CN100509933C - Hardening particle, manufacturing method of hardening particle and binder - Google Patents
Hardening particle, manufacturing method of hardening particle and binder Download PDFInfo
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- CN100509933C CN100509933C CNB031035329A CN03103532A CN100509933C CN 100509933 C CN100509933 C CN 100509933C CN B031035329 A CNB031035329 A CN B031035329A CN 03103532 A CN03103532 A CN 03103532A CN 100509933 C CN100509933 C CN 100509933C
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Abstract
An adhesive with short low-temp solidifying time and high storage stability is prepared from the particle hardening agent with surficial metal chelate, silane as coupling agent and epoxy resin through dispersing the first two in the epoxy resin. When the adhesive is heated, said hardening particle is cracked and reacts on said metal chelate to generate cations, which can solidify the epoxy resin.
Description
Technical field
The present invention relates to caking agent, particularly by thermo-compressed with the stiffening agent particle that uses in semi-conductor chip and TCP and the caking agent that substrate is connected.
Background technology
For many years, when semi-conductor chip is connected with substrate with TCP (Tape CarrlerPackage) is connected with LCD (Liquid Crystal Display), when making electric installation, is using the caking agent contain as the Resins, epoxy of thermosetting resin.
In above-mentioned caking agent, the general stiffening agent that makes imidazoles one class of polymerization of epoxy resins with heating that adds is under metal wiring 117 and ITO electrode 113 state of contact, when continuing heating, be subjected to the katalysis of stiffening agent, Resins, epoxy carries out polymerization, and caking agent 125 forms sclerosis.
Electric installation among Fig. 9 (d) under symbol 101 expression caking agents 125 hardening states.In this electric installation 101, under metal wiring 117 and ITO electrode 113 contact conditions, make TCP115 and LCD 111 fixing by hardened caking agent 125, therefore, TCP 115 and LCD 111 be electrical connection also be mechanical connection.
Yet when making above-mentioned adhesive hardens, caking agent must be heated to the high temperature more than 180 ℃, when the pattern of metal wiring 117 is trickle, during heating, makes TCP 115 take place to stretch sometimes and distortion such as bending.Can eliminate this type of problem though reduce Heating temperature, heat treated needs long time, and production efficiency reduces.
As the good caking agent of hardening under the low temperature, in recent years, contain as the radical polymerization resin of acrylate one class and the caking agent of free radical polymerization initiator, compare when caking agent is with use Resins, epoxy like this though developed, under hardening state, electrical characteristic and thermotolerance are all very poor.
Summary of the invention
The present invention develops for solving above-mentioned the deficiencies in the prior art part, its objective is provide a kind of under the condition of low temperature, short period of time hardenable and caking agent that keeping quality is good.
Inventors of the present invention are conceived to not use the stiffening agent of general use and make Resins, epoxy carry out the way of cationoid polymerisation, through further investigation, found that, in caking agent, add silane compound (silane coupling agent) and the metallo-chelate (or metal alkoxide) that has a kind of alkoxyl group in the structure at least, produce positively charged ion when silanol that is got by the silane coupling agent hydrolysis and metallo-chelate reaction, positively charged ion makes polymerization of epoxy resins thus.
Use following reaction formula (5)～(8) that the process that makes epoxy cure with the caking agent that has added metallo-chelate and silane coupling agent is described.
Reaction formula (5)
Reaction formula (7)
Reaction formula (8)
At least the silane compound that contains an alkoxyl group, shown in reaction formula (5), with the water reaction in the caking agent, alkoxyl group adds water decomposition and generates silanol group.
During the caking agent, the metallo-chelate reaction that silanol group and aluminum chelate are such, silane compound combines with aluminum chelate.(reaction formula (6)).
Then, shown in reaction formula (7), silanol group bonded aluminum chelate is when balanced reaction, generate the bronsted acid point by the silanol group coordination that remains in the caking agent, shown in reaction formula (8), make the oxirane ring open loop of Resins, epoxy end by the sensitization proton, with the oxirane ring polymerization (cationoid polymerisation) of other Resins, epoxy.So, in caking agent, add silane coupling agent and metallo-chelate, the thermosetting resin generation cationoid polymerisation that Resins, epoxy is such.Therefore the reaction of reaction formula (6)～reaction formula (8) is to carry out under the solidification value of caking agent before being lower than (more than 180 ℃), compared with former caking agent, but above-mentioned caking agent low temperature, short period of time solidifies.
