naphthoquinone (as described above) as a hydrazine was introduced in portions. At this time, the molar ratio of 1,4-naphthoquinone to HCA was 1,4-naphthoquinone/HCA=0.68. After heating the reaction, EPOTOHTO TX-0908 (as described above) 226.4 g as a bifunctional epoxy resin having a sulfur atom in the skeleton, and EPOTOHTO YDPN-638 as a polyfunctional epoxy resin having an average number of functional groups of 2.1 or more were fed. 117.3 g (as described above) was stirred while introducing nitrogen gas, heated to 130 ° C, and toluene was removed to the outside of the system. Then, 0.16 g of triphenylphosphine (as described above) as a catalyst was added, and the reaction temperature was maintained at 160 ° C to 165 ° C for 4 hours to obtain a phosphorus-containing epoxy resin H. The obtained phosphorus-containing epoxy resin H had an epoxy equivalent of 563 g/eq, a phosphorus content of 2.9% by weight, a sulfur content of 3.7% by weight, and a softening point of 110 °C.
在備有攪拌裝置、溫度計、冷卻管、氮氣導入裝置的4口玻璃製可分離式燒瓶中,饋入作為化學式(2)所示磷化合物之HCA(如前述)70.0g與甲苯160g,一邊於氮氣環境下攪拌,一邊加熱使完全溶解。然後,一邊注意因反應熱所致之升溫,一邊分次投入作為醌類之1,4-萘醌(如前述)46.4g。此時之1,4-萘醌與HCA之莫耳比為1,4-萘醌/HCA=0.88。加熱反應後,饋入作為骨架內具有硫原子之2官能環氧樹脂的EPOTOHTO TX-0908(如前述)172.8g、以及作為2官能環氧樹脂的EPOTOHTO YD-128(東都化成股份公司製,雙酚A型環氧樹脂,環氧當量:187g/eq)211.2g,一邊導入氮氣一邊進行攪拌,加熱至130℃並將甲苯去除至系統外。然後,添加作為觸媒之三苯基膦(如前述)0.11g,一邊使反應溫度保持於160℃至165℃一邊反應4小時,獲得含磷環氧樹脂I。所得之含磷環氧樹脂I之環氧當量為384g/eq,含磷率為2.0重量%,含硫率為3.0重量%,軟化點為70℃。In a four-port separable flask equipped with a stirring device, a thermometer, a cooling tube, and a nitrogen gas introduction device, 70.0 g of HCA (as described above) and 160 g of toluene were fed as a phosphorus compound represented by the chemical formula (2). Stir under a nitrogen atmosphere and heat to dissolve completely. Then, while paying attention to the temperature rise due to the heat of reaction, 46.4 g of 1,4-naphthoquinone (as described above) as a hydrazine was introduced in portions. At this time, the molar ratio of 1,4-naphthoquinone to HCA was 1,4-naphthoquinone/HCA=0.88. After heating the reaction, 172.8 g of EPOTOHTO TX-0908 (as described above) having a bifunctional epoxy resin having a sulfur atom in the skeleton, and EPOTOHTO YD-128 (available as Dongdu Chemical Co., Ltd.) as a bifunctional epoxy resin were fed. A phenol A type epoxy resin, epoxy equivalent: 187 g/eq) 211.2 g, stirred while introducing nitrogen gas, heated to 130 ° C, and toluene was removed to the outside of the system. Then, 0.11 g of triphenylphosphine (as described above) as a catalyst was added, and the reaction temperature was maintained at 160 ° C to 165 ° C for 4 hours to obtain a phosphorus-containing epoxy resin I. The obtained phosphorus-containing epoxy resin I had an epoxy equivalent of 384 g/eq, a phosphorus content of 2.0% by weight, a sulfur content of 3.0% by weight, and a softening point of 70 °C.
在備有攪拌裝置、溫度計、冷卻管、氮氣導入裝置的4口玻璃製可分離式燒瓶中,饋入作為化學式(2)所示磷化合物之HCA(如前述)70.0g與甲苯160g,一邊於氮氣環境下攪拌,一邊加熱使完全溶解。然後,一邊注意因反應熱所致之升溫,一邊分次投入作為醌類之1,4-萘醌(如前述)46.4g。此時之1,4-萘醌與HCA之莫耳比為1,4-萘醌/HCA=0.88。加熱反應後,饋入作為骨架內具有硫原子之2官能環氧樹脂的EPOTOHTO YSLV-50TE(如前述)300.0g,一邊導入氮氣一邊進行攪拌,加熱至130℃並將甲苯去除至系統外。然後,添加作為觸媒之三苯基膦(如前述)0.12g,一邊使反應溫度保持於160℃至165℃一邊反應4小時,獲得含磷環氧樹脂J。所得之含磷環氧樹脂J之環氧當量為370g/eq,含磷率為2.4重量%,含硫率為7.1重量%,軟化點為106℃。In a four-port separable flask equipped with a stirring device, a thermometer, a cooling tube, and a nitrogen gas introduction device, 70.0 g of HCA (as described above) and 160 g of toluene were fed as a phosphorus compound represented by the chemical formula (2). Stir under a nitrogen atmosphere and heat to dissolve completely. Then, while paying attention to the temperature rise due to the heat of reaction, 46.4 g of 1,4-naphthoquinone (as described above) as a hydrazine was introduced in portions. At this time, the molar ratio of 1,4-naphthoquinone to HCA was 1,4-naphthoquinone/HCA=0.88. After heating the reaction, 300.0 g of EPOTOHTO YSLV-50TE (as described above) which is a bifunctional epoxy resin having a sulfur atom in the skeleton was fed, and the mixture was stirred while introducing nitrogen gas, heated to 130 ° C, and toluene was removed to the outside of the system. Then, 0.12 g of triphenylphosphine (as described above) as a catalyst was added, and the reaction temperature was maintained at 160 ° C to 165 ° C for 4 hours to obtain a phosphorus-containing epoxy resin J. The obtained phosphorus-containing epoxy resin J had an epoxy equivalent of 370 g/eq, a phosphorus content of 2.4% by weight, a sulfur content of 7.1% by weight, and a softening point of 106 °C.
