Holomua i ka Lamina Lamina Copper Clad Laminates Epoxy Resin

2022-11-28

  Me ka hiki ʻana mai o ka makahiki ʻike nui, ua komo nā mea uila i kahi pae hou o ka hoʻohui kiʻekiʻe a me ka hilinaʻi kiʻekiʻe. ʻO ka papa kaapuni i paʻi ʻia (PCB), ka papa kumu e pono ai no ka hoʻokomo ʻana iā lākou, ua lilo ia i mea koʻikoʻi a koʻikoʻi o ka hapa nui o nā huahana uila. E like me ka mea nui substrate i ka PCB hana, copper clad laminate (CCL) pāʻani i ʻekolu hana nui: conductive, insulating a me ke kākoʻo. ʻO ka hana, ka maikaʻi, ka hana ʻana, ke kumukūʻai a me ke kiʻekiʻe o ka PCB e hilinaʻi nei i ka mea substrate i kahi nui. I kēia manawa, ua hōʻea ka waiwai o nā mea substrate i ka honua i ʻumi mau piliona kālā. ʻO ka hoʻopuka ʻana o nā mea substrate ma Kina ma kahi o 55 miliona mau mika square, me ka waiwai hoʻopuka ma kahi o 9 biliona yuan.


  According to the types of adhesives used, CCL can be divided into phenolic resin, epoxy resin, polyester, polyimide and other types. According to the reinforcement materials, it can be divided into paper base, glass cloth base and composite base. Among them, glass cloth reinforced epoxy copper clad laminate, such as FR-4 and FR-5, has become the mainstream of printed circuit boards used in electronic products such as electronic computers, communication equipment, instruments and meters. It is speculated that epoxy CCL will be the first in the whole CCL in the future.


1. Ka nui o ka noiʻi a me ka hoʻomohala ʻana


  Ke noʻonoʻo nei i ka hiki ʻana o ke ahi o nā mea, hiki ke hoʻokaʻawale ʻia ka laminate ʻaʻahu keleawe i ʻelua mau ʻāpana: ka pale ahi a me ka pale ahi ʻole, ʻo ia ka mea nui o ka lapalapa ahi. Hiki ke hoʻokaʻawale ʻia nā mea hoʻoheheʻe ahi i loko o ka substrate retardant ahi i loaʻa ka bromine a me ka antimony a me ka substrate ʻōmaʻomaʻo me ka ʻole bromine a me ka antimony, ʻo ia hoʻi ka substrate-friendly substrate.


  Mai ka makahiki 1986, ua loaʻa i ka hoʻomohala ʻana o ka ʻoihana mea halogenated flame retardant i ka pilikia o ka dioxin, ʻo ia hoʻi, ka polybrominated dibenzofuran (PBDF) a me ka polybrominated dibenzodioxane i hana ʻia i ka wā e hoʻopau ʻia ai nā mea pale ahi halogenated a puhi ʻia i ka wela kiʻekiʻe, ʻo ia ke ʻano o ka waiwai. hiki ke hoʻopōʻino i ka ʻili a me nā ʻāpana o loko, a loaʻa ka hopena o ka hoʻolaha ʻana i ka malformation a me ka carcinogenesis o ke kino. No laila, ʻaʻole i loaʻa i nā mea polymer pale ahi halogenated ka māka pale kaiapuni ʻōmaʻomaʻo ma ʻEulopa.


  Mai ka makahiki 1990, ua koi nui ka hoʻomohala ʻenehana o nā huahana uila e hoʻololi i ke kaiapuni. No laila, ʻoi aku ka wikiwiki a me ka wikiwiki o ka hoʻomohala ʻana i nā mea substrate-friendly. ʻO ka hoʻohana ʻana i nā mea substrate pale ahi ʻole halogen i lilo i kuhikuhi koʻikoʻi no ka ʻōmaʻomaʻo o ka hapa nui o nā papa. Hōʻike nui ʻia ia ma: (1) Nui nā ʻāina a i ʻole nā ​​ʻāpana o ka honua (ʻoi loa ʻo ʻEulopa) i hoʻokumu a hoʻolaha i nā lula he nui e pili ana i ka hoʻopaʻa ʻana a i ʻole ka pāpā ʻana i nā mea substrate i loaʻa nā mea pale ahi halogenated, a e hoʻokō ʻia nā kānāwai kūpono a puni 2004. ʻO Kina, ʻo ia ka mea hana nui o nā mea substrate, ʻo ia ka mea nui i ka halogenated flame retardant. (2) Ua hoʻomaka kekahi mau mea hana uila kaulana i ka honua e hoʻohana i ka PCB manuahi halogen.