But, silane coupling agent easily adds water decomposition, and this silanol and metallo-chelate or metal alkoxide is reactive high, if directly be dispersed in caking agent as the stiffening agent particle granulated metal inner complex and metal alkoxides, even normal temperature is the polyreaction of initial ring epoxy resins also, the keeping quality of caking agent is poor.
The present inventor has further carried out research with keen determination, found that: the stiffening agent particle is added to before the caking agent, the hydroxy-containing compounds of silane coupling agent (silanol), alcohol etc. is contacted with the stiffening agent particle surface, when the central metal atom of this compound and stiffening agent particle surface reacted, the keeping quality of caking agent improved.
The present invention is based on that above-mentioned experience finishes, by the 1st kind of embodiment of the present invention be, one or both in the metal alkoxide of metallo-chelate, central metal and at least one the alkoxyl group be combined into that forms with central metal and at least one ligating atom coordination is the stiffening agent particle of main component, wherein, silicon combines with the described central metal of described stiffening agent particle surface by oxygen.
By the 2nd kind of stiffening agent particle that embodiment is the 1st a kind of embodiment of the present invention, wherein interosculate by oxygen with aforementioned central metal bonded silicon.
By the 3rd kind of embodiment of the present invention be, the 1st or 2 kind of embodiment in any one stiffening agent particle, wherein, the substituting group of following general expression (1) expression combines with aforementioned silicon,
(substituent X in the above-mentioned general expression
1Combine with described silicon).
By the 4th kind of embodiment of the present invention, the 1st or 2 kind of embodiment in any one stiffening agent particle, wherein, the substituting group of following general expression (2) expression combines with aforementioned silicon,
(substituent X in the above-mentioned general expression (2)
2～X
4In, at least one substituent X
2～X
4Combine with described silicon).
Here, as substituent X
1, for example can enumerate-CH
2CH
2CH
2-,-CH
2CH
2CH
2NHCH
2CH
2-,-CH
2CH
2CH
2NHC (=O)-etc.In addition, as substituent X
2～X
4, can enumerate phenyl, H ,-(CH) n-(n is an integer) etc., wherein with silicon bonded substituent X
2～X
4Also can be-CH
2CH
2CH
2NHCH
2CH
2-,-CH
2CH
2CHNHC (=O)-etc.
By the 5th kind of embodiment of the present invention be, for the one or both in the metal alkoxide of the metallo-chelate, central metal and at least one the alkoxyl group be combined into that form with central metal and at least one ligating atom coordination is the stiffening agent particle of main component, wherein, carbon combines with the described central metal of described stiffening agent particle surface by oxygen.
By the 6th kind of embodiment of the present invention is the manufacture method of stiffening agent particle, wherein, makes the silane coupling agent hydrolysis of following general expression (3) expression form silanol
(substituent X in the above-mentioned general expression (3)
5-X
7Be alkoxyl group, X
8For having the substituting group of amino or epoxy group(ing)), making one or both in the metal alkoxide of the metallo-chelate that forms with central metal and at least one ligating atom coordination, central metal and at least one alkoxyl group be combined into is that the stiffening agent particle of main component contacts with aforementioned silanol, make the central metal and the reaction of aforementioned silanol of aforementioned stiffening agent particle surface, form the siloxanes of following general expression (4) expression
(in the above-mentioned general expression (4) and silicon bonded oxygen combine substituent X with aforementioned central metal
9, X
10Be alkoxyl group or silanol group, X
11For having the substituting group of amino or epoxy group(ing)).
Be that the method for the manufacturing stiffening agent particle of the 6th kind of embodiment wherein, makes the silicon bonded substituent X of the siloxanes of representing with aforementioned general expression (4) by the 7th kind of embodiment of the present invention
9～X
11In at least one substituting group and Resins, epoxy reaction.
