TWI275602B - Hardener particle, manufacturing method for hardener particle, and adhesive - Google Patents
Hardener particle, manufacturing method for hardener particle, and adhesive Download PDFInfo
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- TWI275602B TWI275602B TW92103252A TW92103252A TWI275602B TW I275602 B TWI275602 B TW I275602B TW 92103252 A TW92103252 A TW 92103252A TW 92103252 A TW92103252 A TW 92103252A TW I275602 B TWI275602 B TW I275602B
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- hardener
- metal
- particles
- adhesive
- general formula
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- 239000002245 particle Substances 0.000 title claims abstract description 164
- 239000000853 adhesive Substances 0.000 title claims abstract description 78
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 78
- 239000004848 polyfunctional curative Substances 0.000 title claims description 144
- 238000004519 manufacturing process Methods 0.000 title claims description 23
- 229910052751 metal Inorganic materials 0.000 claims abstract description 117
- 239000002184 metal Substances 0.000 claims abstract description 117
- 239000003822 epoxy resin Substances 0.000 claims abstract description 38
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 38
- 239000013522 chelant Substances 0.000 claims abstract description 33
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims abstract description 28
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 26
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 19
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- 150000002739 metals Chemical class 0.000 claims abstract description 3
- 150000001875 compounds Chemical class 0.000 claims description 31
- 125000001424 substituent group Chemical group 0.000 claims description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 25
- 229920005989 resin Polymers 0.000 claims description 18
- 239000011347 resin Substances 0.000 claims description 18
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 16
- 239000001301 oxygen Substances 0.000 claims description 14
- 229910052760 oxygen Inorganic materials 0.000 claims description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 13
- 125000003277 amino group Chemical group 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 12
- 229920001187 thermosetting polymer Polymers 0.000 claims description 7
- 125000002091 cationic group Chemical group 0.000 claims description 6
- 239000003446 ligand Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 claims description 6
- 229930182558 Sterol Natural products 0.000 claims description 5
- 150000003432 sterols Chemical class 0.000 claims description 5
- 235000003702 sterols Nutrition 0.000 claims description 5
- 238000006467 substitution reaction Methods 0.000 claims description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical group [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 3
- 150000002923 oximes Chemical class 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000002738 chelating agent Substances 0.000 claims description 2
- 125000003544 oxime group Chemical group 0.000 claims description 2
- 239000003229 sclerosing agent Substances 0.000 claims 2
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 claims 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims 1
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 229910052797 bismuth Inorganic materials 0.000 claims 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims 1
- 210000003298 dental enamel Anatomy 0.000 claims 1
- 239000007789 gas Substances 0.000 claims 1
- 239000002689 soil Substances 0.000 claims 1
- 229910052727 yttrium Inorganic materials 0.000 claims 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 28
- 150000001768 cations Chemical class 0.000 abstract description 19
- 230000002708 enhancing effect Effects 0.000 abstract 1
- 230000008878 coupling Effects 0.000 description 56
- 238000010168 coupling process Methods 0.000 description 56
- 238000005859 coupling reaction Methods 0.000 description 56
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 52
- 229910000077 silane Inorganic materials 0.000 description 52
- 239000011247 coating layer Substances 0.000 description 20
- 238000003860 storage Methods 0.000 description 15
- DIOQZVSQGTUSAI-UHFFFAOYSA-N n-butylhexane Natural products CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 229910052782 aluminium Inorganic materials 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- 239000007822 coupling agent Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- -1 silicane compound Chemical class 0.000 description 7
- 229920005992 thermoplastic resin Polymers 0.000 description 7
- 239000004593 Epoxy Substances 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 239000002313 adhesive film Substances 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
- ULDHMXUKGWMISQ-UHFFFAOYSA-N carvone Chemical compound CC(=C)C1CC=C(C)C(=O)C1 ULDHMXUKGWMISQ-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- CDOSHBSSFJOMGT-UHFFFAOYSA-N linalool Chemical compound CC(C)=CCCC(C)(O)C=C CDOSHBSSFJOMGT-UHFFFAOYSA-N 0.000 description 4
- 239000004575 stone Substances 0.000 description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000005973 Carvone Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 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 2
- 238000010276 construction Methods 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 239000004849 latent hardener Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000013034 phenoxy resin Substances 0.000 description 2
- 229920006287 phenoxy resin Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000001490 (3R)-3,7-dimethylocta-1,6-dien-3-ol Substances 0.000 description 1
- CDOSHBSSFJOMGT-JTQLQIEISA-N (R)-linalool Natural products CC(C)=CCC[C@@](C)(O)C=C CDOSHBSSFJOMGT-JTQLQIEISA-N 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- RAXXELZNTBOGNW-UHFFFAOYSA-N 1H-imidazole Chemical compound C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 101100206181 Arabidopsis thaliana TCP15 gene Proteins 0.000 description 1
- MHZGKXUYDGKKIU-UHFFFAOYSA-N Decylamine Chemical compound CCCCCCCCCCN MHZGKXUYDGKKIU-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 101100208473 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) lcm-2 gene Proteins 0.000 description 1
- 241000239226 Scorpiones Species 0.000 description 1
- 229910008051 Si-OH Inorganic materials 0.000 description 1
- 229910006358 Si—OH Inorganic materials 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 241001147388 Uncia Species 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000004840 adhesive resin Substances 0.000 description 1
- 229920006223 adhesive resin Polymers 0.000 description 1
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Natural products C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 1
- 125000005577 anthracene group Chemical group 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- XTKDAFGWCDAMPY-UHFFFAOYSA-N azaperone Chemical compound C1=CC(F)=CC=C1C(=O)CCCN1CCN(C=2N=CC=CC=2)CC1 XTKDAFGWCDAMPY-UHFFFAOYSA-N 0.000 description 1
- XYOVOXDWRFGKEX-UHFFFAOYSA-N azepine Chemical compound N1C=CC=CC=C1 XYOVOXDWRFGKEX-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical group CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 229930182470 glycoside Natural products 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 229930007744 linalool Natural products 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical compound C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 description 1
- CQBIFASRYMRWLF-UHFFFAOYSA-N oxidosulfanium Chemical group [SH2]=O CQBIFASRYMRWLF-UHFFFAOYSA-N 0.000 description 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-M phenolate Chemical compound [O-]C1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-M 0.000 description 1