  I ka hopena o ke kenekulia 20, ua hoʻonui nui ʻia ka nānā ʻana i ka noiʻi ʻana i ka laminate epoxy resin copper clad laminate pili i ka lapalapa ahi. No ka mea, ʻo ka epoxy resin copper clad laminate, me ka pepa i hoʻokumu ʻia, ka lole aniani, ka composite a me ka papa multilayer, ʻo ia ke ʻano nui o nā mea substrate, a ʻo ka hapa nui o ia mau mea he mea pale ʻole i ke ahi. Lawe i ka FR4 pepa mea substrate, ʻoi aku ka nui ma mua o 95%, ma ke ʻano he laʻana. He ʻano pā kēia me ka bromine flame retardant. E nānā i ka Papa 1 no kona ʻano maʻamau.


FR4 pepa


Tab.1 Hoʻokumu maʻamau o FR–4 Hoʻopili


Inoa Material

Ka maikaʻi/kope

Brominated epoxy resin (maʻiʻo paʻa 80%)

125

Dicyandiamide (DICY)

2.9

Dimethylformamide (DMF)

15

Ethylene glycol methyl ether

15

2-Methylimidazole

0.02 ~ 0.12


  No laila, he waiwai kaiapuni nui a me ka waiwai waiwai ka hoʻomohala ʻana i nā lau epoxy resin epoxy ʻaʻole hiki ke hoʻopaʻa i ke ahi no ka hoʻololi ʻana i nā ʻano halogen kiʻekiʻe a i ʻole nā ​​​​pepa halogen haʻahaʻa.


2. Ke ala noiʻi a me ka hoʻomohala ʻana


  ʻO ka hana ʻana o nā mea substrate ma ke ʻano he ʻekolu mau kaʻina: ka hana pena resin, ka impregnation a me ka maloʻo ʻana o ka huahana semi-finished, a me ka hana ʻana a me ke kaomi ʻana. ʻO nā mea nui ka resin polymer, nā mea hoʻoikaika a me ka foil keleawe. Koe wale no nā mea pepa, hoʻoikaika i nā mea a me nā ʻāpana keleawe i ka lapalapa ahi a ʻaʻole pono e mālama i ka lapalapa ahi. No laila, he mea koʻikoʻi ka lapalapa ahi o ka resin epoxy no nā mea substrate. ʻO ka epoxy resin based substrate material resin paint me ka epoxy resin, curing agent, curing accelerator a me ka solvent. Epoxy resin e like me ka mea hoʻopili; Hoʻopili ka mea ho'ōla me ka hui epoxide a i ʻole ka hui hydroxyl i loko o ka resin epoxy, ma laila e ho'ōla a hoʻopili i ka resin epoxy; Hoʻohana ʻia ka Accelerator no ka hoʻomaʻamaʻa ʻana i ka resin; Hoʻohana nui ʻia nā solvents e hoʻopau i ka epoxy resin a me ka curing agent, i hoʻoneʻe ʻia i ka wā impregnation a me ke kaomi ʻana. Hiki ke hoʻomaka ʻia ka hoʻomohala ʻana i ka epoxy CCL e hoʻopaʻa ai i ka lapalapa o ke kaiapuni mai kēia mau ʻano ʻekolu: (1) hoʻomohala i ka epoxy resin epoxy retardant free halogen; (2) E hoʻohana i ka lāʻau lapaʻau ʻaʻole halogen. (3) Hoʻohui i ka mea pale ahi halogen ʻole.


a) E aʻo i ka Halogen free Flame Retardant Epoxy Resin


  E like me nā ʻano o nā mea pale ahi, hiki ke hoʻokaʻawale ʻia nā mea pale ahi i nā moʻo halogen (ka moʻo bromine a me ka moʻo chlorine), moʻo phosphorus, moʻo nitrogen, moʻo silicon, moʻo antimony, moʻo boron, a me nā mea ʻē aʻe. , nitrogen, silicon a me nā mea ʻē aʻe e pale ai i ke ahi e pani i ka tetrabromobisphenol i hoʻohana nui ʻia i kēia manawa ʻO ka resin epoxy ke ala nui e hoʻomohala ai i ka epoxy resin epoxy retardant ʻole halogen.


i. E aʻo i ka resin epoxy me ka nitrogen


  ʻO ka Nitrogen i loko o ka epoxy resin ka mea nui i hoʻohana ʻia e hoʻololi i ka resin epoxy brominated i ka hana ʻana i ka flame retardant CCL, me ka glycidylamine epoxy resin a me ka polyisocyanurate oxazolidone resin.