Be that the method for the manufacturing stiffening agent particle of the 7th kind of embodiment wherein, and contains amino in the substituent structure of aforementioned epoxy resins reaction by the 8th kind of embodiment of the present invention.
By the 9th kind of embodiment of the present invention be, the manufacture method of stiffening agent particle, wherein, making one or both in the metal alkoxide of the metallo-chelate that forms with central metal and at least one ligating atom coordination, central metal and at least one alkoxyl group be combined into is that the stiffening agent particle of main component contacts with hydroxyl compound, makes the central metal and the reaction of described hydroxyl compound of aforementioned stiffening agent particle surface.
By the 10th kind of embodiment of the present invention be, the method for the manufacturing stiffening agent particle of the 9th kind of embodiment, wherein, hydroxyl compound is an alcohol.
Be that in the manufacture method by the stiffening agent particle of the 10th kind of embodiment of the present invention, described alcohol is tripropylene glycol by the 11st kind of embodiment of the present invention.
By the 12nd kind of embodiment of the present invention is caking agent, wherein contains the stiffening agent particle of any record in thermosetting resin, silane coupling agent and the 1st～5 kind of embodiment.
The present invention is made of above, the silane coupling agent of general expression (3) expression contacts with the stiffening agent particle surface, at first, the alkoxyl group of silane coupling agent adds water decomposition and generates silanol, the metallo-chelate of stiffening agent particle surface or metal alkoxides and this silanol dehydrating condensation, silicon in the silanol combines with central metal in metallo-chelate or the metal alkoxides by oxygen, obtains stiffening agent particle of the present invention.
Silane coupling agent adds water decomposition by moisture that is attached to the stiffening agent particle surface and airborne moisture etc., in order to handle quickly, adds water in silane coupling agent, is used for the stiffening agent particle reaction reagent of silanolate in advance effective.
The present invention, because siloxanes combines with the central metal of stiffening agent particle surface, when in caking agent, adding stiffening agent particle of the present invention, under the silane coupling agent normal temperature in the caking agent not with the stiffening agent particle reaction, caking agent does not solidify, during the hot pressing caking agent, and stiffening agent particle expanded by heating, because of physical impact such as pressurizations, the stiffening agent particle of thermal expansion divides, exposes the part beyond the stiffening agent particle surface.
Because siloxanes does not combine with being positioned at the central metal of stiffening agent particle surface with outside part, by heating, the silane coupling agent reaction in this central metal and the caking agent generates positively charged ion, and Resins, epoxy carries out cationoid polymerisation, and caking agent solidifies.So, stiffening agent particle of the present invention has the function of so-called potentiality stiffening agent.
Also the solidification value (more than 180 ℃) than former caking agent is low for the temperature of reaction of metal alkoxides, metallo-chelate and silane coupling agent, so, compared with former caking agent, but caking agent low temperature of the present invention, short period of time solidify.
Also there is positively charged ion to generate in the operation of the central metal of stiffening agent particle surface and silane coupling agent reaction, so when the stiffening agent particle that the surface has just been formed siloxanes directly joins in the caking agent, by remaining in the positively charged ion of stiffening agent particle surface, caking agent might solidify at normal temperatures, but before the stiffening agent particle joins in the caking agent, if water or organic solvent are cleaned, can from the stiffening agent particle, residual positively charged ion and superfluous silane coupling agent be removed.
Use when except that alkoxyl group, also containing amino aminosilane coupling agent in the substituting group, form the siloxanes that contains amino.Stiffening agent particle with this state contacts with Resins, epoxy again, amino in the siloxanes and the reaction of the oxirane ring of Resins, epoxy, coupling collar epoxy resins on siloxanes.Therefore, the siloxane structure of the stiffening agent particle surface more complicated that becomes, the physical strength of stiffening agent particle is higher.
Replace silane coupling agent, hydroxy-containing compounds such as alcohol are contacted with the stiffening agent particle surface, the hydroxyl dehydrating condensation of the metallo-chelate of stiffening agent particle surface or metal alkoxides and this compound, the central metal of stiffening agent particle surface combines with this compound by oxygen.The stiffening agent particle that obtains like this is identical when forming siloxanes, has latent hardening agent function.
