CN116445113A - 一种适用于hdi覆铜板的粘合剂及其制备方法与应用 - Google Patents
一种适用于hdi覆铜板的粘合剂及其制备方法与应用 Download PDFInfo
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- 239000000853 adhesive Substances 0.000 title claims abstract description 38
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000003822 epoxy resin Substances 0.000 claims abstract description 28
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 28
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229920005989 resin Polymers 0.000 claims abstract description 25
- 239000011347 resin Substances 0.000 claims abstract description 25
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 18
- 239000011574 phosphorus Substances 0.000 claims abstract description 18
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 15
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 14
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- 238000003756 stirring Methods 0.000 claims description 24
- 229910052802 copper Inorganic materials 0.000 claims description 12
- 239000010949 copper Substances 0.000 claims description 12
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 8
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 8
- 239000004843 novolac epoxy resin Substances 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 4
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 claims description 4
- HXDOZKJGKXYMEW-UHFFFAOYSA-N 4-ethylphenol Chemical compound CCC1=CC=C(O)C=C1 HXDOZKJGKXYMEW-UHFFFAOYSA-N 0.000 claims description 4
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 claims description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 4
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 claims description 4
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- HASUCEDGKYJBDC-UHFFFAOYSA-N 1-[3-[[bis(oxiran-2-ylmethyl)amino]methyl]cyclohexyl]-n,n-bis(oxiran-2-ylmethyl)methanamine Chemical compound C1OC1CN(CC1CC(CN(CC2OC2)CC2OC2)CCC1)CC1CO1 HASUCEDGKYJBDC-UHFFFAOYSA-N 0.000 claims description 2
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 2
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims description 2
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 claims description 2