  ʻO Glycidylamine epoxy resin ka triglycidylamine cyanate me ka triazine ma ke ʻano he iwi iwi nui, p-aminophenol epoxy resin a me diaminodiphenylmethane epoxy resin. ʻO Triglycidyl melamine cyanate he pauka keʻokeʻo keʻokeʻo, me ke kaumaha molekala pili o 297.29, kahi heheʻe o 102 ~ 105 ℃, kahi waiwai epoxy o 102 ~ 108 g / mol, ʻekolu mau pūʻulu epoxy i loko o ka mole, a me kahi mea nitrogen o luna. a hiki i ka 14% (kahi hakina nui). No laila, hoʻopau iā ia iho. Loaʻa iā ia nā hiʻohiʻona o ke kiʻekiʻe cross-linking density, kiʻekiʻe wela ke kūpaʻa a me ka pale arc maikaʻi.


  Ma muli o ka nui o nā apo lima a me ʻeono i loko o ka hale, ʻoi aku ka maikaʻi o ia mau mea i ka lapalapa ahi, ke kūpaʻa wela, ke kūpaʻa dielectric a me ka ikaika mechanical. ʻO kāna mau mea maka he isocyanate a me ka resin epoxy.


ii. E aʻo i ka phosphorus i loaʻa ka epoxy resin


  ʻO ka hoʻokomo ʻana o ka phosphorus i loko o ka epoxy resin hiki ke loaʻa iā ia ke kūpaʻa wela maikaʻi a me ka retardancy ahi. Ke hoʻomehana ʻia nā mea polymer i ka lewa, hiki ke hoʻoheheʻe ʻia e hana i nā mea hoʻoheheʻe volatile. Ke kiʻekiʻe ka neʻe ʻana o nā mea puhi ahi a me ka mahana o ka ʻōnaehana, hiki ke hoʻopau ʻia. Hiki ke hoʻokaʻawale ʻia ka mīkini hoʻopaʻa ahi i loko o ke kinoea me ka hoʻopaʻa ʻana i ke ahi. ʻO ka mīkini pale ahi o ka phosphorus ka mea nui o ka condensation mechanism. Ke hoʻomehanaʻia ka mea, hana ia i ka phosphorus i loko o ka waikawa, hiki ke hoʻololi i ka dehydration o ka hui i loko o ke kalapona, e ho'ēmi ana i ka nui o ka poho o ka mea a me ka hanauna o nā mea puhi ahi, aʻo ka hapa nui o ka phosphorus e mau ana i ka papa kalapona. ʻO ka papa kalapona i hoʻokumu ʻia ma luna o ka ʻili o ka mea i loaʻa i ka lapalapa ahi maikaʻi ma muli o kēia mau ʻano. ʻO ka mea mua, hiki ke kiʻekiʻe i ka 60% ka oxygen index o ka papa kalapona ponoʻī, a paʻakikī ke puhi, hoʻokaʻawale ʻia ka wela a hoʻokaʻawale ʻia ka oxygen, kahi e hoʻopau ai ka puhi ʻana; ʻO ka lua, ʻo ka papa kalapona he haʻahaʻa haʻahaʻa haʻahaʻa, e hōʻemi ana i ka wela i hoʻoili ʻia i ka substrate a hoʻolohi i ka decomposition thermal o ka substrate; ʻO ke kolu, ʻo ka phosphorus i koe i loko o ka papa kalapona ka hapa nui i loko o ke ʻano o ka waiwai semi-solid viscous, i hana i kahi kiʻiʻoniʻoni wai e uhi ana i ka papa kalapona ma ka ʻili waiwai, hiki ke hōʻemi i ka permeability o ka papa kalapona a pale i ka papa kalapona mai kahi hou aku. oxidation. I kēia manawa, ʻelua mau ʻano o ka phosphorus i loaʻa i ka epoxy resin:


  Hiki ke ho'ōla iā lākou e ka amine a i ʻole anhydride, a i ʻole hiki ke hoʻōla ʻia ma ka hoʻomehana ʻana iā lākou iho. Loaʻa iā lākou nā pono o ka viscosity haʻahaʻa a me ke ola lawelawe lōʻihi.


iii. E aʻo e pili ana i ke silika me ka resin epoxy


Hiki ke hoʻohana ʻia kekahi polymer silicone me ka hui epoxy e like me ka resin epoxy silicone. Hiki ke loaʻa iā lākou e:


(1) Condensation reaction of diphenylpropane epoxy resin me ka haʻahaʻa molecular weight polysilane i loaʻa ka methoxy, ethoxy a me ka hydroxyl;


(2) Alkoxy dealcoholization pane ma waena o epoxy propanol a me polysilane;


(3) Hoʻohui ʻia o ka propylene oxide allyl ether me ka hydrogen hana i loko o ka polysilane;


(4) Hoʻopaneʻe ka Peroxide i nā mea paʻa pālua unsaturated ma polysilane;


(5) ʻO ka paʻakai sodium Diphenolpropane, ka epichlorohydrin a me ka alkyl halide i loaʻa.


  Hoʻohana ʻia ka hopena Polysiloxane a me nā ʻano hana ʻē aʻe e hoʻomākaukau ai i ka # 665 silicone epoxy resin.


  Loaʻa ka maikaʻi o ka silicon epoxy resin organic a me ka resin epoxy. Loaʻa iā ia nā hiʻohiʻona maikaʻi loa o ka lapalapa ahi, ka pale ʻana i ka wai, ka pale ʻana i ka wai, ka wela wela, a me nā mea ʻē aʻe.


b) E aʻo ʻia ma luna o ka lāʻau lapaʻau pale ahi


  ʻO ka epoxy resin ponoʻī he thermoplastic polymer prepolymer, a ʻaʻohe waiwai o ka epoxy resin maʻemaʻe. Ke hoʻohui wale ʻia ka lāʻau lapaʻau e lilo i ʻekolu-dimensional reticular structure, e hōʻike ana i kahi ʻano o nā hiʻohiʻona maikaʻi loa. Kapa ʻia ka lāʻau lapaʻau ʻo hardener. ʻO ka lāʻau lapaʻau o ka resin epoxy he amine, anhydride, polymer prepolymer, latent curing agent, a pēlā aku. I kēia manawa, ʻo ka hapa nui o nā lāʻau lapaʻau pale ahi he mau pūhui i loaʻa ka nitrogen, phosphorus a i ʻole phosphorus nitrogen i ka manawa like.


  ʻO nā Phosphoramides me nā hale aʻe he papa koʻikoʻi o nā lāʻau lapaʻau pale ahi, aia ka phosphorus a me ka nitrogen. Ma muli o ka hopena synergistic o ka phosphorus a me ka nitrogen i loko o ka lapalapa ahi, hiki i kēia mau pūhui ke hoʻomaikaʻi nui i ka retardancy lapalapa o nā mea. Hōʻike ka papa 2 i nā hopena hoʻāʻo hoʻoheheʻe ʻana o epoxy resin e51 ʻōnaehana hoʻōla ʻia me ka phosphorus amine a me ka non phosphorus amine curing agent.


EPOXY RESIN E51


Tab.2 Nā hualoaʻa hoʻāʻo ʻana o ka hoʻāhu ʻana o ka hoʻōla ʻana o E-51 me nā mea paʻakikī phosphor a i ʻole


Māhele

ʻO Diethylenetriamines


Pūnaehana hoʻōla

DETA/(E–51)

DETAPP/(E–51)

100 g E – 51 Ka nui o ka lāʻau lapaʻau i hoʻohui ʻia/g

10.5

35.8

Kūlana hoʻōla

a

b

Ka hopena o ka puhi ʻana i ka ʻeleʻele/mm · min^-1

Ⅲ—16

Ⅱ—40


  Hōʻike nā hualoaʻa i ka papaʻaina hiki ke hoʻomaikaʻi ʻia ka hoʻopaneʻe ahi o ka ʻōnaehana resin mai ka Papa III a i ka Papa II e ka phosphorus amine curing agent.


c) E aʻo e pili ana i ka hoʻomākaukau ʻana i ka ʻōnaehana Epoxy Resin e hoʻopaʻa ai i ke ahi ma o ka hoʻohui ʻana i ka mea pale ahi non halogen.