Use hydroxy-containing compounds alcohol, though the kind of alcohol is not had special restriction, when using ethanol as monovalent alcohol, the crosslinking structure of stiffening agent particle surface forms difficulty, is one dimension straight chain shape with central metal bonded molecule.At this moment, it is low to cover the rigidity of membranaceous molecule on stiffening agent surface.But use monovalent alcohol, make this functional group and other substance reaction, can improve the rigidity of the membranaceous molecule of stiffening agent particle surface with hyperergy functional group.
As hydroxy-containing compounds, for example also can use carboxylic acid in addition.
In caking agent, add thermoplastic resin, make the cohesive force increase of caking agent owing to the character of thermoplastic resin, therefore the binding property of caking agent improves, when using the high thermoplastic resin of polarity, thermoplastic resin not only participates in the curing reaction of resinous principle, and combine with inorganic materials by silane coupling agent, so it is high and the high caking agent of affinity of thing with the quilt of being made up of inorganic materials to obtain solidified nature.
The accompanying drawing simple declaration
[Fig. 1] (a)～(d): the explanatory view of making the present invention's first routine stiffening agent particle operation.
[Fig. 2] (a) and (b): the example explanatory view of making bonding membrane process with stiffening agent particle of the present invention.
[Fig. 3] (a)～(d): the first half explanatory view that LCD is connected operation with TCP with caking agent of the present invention.
[Fig. 4] (e), (f): TCP is connected the latter half explanatory view of operation with LCD.
[Fig. 5]: make TCP position on LCD close right plane explanatory view.
[Fig. 6] (a) and (b): the explanatory view of making the present invention's second routine stiffening agent particle operation.
[Fig. 7] (a) and (b): the explanatory view of making the present invention's the 3rd routine stiffening agent particle operation.
[Fig. 8] (a)～(c): use caking agent of the present invention to connect the explanatory view of other example of TCP and LCD operation.
[Fig. 9] (a)～(d): the caking agent of technology connects the explanatory view of TCP and LCD operation before using.
[nomenclature]
25,75...... caking agent (coating layer)
30,40,50...... stiffening agent particle
34,44,54...... central metal
32,45...... siloxanes (polysiloxane)
The working of an invention form
Below describe caking agent of the present invention in detail
The left of chemical formula is represented shown in Fig. 1 (a) is an example of the silane coupling agent that uses of the present invention.This silane coupling agent has four substituent X
a～X
d, three substituent X wherein
b～X
dCombine with silicon in the silane coupling agent by oxygen, therefore, this silane coupling agent contains three alkoxyl groups.
After this silane coupling agent was heated to certain temperature, the stiffening agent particle that granulated metal inner complex or metal alkoxide (central metal is an aluminium here) are constituted was dispersed in the silane coupling agent, stirs and be incubated this silane coupling agent at a certain temperature.
Water in air divide with the moisture that is attached to the stiffening agent particle surface with after silane coupling agent contact, three alkoxyl groups are distinguished hydrolysis formation hydroxyls in the silane coupling agent.The right-hand expression silane coupling agent of chemical formula shown in Fig. 1 (a) adds the silanol that water decomposition obtains.
Continue the limit and keep certain temperature limit and stir silane coupling agent, silane coupling agent reacts because of the silanol that adds water decomposition and the generate central metal 34 with stiffening agent particle 31 surfaces, and the silicon in the silanol combines the formation siloxanes by oxygen with central metal 34.At this moment silanol and other silanol reaction forms polysiloxane on stiffening agent particle 31 surfaces.
Fig. 1 (c) represents its state, with the polysiloxane of the 32 expression stiffening agent particles of the symbol among the figure, 31 surface formation.Each silicon combines with the central metal 34 on stiffening agent particle 31 surfaces respectively in the polysiloxane 32, and its result is that the formation unit siloxanes of polysiloxane 32 distributes with the unit molecule stratiform on stiffening agent particle 31 surfaces.In addition, each silicon mutually combines by oxygen in the polysiloxane 32, therefore, and the physical strength height of polysiloxane 32.