在備有攪拌裝置、溫度計、冷卻管、氮氣導入裝置的4口玻璃製可分離式燒瓶中,饋入作為骨架內具有硫原子之2官能環氧樹脂的EPOTOHTO TX-0908(如前述)315.8g、以及作為化學式(1)所示磷化合物之HCA-NQ(如前述)181.8g,一邊於氮氣環境下攪拌,一邊加熱至130℃。此時,不使用化學式(2)所示磷化合物。然後,添加作為觸媒之三苯基膦(如前述)0.18g,一邊使反應溫度保持於170℃至190℃一邊反應4小時,獲得含磷環氧樹脂K。所得之含磷環氧樹脂K之環氧當量為1,080g/eq,含磷率為3.0重量%,含硫率為5.2重量%,軟化點為140℃以上而無法測定。In a 4-port separable flask equipped with a stirring device, a thermometer, a cooling tube, and a nitrogen gas introduction device, EPOTOHTO TX-0908 (as described above) which is a bifunctional epoxy resin having a sulfur atom in the skeleton was fed, 315.8 g. Further, 181.8 g of HCA-NQ (as described above) as a phosphorus compound represented by the chemical formula (1) was heated to 130 ° C while stirring under a nitrogen atmosphere. At this time, the phosphorus compound represented by the chemical formula (2) is not used. Then, 0.18 g of triphenylphosphine (as described above) as a catalyst was added, and the reaction temperature was maintained at 170 ° C to 190 ° C for 4 hours to obtain a phosphorus-containing epoxy resin K. The obtained phosphorus-containing epoxy resin K had an epoxy equivalent of 1,080 g/eq, a phosphorus content of 3.0% by weight, a sulfur content of 5.2% by weight, and a softening point of 140 ° C or more, which was impossible to measure.
在備有攪拌裝置、溫度計、冷卻管、氮氣導入裝置的4口玻璃製可分離式燒瓶中,饋入作為骨架內具有硫原子之2官能環氧樹脂的EPOTOHTO YSLV-50TE(如前述)332.0g、作為2官能以上之酚化合物的4,4’-雙酚S(如前述)96.3g、以及作為化學式(1)所示磷化合物之HCA-NQ(如前述)71.3g,一邊於氮氣環境下攪拌,一邊加熱至130℃。此時,不使用化學式(2)所示磷化合物。然後,添加作為觸媒之三苯基膦(如前述)0.17g,一邊使反應溫度保持於170℃至190℃一邊反應4小時,獲得含磷環氧樹脂L。所得之含磷環氧樹脂L之環氧當量為651g/eq,含磷率為1.2重量%,含硫率為9.1重量%,軟化點為140℃以上而無法測定。In a 4-port separable flask equipped with a stirring device, a thermometer, a cooling tube, and a nitrogen gas introduction device, EPOTOHTO YSLV-50TE (as described above) 332.0 g as a bifunctional epoxy resin having a sulfur atom in the skeleton was fed. And 96.3 g of 4,4′-bisphenol S (as described above) as a bifunctional or higher phenol compound, and 71.3 g of HCA-NQ (as described above) as a phosphorus compound represented by the chemical formula (1), under a nitrogen atmosphere Stir and heat to 130 °C. At this time, the phosphorus compound represented by the chemical formula (2) is not used. Then, 0.17 g of triphenylphosphine (as described above) as a catalyst was added, and the reaction temperature was maintained at 170 ° C to 190 ° C for 4 hours to obtain a phosphorus-containing epoxy resin L. The obtained phosphorus-containing epoxy resin L had an epoxy equivalent of 651 g/eq, a phosphorus content of 1.2% by weight, a sulfur content of 9.1% by weight, and a softening point of 140 ° C or more, which could not be measured.