- 229940031826 phenolate Drugs 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 229920002098 polyfluorene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
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- 238000011160 research Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000002485 urinary effect Effects 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Landscapes
- Adhesives Or Adhesive Processes (AREA)
- Epoxy Resins (AREA)
Abstract
Description
1275602 玖、發明說明 【發明所屬之技術領域】 本發明係有關接著劑，尤其是與半導體晶片與TCP利用 熱壓著方式連接時所使用之接著劑的硬化劑粒子有關。 【先前技術】 過去，在基板上要接著半導體晶片時，或是TCP (TapeBACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an adhesive, particularly to a hardener particle of an adhesive used when a semiconductor wafer and a TCP are thermally bonded. [Prior Art] In the past, when a semiconductor wafer was to be attached to a substrate, or TCP (Tape)
Carrier Package)與 LCD (Liquid Crystal Display)在接著製造電 氣設備時，都是採用含熱硬化性樹脂環氧樹脂的接著劑。 如第9 (a)圖的符號ill所顯示的LCD，LCD111包含玻 璃基板112、配置在玻璃基板112上的ITO電極（Indium tinoxide) 113。LCD111在與後述的TCP接著時，首先要在 LCD111的ITO電極113所要配置的面上塗上接著劑。第9 (b) 圖的符號125是LCD111上塗抹了接著劑後的情形。 第9 (C)圖的符號115所示為TCP，TCP115包括了基座 膠膜（base film) 116、配置在基座膠膜116表面上的金屬配線 117。TCP 115的金屬配線117在所配置的面，是朝著lcd 111 上的接著劑125配置，在對準位置後，tcPI 15的金屬配線117 的配置面會被按向接著劑125。 在這個狀態下壓住加熱的話，接著劑125會軟化，金屬配 線117會將軟化了的接著劑125按往後退，接觸到IT〇電極i J 3 的表面。 在上述的接著劑上，一般都添加了加熱後會與環氧樹脂重 1275602 合、像imidazol類的硬化劑，當金屬配線ι17與IT〇電極ll3 在黏接狀態下繼續加熱的話，由於硬化劑的觸媒作用，备使環 氧樹脂重合，讓接著劑125硬化。 第7(C)圖的符號1〇1所示的是接著劑ι25在硬化後狀態 下的電氣設備。該電氣設備101在金屬配線117與IT〇電極113 相接的狀態下，透過硬化了的接著劑125將TCP115與LCD111 固定住。因此TCP115與LCD111在電力上、機械上都相連接 在一起了。 但疋，上述的接著劑在使其硬化時，須以i 8〇。〇以上高溫 將接著劑加熱，當金屬配線117的電路非常細微時，加熱時會 造成TCP115發生伸長或縮短等變形的情形。這個問題可以藉 由降低加熱溫度來解決，但是就會延長加熱處理所需的時間， 降低生產性。 低溫下硬化性也很優異的接著劑在近年來開發出了丙烯 酸(A响e)之類邏輯重合性樹脂以及含有邏輯重合開始劑的 接著劑。但是這類接著劑和使用環氧樹脂相較之下，硬化狀態 下的電氣特性與耐熱性都較差。 【發明内容】 有鑑於此，本發明乃是為了解決上述舊有技術的問題所創 作的:其目的是為了提供—種能在低溫、短時間的條件下硬 化，同時具有優秀保存性的接著劑。 本發明的發明者等，不採用一般所使用 的硬化劑，而著眼 、l2756〇2 於使環氧樹脂做陽離子重合的手法上。經過反覆研究，找出了 以下方法：在構造中至少將一個烧氧基、構造中含有矽烧化合 物（石夕燒偶合劑（Silane Coupling))以及金屬螯合物（或是金屬 Alcolart)添加到接著劑中，利用金屬螯合物與矽烷偶合劑 (Silane Coupling)反應時所產生的陽離子讓環氧樹脂重合（陽離 子重合）。 添加了金屬螯合物與矽烷偶合劑（Silane Coupling)的接著 劑’讓環氧樹脂硬化的硬化工程以下列反應式（5)〜（8)來說明如 下。 【化5】 X-Si-〇R+H20—> X-Si-OH+R-OH 反應式（5) 丄1 + OH-Si-X 佥Carrier Package) and LCD (Liquid Crystal Display) use an adhesive containing a thermosetting resin epoxy resin in the subsequent manufacture of electrical equipment. As shown in the symbol ill of Fig. 9(a), the LCD 111 includes a glass substrate 112 and an ITO electrode 113 disposed on the glass substrate 112. When the LCD 111 is next to the TCP to be described later, first, an adhesive is applied to the surface on which the ITO electrode 113 of the LCD 111 is to be placed. The symbol 125 in Fig. 9(b) is the case where the adhesive is applied to the LCD 111. Reference numeral 115 in Fig. 9(C) shows TCP, and TCP 115 includes a base film 116 and a metal wiring 117 disposed on the surface of the susceptor film 116. The metal wiring 117 of the TCP 115 is disposed toward the adhesive 125 on the lcd 111 on the disposed surface, and after the alignment position, the arrangement surface of the metal wiring 117 of the tcPI 15 is pressed toward the adhesive 125. When the heating is pressed in this state, the adhesive 125 softens, and the metal wiring 117 pushes the softened adhesive 125 back to contact the surface of the IT 〇 electrode i J 3 . On the above-mentioned adhesive, a hardener which is combined with an epoxy resin and has a weight of 1,275,602 and an imidazol type is generally added. When the metal wiring ι17 and the IT〇 electrode 113 are heated in a bonded state, the hardener is added. The catalyst acts to make the epoxy resin overlap and harden the adhesive 125. The symbol 1〇1 of Fig. 7(C) shows the electrical equipment in the state in which the adhesive ι25 is hardened. In the state where the metal wiring 117 is in contact with the IT 〇 electrode 113, the electric device 101 fixes the TCP 115 and the LCD 111 through the cured adhesive 125. Therefore, the TCP 115 and the LCD 111 are electrically and mechanically connected. However, the above-mentioned adhesive must be i 8 在 when it is hardened. The high temperature of the crucible is heated by the adhesive. When the circuit of the metal wiring 117 is very fine, the TCP 115 may be deformed by elongation or shortening when heated. This problem can be solved by lowering the heating temperature, but it will prolong the time required for the heat treatment and reduce the productivity. In the recent years, an adhesive having excellent curability at low temperature has developed a logic-adhesive resin such as acrylic acid (A ringing e) and a binder containing a logical coincidence initiator. However, such an adhesive is inferior in electrical properties and heat resistance in a hardened state as compared with the use of an epoxy resin. SUMMARY OF THE INVENTION In view of the above, the present invention has been made to solve the above problems of the prior art: the purpose is to provide an adhesive capable of hardening under low temperature and short time conditions while having excellent preservability. . The inventors of the present invention do not use a hardener which is generally used, but pay attention to the method of making the epoxy resin cation-coincident. After repeated research, the following methods were found: at least one alkoxy group in the structure, a silicane compound (Silane Coupling) and a metal chelate (or metal Alcolart) were added to the structure. In the subsequent agent, the cation generated by the reaction of the metal chelate with the silane coupling agent (Silane Coupling) causes the epoxy resin to overlap (cationic superposition). A hardening process in which a metal chelate compound and a silane coupling agent (Silane Coupling) is added to harden an epoxy resin is explained by the following reaction formulas (5) to (8). [Chemical 5] X-Si-〇R+H20—> X-Si-OH+R-OH Reaction formula (5) 丄1 + OH-Si-X 佥
Al-0-Si-X+RH 反應式（6)Al-0-Si-X+RH reaction formula (6)
^Al-O-Si-X+X-Si-OH—^Al-O-Si-X+X-Si-OH-
X-Si 尽 Jf Al-〇-Si-X 反應式（7) R-CH-CH2 — R-CH-CH2 \〇/ H+ />H* R-CH-CH2 r-ch-ch2 o R-CH-(^H2 反應式（8) 1275602 至少擁有一個烷氧基的矽烷化合物，如反應式（5)所示， 與接著劑中的水反應’烧氧基就會加水分解，成為秒烧醇 (Silanol)基。 將接著劑加熱，矽烷醇基會與像鋁螯合物這類的金屬螯合 物產生反應，矽烷化合物會與鋁螯合物結合。（反應式（6)) 然後如反應式（3)所示，矽烷醇基與結合了的鋁螯合物因 為平衡反應，接著劑中殘留的其他矽烷醇基會配位，產生 Branstade酸點，如反應式（4)所示，因為活性化了的質子的關 係，位於環氧樹脂末端的環氧環就會打開環，與其他的環氧樹 脂的環氧環相重合（陽離子重合）。因此，將矽烷偶合劑（Silane Coupling)與金屬螯合劑添加到接著劑中時，像環氧樹脂這類的 熱硬化樹脂就會發生陽離子重合。反應式（2)〜（4)所示的反應， 是在比舊有接著劑硬化的溫度（18〇°c以上）還低的溫度下進 行的，因此前述的接著劑比起舊有的接著劑，可在較低溫、短 時間内硬化。 但是，矽烷偶合劑（Silane Coupling)容易加水分解，而且 與該矽醇（Silanol)，金屬螯合物或金屬Alcolart的反應性报 南’因此當以粉體狀的金屬螯合物或金屬Alcolart作為硬化性 粒子直接分散到接著劑中時，在常溫下也會與環氧樹脂發生重 合反應，接著劑的保存性很差。 本發明即是基於上述創見的結果，發現在硬化劑粒子添加 、1275602 著4之則，讓硬化劑粒子表面舆石夕炫偶合劑（Silane Couphng)(矽醇）或乙醇等含有氫氧基之化合物接觸，讓該化 合物與硬化劑粒子表面的中心、金屬產生反應，就能提高接著劑 的保存性。 本發明係根據以上的見地，申她 — ^ 甲明專利乾圍1所記載的發 明’係一種硬化劑粒子 千其主成&包含中心金屬有一個配位子 配位的金屬螯合物，或 疋γ I屬田中至少有一個與烷氧基 (Alk〇Xy)結合的金屬Alcolart，兩者之 w。 句者之一或兩者皆具的硬化 背J粒子’在位於前述硬 … 4更化㈣子表面的前述中心金屬中，石夕透 過氧結合之硬化劑粒子。 申請專利範圍2所記載之發明备 戰之^月係如申請專利範圍1所記 載之硬化劑粒子，甘命> L, » Α 合。UK中心金屬結合的秒，透過氧相互結 申請專利範圍3所記#夕恭日日^ ^ 載之4又月，係如申請專利範圍1或申 請專利範圍2之任何一頊^截 乂 ^己载，則述石夕，如以下一般式所 【化6】 … ΝΗ2 般式（1) X1 (上述一般式中’置換基X1與前㈣結合。） 該硬化劑粒子，與上述所示之置換基相結合。 