Secondly, the stiffening agent particle 31 that has formed polysiloxane 32 states is removed from silane coupling agent.At this state, silane coupling agent and central metal 34 react the positively charged ion 36 (hydrogen ion) of generation, do not remain in polysiloxane 32 surfaces with superfluous silane coupling agent of this central metal bonded (also comprising silanol).
Wash the stiffening agent particle 31 of this state, remove residual positively charged ion 36 and silane coupling agent, obtain the stiffening agent particle 30 (Fig. 1 (d)) of the present invention's first example.
The caking agent of the present invention of the stiffening agent particle 30 that uses the present invention's first example and the operation of using caking agent of the present invention to make electrical means are described.At first stiffening agent particle 30, electroconductive particle and the solvent with thermosetting resin Resins, epoxy, thermoplastic resin, silane coupling agent, the present invention's first example mixes in certain proportion, stirs, and makes the starchiness caking agent.
At this state, because polysiloxane 32 combines with the central metal 34 on stiffening agent particle 30 surfaces, silane coupling agent in the caking agent and central metal 34 do not react, and can not generate positively charged ion.The positively charged ion that residues in addition in the polysiloxane 32 also is removed.Therefore, cationic polymerization does not take place in Resins, epoxy in the caking agent, and caking agent does not solidify under the normal temperature.
The bonding film of symbol 20 expressions formation coating layer 25 states among Fig. 2 (b).Be dispersed in electroconductive particle in the caking agent with schematic symbol 27 expression with stiffening agent particle 30.
Several ITO electrodes 13 (Indium Tin Oxide) that Fig. 3 (a) symbol 11 expression LCD, LCD11 have glass substrate 12, form in a narrow margin in glass substrate 12 one sides constitute, and illustrate 5 ITO electrodes 13 here.
The coating layer 25 of the bonding film 20 shown in Fig. 2 (b) is pressed in the part (Fig. 3 (b)) that connects aftermentioned TCP in the formation face of ITO electrode 13 of LCD11.The bonding force of bonding film 21 shown in Fig. 2 (b) and coating layer 25 is littler than the bonding force of 13 at coating layer 25 and ITO electrode, so coating layer 25 remains in LCD11 and goes up (Fig. 3 (c)) when peeling off stripping film 21.
The sectional drawing of the A-A line of Fig. 3 (d) presentation graphs 5, the side that the metal wiring 17 of TCP15 is arranged is towards the arrangement plane of the ITO electrode 13 of LCD11, make the coating layer 25 of the end of TCP15 facing to ITO electrode 13 surfaces, involutory mutually between the ITO electrode 13 of LCD11 and the metal wiring 17 of TCP15.
At this state, on coating layer 25, push metal wiring 17 arrangement plane of TCP15, lap limit between TCP15 and LCD11 is pushed with its whole heating in the limit, because of heating coating layer 25 softens, squeeze out remollescent coating layer 25 because of pushing metal wiring 17, the electroconductive particle 27 in the residual coating layer 25 wraps between metal wiring 17 and ITO electrode 13 (Fig. 4 (e)).At this state, continue heating and push, the part outside stiffening agent particle 30 surfaces is exposed in heating and this curings particle 30 of thermal expansion breaks because of pressurization and expansion.Siloxanes does not combine with metallo-chelate or metal alkoxides outside stiffening agent particle 31 surfaces, so the disruptive stiffening agent particle of symbol 35 expressions is when silane coupling agent in the coating layer 25 contacts in Fig. 4 (f), silane coupling agent reaction in metallo-chelate or metal alkoxides and the coating layer 25 generates positively charged ion.
Resins, epoxy in the coating layer 25 carries out polymerization (cationoid polymerisation) by positively charged ion, in metal wiring 17 and 13 clampings of ITO electrode that coating layer 25 solidifies (Fig. 4 (f)) under the state of conducting particles 27.
Electrical means under the state that the symbol 10 expression coating layers 25 of Fig. 4 (f) have solidified.In this electrical means 10, metal wiring 17 and ITO electrode 13 not only are electrically connected by conducting particles 27, and LCD11 and TCP15 carry out mechanicalness and are connected by solidifying coating layer 25.