在備有攪拌裝置、溫度計、冷卻管、氮氣導入裝置的4口玻璃製可分離式燒瓶中,饋入作為化學式(2)所示磷化合物之HCA(如前述)90.0g與甲苯210g,一邊於氮氣環境下攪拌,一邊加熱使完全溶解。然後,一邊注意因反應熱所致之升溫,一邊分次投入作為酉昆類之1,4-萘醌(如前述)67.0g。此時之1,4-萘醌與HCA之莫耳比為1,4-萘醌/HCA=0.99。加熱反應後,饋入作為2官能環氧樹脂的EPOTOHTO YD-128(如前述)324.6g,一邊導入氮氣一邊進行攪拌,加熱至130℃並將甲苯去除至系統外。此時,不使用骨架內具有硫原子之2官能環氧樹脂。然後,添加作為觸媒之三苯基膦(如前述)0.16g,一邊使反應溫度保持於160℃至165℃一邊反應4小時,獲得含磷環氧樹脂M。所得之含磷環氧樹脂M之環氧當量為529g/eq,含磷率為2.7重量%,含硫率為0重量%,軟化點為104℃。In a four-port separable flask equipped with a stirring device, a thermometer, a cooling tube, and a nitrogen gas introduction device, 90.0 g of HCA (as described above) and 210 g of toluene were fed as a phosphorus compound represented by the chemical formula (2). Stir under a nitrogen atmosphere and heat to dissolve completely. Then, while paying attention to the temperature rise due to the heat of reaction, 67.0 g of 1,4-naphthoquinone (as described above) as a quinone was added in portions. At this time, the molar ratio of 1,4-naphthoquinone to HCA was 1,4-naphthoquinone/HCA=0.99. After heating the reaction, 324.6 g of EPOTOHTO YD-128 (as described above) as a bifunctional epoxy resin was fed, and the mixture was stirred while introducing nitrogen gas, heated to 130 ° C, and toluene was removed to the outside of the system. At this time, a bifunctional epoxy resin having a sulfur atom in the skeleton is not used. Then, 0.16 g of triphenylphosphine (as described above) as a catalyst was added, and the reaction temperature was maintained at 160 ° C to 165 ° C for 4 hours to obtain a phosphorus-containing epoxy resin M. The obtained phosphorus-containing epoxy resin M had an epoxy equivalent of 529 g/eq, a phosphorus content of 2.7% by weight, a sulfur content of 0% by weight, and a softening point of 104 °C.
依據表1所示之調配處方調配含磷環氧樹脂(X)、硬化劑(Y)、其他環氧樹脂、硬化促進劑等。以甲基乙基酮溶解含磷環氧樹脂與其他環氧樹脂,並添加作為預先溶解於乙二醇單甲謎(methyl cellosolve)及二甲基甲醯胺之硬化劑(Y)的雙氰胺(DICY,活性氫當量:21.0g/eq)、以及作為硬化促進劑的2-乙基-4-甲基咪唑(四國化成股份公司製,2E4MZ),以使不揮發份成為50重量%之方式調製樹脂清漆。然後,使用所得之樹脂清漆,含浸於基材之玻璃布(日東紡績股份公司製,WEA 116E 106S 136,厚度100μm),將經含浸之玻璃布於150℃之熱風循環式烘箱乾燥8分鐘,獲得預浸片。其次,將所得之預浸片4片與銅箔(三井金屬礦業股份公司製,3EC-III,厚度35μm)重疊,以130℃×15分鐘及190℃×2.0MPa×70分鐘之條件進行加熱與加壓,獲得0.6mm厚之積層板。對於所得之各個積層板,進行銅箔剝離強度、層間剝離強度、難燃性、玻璃轉移溫度、線熱膨脹係數、吸水率、焊接耐熱性之各物性之試驗。其結果示於表2。Phosphorus-containing epoxy resin (X), hardener (Y), other epoxy resin, hardening accelerator, etc. are prepared according to the formulation shown in Table 1. Dissolving phosphorus-containing epoxy resin and other epoxy resin with methyl ethyl ketone, and adding dicyandiamide as a hardener (Y) predissolved in ethylene glycol cellosolve and dimethylformamide Amine (DICY, active hydrogen equivalent: 21.0 g/eq), and 2-ethyl-4-methylimidazole (2E4MZ, manufactured by Shikoku Kasei Co., Ltd.) as a hardening accelerator to make the nonvolatile content 50% by weight The method is to modulate the resin varnish. Then, using the obtained resin varnish, glass cloth impregnated with the substrate (WEA 116E 106S 136, thickness 100 μm, manufactured by Nitto Denko Co., Ltd.), and the impregnated glass cloth was dried in a hot air circulating oven at 150 ° C for 8 minutes. Prepreg. Next, four pieces of the obtained prepreg were superposed on copper foil (3EC-III, thickness 35 μm, manufactured by Mitsui Mining Co., Ltd.), and heated at 130 ° C × 15 minutes and 190 ° C × 2.0 MPa × 70 minutes. Pressurized to obtain a 0.6 mm thick laminate. Each of the obtained laminated sheets was subjected to tests for physical properties such as copper foil peel strength, interlayer peel strength, flame retardancy, glass transition temperature, linear thermal expansion coefficient, water absorption ratio, and solder heat resistance. The results are shown in Table 2.