申請專利範圍4所記载發 ^月係如申請專利範圍1或1 ^ 1275602 两述秒 如以下一般式所示（2) 請專利範圍2之钮打 s 又任何一項記載 【化7】X-Si by Jf Al-〇-Si-X Reaction formula (7) R-CH-CH2 — R-CH-CH2 \〇/ H+ />H* R-CH-CH2 r-ch-ch2 o R- CH-(^H2 Reaction formula (8) 1275602 A decane compound having at least one alkoxy group, as shown in the reaction formula (5), reacts with water in the binder, and the alkoxy group is hydrolyzed to form a second calcined alcohol. (Silanol) base. The adhesive is heated, the stanol group reacts with a metal chelate such as an aluminum chelate, and the decane compound combines with the aluminum chelate (reaction formula (6)) and then reacts. As shown in the formula (3), the decyl alcohol group and the combined aluminum chelate compound are coordinated by the equilibrium reaction, and other stanol groups remaining in the binder are coordinated to produce a Branstade acid point, as shown in the reaction formula (4), because The relationship between the activated protons, the epoxy ring at the end of the epoxy resin opens the ring and coincides with the epoxy ring of other epoxy resins (cationic overlap). Therefore, the silane coupling agent (Silane Coupling) When a metal chelating agent is added to an adhesive, a thermosetting resin such as an epoxy resin undergoes cation overlap. Reaction formulas (2) to (4) The reaction is carried out at a temperature lower than the temperature at which the old adhesive is hardened (above 18 ° C), so that the aforementioned adhesive can be hardened at a lower temperature and in a shorter time than the old adhesive. However, the silane coupling agent (Silane Coupling) is easily hydrolyzed and reacts with the sterol (Silanol), metal chelate or metal Alcolart. Therefore, when it is a powdery metal chelate or metal Alcolart When the curable particles are directly dispersed in the adhesive, the reaction proceeds to the epoxy resin at room temperature, and the storage property of the adhesive is poor. The present invention is based on the results of the above-mentioned findings and is found to be added to the hardener particles. 1275602 According to 4, the surface of the hardener particles is contacted with a compound containing a hydroxyl group such as Silane Couphng (sterol) or ethanol, and the compound reacts with the center of the surface of the hardener particle and the metal. According to the above findings, the invention is based on the above-mentioned findings - the invention described in the patent of the company is a kind of hardener particle. a metal chelate containing a ligand coordinated to the central metal, or a metal Alcolart having at least one alkoxy group (Alk〇Xy) in the field of 疋γI, both of which are w. One or both of the hardened back J particles 'in the aforementioned central metal located on the surface of the above-mentioned hardened (four) sub-surface, the ceremonial oxygen-bonded hardener particles. The invention described in claim 2 is prepared for ^月 is the hardener particles described in Patent Application No. 1, and is called L, », Α. UK center metal combined seconds, through the oxygen mutual agreement patent application scope 3 records #夕恭日日 ^ ^ 4 months, such as the application for patent scope 1 or the scope of patent application 2 顼 ^ 乂 ^ In the case of Shi Xi, the following general formula [Chem. 6] ... ΝΗ 2 General formula (1) X1 (In the above general formula, 'substituent X1 is combined with the former (four).) The hardener particles, and the replacement shown above The base phase is combined. Apply for the patent range 4, such as the patent application scope 1 or 1 ^ 1275602 two seconds as shown in the following general formula (2) Please click the patent range 2 button s and any record [Chem. 7]
…一般式（2) X4至少有一個置 (上述—般式（2)中，置換基X2〜X4中，χ2 換基與前述矽結合。） 該硬化劑粒子與上述所示之置換基相結合。 在此，取代基X1可為_Ch2CH2cH2_、 Ch2=2CH2NHCH2Ch2_、_CH2CH2CH2NHCd·，取代基 χ2 可為苯基、H、(Ch2)n_ (η為整數），與石夕輕合的取代基 可為-O^CH^Ct^NHCi^Ch2-、-CH2CH2CH2NHC(=0)-。 申請專利範圍5所記載之發明，係、一種硬化劑粒子，其主 成份包含中心金屬有一個配位子配位的金屬螯合物，或是中心 金屬田中至少有一個與烷氧基（Alk〇xy)結合的金屬八丨⑶^戍， 兩者之一或兩者皆具的硬化劑粒子，在位於前述硬化劑粒子表 面的前述中心金屬中，透過氧與碳結合之硬化劑粒子。 申請專利範圍6所記載之發明，係一種硬化劑粒子的製造 方法，一般式（3) 1275602 【化8】 X6 X7 Ji—_χ8General formula (2) X4 has at least one set (in the above formula (2), in the substituents X2 to X4, the χ2 group is bonded to the above ruthenium.) The hardener particles are combined with the above-described substituents. . Here, the substituent X1 may be _Ch2CH2cH2_, Ch2=2CH2NHCH2Ch2_, _CH2CH2CH2NHCd., the substituent χ2 may be phenyl, H, (Ch2)n_ (η is an integer), and the substituent bonded to Shi Xi may be -O ^CH^Ct^NHCi^Ch2-, -CH2CH2CH2NHC(=0)-. The invention described in claim 5 is a hardener particle whose main component comprises a metal chelate compound in which a central metal has a ligand coordination, or at least one of a central metal field and an alkoxy group (Alk〇) The xy) bonded metal gossip (3) is a hardener particle having one or both of them, and the hardener particles which are combined with oxygen and carbon are transmitted through the center metal located on the surface of the hardener particle. The invention described in Patent Application No. 6 is a method for producing a hardener particle, and the general formula (3) 1275602 [Chemical 8] X6 X7 Ji-_χ8
5 一般式（3) (述身又式（3)中的置換基Χ5〜Χ6中，至少有一個置換基為 燒氧基。） 、、弋子所示之妙烧偶合劑（Silane Coupling)經加水分解形 成㈣（SllanGl) ’中心金屬至少有-個配位子為結合過之金屬 螯口物4疋在中心金屬中至少有—個與烧氧基結合之金屬 A—an，該硬化劑粒子之主成份為以上其中一種，或兩種皆 有，又，一種硬化劑粒子的製造方法，該製造方法係為與前述 石夕醇接觸，讓位於前述硬化劑粒子表面的中心、金屬與前述的石夕 醇反應，形成下列-般式⑷所示之石夕氧燒如⑽狀）的硬化劑 粒子製造方法。 【化9】 X10 般式（4) x9」i—X11 (上述一般式（4)中，與矽結合的氧盥前 半述的中心金屬結合。） 申請專利範圍7所記載之發明，择 係如申請專利範圍6所記 載之硬化劑粒子的製造方法，該方法择A &、、 ’、在爾述一般式（4)所示與 矽氧烷的矽結合的置換基X9〜X11中，吞ϊ 至少有一個置換基與環 1275602 氧樹脂產生反應。 申吻專利範圍8所記載之發明，係如申請專利範圍7所記 載之硬化跡子的製造料，在前述與前述環氧樹脂產生反應 的置換基的構造中含有氨基。 申明專利圍9所記載之發明，係如中請專利範圍8所記 載之硬化齡子的製造方法。該硬化劑粒子的主成份含以下一 種或兩種白具’即在中心金屬有一個配位子配位的金屬螯合 物或疋在中心金屬當中至少有一個與烧氧基（Alkoxy )結合 的金屬Alcolart。此硬化劑粒子與含氫氧基之化合物接觸，讓 位於刖述硬化劑粒子表面之前述中心金屬與含有前述氯氧基 之化合物產生反應。 申明專利圍1G所記載之發明，係如中請專利範圍9所 記載之硬化餘子的製造方法。其前述含有氫氧基之化合物是 由乙醇所構成。 申π專利圍11所§己載之發明，係如中請專利範圍9所 記載之硬㈣粒子的製造方法。其前述含有氫氧基之化合物係 由二丙二醇（Tdpropyiene glyc〇1)所構成。 申請專利範圍 12所記載之發明，係一種接著劑，含有熱 硬化性樹脂、矽烷偶合劑（Silane5 General formula (3) (In the substitution formula 35 to Χ6 in the formula (3), at least one of the substituents is an alkoxy group.), and the Silane Coupling shown by the scorpion Addition of water to form (4) (SllanGl) 'The central metal has at least one ligand which is a combined metal chelate 4疋. At least one metal A-an combined with an alkoxy group in the central metal, the hardener particle The main component is one of the above, or both, and a method for producing a hardener particle, which is in contact with the aforementioned linalol to give a center of the surface of the hardener particle, a metal and the foregoing The reaction of the linalool forms a method for producing a hardener particle of the following (10) as shown in the following formula (4). X10 General formula (4) x9"i-X11 (In the above general formula (4), the central metal of the first half of the oxygen oxime bonded to ruthenium is bonded.) The invention described in claim 7 is selected as follows. A method for producing a hardener particle according to Patent Application No. 6, wherein the method selects A &,, and, in the substitution group X9 to X11 which is bonded to the oxime of the oxime represented by the general formula (4), is swallowed.至少 At least one of the substituents reacts with the ring 1275602 oxygen resin. The invention described in Patent Application No. 8 is a material for producing a hardened trace as described in Patent Application No. 7, and an amino group is contained in the structure of the substituent which reacts with the epoxy resin. The invention described in Patent Publication No. 9 is a method for producing a curing age as described in Patent Application No. 8. The main component of the hardener particles contains one or two of the following: a metal chelate having a ligand coordinated to the central metal or at least one of the central metals bonded to the alkoxy group. Metal Alcolart. The hardener particles are contacted with the hydroxyl group-containing compound to cause the central metal located on the surface of the hardener particles to react with the compound containing the above oxy group. The invention described in Patent Publication 1G is a method for producing a hardened remainder as described in Patent Application No. 9. The above-mentioned compound containing a hydroxyl group is composed of ethanol. The invention of § 专利 专利 11 is a method for producing hard (tetra) particles as described in Patent Application No. 9. The above-mentioned compound containing a hydroxyl group is composed of dipropylene glycol (Tdpropyiene glyc glycoside 1). Patent Application No. 12 is an adhesive comprising a thermosetting resin and a decane coupling agent (Silane).