  Hoʻohana ʻia ka flame retardant no ka hoʻomaikaʻi ʻana i ke kūpaʻa ʻana o ka lapalapa o nā mea, ʻo ia hoʻi, e pale i nā mea mai ka hoʻā ʻana a pale i ka laha ʻana o ka lapalapa. Hiki ke hoʻokaʻawale ʻia nā mea pale ahi i ke ʻano additive a me ke ʻano reactive. ʻO 85% o nā mea pale ahi i hoʻohana ʻia i kēia manawa he ʻano hoʻohui. ʻO ka hoʻohui ʻana i ka lapalapa ahi i ka ʻōnaehana resin epoxy he ala pololei a maikaʻi hoʻi e hoʻomaikaʻi ai i kona retardancy lapalapa. Hoʻohana ʻia nā mea hoʻopaʻa ahi ʻole e like me Al (OH) 3, Mg (OH) 2 a me ka phosphorus ʻulaʻula a me nā mea hoʻopaʻa ahi phosphorus e like me trimethyl phosphate, triphenyl ester a me m-cresol no ke kaiapuni epoxy resin copper clad laminate. A hoʻohana pinepine ʻia lākou i ka manawa like e pāʻani i kahi hana synergistic. Ua hoʻomākaukau ʻia ka epoxy resin copper-clad sheet mai 270 mau ʻāpana o ka epoxy resin, 185 mau ʻāpana o ka resin epoxy nitrogen-containing, 100 mau ʻāpana o ka alumini hydroxide, 60 mau ʻāpana o ka phosphate ester a me 0.1 ʻāpana o 2-ethyl-4-methylimidazole i hoʻohana ʻia e Honda. Xinxing. ʻO ka waiwai pale ahi i hiki i ka V-0, a he ikaika ka peel maikaʻi a me ke kūpaʻa wela. Eia kekahi, hiki ke hoʻomākaukau ʻia ka ʻōnaehana resin epoxy resin haʻahaʻa haʻahaʻa me ka hoʻohana ʻana iā Al (OH) 3 a me ka phosphorus ʻulaʻula. E nānā i ka Papa 3 no ke kumu.


Tab.3 Pūnaehana EP pale ahi me ka haʻahaʻa haʻahaʻa o ka uahi


Nā meahana

Epoxy Resin E44

Al(OH)3

ʻulaʻula phosphorus

Zirconia

Triethylenetetramine

Maikaʻi/Mahele

100

50 ~ 150

15 ~ 20

1 ~ 3

10


3. Ka hopena a me ka manaʻo


  Ua hoʻomaka ʻia ka hoʻomaka ʻana o ka noiʻi ʻana ma kēia kahua ma Kina. No ka mea, ʻo ka noiʻi a me ka hoʻomohala ʻana o kēia ʻano CCL e pili ana i ka ʻepekema pale ahi, ka ʻepekema uila, ka ʻepekema waiwai a me nā hoʻopaʻapaʻa ʻē aʻe, a pono kā lākou hui pū ʻana. Ma hope o ke komo ʻana o Kina i WTO, e kū mālie nā kānāwai like ʻole a me nā hoʻoponopono ma Kina me nā kūlana honua, a ʻoi aku ka kiʻekiʻe o nā koi no ka lapalapa ahi a me ke kaiapuni. No laila, pono e hoʻoikaika ʻia ka noiʻi ʻana a me ka hoʻomohala ʻana i ka CCL pale ahi e pili ana i ka honua. Manaʻo ka mea kākau e hoʻoikaika ʻia kēia mau mea. ʻO ka mea mua, pono mākou e noiʻi ikaika a hoʻomohala i ka phosphorus pili i ka honua, nitrogen a me ka inorganic flame retardants kūpono no nā noi ʻoihana uila e lanakila ai i nā hemahema o nā mea pale ahi maʻamau i kēia manawa, e like me ke kiʻekiʻe o nā mea haumia e like me ka chloride ions, ka mobility kiʻekiʻe, a me ka hopena i ka hana uila. I kēia manawa, he hana koʻikoʻi, hoʻokele waiwai a maikaʻi hoʻi ia e hoʻololi i ka retardancy lapalapa o nā mea ma o ka hoʻohui ʻana i nā mea pale ahi. ʻO ka lua, ʻo ke ala kumu e hoʻoponopono ai i ka pilikia ʻo ka hoʻomohala ʻana i kahi ʻano hou o ka epoxy resin me ka intrinsic flame retardancy, hiki ke lanakila i nā pilikia e like me ka hana mechanical a me ka uila i hana ʻia e ka hoʻohui ʻana i nā retardants ahi. Eia naʻe, ʻo ke kumu kūʻai paha ke kūʻē nui. ʻO ke kolu, e hoʻomohala a hoʻohana i nā lāʻau lapaʻau pale ahi e loaʻa ana ka nitrogen, phosphorus, phosphorus nitrogen a i ʻole polyimide a me nā mea hoʻololi ʻē aʻe, hiki ke hoʻomaikaʻi i ka retardancy lapalapa o CCL a me ka pale wela o nā mea.


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