實施例1、實施例2、實施例3、實施例4、實施例7、比較例1、比較例2、比較例3、比較例6所使用之含磷環氧樹脂(X)係藉由使用在與環氧樹脂(a)反應前先令化學式(2)所示化合物與1,4-萘醌反應獲得之磷化合物類(b)並進行反應而獲得者,實施例5所使用之含磷環氧樹脂(X)係藉由使用預先合成之化學式(1)所示化合物與化學式(2)所示化合物作為磷化合物類(b)並進行反應而獲得者,實施例6、比較例4、比較例5所使用之含磷環氧樹脂(X)係藉由僅使用預先合成之化學式(1)所示磷化合物進行反應而獲得者。此外,實施例3、實施例4、實施例5、實施例7、比較例3、比較例6亦使用含磷環氧樹脂(X)以外的不含磷之環氧樹脂。The phosphorus-containing epoxy resin (X) used in Example 1, Example 2, Example 3, Example 4, Example 7, Comparative Example 1, Comparative Example 2, Comparative Example 3, and Comparative Example 6 was used. a phosphorus compound (b) obtained by reacting a compound represented by the chemical formula (2) with a 1,4-naphthoquinone before the reaction with the epoxy resin (a), and a reaction is carried out, and the phosphorus used in the embodiment 5 is used. The epoxy resin (X) is obtained by reacting a compound represented by the chemical formula (1) synthesized in advance with a compound represented by the chemical formula (2) as a phosphorus compound (b), and Example 6, Comparative Example 4, The phosphorus-containing epoxy resin (X) used in Comparative Example 5 was obtained by reacting only the phosphorus compound represented by the chemical formula (1) synthesized in advance. Further, in Example 3, Example 4, Example 5, Example 7, Comparative Example 3, and Comparative Example 6, a phosphorus-free epoxy resin other than the phosphorus-containing epoxy resin (X) was also used.
比較例1在合成含磷環氧樹脂時雖使用66重量%之骨架內具有硫原子之2官能環氧樹脂類,但由於相對於化學式(1)化合物1莫耳,化學式(2)化合物之莫耳比為0.46,亦即化學式(2)化合物之使用量係多於0.06莫耳,故吸水率高達1.7%,耐濕性不佳,焊接耐熱性亦不佳。此外,雖然多用多官能環氧樹脂,但其玻璃轉移溫度為155℃,耐熱性難謂高。層間剝離強度亦未達1.0kN/m,而未成為具實用性之積層板。比較例2在合成含磷環氧樹脂時僅使用45重量%(亦即未達50重量%)之骨架內具有硫原子之2官能環氧樹脂類,又,相對於化學式(1)化合物1莫耳,化學式(2)化合物之莫耳比為0.14,亦即化學式(2)化合物之使用量係多於0.06莫耳,故即使含磷率為2重量%亦無法獲得難燃性,且耐熱性低、吸水率高。比較例3在合成含磷環氧樹脂時雖使用100重量%之骨架內具有硫原子之2官能環氧樹脂類,但由於相對於化學式(1)化合物1莫耳,化學式(2)化合物之莫耳比為0.14,亦即化學式(2)化合物之使用量係多於0.06莫耳,故層間剝離強度未達1.0kN/m,且焊接耐熱性亦不佳。比較例4在合成含磷環氧樹脂時雖使用100重量%之骨架內具有硫原子之2官能環氧樹脂類,且未使用化學式(2)化合物,但由於含磷率高達3重量%,故環氧樹脂之軟化點高達140℃以上,使對於玻璃布之含浸性惡化,而使層間剝離強度未達1.0kN/m,焊接耐熱性不佳。比較例5在合成含磷環氧樹脂時雖使用100重量%之骨架內具有硫原子之2官能環氧樹脂類,且未使用化學式(2)之磷化合物,但由於含硫率高達9.1重量%,故吸水率高達2.2重量%,且耐濕性不佳。再者,樹脂之軟化點高達140℃以上,使對於玻璃布之含浸性惡化,而使層間剝離強度未達1.0kN/m,焊接耐熱性不佳。比較例6在合成含磷環氧樹脂時由於未使用骨架內具有硫原子之2官能環氧樹脂類,故玻璃轉移溫度亦為138℃而耐熱性不高,含磷率為2.07重量%而無難燃性,未成為具實用性之積層板。Comparative Example 1 used 66% by weight of a bifunctional epoxy resin having a sulfur atom in the skeleton when synthesizing the phosphorus-containing epoxy resin, but the compound of the chemical formula (2) was not related to the compound 1 of the chemical formula (1). The ear ratio is 0.46, that is, the compound of the chemical formula (2) is used in an amount of more than 0.06 mol, so the water absorption rate is as high as 1.7%, the moisture resistance is poor, and the solder heat resistance is also poor. Further, although a polyfunctional epoxy resin is often used, the glass transition temperature is 155 ° C, and heat resistance is difficult to be high. The interlaminar peel strength was also less than 1.0 kN/m, and it did not become a practical laminate. In Comparative Example 2, only 45% by weight (i.e., less than 50% by weight) of a bifunctional epoxy resin having a sulfur atom in the skeleton was used in synthesizing the phosphorus-containing epoxy resin, and, in contrast, the compound of the chemical formula (1) In the ear, the molar ratio of the compound of the formula (2) is 0.14, that is, the compound of the formula (2) is used in an amount of more than 0.06 mol, so that even if the phosphorus content is 2% by weight, flame retardancy cannot be obtained, and heat resistance is obtained. Low and high water absorption. In Comparative Example 3, although 100% by weight of a 2-functional epoxy resin having a sulfur atom in the skeleton was used in the synthesis of the phosphorus-containing epoxy resin, the compound of the chemical formula (2) was not related to the compound 1 of the chemical formula (1). The ear ratio is 0.14, that is, the compound of the chemical formula (2) is used in an amount of more than 0.06 mol, so the interlayer peel strength is less than 1.0 kN/m, and the solder heat resistance is also poor. In Comparative Example 4, although 100% by weight of a