- CWLKGDAVCFYWJK-UHFFFAOYSA-N 3-aminophenol Chemical compound NC1=CC=CC(O)=C1 CWLKGDAVCFYWJK-UHFFFAOYSA-N 0.000 claims description 2
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 claims description 2
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims description 2
- 239000010445 mica Substances 0.000 claims description 2
- 229910052618 mica group Inorganic materials 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 229920001955 polyphenylene ether Polymers 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 239000000758 substrate Substances 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 239000011889 copper foil Substances 0.000 abstract description 5
- 238000003754 machining Methods 0.000 abstract description 4
- 238000010521 absorption reaction Methods 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 9
- 239000003063 flame retardant Substances 0.000 description 5
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 4
- 238000010030 laminating Methods 0.000 description 4
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- 238000005516 engineering process Methods 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 238000003475 lamination Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
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- 150000002500 ions Chemical class 0.000 description 2
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- 230000009477 glass transition Effects 0.000 description 1
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- 239000012433 hydrogen halide Substances 0.000 description 1
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- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
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- 230000002195 synergetic effect Effects 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
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- B32B15/00—Layered products comprising a layer of metal
- B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
- B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
- B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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- C—CHEMISTRY; METALLURGY
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- 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
- C08G59/62—Alcohols or phenols
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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- C09J179/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09J161/00 - C09J177/00
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- 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
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/46—Manufacturing multilayer circuits
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/02—Composition of the impregnated, bonded or embedded layer
- B32B2260/021—Fibrous or filamentary layer
- B32B2260/023—Two or more layers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/04—Impregnation, embedding, or binder material
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
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- C—CHEMISTRY; METALLURGY
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Abstract
本发明涉及一种适用于HDI覆铜板的粘合剂及其制备方法,所述的粘合剂中各组分按重量份数计分别为:酚醛环氧树脂10‑30份、多官能团环氧树脂20‑50份、苯并噁嗪树脂20‑50份、含磷固化剂10‑30份、咪唑类促进剂0.001‑1份、无机填料60‑150份以及有机溶剂20‑80份。采用本发明所述的粘合剂制备的环氧玻璃布基覆铜箔板Tg>160℃(DSC);Z轴CTE<3.0%;耐热性方面:TD≥380℃,T288>60min;铜箔剥离强度(1OZ)>1.2N/mm;另外具备很低的吸水率和良好的机械加工性能及尺寸稳定性,并且阻燃达到UL94V‑0级,制备的覆铜板具备非常优异的综合性能,可完全满足HDI基板的生产要求。
Description
技术领域
本发明涉及覆铜板制备技术领域,具体涉及一种适用于HDI覆铜板的粘合剂及其制备方法与应用。
背景技术
含卤素的阻燃覆铜板在燃烧过程中存在发烟量大,气味难闻,且会释放出有毒和腐蚀性卤化氢气体等缺点,人体摄入后无法排出,影响健康。因此,许多国家逐步禁止在电子设备中使用含卤阻燃剂,要求电子用覆铜板不得使用含卤素阻燃的材料。
同时,随着电子产品不断向薄、轻、短、小及高速信息化的需求,印制电路板(PCB)在电路设计与制程技术上日益复杂精进,逐渐往细导线、窄间距、高集成、多层化发展。积层法多层板的出现,开创了一个HDI(High Density Interconnector)多层板制造技术的新时代。因此,为满足HDI高集成、多次压合等特殊工艺制程需求,PCB制造商对基材的性能等有越来越高的要求。生产高多层的HDI线路板要求覆铜板必须具有良好的尺寸安定性及耐热性;为满足信息高速传播、信号完整性与真实性,要求覆铜板具有低介电常数(Dk)及低介电损耗正切值(Df);除此之外还需具有优良的机械加工性、耐离子迁移、耐化性等各项性能。普通的FR-4环氧体系覆铜板因具有较大的热膨胀系数而无法在PCB生产过程中满足HDI线路板所需的尺寸安定性,同时耐热性、介电性也难以达到要求。而特殊的树脂如聚四氟乙烯树脂、聚苯醚树脂等虽各项性能良好,但价格高昂,且加工工艺特殊,在HDI领域的发展受到限制。
因此,开发出一款性能优越、成本低廉的,且满足HDI制程的高可靠性覆铜板已成为迫切的市场需求。
发明内容
本发明的目的是提供一种适用于HDI覆铜板的粘合剂及其制备方法与应用,制备的覆铜板可满足HDI基板的生产要求。
本发明的目的可以通过以下技术方案来实现:一种适用于HDI覆铜板的粘合剂,所述的粘合剂包括以下重量份组分:
酚醛环氧树脂10-30份;
多官能团环氧树脂20-50份;
苯并噁嗪树脂20-50份;
含磷固化剂10-30份;
咪唑类促进剂0.001-1份;
无机填料60-150份;
有机溶剂20-80份。
优选地,所述的酚醛环氧树脂包括苯酚线性酚醛环氧树脂、邻甲酚线性酚醛环氧树脂、双酚A型酚醛环氧树脂或双酚F型酚醛环氧树脂中的一种或多种。
优选地,所述的酚醛环氧树脂为山东圣泉生产的牌号8020-65M树脂,所使用的线性酚醛树脂可改善聚合物以及制品的耐热性和机械性能,其分子量分布窄,游离酚与杂质离子含量低,均达到ppm级,其指标如下:
优选地,所述的多官能团环氧树脂包括1,1,2,2-四(对羟基苯基)乙烷四缩水甘油醚环氧树脂、4,4-二氨基二苯甲烷环氧树脂、三缩水甘油基对氨基苯酚、三缩水甘油基间氨基苯酚或1,3-双(N,N-二缩水甘油氨甲基)环己烷中的一种或多种。
优选地,所述的多官能团环氧树脂为1,1,2,2-四(对羟基苯基)乙烷四缩水甘油醚环氧树脂,其结构式为
优选地,所述的苯并噁嗪树脂包括双酚A型苯并恶嗪、双酚F型苯并恶嗪、双环戊二烯型苯并恶嗪(DCPD-Boz)、二氨基二苯醚型苯并噁嗪(ODA-Boz)、聚苯醚型苯并恶嗪(PPO-Boz)或4,4’-二氨基二苯基甲烷型苯并恶嗪(MDA-Boz)中的一种或多种。
优选地,所述的苯并噁嗪树脂为长春化工生产的牌号PF-3500树脂。
优选地,所述的含磷固化剂包括双酚A型含磷酚醛树脂,其由含磷化合物与双酚A型环氧树脂缩合反应制得。
进一步优选地,所述的双酚A型环氧树脂为陶氏化学生产的牌号XZ-92741树脂。
优选地,所述的咪唑类促进剂包括2-乙基-4-甲基咪唑或2-苯基咪唑中的一种或多种。
进一步优选地,所述的咪唑类促进剂为2-乙基-4-甲基咪唑。
优选地,所述的无机填料包括氢氧化铝微粉、软性硅微粉、云母粉或滑石粉中的一种或多种。
优选地,所述的无机填料的粒径分布为1-15μm,D50分布在1-3μm,纯度在99.6wt%以上。
加入无机填料的主要作用是帮助体系固化后达到UL 94V-0级的阻燃要求以及提高体系固化后的韧性,改善下游印制电路板加工过程中的钻孔效果,提高孔壁质量,降低钻头磨损。
优选地,所述的有机溶剂包括丙酮、丁酮、环己酮、丙二醇单甲醚、N,N-二甲基甲酰胺、甲苯等中的一种或多种。
进一步优选地,所述的有机溶剂为丁酮和N,N-二甲基甲酰胺的混合溶剂。
一种上述适用于HDI覆铜板的粘合剂的制备方法,包括以下步骤:
步骤(1):在搅拌槽内依次加入有机溶剂以及苯并噁嗪树脂后,开启搅拌器,以1000-2000转/分的转速搅拌30-60分钟;
步骤(2):再向搅拌槽中依次加入多官能团环氧树脂、酚醛环氧树脂以及含磷固化剂,以1000-2000转/分的转速搅拌30-60分钟;
步骤(3):开启冷却水循环并以1400-1600转/分的转速继续搅拌1-2小时,再加入无机填料搅拌2-4小时;
步骤(4):再将预先溶解于有机溶剂的咪唑类促进剂加入搅拌槽内,以1000-1500转/分的转速搅拌1-3小时,即制得粘合剂。
进一步优选地,步骤(1)和(3)中所述的搅拌槽内温度为20-40℃。
一种上述适用于HDI覆铜板的粘合剂的应用,将所述粘合剂应用于制备环氧玻璃布基覆铜箔板。
优选地,制备环氧玻璃布基覆铜箔板的方法包括以下步骤:
1.将粘合剂双面涂覆在2116型增强材料E-Glass上,在171℃烤箱中烘烤3-5min得到半固化片。
其参数控制如下:
半固化片上胶速度:6-15m/min;
凝胶时间:240-360秒;
树脂含量:40%-70%;
树脂流动度:20%-35%;
挥发份:0.1-0.75%。
2.将上述制备的半固化粘合片以5张半固化片上下各覆一张1OZ铜箔为叠构,放入层压机中压合得到层压板,以此层压板进行特性评估。
其中,压板参数为:
真空度:-0.05~0.10MPa;
压力:261-564psi;
热盘温度:170-220℃;
高温段固化时间:80-100min。
板材排版结构:5张2116型半固化片压合后厚度为0.656mm。
与现有技术相比,本发明具有以下优点:
1.本发明粘合剂的制备过程中,采用多固化体系,苯并噁嗪树脂固化剂、酚醛环氧树脂固化剂以及含磷固化剂以独特比例协同固化,可有效改善材料固化所需条件,减少固化时间,并改善固化后的可靠性;含磷固化剂还可提高基板阻燃效果;
2.本发明粘合剂的制备过程中,体系使用的多官能团环氧树脂固化后可得到较高的交联密度,因此具有低的热膨胀系数、较高的玻璃化转变温度及良好的热稳定性,同时与该粘合剂中含有的无机填料共同协同,可提供优异的尺寸安定性;
3.本发明粘合剂的制备过程中,体系使用阻燃性较好的苯并噁嗪树脂并复配含磷固化剂,苯并噁嗪树脂的氮与含磷固化剂中的磷协同作用,可大幅提高基板的阻燃效果,使其达到UL94 V-0级,同时具有较高的耐热性;
4.本发明粘合剂制备的环氧玻璃布基覆铜箔板Tg>160℃(DSC);Z轴CTE<3.0%;耐热性方面:TD≥380℃,T288>60min;铜箔剥离强度(1OZ)>1.2N/mm;另外具备很低的吸水率和良好的机械加工性能及尺寸稳定性,并且阻燃达到UL94V-0级,制备的覆铜板具备非常优异的综合性能,可完全满足HDI基板的生产要求。
具体实施方式
下面对本发明的实施例作详细说明,以下实施例在以本发明技术方案为前提下进行实施,给出了详细的实施方式和具体的操作过程,但本发明的保护范围不限于下述的实施例。
以下实施例中所使用的试剂皆为市售试剂。以下实施例中所使用的设备皆为市售设备。
按照下表所示的各组分的重量份数制备粘合剂:
其中,酚醛环氧树脂为山东圣泉生产的牌号8020-65M树脂,多官能团环氧树选用1,1,2,2-四(对羟基苯基)乙烷四缩水甘油醚环氧树脂,苯并噁嗪树脂为长春化工生产的牌号PF-3500树脂,含磷固化剂为双酚A型含磷酚醛树脂,咪唑类促进剂选用2-乙基-4-甲基咪唑,无机填料选用软性硅微粉,有机溶剂选用丁酮与N,N-二甲基甲酰胺的混合溶剂。