Coupling)，以及如中請專利範 圍 至5之任何一項所記載之硬化劑粒子。 本發明的構成如上，當硬彳卜添| ▲ 更化J粒子表面與一般式（3)所示 12 1275602 之石夕院偶合劑（Silane Coupling)接觸，首先，石夕烧偶合劑（Silane Coupling)的烧氧基（Alkoxy)會加水分解成為石夕烧醇 (Silanol)，該矽烷醇會與位於硬化劑粒子表面的金屬螯合物， 或是金屬Alcolart脫水結合，該金屬螯合物或金屬Alcolart的 中心金屬與石夕烧醇的石夕會透過氧結合石夕氧烧（Siloxane)結合，獲 得本發明之硬化劑粒子。 另外，石夕烧偶合劑（Silane Coupling)會因為附著在硬化劑 粒子表面的水分、空氣中的水分加水分解，但是為了促進處理 速度，也可以將石夕烧偶合劑（Silane Coupling)加水，事先進行石夕 烷醇（Silanol)化後再予硬化劑粒子反應亦可。 由於位於本發明之硬化劑表面的中心金屬與矽氧烷 (Siloxane)結合，因此本發明之硬化劑粒子在添加到接著劑時， 在常溫下硬化劑粒子不會與接著劑中的矽烷偶合劑（Silane Coupling)發生反應，接著劑不會硬化，當接著劑被熱壓著時， 因為加熱會使硬化劑粒子產生熱膨脹，熱膨脹了的硬化劑粒子 會因為加壓等物理性衝擊而破裂，硬化劑粒子表面以外的部份 會露出。 由於不位於硬化劑粒子表面的中心金屬不會與矽氧烷 (Siloxane)結合，該中心金屬與接著劑中的石夕烧偶合劑（Silane Coupling)會因為加熱產生反應，生成陽離子。陽離子與環氧樹 脂發生重合（陽離子重合），接著劑會硬化。因此本發明之硬 13 1275602 化性粒子具有所謂的潛在性硬化劑的機能。 而且，硬化劑粒子與矽烷偶合劑（Silane Coupling)的反 應，比統的接著劑發生熱硬化的溫度（180°c以上）還低溫， 因此本發明之接著劑能以更低溫、更短時間内硬化。 此外’硬化劑粒子表面的中心金屬與石夕烧偶合劑（SUane Coupling)發生反應的工程中也會產生陽離子，所以在接著劑中 添加表面剛形成石夕氧烧（Siloxane)的硬化劑粒子，因為殘留在硬 化劑粒子表面的陽離子，可能會造成接著劑在常溫下硬化，但 是在將硬化劑粒子添加到接著劑之前，如果以水或有機溶劑將 之洗淨，就可以去除硬化劑粒子上殘餘的陽離子或過剩的石夕烧 偶合劑（Silane Coupling)等。 如果使用非烧乳基置換基’如有氨基之氨基（Amino)碎烧 偶合劑（Silane Coupling)時，會形成含氨基之矽氧烷 (Siloxane)。在此狀態之硬化劑粒子，如又接觸到環氧樹脂，與 碎氧烧（Siloxane)的氨基、環氧樹脂的環氧環反應時，環氧樹脂 就會與矽氧烷（Siloxane)結合。因此，硬化劑粒子的表面的石夕氧 烷（Siloxane)的構造會變得更複雜，硬化劑粒子的機械性強度也 會更高。 如果以乙醇等含有氫氧基之化合物代替石夕烧偶合劑 (Silane Coupling)與硬化劑粒子表面接觸的話，硬化劑粒子表面 的金屬螯合物或金屬Alcolart與該化合物的氫氧基發生脫水縮 14 1275602 合，位於硬化劑粒子表面的中心金屬會透過氧與該化合物結 合。如此所得到的硬化劑粒子會與形成矽氧烷（Sil〇xane)相同 地，具有潛在性硬化劑的機能。 如果使用乙醇作為含氫氧基之化合物時，雖然乙醇的種類 沒有特別限定，如果使用一價乙醇類的乙醇時，硬化劑粒子表 面很難形成架橋結構，與中心金屬結合的分子會變成一次元的 直鎖狀。在此情形下，包覆在硬化劑表面的膜狀分子的剛性會 變低。但疋，如果採用反應性高，具有官能基的一價乙醇的話， ◎亥g ib基會與其他物質反應，也可讓硬化劑粒子表面的膜狀分 子剛性提高。 此外，含氳氧基的化合物還可以使用香芹酮（carvone) 酸。 接著劑中如果添加熱可塑性樹脂，熱可塑性樹脂的性質可 增加接著劑的凝結力，提高接著劑的接著力。如果使用極性很 高的熱可塑性樹脂，熱可塑性樹脂不僅可帶來樹脂成份的硬化 反應’還可透過矽烧偶合劑（Snane coupling)與無機材料結合， 提高硬化性，且所獲得的接著劑與無機材料構成之被黏著體具 有更面的親和性。 為讓本發明之上述目的、特徵、和優點能更明顯易懂，下 文特舉一較佳實施例，並配合所附圖式，作詳細說明如下： 【實施方式】 15 1275602 以下說明製造本發明之接著劑的工程。 第1(a)圖所示之化學式左方為使用本發明之矽烷偶合劑 (Silane Coupling)的一例。該石夕院偶合劑（Silane Coupling)擁有 4個置換基Xa〜Xd，其中3個置換基Xb〜Xd會透過氧與矽烷 偶合劑（Silane Coupling)的石夕結合。因此，該石夕烧偶合劑（Silane Coupling)擁有 3 個烧氧基（Alkoxy )。 該石夕烧偶合劑（Silane Coupling)在加熱到規定溫度後，粉 狀體金屬螯合物或金屬Alcolart (這裡的中心金屬為铭）所構 成的硬化劑粒子會分散到碎烧偶合劑（Silane Coupling)中，將該 石夕烧偶合劑（Silane Coupling)保持在規定温度，同時進行擾拌。 空氣中的水分、硬化劑粒子表面所附著的水份如果接觸到 石夕炫偶合劑（Silane Coupling)，石夕烧偶合劑（Silane Coupling)的 3個烧氧基（Alkoxy )會分別加水分解，成為氫氧基。第1 (a)圖 的化學式右邊為秒烧偶合劑（Silane Coupling)加水分解後的石夕 醇（Silanol ) 〇 第1(b)圖的符號31所示為分散到矽烷偶合劑（Silane Coupling)中的硬化劑粒子。該圖的符號34為位於硬化劑粒子 31表面的中心金屬（這裡使用的是鋁），中心金屬34與置換基 X0結合。如果硬化劑粒子31為鋁螯合物的話，置換基X0為 配位子。如果硬化劑粒子3 1為IS Alcolart時，置換基X0則為 烧氧基。 16 1275602 將石夕烧偶合劑（Silane Coupling)維持在規定溫度繼續擾拌 的話，硬化劑粒子31表面的中心金屬34會因為矽烷偶合劑 (Silane Coupling)的加水分解所生成的石夕醇反應，石夕醇中的石夕透 過氧與中心金屬34結合，形成石夕氧烧（Siloxane)。此時，石夕醇、 其他的矽醇會發生反應，在硬化劑粒子31表面形成聚矽氧烷 (Poly-Siloxane) 〇 第1(c)圖所示為上述狀態，該圖的符號32為形成於硬化 劑粒子3 1表面的聚石夕氧烧（Poly-Siloxane)。聚石夕氧烧 (Poly-Siloxane)32中的各石夕，會分別與位於硬化劑粒子31表面 的中心金屬34，這麼一來，構成聚石夕氧烧（Poly-Siloxane)32的 石夕氧烧（Siloxane)，會在硬化劑粒子31表面配置成單分子層 狀。此外，聚石夕氧烧（Poly-Siloxane)32的各個石夕會透過氧相互 結合，所以也會提高聚矽氧烷（Poly-Siloxane)32的機械性強度。 接著，聚石夕氧烧（Poly-Siloxane)32會將所形成狀態下的硬 化劑粒子3 1從Silane Coupling中拉出來。在此狀態下，石夕烧 偶合劑（Silane Coupling)與中心金屬34在發生反應時所產生的 陽離子3 6 (氫離子）與未與該中心金屬結合、過剩的石夕烧偶合 劑（Silane Coupling)(含石夕醇（Silanol)會殘留在聚石夕氧烧 (Poly-Siloxane) 32 的表面。 在此狀態下的硬化劑粒子31經過水洗，就會除去殘留的 陽離子36與矽烷偶合劑（Silane Coupling)，得到本發明第一例 17 1275602 之硬化劑粒子30 (第1(d)圖）。 接下來，說明使用本發明第一例之硬化劑粒子3〇所製造 的本發明劑，以及使用本發明之接著劑製造電器裝置的工程。 將屬熱硬化性樹脂的環氧樹脂、熱可塑性樹脂、石夕烧偶合劑 (Silane Coupling)、本發明第—例之硬化劑粒子3〇、導電性粒 子、溶劑分別依規定的添加比率混合攪拌，做成糨糊狀的接著 劑。 在此狀悲下，硬化劑粒子3〇表面的中心金屬34與聚石夕氧 烷（P〇ly-Sil〇xane)32結合在一起，因此接著劑中的矽烷偶合劑 (Silane Coupling)與中心金屬34不會發生反應，不會生成陽離 子。此外，殘留在聚石夕氧燒（p〇ly_Sil〇xane)32的陽離子也被去 除了，因此接著劑中環氧樹脂不會發生陽離子重合反應，接著 劑在常溫下不會硬化。 第2(a)圖的符號21所顯示的是剝離膠膜。將上述接著劑 以一定量塗抹於此剝離膠膜21表面，乾燥後接著劑中的溶劑 會揮發掉，形成接著劑的塗佈層（第2(b)圖）。 第2(b)圖的付波20顯不的是形成了塗佈層25狀態的接 著膜。該圖的符號27所示為隨著潛在性硬化劑30 —起分散到 接著劑中的導電性粒子。 第3(a)圖的符號u所示為LCD，LCD11在玻璃基板12、 玻璃基板12的一面上形成狹窄、多支的IT〇電極13(Indiurntin 18 1275602 oxide )。此圖所示為5條的IT〇電極丨3。 在LCD 11开y成ITO電極13的面上，連接後述的部 份對準第2(b)圖所示支接著膜2〇的塗佈層乃（第3(b)圖）。 剝離膜2丨與塗佈層25的接著力，由於比塗佈層25與汀〇電 極13之間的還小，因此當剝離膜21剝離後，塗佈層乃就留 在LCD11上（第3(c)圖）。 第5圖符號15所示為TCP。TCpi5有長形的基礎膜16, 在基礎膜16的一面上，狹窄的金屬配線17沿著基礎膜16的 長度方向配置（在此的圖示為5條的金屬配線）了好幾條。金 屬配線17在長度方向的末端分別位於基礎膜16的長度方向的 末端。 第3(d)圖所示為第5圖中A-A線截面圖，在配置有TCpl5 金屬配線17那一側的面上，朝向配置有LCD11IT〇電極， TCP15的一端與IT0電極13的塗佈層25相對，lcdii的ιτ〇 電極I3與TCPI5的金屬配線17相互相對。 在此狀態下，將TCP15的金屬配線17所配置的面按壓向 塗佈層25,將相重疊的部份按壓在一起，然 後整體作加熱，這麼一來塗佈層25就會軟化，因為按壓金屬 配線17會將軟化了的塗佈層25按壓後退，殘留的塗佈層25 中的導電性粒子27就會被夾在金屬配線17與IT〇電極13之 間（第4(e)圖）。 19 1275602 在這個狀態下如果繼續加熱按壓，加熱會使因為熱膨脹之 該硬化性粒子30加壓膨脹而破裂，硬化劑粒子3〇表面以外的 部份就會外露。硬化劑粒子3 1表面以外部份的金屬螯合物或 金屬Alcolart由於未與矽氧烷（Sil〇xane)結合，因此，第4(f)圖 的符號35所示破裂了的硬化劑粒子會與塗布層25中的石夕炫偶 合劑（Silane Coupling)接觸，塗布層25中的矽烷偶合劑（silane Coupling)、金屬螯合物或金屬Alcolart產生反應，生成陽離子。 塗佈層25中的陽離子就會被釋放出來。該陽離子會使環 氧進行（陽離子重合），金屬配線17與It〇電極13就會在包夾 住導電性粒子27,在此狀態下塗佈層25就會硬化。（第4(f)圖） 第4(f)圖的符號1 〇所示為塗佈層25在硬化狀態下的電 氣設備。該電氣設備10不僅其金屬配線17與It()電極13透過 導電性粒子27電子得以繼續連接，LCDU與TCpi5也會硬化 了的塗佈層25而產生機械性的連接。 這麼來’本發明之接著劑不僅擁有優秀的保存性，還因 為陽離子的重合而使環氧樹脂硬化，比過去的硬化劑更能在低 溫、短時間下讓接著劑硬化。 以上說明了將硬化劑粒子分散到矽烷偶合劑（以丨⑽㊁ Coupling)之方法，但本發明之用途並不在此限。 第6(a)圖的符號41所示與第1(句圖相同為硬化劑粒 子在硬化劑粒子41表面的中心金屬44中，結合了與第i (a) 20 1275602 〜（d)圖相同工程所形成的聚矽氧烷（p〇ly_sil〇xane) 42。該圖 的符號43所示，為不透過氧直接與聚矽氧烷（p〇ly_sil〇xane)42 的石夕直接結合的置換基’這裡的置換基43包括與矽結合的置 換基Xa’，以及與該置換基Xa，末端接合的氨基。因此，在此 狀態下氨基露出在聚矽氧烷（P〇ly_Sil〇xane)42的表面。 將常溫下呈液態的環氧樹脂加熱後，保持在固定溫度，將 第6(a)圖所示狀態的硬化劑粒子41分散到該環氧樹脂中。 第6(a)圖的符號46所示為該環氧樹脂的化學式。環氧樹 脂46包含了主骨骼Ra以及與主骨骼Ra末端結合的環氧環， 當硬化劑粒子41表面的聚矽氧烷（p〇ly-Sil〇xane)42的氨基與環 氧樹脂46接觸，氨基會與環氧樹脂46發生反應，得到本發明 第二例之硬化劑粒子40。這裡所示圖樣為對1個氨基，2個環 氧樹脂的環氧環發生反應的情形。 第6(b)圖的符號45為環氧樹脂46結合狀態下的聚矽氧 烷（Poly-Siloxane)。該聚矽氧烷（p〇iy_sil〇xane)45 與第 6(a)圖 的聚石夕氧烧（Poly-Siloxane)42比較起來構造更為複雜，因此本 發明第二例之硬化劑粒子40的機械強度更高。 此外，以上雖然說明了矽烷偶合劑（silane Coupling)與硬 化劑粒子表面的中心金屬發生反應的情形，但是本發明並不限 於此’只要擁有能與構成硬化劑粒子的金屬螯合物或金屬 Alcolart產生反應的官能基，也可以使用乙醇、香芹酮（carvone ) 21 、1275602 酉文等等的樹脂（聚合物、單體（m〇n〇mer)、齊聚合物（〇lig〇mer) 等）。 第7(a)圖的符號56為擁有2個氫氧基之乙醇（（di〇le)，Coupling), and the hardener particles as described in any one of the patents to 5th. The composition of the present invention is as described above, when the surface of the modified J particles is in contact with the Silane Coupling of 12 1275602 shown in the general formula (3), first, the Silane Coupling (Silane Coupling) The alkoxy group (Alkoxy) is hydrolyzed into Silanol, which is combined with a metal chelate on the surface of the hardener particles or a metal Alcolart dehydrated. The metal chelate or metal The central metal of Alcolart and the stone stalk of the smelting alcohol are combined by oxygen-bonded Siloxane to obtain the hardener particles of the present invention. In addition, Silane Coupling will decompose water due to moisture adhering to the surface of the hardener particles and moisture in the air. However, in order to promote the processing speed, it is also possible to add water to the Silane Coupling. It is also possible to carry out the reaction of the hardener particles after the Silanolization. Since the center metal located on the surface of the hardener of the present invention is combined with Siloxane, the hardener particles of the present invention are added to the adhesive, and the hardener particles do not react with the decane coupling agent in the adhesive at normal temperature. (Silane Coupling) reacts, the adhesive does not harden, and when the adhesive is heat-pressed, the heat-expanded hardener particles are thermally expanded due to heating, and the thermally expanded hardener particles are broken due to physical impact such as pressurization, hardening. Parts other than the surface of the agent particles are exposed. Since the central metal not located on the surface of the hardener particles does not bind to Siloxane, the central metal and the Silane Coupling in the adhesive cause a reaction due to heating to form a cation. The cations coincide with the epoxy resin (cationic overlap) and the binder hardens. Therefore, the hard 13 1275602 particles of the present invention have the function of a so-called latent hardener. Moreover, the reaction between the hardener particles and the silane coupling agent (Silane Coupling) is lower than the temperature at which the bonding agent