bifunctional epoxy resin having a sulfur atom in the skeleton was used in synthesizing the phosphorus-containing epoxy resin, and the compound of the chemical formula (2) was not used, since the phosphorus content was as high as 3% by weight, The softening point of the epoxy resin is as high as 140 ° C or more, which deteriorates the impregnation property of the glass cloth, and the interlayer peeling strength is less than 1.0 kN/m, and the solder heat resistance is not good. In Comparative Example 5, although 100% by weight of a bifunctional epoxy resin having a sulfur atom in the skeleton was used in synthesizing the phosphorus-containing epoxy resin, and the phosphorus compound of the chemical formula (2) was not used, the sulfur content was as high as 9.1% by weight. Therefore, the water absorption rate is as high as 2.2% by weight, and the moisture resistance is not good. Further, the softening point of the resin is as high as 140 ° C or more, so that the impregnation property to the glass cloth is deteriorated, and the interlayer peeling strength is less than 1.0 kN/m, and the solder heat resistance is not good. In Comparative Example 6, in the synthesis of the phosphorus-containing epoxy resin, since the bifunctional epoxy resin having a sulfur atom in the skeleton was not used, the glass transition temperature was also 138 ° C, the heat resistance was not high, and the phosphorus content was 2.07 wt% without difficulty. Flammability, has not become a practical laminate.
相對於此,實施例1在合成含磷環氧樹脂時係使用81重量%之骨架內具有硫原子之2官能環氧樹脂類、與19重量%之平均官能基數目為2.1以上之多官能環氧樹脂類,且相對於化學式(1)化合物1莫耳,化學式(2)化合物之莫耳比為0.05,亦即化學式(2)化合物之使用量係未達0.06莫耳,故吸水率係1.0%而為低,耐濕性佳,含磷率為1.8重量%而未達2重量%,難燃性亦佳。並且,玻璃轉移溫度亦高達165℃,焊接耐熱性佳,層間剝離強度亦為1.1kN/m,而為實用性十分高之積層板。實施例2在合成含磷環氧樹脂時係使用100重量%之骨架內具有硫原子之2官能環氧樹脂類,且相對於化學式(1)化合物1莫耳,化學式(2)化合物之莫耳比為0.02,亦即化學式(2)化合物之使用量係未達0.06莫耳,並且含磷率為1.3重量%,含硫率為7重量%,故為耐濕性、接著性優良之積層板。由於完全未使用平均官能基數目為2.1以上之多官能環氧樹脂類,故雖然難燃性為V-0,但至熄火為止之時間相較於實施例1和實施例4為稍長,玻璃轉移溫度亦為161℃而雖然相較於實施例1和實施例4為較差,但仍為可充分使用於耐熱用途之積層板。實施例3在合成含磷環氧樹脂時係使用100重量%之骨架內具有硫原子之2官能環氧樹脂類,且相對於化學式(1)化合物1莫耳,化學式(2)化合物之莫耳比為0.03,亦即化學式(2)化合物之使用量係未達0.06莫耳,並且含硫率為4.2重量%,故含磷率為1.3重量%而未達2重量%,難燃性佳,並且為耐濕性、耐熱性、接著性優良之積層板。實施例4在合成含磷環氧樹脂時係使用91重量%之骨架內具有硫原子之2官能環氧樹脂類、與9重量%之平均官能基數目為2.1以上之多官能環氧樹脂類,且相對於化學式(1)化合物1莫耳,化學式(2)化合物之莫耳比為0.01,亦即化學式(2)化合物之使用量係未達0.06莫耳,並且含硫率為4.2重量%,故含磷率為1.7重量%而未達2重量%,難燃性佳,並且為耐濕性、耐熱性、接著性優良之積層板。實施例5在合成含磷環氧樹脂時係使用100重量%之骨架內具有硫原子之2官能環氧樹脂類,且相對於化學式(1)化合物1莫耳,化學式(2)化合物之莫耳比為0.03,亦即化學式(2)化合物之使用量係未達0.06莫耳,並且含硫率為5.9重量%,故含磷率為0.9重量%而未達1重量%,難燃性佳,並且為耐濕性、耐熱性、接著性優良之積層板。實施例6在合成含磷環氧樹脂時係使用100重量%之骨架內具有硫原子之2官能環氧樹脂類,且未使用化學式(2)之磷化合物而僅使用化學式(1)之磷化合物,並且含磷率為1.0重量%,含硫率為7.7重量%,故為耐濕性、接著性優良之積層板。由於完全未使用平均官能基數目為2.1以上之多官能環氧樹脂類,故雖然難燃性為V-0,但至熄火為止之時間係相較於實施例1和實施例4為稍微較長,玻璃轉移溫度亦為160℃而雖然相較於實施例1和實施例4為較差,但仍為可充分使用於耐熱用途之積層板。實施例7在合成含磷環氧樹脂時係使用51重量%之骨架內具有硫原子之2官能環氧樹脂類、與49重量%之骨架內不具有硫原子之2官能環氧樹脂類,且相對於化學式(1)之磷化合物1莫耳,化學式(2)之磷化合物之莫耳比為0.01,亦即化學式(2)之磷化合物之使用量係未達0.06莫耳,並且含硫率為2.4重量%,故含磷率為1.8重量%而未達2重量%,難燃性佳,並且為耐濕性、耐熱性、接著性優良之積層板。On the other hand, in the synthesis of the phosphorus-containing epoxy resin of Example 1, 81% by weight of a bifunctional epoxy resin having a sulfur atom in the skeleton and 19% by weight of a polyfunctional ring having an average number of functional groups of 2.1 or more were used. Oxygen resin, and the molar ratio of the compound of the formula (2) is 0.05 with respect to the compound 1 of the formula (1), that is, the compound of the formula (2) is used in an amount of less than 0.06 mol, so the water absorption rate is 1.0. % is low, moisture resistance is good, phosphorus content is 1.8% by weight, and less than 2% by weight, and flame retardancy is also good. Moreover, the glass transition temperature is also as high as 165 ° C, the solder heat resistance is good, and the interlayer peel strength is also 1.1 kN/m, which is a laminate having a very high practicality. In the synthesis of the phosphorus-containing epoxy resin, Example 2 uses 100% by weight of a 2-functional epoxy resin having a sulfur atom in the skeleton, and is a molar compound of the compound of the formula (1) with respect to the compound 1 of the formula (1). The ratio of 0.02, that is, the compound of the formula (2) is used in an