上述粘合剂的具体制备过程为:
步骤(1):在搅拌槽内依次加入有机溶剂以及苯并噁嗪树脂后,开启高速搅拌器,以1500转/分的转速,控制槽体温度在30℃下持续搅拌40分钟;
步骤(2):再向搅拌槽中依次加入多官能团环氧树脂、酚醛环氧树脂以及含磷固化剂,以1500转/分的转速搅拌40分钟;
步骤(3):开启冷却水循环控制槽体温度在30℃下,并以1500转/分的转速继续搅拌1.5小时,再加入无机填料搅拌3小时;
步骤(4):再将预先溶解于有机溶剂的咪唑类促进剂加入搅拌槽内,以1300转/分的转速搅拌2小时,调胶完成,即制得粘合剂。
将上述粘合剂双面涂覆在2116型增强材料E-Glass上,在171℃烤箱中烘烤4min得到半固化片。
其参数控制如下:
半固化片上胶速度:10m/min;
凝胶时间:300秒;
树脂含量:50%;
树脂流动度:25%;
挥发份:0.4%。
将上述制备的半固化粘合片以5张半固化片上下各覆一张1OZ铜箔为叠构,放入层压机中压合得到层压板,以此层压板进行特性评估。
其中,压板参数为:
真空度:0.05MPa;
压力:350psi;
热盘温度:200℃;
高温段固化时间:90min。
板材排版结构:5张2116型半固化片压合后厚度为0.656mm。
对上述制备的覆铜板进行性能测试,结果如下表所示。
从上表可以看出,采用本发明所述的粘合剂制备的环氧玻璃布基覆铜箔板Tg>160℃,Z轴CTE<3.0%;耐热性方面:TD≥380℃,T288>60min;铜箔剥离强度(1OZ)>1.2N/mm;另外具备很低的吸水率和良好的机械加工性能及尺寸稳定性,并且阻燃达到UL94V-0级,制备的覆铜板具备非常优异的综合性能,具有优异的尺寸安定性、机械加工性及良好的耐热性和阻燃性,完全适用于高密度互连积层板。
上述的对实施例的描述是为便于该技术领域的普通技术人员能理解和使用发明。熟悉本领域技术的人员显然可以容易地对这些实施例做出各种修改,并把在此说明的一般原理应用到其他实施例中而不必经过创造性的劳动。因此,本发明不限于上述实施例,本领域技术人员根据本发明的揭示,不脱离本发明范畴所做出的改进和修改都应该在本发明的保护范围之内。
Claims (10)
1.一种适用于HDI覆铜板的粘合剂,其特征在于,所述的粘合剂包括以下重量份组分:
酚醛环氧树脂10-30份;
多官能团环氧树脂20-50份;
苯并噁嗪树脂20-50份;
含磷固化剂10-30份;
咪唑类促进剂0.001-1份;
无机填料60-150份;
有机溶剂20-80份。
2.根据权利要求1所述的适用于HDI覆铜板的粘合剂,其特征在于,所述的酚醛环氧树脂包括苯酚线性酚醛环氧树脂、邻甲酚线性酚醛环氧树脂、双酚A型酚醛环氧树脂或双酚F型酚醛环氧树脂中的一种或多种。
3.根据权利要求1所述的适用于HDI覆铜板的粘合剂,其特征在于,所述的多官能团环氧树脂包括1,1,2,2-四(对羟基苯基)乙烷四缩水甘油醚环氧树脂、4,4-二氨基二苯甲烷环氧树脂、三缩水甘油基对氨基苯酚、三缩水甘油基间氨基苯酚或1,3-双(N,N-二缩水甘油氨甲基)环己烷中的一种或多种。
4.根据权利要求1所述的适用于HDI覆铜板的粘合剂,其特征在于,所述的苯并噁嗪树脂包括双酚A型苯并恶嗪、双酚F型苯并恶嗪、双环戊二烯型苯并恶嗪、二氨基二苯醚型苯并噁嗪、聚苯醚型苯并恶嗪或4,4’-二氨基二苯基甲烷型苯并恶嗪中的一种或多种。
5.根据权利要求1所述的适用于HDI覆铜板的粘合剂,其特征在于,所述的含磷固化剂包括双酚A型含磷酚醛树脂。
6.根据权利要求1所述的适用于HDI覆铜板的粘合剂,其特征在于,所述的咪唑类促进剂包括2-乙基-4-甲基咪唑或2-苯基咪唑中的一种或多种。
7.根据权利要求1所述的适用于HDI覆铜板的粘合剂,其特征在于,所述的无机填料包括氢氧化铝微粉、软性硅微粉、云母粉或滑石粉中的一种或多种;所述的无机填料的粒径分布为1-15μm,D50分布在1-3μm,纯度在99.6wt%以上。
8.根据权利要求1所述的适用于HDI覆铜板的粘合剂,其特征在于,所述的有机溶剂包括丙酮、丁酮、环己酮、丙二醇单甲醚、N,N-二甲基甲酰胺、甲苯等中的一种或多种。
9.一种如权利要求1~8任一项所述的适用于HDI覆铜板的粘合剂的制备方法,其特征在于,包括以下步骤:
步骤(1):在搅拌槽内依次加入有机溶剂以及苯并噁嗪树脂后,开启搅拌器,以1000-2000转/分的转速,在槽体温度为20-40℃下搅拌30-60分钟;
步骤(2):再向搅拌槽中依次加入多官能团环氧树脂、酚醛环氧树脂以及含磷固化剂,以1000-2000转/分的转速搅拌30-60分钟;
步骤(3):开启冷却水循环控制槽体温度在20-40℃下,并以1400-1600转/分的转速继续搅拌1-2小时,再加入无机填料搅拌2-4小时;
步骤(4):再将预先溶解于有机溶剂的咪唑类促进剂加入搅拌槽内,以1000-1500转/分的转速搅拌1-3小时,即制得粘合剂。
10.一种如权利要求1~8任一项所述的适用于HDI覆铜板的粘合剂的应用,其特征在于,将所述粘合剂应用于制备环氧玻璃布基覆铜箔板。
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