is thermally hardened (180 ° C or more), so that the adhesive of the present invention can be cooled in a lower temperature and in a shorter time. hardening. In addition, cations are also generated in the process in which the central metal on the surface of the hardener particles reacts with the SUane Coupling, so that the hardener particles immediately forming the surface of Siloxane are added to the adhesive. Because the cation remaining on the surface of the hardener particles may cause the adhesive to harden at normal temperature, the hardener particles may be removed if it is washed with water or an organic solvent before the hardener particles are added to the adhesive. Residual cations or excess Silane Coupling and the like. If a non-calcined base-replacement group such as an amino group (Amino) calcining coupling agent (Silane Coupling) is used, an amino group-containing azepine (Siloxane) is formed. The hardener particles in this state, if contacted with an epoxy resin, are combined with the amino ring of Siloxane and the epoxy ring of the epoxy resin, and the epoxy resin is combined with Siloxane. Therefore, the structure of the surface of the hardener particles of Siloxane becomes more complicated, and the mechanical strength of the hardener particles is also higher. If a compound containing a hydroxyl group such as ethanol is used in place of the surface of the hardener particles instead of the Silane Coupling, the metal chelate or metal Alcolart on the surface of the hardener particles is dehydrated with the hydroxyl group of the compound. 14 1275602 The central metal on the surface of the hardener particles will combine with the compound through oxygen. The hardener particles thus obtained have the function of a latent hardener similarly to the formation of a siloxane (Sil〇xane). When ethanol is used as the compound containing a hydroxyl group, although the kind of the ethanol is not particularly limited, if a monovalent ethanol-based ethanol is used, it is difficult to form a bridging structure on the surface of the hardener particle, and the molecule bonded to the central metal becomes a single element. Straight lock. In this case, the rigidity of the film-like molecules coated on the surface of the hardener becomes low. However, if a monovalent ethanol having a high reactivity and a functional group is used, the oxime ib group reacts with other substances, and the film-like molecular rigidity on the surface of the hardener particles can be improved. Further, as the methoxy group-containing compound, carvone acid can also be used. If a thermoplastic resin is added to the subsequent agent, the properties of the thermoplastic resin can increase the cohesive force of the adhesive and increase the adhesion of the adhesive. If a highly polar thermoplastic resin is used, the thermoplastic resin can not only bring about a hardening reaction of the resin component, but also can be combined with an inorganic material through a Snane coupling to improve the hardenability, and the obtained adhesive is The adherend composed of an inorganic material has a more affinitive affinity. The above described objects, features, and advantages of the present invention will become more apparent from the description of the appended claims appended claims The engineering of the adhesive. The left side of the chemical formula shown in Fig. 1(a) is an example of a silane coupling agent (Silane Coupling) using the present invention. The Silane Coupling has four substituents Xa to Xd, and three of the substituents Xb to Xd are combined with oxygen and a samarane coupler (Silane Coupling). Therefore, the Silane Coupling has three alkoxy groups (Alkoxy). After the heating of the Silane Coupling to a specified temperature, the hardener particles composed of the powder metal chelate or the metal Alcolart (the central metal here) are dispersed to the crushing coupler (Silane). In Coupling, the Silane Coupling is kept at a predetermined temperature while being disturbed. If the moisture in the air and the water adhering to the surface of the hardener particles are in contact with the Silane Coupling, the three alkoxy groups of the Silane Coupling will be hydrolyzed separately. Become a hydroxyl group. The chemical formula on the 1st (a) is the Silane Coupling and the water-decomposed Silanol. The symbol 31 in Figure 1(b) shows the dispersion to the silane coupling agent (Silane Coupling). Hardener particles in. Reference numeral 34 in the figure is a center metal (aluminum used herein) on the surface of the hardener particles 31, and the center metal 34 is bonded to the substituent X0. If the hardener particles 31 are aluminum chelate compounds, the substituent X0 is a ligand. When the hardener particles 31 are IS Alcolart, the substituent X0 is an alkoxy group. 16 1275602 If the Silane Coupling is maintained at the specified temperature and continues to be disturbed, the central metal 34 on the surface of the hardener particles 31 will react with the sulphate produced by the hydrolysis of the silane coupling agent (Silane Coupling). Shi Xi, in Shishi alcohol, combines oxygen with central metal 34 to form Siloxane. At this time, the reaction of the linalool and other sterols occurs, and poly-Siloxane is formed on the surface of the hardener particles 31. The first state is shown in Fig. 1(c), and the symbol 32 of the figure is Poly-Siloxane formed on the surface of the hardener particles 31. Each of the stones in the Poly-Siloxane 32 will be respectively associated with the central metal 34 located on the surface of the hardener particles 31, thus forming a poly-Siloxane 32 stone eve. Siloxane is disposed in the form of a monomolecular layer on the surface of the hardener particles 31. Further, each of the stones of the Poly-Siloxane 32 is bonded to each other by oxygen, so that the mechanical strength of the poly-Siloxane 32 is also increased. Next, Poly-Siloxane 32 pulls the hardener particles 31 in the formed state out of the Silane Coupling. In this state, the cation 3 6 (hydrogen ion) generated by the reaction between the Silane Coupling and the central metal 34 is combined with the excess of the center metal (Silane Coupling). (Silanol is left on the surface of Poly-Siloxane 32. The hardener particles 31 in this state are washed with water to remove residual cations 36 and decane coupling agents ( Silane Coupling), the hardener particles 30 of the first example 17 1275602 of the present invention are obtained (Fig. 1(d)). Next, the inventive agent produced by using the hardener particles 3 of the first example of the present invention, and The use of the adhesive of the present invention for the manufacture of an electrical device. The epoxy resin, the thermoplastic resin, the Silane Coupling of the thermosetting resin, the hardener particles of the first embodiment of the present invention, and the conductive The particles and the solvent are mixed and stirred at a predetermined addition ratio to form a paste-like adhesive. In this case, the center metal 34 of the hardener particles 3 and the polyoxetane (P〇ly-Sil〇) Xane)32 knot When combined, the silane coupling agent (Silane Coupling) in the adhesive does not react with the central metal 34, and no cation is formed. Further, the cation remaining in the polyfluorene (p〇ly_Sil〇xane) 32 is also After being removed, the epoxy resin does not undergo a cationic superposition reaction in the adhesive, and the adhesive does not harden at normal temperature. The symbol 21 of Fig. 2(a) shows a peeling film. The amount is applied to the surface of the release film 21, and after drying, the solvent in the adhesive is volatilized to form a coating layer of the adhesive (Fig. 2(b)). The wave 20 of the second (b) is not shown. It is an adhesive film in a state in which the coating layer 25 is formed. Reference numeral 27 in the figure shows conductive particles dispersed in the adhesive together with the latent curing agent 30. The symbol u in Fig. 