amount of less than 0.06 mol, and the phosphorus content is 1.3% by weight, and the sulfur content is 7 wt%, so that the laminate is excellent in moisture resistance and adhesion. . Since the polyfunctional epoxy resin having an average number of functional groups of 2.1 or more was not used at all, the flame retardancy was V-0, but the time until the flameout was slightly longer than that of Examples 1 and 4. The transfer temperature was also 161 ° C and although it was inferior to those of Example 1 and Example 4, it was a laminate which can be sufficiently used for heat-resistant use. In the synthesis of the phosphorus-containing epoxy resin, Example 3 uses 100% by weight of a 2-functional epoxy resin having a sulfur atom in the skeleton, and is a molar compound of the compound of the formula (1) with respect to the compound 1 of the formula (1). The ratio is 0.03, that is, the compound of the formula (2) is used in an amount of less than 0.06 mol, and the sulfur content is 4.2% by weight, so the phosphorus content is 1.3% by weight and less than 2% by weight, and the flame retardancy is good. Moreover, it is a laminated board excellent in moisture resistance, heat resistance, and adhesion. In the synthesis of the phosphorus-containing epoxy resin, in Example 4, 91% by weight of a bifunctional epoxy resin having a sulfur atom in the skeleton and 9 wt% of a polyfunctional epoxy resin having an average number of functional groups of 2.1 or more were used. And the molar ratio of the compound of the formula (2) is 0.01 with respect to the compound 1 of the formula (1), that is, the compound of the formula (2) is used in an amount of less than 0.06 mol, and the sulfur content is 4.2% by weight. Therefore, the phosphorus content is 1.7% by weight and less than 2% by weight, and it is excellent in flame retardancy, and is a laminate having excellent moisture resistance, heat resistance, and adhesion. In the synthesis of the phosphorus-containing epoxy resin, Example 5 uses 100% by weight of a 2-functional epoxy resin having a sulfur atom in the skeleton, and is a molar compound of the compound of the formula (1) with respect to the compound 1 of the formula (1). The ratio is 0.03, that is, the compound of the formula (2) is used in an amount of less than 0.06 mol, and the sulfur content is 5.9% by weight, so the phosphorus content is 0.9% by weight and less than 1% by weight, and the flame retardancy is good. Moreover, it is a laminated board excellent in moisture resistance, heat resistance, and adhesion. In the synthesis of the phosphorus-containing epoxy resin, Example 6 uses 100% by weight of a bifunctional epoxy resin having a sulfur atom in the skeleton, and the phosphorus compound of the formula (2) is not used, and only the phosphorus compound of the chemical formula (1) is used. Further, since the phosphorus content is 1.0% by weight and the sulfur content is 7.7% by weight, it is a laminate having excellent moisture resistance and adhesion. Since the polyfunctional epoxy resin having an average number of functional groups of 2.1 or more was not used at all, although the flame retardancy was V-0, the time until the flameout was slightly longer than that of Examples 1 and 4. The glass transition temperature was also 160 ° C and although it was inferior to those of Example 1 and Example 4, it was a laminate which can be sufficiently used for heat-resistant use. In the synthesis of the phosphorus-containing epoxy resin, Example 7 uses 51% by weight of a 2-functional epoxy resin having a sulfur atom in the skeleton, and 49% by weight of a 2-functional epoxy resin having no sulfur atom in the skeleton, and Compared with the phosphorus compound 1 of the formula (1), the molar ratio of the phosphorus compound of the formula (2) is 0.01, that is, the phosphorus compound of the formula (2) is used in an amount of less than 0.06 mol, and the sulfur content is Since it is 2.4% by weight, the phosphorus content is 1.8% by weight and is less than 2% by weight, and it is excellent in flame retardancy and is a laminate having excellent moisture resistance, heat resistance and adhesion.