3(a) is shown. For the LCD, the LCD 11 forms a narrow, multi-legged IT 〇 electrode 13 (Indiurntin 18 1275602 oxide ) on one side of the glass substrate 12 and the glass substrate 12. This figure shows five IT 〇 electrodes 丨 3. On the LCD 11 y is formed on the surface of the ITO electrode 13 and the portion to be described later is aligned with the support shown in the second (b) diagram. The coating layer of the film 2〇 is (Fig. 3(b)). The adhesion of the release film 2丨 to the coating layer 25 is smaller than that between the coating layer 25 and the Ting electrode 13, so when peeling off After the film 21 is peeled off, the coating layer remains on the LCD 11 (Fig. 3(c)). Figure 15 is a symbol of Figure 15. TCP TCpi5 has an elongated base film 16 on one side of the base film 16. The narrow metal wires 17 are arranged along the longitudinal direction of the base film 16 (here, five metal wires are illustrated here). The ends of the metal wires 17 in the longitudinal direction are respectively located at the ends in the longitudinal direction of the base film 16. Fig. 3(d) is a cross-sectional view taken along line AA of Fig. 5, on the side on the side where the TCpl5 metal wiring 17 is disposed, facing the coating layer on which the LCD11IT〇 electrode, the one end of the TCP 15 and the IT0 electrode 13 are disposed. In contrast, the metal wirings 17 of the lcdii electrode I3 and the TCPI5 are opposed to each other. In this state, the surface on which the metal wiring 17 of the TCP 15 is placed is pressed against the coating layer 25, and the overlapping portions are pressed together, and then heated as a whole, so that the coating layer 25 is softened because of pressing. The metal wiring 17 presses and retreats the softened coating layer 25, and the conductive particles 27 in the remaining coating layer 25 are sandwiched between the metal wiring 17 and the IT 〇 electrode 13 (Fig. 4(e)) . 19 1275602 In this state, if the heating and pressing are continued, the heating causes the hardenable particles 30 which are thermally expanded to be ruptured by pressurization, and the portion other than the surface of the hardener particles 3 is exposed. Since the metal chelate or metal Alcolart of the portion other than the surface of the hardener particle 3 1 is not bonded to the sulfonium oxide, the cleavage agent particle shown by the symbol 35 of the fourth figure (f) will In contact with the Silane Coupling in the coating layer 25, a silane coupling agent, a metal chelate compound or a metal Alcolart in the coating layer 25 reacts to form a cation. The cations in the coating layer 25 are released. This cation causes the oxygen to proceed (cation superposition), and the metal wiring 17 and the It 〇 electrode 13 sandwich the conductive particles 27, and the coating layer 25 is hardened in this state. (Fig. 4(f)) The symbol 1 of Fig. 4(f) shows the electric device in which the coating layer 25 is in a hardened state. In the electric device 10, not only the metal wiring 17 and the It () electrode 13 are continuously connected to each other through the conductive particles 27, but the LCD layer and the TCpi 5 are also hardened by the coating layer 25 to be mechanically connected. Thus, the adhesive of the present invention not only has excellent preservability, but also hardens the epoxy resin due to the overlapping of the cations, and hardens the adhesive at a lower temperature and in a shorter time than the conventional hardener. The method of dispersing the hardener particles to the decane coupling agent (by hydrazine (10) two Coupling) has been described above, but the use of the present invention is not limited thereto. The symbol 41 in Fig. 6(a) is the same as the first one (the sentence diagram is the same as the hardener particles in the center metal 44 on the surface of the hardener particles 41, and is combined with the i-th (i) 20 1275602 to (d). A polyoxane (p〇ly_sil〇xane) 42 formed by engineering. As shown by the symbol 43 in the figure, it is a direct replacement of the polyoxane (p〇ly_sil〇xane) 42 without oxygen. The substituent "wherein" includes a substituent Xa' bonded to an anthracene, and an amino group bonded to the terminal of the substituent Xa. Therefore, in this state, the amino group is exposed to a polyoxyalkylene (P〇ly_Sil〇xane) 42. After heating the epoxy resin which is liquid at normal temperature and maintaining it at a fixed temperature, the hardener particles 41 in the state shown in Fig. 6(a) are dispersed in the epoxy resin. Fig. 6(a) The chemical formula of the epoxy resin is shown by the symbol 46. The epoxy resin 46 contains the main skeleton Ra and an epoxy ring bonded to the end of the main skeleton Ra, when the polysiloxane (p〇ly-Sil) on the surface of the hardener particle 41 The amino group of 〇xane 42 is contacted with epoxy resin 46, and the amino group is reacted with epoxy resin 46 to obtain a second example of the present invention. Hardener particles 40. The pattern shown here is a reaction in which an epoxy ring of one amino group and two epoxy resins is reacted. Symbol 45 in Fig. 6(b) is a polysiloxane in the bonded state of epoxy resin 46. Poly-Siloxane. The polypyroxane (p〇iy_sil〇xane) 45 is more complicated in construction than the Poly-Siloxane 42 of Figure 6(a), so the present invention The hardener particles 40 of the two examples have higher mechanical strength. Further, although the above illustrates the case where the silane coupling agent reacts with the central metal on the surface of the hardener particles, the present invention is not limited to this as long as it has energy. A resin which reacts with a metal chelate compound or a metal Alcolart constituting a hardener particle, and a resin (polymer, monomer (m〇n〇) of ethanol, carvone 21, 12756602, etc. may also be used. Mer), homopolymer (〇lig〇mer), etc. Symbol 56 in Figure 7(a) is ethanol with two hydroxyl groups ((di〇le),
Diole56擁有與主骨格Rb以及與主骨格Rb結合的2個氫氧 基。在保持固定溫度的Di〇le56中，分散與第1(b)圖所示相同 狀態之硬化劑粒子51，攪拌，在第1(b)〜1(c)圖所視情形中， 在Di〇le56的2個氫氧基中，一個氫氧基會與位於硬化劑粒子 51表面的中心金屬54反應。 第7(b)圖的付號50為因為Di〇le56的反應，而讓中心金 屬54中與烷氧基（Alkoxy) 52結合了的硬化劑粒子。 【實施例】 硬化劑粒子使用粉體狀的金屬鋁螯合物（川研精練化學 (株）公司製造的Alimiiun Acetyl acetactate )(商品名稱「鋁 螯a物A(W)」，平均粒徑5 /z m )，將該硬化劑粒子3丨分散到 加熱到40°(：的氨基（八1^11〇)矽烷偶合劑（川奶€〇：〇叩11吨）（曰 本UNICA公司製，商品名「A-11〇〇」）巾，將該氨基矽 烷偶合劑（Silane Coupling)保溫在4(rc攪拌24小時，反應過後 將硬化劑粒子31撈起，水洗、乾燥即得到第1(d)圖所示，本 發明第一例之硬化劑粒子30。 然後，將上述第一例的硬化劑粒子30分散到加熱到4(rc 的雙酚（bisphenol) A型環氧樹脂（油化SheliEp〇xy (株） 22 1275602 公司製造，商品名稱[「EP828」]中，將該環氧樹脂保溫在4〇 QC ’同時予以攪拌，撈起硬化劑粒子41，將硬化劑粒子41分 散到有機溶劑甲苯當中，經過過濾即得本發明第二例之硬化劑 粒子40。 另位’使用與前述第一例相同的硬化劑粒子3〇，以及相 同的粉體狀硬化劑粒子51的金屬螯合物，將之分散到保溫在 40°C 的 Diole(旭硝子（株）公司製的 TPC( hi Propylene Glycol) 中，攪拌24小時候，將硬化劑粒子撈起，洗淨，取得本發明 第三例的硬化劑粒子5 0。 然後將各第一〜第三例的硬化劑粒子30、40、50分別以 2重量部’以及熱可塑性樹脂酸鹽（phenoxy )樹脂（ρ}^η0Χγ Associates(株）製造）50重量部、熱硬化性樹脂脂酚鹽（phen〇xy ) 樹脂（東都化成（株）製造，商品名稱「γρ50」）5〇重量部、Diole 56 has two hydroxyl groups bonded to the main skeleton Rb and to the main skeleton Rb. In the Di〇le 56 which is maintained at a fixed temperature, the hardener particles 51 in the same state as shown in Fig. 1(b) are dispersed and stirred, as in the case of the first (b) to the first (c), in Di〇 Of the two hydroxyl groups of le56, one hydroxyl group reacts with the central metal 54 located on the surface of the hardener particles 51. The reference numeral 50 in Fig. 7(b) is a hardener particle in which a central metal 54 is bonded to an alkoxy group 52 due to the reaction of Di〇le56. [Examples] As the hardener particles, a powdery metal aluminum chelate compound (Alimiiun Acetyl acetactate manufactured by Kawasaki Seiko Chemical Co., Ltd.) (trade name "aluminum chelate a material A (W)", average particle size 5 was used. /zm ), the hardener particles 3 丨 are dispersed to a 40 ° (: amino group (eight 1 ^ 11 〇) decane coupling agent (Chuan milk 〇: 〇叩 11 tons) (manufactured by UN本 UNICA, products Name "A-11〇〇") towel, the amino decane coupling agent (Silane Coupling) is kept at 4 (rc is stirred for 24 hours, after the reaction, the hardener particles 31 are picked up, washed with water, and dried to obtain the first (d) The figure shows the hardener particles 30 of the first example of the present invention. Then, the hardener particles 30 of the above first example are dispersed to a bisphenol A type epoxy resin heated to 4 (rc) (oiled SheliEp〇) XY Corporation 22 1275602 Manufactured by the company, the product name ["EP828"], the epoxy resin is kept at 4 〇 QC ' while stirring, the hardener particles 41 are picked up, and the hardener particles 41 are dispersed in the organic solvent toluene. Among them, the hardener particles 40 of the second example of the present invention are obtained by filtration. The same as the hardener particles 3〇 of the first example, and the metal chelate compound of the same powdery hardener particle 51, which was dispersed in Diole (Tactical Asahi Co., Ltd. product) manufactured by Asahi Glass Co., Ltd. In the case of stirring for 24 hours, the hardener particles are picked up and washed to obtain the hardener particles 50 of the third example of the present invention. Then, the first to third examples of the hardener particles 30 and 40 are obtained. 50 parts by weight and thermosetting resin phenolate (phen〇xy) resin (Tongdu Chemical Co., Ltd.), which is a weight of 2 parts by weight and a thermoplastic resin (Phenoxy resin). ) Manufacturing, product name "γρ50") 5〇 weight,
Epoxy矽烷偶合劑（Silane Coupling)(日本UNICA (株）公司 製，商品名「Α — 1δ7」）1重量部以及導電性粒子5重量部分 別混合，製成3種接著劑。 接著，使用3種接著劑，依照第（a)、（b)圖的工程，製 作實施例1〜3的接著膜20，使用實施例1〜3的接著膜2〇進 行下列的「室溫保存試驗」與「40°C保存試驗」。 〔室溫保存試驗〕 利用這些實施例1〜3的接著膜20，在上述第3(a)〜 3(d) 23 1275602 圖、第4 (e)、4(f)圖的工程，在TCpi5與LCD11連接後，測 定LCD11上TCP15剝離時的剝離強度（初期剝離強度）。 另外，利用這些實施例i〜3的接著膜2〇，在室溫（25它） 下分別保存1曰、3曰、7日，使用保存過後的各接著膜2〇 以上述相同的工程，分別連接TCP15與LCD11之後，測定 LCD11上TCP15剝離時的剝離強度（保存後剝離強度）。 此外’ TCP15是以25/z m的金屬配線以25// m的間隔配 置，LCD11是表面積每lcm2的電阻是由ι〇ω的ITO電極13 所形成，在tCP15與LCD11相重疊的部份加上了 3Mpa的荷 重，做10移釦加熱，讓塗佈層25的溫度升高到後相連 接0 〔40°c保存試驗〕 這個試驗除了將接著膜20的保存溫度從室溫調整到4〇它 之外乂幻述的至概保存試驗」中相同條件保存接著膜2〇， 待TCP15與LCD11連接後，測定保存後剝離強度。 在上述的「室溫保存試驗」與「4〇〇c保存試驗」中，保存 後剝離強度如達初期剝離強度的9〇%以上則畫「◎」，8〇%以上 90%以下晝「〇」，70%以上8〇%以下晝「△」，鳩以下晝「χ_ 以資評估，其評價結果如下表1所記載。 表1 24 l2756〇2Epoxy Coupling (Silane Coupling, manufactured by Nippon Co., Ltd., trade name "Α-1δ7") was mixed with 1 part by weight and 5 parts by weight of conductive particles to prepare three kinds of adhesives. Next, using the three kinds of adhesives, the bonding film 20 of Examples 1 to 3 was produced in accordance with the works of the drawings (a) and (b), and the following "Crystal Temperature Storage" was carried out using the bonding film 2 of Examples 1 to 3; Test" and "40 ° C preservation test". [Room-temperature storage test] Using the adhesive film 20 of Examples 1 to 3, the above-mentioned 3(a) to 3(d) 23 1275602, and the 4th (e) and 4(f) drawings, in TCpi5 After the connection to the LCD 11, the peel strength (initial peel strength) at the time of peeling off the TCP 15 on the LCD 11 was measured. Further, the adhesive film 2 of the examples i to 3 was stored at room temperature (25 Å) for 1 曰, 3 曰, and 7 days, and each of the deposited films 2 保存 was stored in the same manner as described above. After connecting the TCP 15 and the LCD 11, the peel strength (peeling strength after storage) at the time of peeling off the TCP 15 on the LCD 11 was measured. In addition, 'TCP15 is arranged at 25/zm metal wiring at intervals of 25//m. The LCD11 has a surface area per lcm2. The resistance is formed by the ITO electrode 13 of ι〇ω, and the overlap between tCP15 and LCD11 is added. The load of 3Mpa, 10 push-button heating, let the temperature of the coating layer 25 rise to the post-phase connection 0 [40 ° c preservation test] This test except that the storage temperature of the film 20 is adjusted from room temperature to 4 〇 it The film 2 was stored under the same conditions as in the above-mentioned "preservation test", and after the connection between the TCP 15 and the LCD 11, the peel strength after storage was measured. In the above-mentioned "room temperature storage test" and "4〇〇c storage test", if the peel strength after storage is 9% or more of the initial peel strength, "◎", 8〇% or more and 90% or less are drawn. 70% or more and 8〇% or less 昼 "△", 鸠 鸠 昼 χ 以 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _
1 L溫保存 4 0 C保存 1曰 3曰 7曰 1曰 3曰 7曰 實施例1 -- ◎ ◎ 〇 〇 〇 Δ 實施例2 ◎ ◎ ◎ ◎ ◎ ◎ 比較例1 -一.. ◎ ◎ ◎ ◎ ◎ 〇 比較例2 〜—.— 〇 Δ X X X X 上表1的比較例1、2是將實施例i、2所使用的2種硬 化齊I丨粒子，不形成膠囊就直接添加到接著劑中。 從上述表1中可看出，使用本發明第一例〜第三例的硬化 劑粒子30, 40, 50的實施例丄〜3當中，「室溫保存試驗」與「4〇 C保存試驗」的評價結果都十分良好，確認了使用本發明之硬 化劑粒子所製造的接著劑具有優秀的保存性。 尤其是本發明第-例的硬化劑粒子3〇與經過環氧樹脂處 理的第二例硬化劑粒子40比較時，第一例、第三例的硬化劑 粒子30、50使用時比較之下，在贼、7日間保存的條件下， 接著力幾乎不會減低。 以上說明了使用接著劑製造接著膜的情形，但是本發明的 用途不僅限於此，例如接著劑也可以直接以檢糊狀來使用。 第8⑷冑的符號U所示與第3(a) _示相同’為咖’ 該LCD11在與TCP15相連接時，首先要在lcdu電極 13表面上’在與TCP15相連接的部份塗抹本發明之接著劑， 25 1275602 形成接.著劑的塗佈層75(第8(b)圖）。 然後在上第3(d)圖的工程中進行1^1>15的對準位子後， 在上述第4(e)、4⑴圖的工程中，將TCP15與LCD11相連接， 就可得到電氣設備40 (第8(c)圖）。 以上說明了使用接著劑連接Tcpi5與LCDU的情形，但 疋本發明之用途也不限於此，在基板與半導體晶片的連接上， 各種電氣設備的製造上都可使用。 以上疋指將導電性粒子分散到接著劑中的情形來作說 明，但本發明之用途也不限於此，例如不含導電性粒子的接著 劑也包含在本發明之範圍内。 金屬螯合物可以使用錯螯合物、鈦螯合物、鋁螯合物等各 種金屬螯合物，其中，最好採用反應性最高的！呂螯合物。 以上的熱硬化性樹脂以環氧樹脂為例進行說明，但本發明 的用途不限於此。如果是陽離子重合樹脂，例如尿素樹脂、三 來氰氨（meiamin)樹脂、酚醛樹脂、乙烯醚樹 脂、Oxetane樹脂等等各種樹脂，但是如考慮到硬化後的接著 劑強度等，最好還是採用環氧樹脂。 另外’本發明所採用的矽烷偶合劑（Silane Coupling)，最 好能採用下列式子（9)所示的物質。 26 1275602 【化10】 X14 X———X15……一般式（9) 必2 上列一般式子（9)裡，在置換基X12〜X15中至少有一個置 換基是烧氧基（alkoxy )。此外，在烧氧基之外的置換基X12〜 X 當中’最好至少有一個置換基是環氧或乙稀基，具有環氧 置換基者尤其最好是之Glycidyl基。 熱可塑性樹脂除Phenoxy樹脂外，例如聚乙稀樹脂、尿烧 樹月旨、Polyvinyl acetale、Ethylene vinyle Acetate、Polybutatien 橡膠等橡膠類也可以使用。此外，本發明之接著劑也可添加 老化防止劑、填充劑、著色劑等等添加劑。 以上’與硬化劑粒子接觸的矽烷偶合劑（Silane Coupling)，除烷氧基以外的置換基，以具有氨基的氨基（Amin〇) 石夕烧偶合劑（Silane Coupling)作說明，但本發明並不在此限。矽 烧偶合劑（Silane Coupling)基除烷氧基以外的置換基，也可以使 用乙烯基、環氧基、甲基丙烯酸（Methacryl )基、硫氫（Mercapto ) 基、異氰酸（Isocyano)基等等置換基之物質。 與本發明第一例之硬化劑粒子反應之物質亦不限定為環 氧樹脂。例如非烷氧基的製作使用含異氰酸基的矽烷偶合劑 (Sdane Coupling)，在製作第一例的硬化劑粒子時，如果以 27 1275602 代替環氧樹脂，異氰酸基與Diole反應，在硬化劑粒子表面就 會形成尿烧樹脂。 與聚石夕氧烧（Poly-siloxane)反應的物質與石夕烧偶合劑 (Silane Coupling)的種類組合並無特別限定，要看石夕烧偶合劑 (Silane Coupling)的置換基的種類來決定。 以上說明了將硬化劑粒子31, 41，51分散到矽烷偶合劑 (Silane Coupling)或Diole中時，硬化劑粒子31，41，51與石夕烧 偶合劑（Silane Coupling)或Diole接觸時的情形，但本發明並不 在此限，例如將石夕烧偶合劑（Silane Coupling)或Diole喷霧在硬 化劑粒子上，使石夕烧偶合劑（Silane Coupling)或Diole接觸硬化 劑粒子亦可。 位於本發明之硬化劑粒子表面的中心金屬，由於會與矽氧 烷（Siloxane)或烷氧基結合，因此在接著劑中，不會與矽烷偶合 劑（Silane Coupling)產生反應。而且，本發明之接著劑，會因為 環氧樹脂的陽離子重合反應而硬化。陽離子的重合反應比過去 舊有的硬化劑重合反應發生的溫度還低，因此，本發明之接著 劑與過去的接著劑比較下，能在低溫、短時間内硬化。 綜上所述，雖然本發明已以一較佳實施例揭露如上，然其 並非用以限定本發明，任何熟習此技藝者，在不脫離本發明之 精神和範圍内，當可作各種之更動與潤飾，因此本發明之保護 範圍當視後附之申請專利範圍所界定者為準。 28 1275602 【圖式簡單說明】 第1(a)〜1(d)圖係為本發明第一例之硬化劑粒子製造工程 之一例的說明用圖面。 第2(a)、2(b)圖係為使用本發明之硬化劑粒子製造接著膜 的一工程例說明用圖面。 第3(a)〜3(d)圖係為使用本發明之接著劑黏接lcd與TCP 的前半段工程說明用圖面。 第4(e)、4(f)圖係為TCP與LCD黏接之後半工程的說明 用圖面。 第5圖係說明TCP與LCD在對準位置狀態下的平面圖。 第6(a)、6(b)圖係為本發明第二例之硬化劑粒子製造工程 之一例的說明用圖面。 第7(a)、7(b)圖係為本發明第三例之硬化劑粒子製造工程 之'一例的說明用圖面。 第8(a)〜8(c)圖係說明使用本發明之接著劑黏接TCP與 LCD之其他工程例的說明圖。 第9 (a)〜9(d)圖係為傳統技術之接著劑，黏接LCD與 TCP之工程的說明圖。 圖式標號說明 25、75 :接著劑（塗佈層） 30, 40, 50 :硬化劑粒子 29 1275602 31 :硬化劑粒子 34, 44, 54 :中心金屬 32, 45 :石夕氧烧（Siloxane)(聚石夕氧烧（Poly-Siloxane) 36 :陽離子 301 L temperature storage 4 0 C storage 1 曰 3 曰 7 曰 1 曰 3 曰 7 曰 Example 1 - ◎ ◎ 〇〇〇 Δ Example 2 ◎ ◎ ◎ ◎ ◎ ◎ Comparative Example 1 - one.. ◎ ◎ ◎ ◎ ◎ 〇 Comparative Example 2 ～—.