如此,實施例中係相對於化學式(1)所示化合物1莫耳使化學式(2)所示化合物為0.06莫耳以下,且使用50重量%以上之骨架內具有硫原子之2官能環氧樹脂類而合成含磷環氧樹脂,將該含磷環氧樹脂作為必須成分,使環氧樹脂之含磷率為0.5重量%至未達2.0重量%,且使含硫率為2重量%至9重量%,在該等實施例中,難燃性與接著力、耐熱性、耐濕性皆優異。尤其是藉由將環氧樹脂之含磷率調整為0.5重量%至未達2.0重量%,且將含硫率調整為2重量%至9重量%,即可一邊保持耐熱性,一邊降低吸水率、且使焊接耐熱性提升。此外,如實施例5或實施例6所示,即使含磷率為1重量%以下亦可滿足難燃性,故獲得耐濕性優異之積層板。再者,如實施例3、實施例4、實施例5、實施例7所示,亦可併用不含磷之環氧樹脂,尤其是藉由併用平均官能基數目為2.1以上之多官能環氧樹脂類,在獲得高耐熱性之同時,亦可獲得接著力、難燃性優異之環氧樹脂組成物。Thus, in the examples, the compound represented by the formula (1) is a compound represented by the formula (2), and the compound represented by the formula (2) is 0.06 mol or less, and 50% by weight or more of a bifunctional epoxy resin having a sulfur atom in the skeleton is used. A phosphorus-containing epoxy resin is synthesized, and the phosphorus-containing epoxy resin is used as an essential component, so that the phosphorus content of the epoxy resin is from 0.5% by weight to less than 2.0% by weight, and the sulfur content is from 2% by weight to 9%. % by weight, in these examples, excellent in flame retardancy, adhesion, heat resistance, and moisture resistance. In particular, by adjusting the phosphorus content of the epoxy resin to 0.5% by weight to less than 2.0% by weight, and adjusting the sulfur content to 2% by weight to 9% by weight, the heat resistance can be maintained while reducing the water absorption rate. And the solder heat resistance is improved. Further, as shown in Example 5 or Example 6, even if the phosphorus content is 1% by weight or less, the flame retardancy can be satisfied, and thus a laminated board excellent in moisture resistance can be obtained. Further, as shown in Example 3, Example 4, Example 5, and Example 7, a phosphorus-free epoxy resin may be used in combination, especially by using a polyfunctional epoxy having an average number of functional groups of 2.1 or more. In the resin, an epoxy resin composition excellent in adhesion and flame retardancy can be obtained while obtaining high heat resistance.
本發明係最適合作為以電子電路基板所用之覆銅積層板為代表之電氣絕緣材料,亦適合作為電子零件所用之密封材、成形材、鑄模材、接著劑、薄膜材,且亦有效於作為電氣絕緣塗料用材料。The present invention is most suitable as an electrical insulating material typified by a copper-clad laminate for use in an electronic circuit board, and is also suitable as a sealing material, a molding material, a molding material, an adhesive, and a film material for electronic components, and is also effective as Materials for electrical insulation coatings.
Claims (11)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2009089483A JP5441477B2 (en) | 2009-04-01 | 2009-04-01 | Flame retardant phosphorus-containing epoxy resin composition and cured product thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
TW201041928A TW201041928A (en) | 2010-12-01 |
TWI460199B true TWI460199B (en) | 2014-11-11 |
Family
ID=42828446
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
TW099107407A TWI460199B (en) | 2009-04-01 | 2010-03-15 | Flame retardant phosphor-containing epoxy resin composition and cured article thereof |
Country Status (5)
Country | Link |
---|---|
JP (1) | JP5441477B2 (en) |
KR (1) | KR20120022730A (en) |
CN (1) | CN102369229B (en) |
TW (1) | TWI460199B (en) |
WO (1) | WO2010114166A1 (en) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5579008B2 (en) * | 2010-09-29 | 2014-08-27 | 新日鉄住金化学株式会社 | Phosphorus-containing epoxy resin |
JP6067699B2 (en) * | 2012-06-15 | 2017-01-25 | 新日鉄住金化学株式会社 | Phosphorus-containing epoxy resin, composition containing epoxy resin as essential component, and cured product |
JP7037314B2 (en) * | 2017-09-26 | 2022-03-16 | 日鉄ケミカル&マテリアル株式会社 | Method for manufacturing phosphorus-containing epoxy resin |
CN110643289A (en) * | 2019-10-10 | 2020-01-03 | 常州斯威克光伏新材料有限公司 | High-temperature-resistant flame-retardant adhesive film |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TW438833B (en) * | 1999-04-16 | 2001-06-07 | Nat Science Council | Phosphorus containing flame retardant advanced epoxy resins, preparation and cured epoxy resins thereof |
TW555809B (en) * | 2000-04-06 | 2003-10-01 | Matsushita Electric Works Ltd | Epoxy resin compositions containing phosphorus, flame retardant resin sheet using said epoxy resin containing phosphorus, resin clad metal foil, prepreg and laminated board, multilayer board |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6291627B1 (en) * | 1999-03-03 | 2001-09-18 | National Science Council | Epoxy resin rendered flame retardant by reaction with 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide |
JP2001123049A (en) * | 1999-10-28 | 2001-05-08 | Dainippon Ink & Chem Inc | Flame-retardant epoxy resin composition |
JP2002188066A (en) * | 2000-10-10 | 2002-07-05 | Toray Ind Inc | Adhesive composition for semiconductor device and adhesive sheet and cover lay film for semiconductor devices |
WO2006006592A1 (en) * | 2004-07-13 | 2006-01-19 | Hitachi Chemical Co., Ltd. | Epoxy resin molding material for sealing and electronic component device |
-
2009
- 2009-04-01 JP JP2009089483A patent/JP5441477B2/en not_active Expired - Fee Related
-
2010
- 2010-03-15 TW TW099107407A patent/TWI460199B/en not_active IP Right Cessation
- 2010-03-31 WO PCT/JP2010/056271 patent/WO2010114166A1/en active Application Filing
- 2010-03-31 KR KR1020117022088A patent/KR20120022730A/en active IP Right Grant
- 2010-03-31 CN CN201080015340.1A patent/CN102369229B/en not_active Expired - Fee Related
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TW438833B (en) * | 1999-04-16 | 2001-06-07 | Nat Science Council | Phosphorus containing flame retardant advanced epoxy resins, preparation and cured epoxy resins thereof |
TW555809B (en) * | 2000-04-06 | 2003-10-01 | Matsushita Electric Works Ltd | Epoxy resin compositions containing phosphorus, flame retardant resin sheet using said epoxy resin containing phosphorus, resin clad metal foil, prepreg and laminated board, multilayer board |
Also Published As
Publication number | Publication date |
---|---|
WO2010114166A1 (en) | 2010-10-07 |
JP2010241870A (en) | 2010-10-28 |
CN102369229A (en) | 2012-03-07 |
CN102369229B (en) | 2014-03-26 |
JP5441477B2 (en) | 2014-03-12 |
TW201041928A (en) | 2010-12-01 |
KR20120022730A (en) | 2012-03-12 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US9215803B2 (en) | Epoxy resin composition and pre-preg, support-provided resin film, metallic foil clad laminate plate and multilayer printed circuit board utilizing said composition | |
CN108623786B (en) | Oxazolidone ring-containing epoxy resin composition, method for producing same, curable resin composition, and cured product | |
KR101794366B1 (en) | Method for producing a phosphorus-containing epoxy resin, epoxy resin composition, and cured product thereof | |
EP2985300B1 (en) | Phosphor-containing phenol formaldehyde resin compound and flame-retardant epoxy resin hardener made from thereof | |
JP6193689B2 (en) | Phosphorus-containing epoxy resin and composition, cured product | |
JP5793086B2 (en) | Epoxy resin, epoxy resin composition and cured product thereof | |
TWI460199B (en) | Flame retardant phosphor-containing epoxy resin composition and cured article thereof | |
JP2020122034A (en) | Epoxy resin composition, and cured product of the same | |
JP5399733B2 (en) | Flame retardant phosphorus-containing epoxy resin composition and cured product thereof | |
JP6228799B2 (en) | Epoxy resin composition and cured product thereof | |
JP6596751B2 (en) | Phosphorus-containing epoxy resin composition and cured product | |
JP5686512B2 (en) | Phosphorus-containing epoxy resin, resin composition, and flame-retardant cured product thereof | |
TWI422609B (en) | A novel flame retardant epoxy resin, an epoxy resin composition containing the epoxy resin as an essential component and a cured product thereof | |
JP5653374B2 (en) | Phosphorus-containing epoxy resin, epoxy resin composition containing the resin, curable epoxy resin composition containing the resin, and cured product obtained therefrom | |
TWI487725B (en) | Flame retardant phosphor-containing epoxy resin composition and cured article thereof | |
WO2014034675A1 (en) | Method for producing cyanuric acid-modified phosphorus-containing epoxy resin, resin composition containing cyanuric acid-modified phosphorus-containing epoxy resin, and cured product of same | |
KR20180009556A (en) | Flame retardant compound and composition comprising the same having excellent in flame retardancy and electrical properties | |
JPH01138241A (en) | Production of flame-retarding paper/phenol resin laminate |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
MM4A | Annulment or lapse of patent due to non-payment of fees |