— 〇Δ XXXX Comparative Examples 1 and 2 of Table 1 above are the two types of hardened iridium particles used in Examples i and 2, and are directly added to the adhesive without forming a capsule. . As can be seen from the above Table 1, in the examples 丄~3 of the hardener particles 30, 40, 50 of the first to third examples of the present invention, "room storage test" and "4〇C storage test" The evaluation results were all very good, and it was confirmed that the adhesive produced by using the hardener particles of the present invention has excellent storage stability. In particular, when the hardener particles 3〇 of the first example of the present invention are compared with the epoxy resin-treated second-type hardener particles 40, the first and third examples of the hardener particles 30 and 50 are used in comparison. Under the conditions of thieves and 7 days of storage, the force will hardly decrease. The case where the adhesive film is produced using an adhesive has been described above, but the use of the present invention is not limited thereto, and for example, the adhesive may be used directly in the form of a paste. The symbol U of the eighth (4) 所示 is the same as that of the third (a) _. The LCD 11 is first connected to the TCP 15 , and firstly, the surface of the lcdu electrode 13 is smeared on the portion connected to the TCP 15 . The adhesive, 25 1275602, forms the coating layer 75 of the coating (Fig. 8(b)). Then, after the alignment position of 1^1>15 is performed in the above-mentioned third (d) drawing, in the above-mentioned fourth (e), 4 (1) drawing, the connection between the TCP 15 and the LCD 11 can be performed to obtain an electric device. 40 (Fig. 8(c)). Although the case of connecting Tcpi5 and LCDU using an adhesive has been described above, the use of the present invention is not limited thereto, and various electrical devices can be used for the connection of the substrate to the semiconductor wafer. The above refers to the case where the conductive particles are dispersed in the adhesive. However, the use of the present invention is not limited thereto, and for example, a binder containing no conductive particles is also included in the scope of the present invention. As the metal chelate compound, various metal chelate compounds such as a mischelating compound, a titanium chelate compound, and an aluminum chelate compound can be used, and among them, it is preferable to use the most reactive one! Lu Che Chelate. The above thermosetting resin is exemplified by an epoxy resin, but the use of the present invention is not limited thereto. If it is a cationically recombined resin, for example, urea resin, meiamin resin, phenol resin, vinyl ether resin, Oxetane resin, etc., but it is preferable to use a ring in consideration of the strength of the adhesive after hardening or the like. Oxygen resin. Further, the silane coupling agent (Silane Coupling) used in the present invention can preferably be the one shown by the following formula (9). 26 1275602 [10] X14 X———X15... General formula (9) must be 2 In the general formula (9), at least one of the substituents in the substituents X12 to X15 is alkoxy. . Further, in the substituents X12 to X other than the alkoxy group, it is preferable that at least one of the substituents is an epoxy group or an ethylene group, and those having an epoxy group are particularly preferably a Glycidyl group. The thermoplastic resin may be used in addition to the Phenoxy resin, such as a polyethylene resin, a urinary resin, a polyvinyl acetale, an Ethylene vinyle Acetate, or a Polybutatien rubber. Further, the adhesive of the present invention may also be added with an additive such as an anti-aging agent, a filler, a colorant or the like. The above-mentioned "Silane Coupling" which is in contact with the hardener particles, a substituent other than the alkoxy group, is described by an amino group (Amin〇), which is an amino group (Silane Coupling), but the present invention Not limited to this. Silane Coupling, a substituent other than an alkoxy group, may also be a vinyl group, an epoxy group, a Methacryl group, a Mercapto group, or an isocyanate group. Substituting the substance of the substituent. The substance which reacts with the hardener particles of the first example of the present invention is also not limited to an epoxy resin. For example, a non-alkoxy group is prepared by using an isocyanate-containing decane coupling agent (Sdane Coupling). When the first-stage hardener particles are produced, if an epoxy resin is replaced by 27 1275602, the isocyanate group reacts with Diole. A urethane resin is formed on the surface of the hardener particles. The combination of the substance which reacts with the poly-siloxane and the type of the Silane Coupling is not particularly limited, and it is determined by the type of the substituent of the Silane Coupling. . The above describes the case where the hardener particles 31, 41, 51 are in contact with the Silane Coupling or Diole when the hardener particles 31, 41, 51 are dispersed in a silane coupling agent (Silane Coupling) or Diole. However, the present invention is not limited thereto. For example, Silane Coupling or Diole may be sprayed on the hardener particles to make the Silane Coupling or Diole contact hardener particles. The central metal located on the surface of the hardener particles of the present invention, because it is combined with a siloxane or an alkoxy group, does not react with a silane coupling agent (Silane Coupling) in the adhesive. Further, the adhesive of the present invention is hardened by the cationic overlapping reaction of the epoxy resin. The superposition reaction of the cation is lower than the temperature at which the conventional hardener superposition reaction occurs, and therefore, the adhesive of the present invention can be hardened at a low temperature and in a short time as compared with the conventional adhesive. In view of the above, the present invention has been described above in terms of a preferred embodiment, and is not intended to limit the invention, and various modifications may be made without departing from the spirit and scope of the invention. And the scope of the present invention is defined by the scope of the appended claims. 28 1275602 [Brief Description of the Drawings] Figs. 1(a) to 1(d) are drawings for explaining an example of the manufacturing process of the hardener particles of the first example of the present invention. Figs. 2(a) and 2(b) are drawings for explaining an example of the construction of the adhesive film using the hardener particles of the present invention. Figures 3(a) to 3(d) are drawings for the first half of the project using the adhesive of the present invention for bonding lcd and TCP. The 4th (e) and 4th (f) diagrams are the descriptions of the semi-engineering after the TCP and LCD are bonded. Figure 5 is a plan view showing the state of the TCP and LCD in an aligned position. 6(a) and 6(b) are drawings for explaining an example of the production process of the hardener particles of the second example of the present invention. 7(a) and 7(b) are drawings for explaining an example of the manufacturing process of the hardener particles of the third example of the present invention. 8(a) to 8(c) are explanatory views showing other engineering examples in which TCP and LCD are bonded using the adhesive of the present invention. The 9th (a) to 9(d) drawings are explanatory diagrams of the conventional technology adhesive and the engineering of bonding LCD and TCP. DESCRIPTION OF SYMBOLS 25, 75: adhesive (coating layer) 30, 40, 50: hardener particle 29 1275602 31 : hardener particle 34, 44, 54: center metal 32, 45: Siloxane (Poly-Siloxane 36: Cation 30
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TW92103252A TWI275602B (en) | 2002-12-02 | 2003-02-17 | Hardener particle, manufacturing method for hardener particle, and adhesive |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TW91134975 | 2002-12-02 | ||
| TW92103252A TWI275602B (en) | 2002-12-02 | 2003-02-17 | Hardener particle, manufacturing method for hardener particle, and adhesive |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| TW200409786A TW200409786A (en) | 2004-06-16 |
| TWI275602B true TWI275602B (en) | 2007-03-11 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW92103252A TWI275602B (en) | 2002-12-02 | 2003-02-17 | Hardener particle, manufacturing method for hardener particle, and adhesive |
Country Status (1)
| Country | Link |
|---|---|
| TW (1) | TWI275602B (en) |
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2003
- 2003-02-17 TW TW92103252A patent/TWI275602B/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| TW200409786A (en) | 2004-06-16 |
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