Thus, caking agent of the present invention is the keeping quality excellence not only, and Resins, epoxy is owing to cationoid polymerisation solidifies, so, compare with the situation of using stiffening agent in the past, can be at low temperature, the chien shih stiffening agent solidifies in short-term.
More than, only narrated stiffening agent particle 31 is dispersed in method in the silane coupling agent, but the present invention is not limited thereto.
After normal temperature was the heating of aqueous Resins, epoxy, insulation at a certain temperature was dispersed in the stiffening agent particle 41 of state shown in Fig. 6 (a) in this Resins, epoxy.
The chemical formula of symbol 46 its Resins, epoxy of expression among Fig. 6 (a).Resins, epoxy 46 contains main framing R
a, with main framing R
aTerminal bonded oxirane ring, when the amino of the polysiloxane 42 on stiffening agent particle 41 surfaces contacted with Resins, epoxy 46, amino and Resins, epoxy 46 reactions obtained the stiffening agent particle 40 of the present invention's second example.Here illustrate the relative situation that amino reacts of 2 oxirane rings of Resins, epoxy 46.
More than, the central metal on stiffening agent surface and the situation of silane coupling agent reaction are illustrated, but the present invention is not limited to these, as long as have the functional group who reacts with metallo-chelate that constitutes stiffening agent or metal alkoxides, also can use alcohol, carboxylic acid, various resin (polymkeric substance, monomer, oligopolymer etc.).
Symbol 56 expressions have the alcohol (dibasic alcohol) of 2 hydroxyls among Fig. 7 (a), and dibasic alcohol 56 has main framing R
b, with main framing R
b2 hydroxyls of bonded.To be scattered in the dibasic alcohol 56 that is incubated at a certain temperature with the stiffening agent particle 51 of the equal state shown in Fig. 1 (b), stir, under the situation shown in Fig. 1 (b)～(c), often in 2 of dibasic alcohol 56 hydroxyls, central metal 54 reactions on hydroxyl and stiffening agent particle 51 surfaces.
Symbol 50 expressions among Fig. 7 (b) are owing to react the stiffening agent particle under central metal 54 and the alkoxyl group 52 bonded states with dibasic alcohol 56.
Embodiment
Use granulated metal inner complex river to grind the aluminium acetylacetonate (trade(brand)name " aluminum chelate A (W) " of fine chemistry corporate system as stiffening agent particle 31, median size 5 μ m), this stiffening agent particle 31 is scattered in the aminosilane coupling agent that is heated to 40 ℃, and (Japan blocks corporate system by the Buddhist nun, trade(brand)name " A-1100 ") in, in 40 ℃ of keeping warm modes this aminosilane coupling agent was stirred 24 hours, after reaction is finished, take out stiffening agent particle 31, washing, dry, the stiffening agent particle 30 that obtains the present invention's first example shown in Fig. 1 (d).
Secondly, the stiffening agent particle 30 of above-mentioned first example is dispersed in the bisphenol A type epoxy resin (trade(brand)name " EP828 " of oiling girdle epoxy resins corporate system) that is heated to 40 ℃, after this Resins, epoxy is stirred on 40 ℃ of limits of insulation, limit, take out stiffening agent particle 41, after stiffening agent particle 41 disperseed in organic solvent toluene, filter, obtain the stiffening agent particle 40 of the present invention's second example.
In addition, use as stiffening agent particle 51 with metallo-chelate as the identical powder shaped of the stiffening agent particle 30 of above-mentioned first example, and be scattered in the dibasic alcohol (TPG of Asahi Glass corporate system (tripropylene glycol)) of 40 ℃ of insulations, stir and take out stiffening agent particle 51 after 24 hours, clean the stiffening agent particle 50 that obtains the present invention's the 3rd example.
Use the stiffening agent particle 30,40,50 of first of 2 mass parts～the 3rd example and 50 mass parts thermoplastic resin phenoxy resins (benzene oxygen association corporate system), the thermosetting resin bisphenol A type epoxy resin (oiling girdle epoxy resins corporate system trade(brand)name " EP828 ") of 50 mass parts, epoxy silane coupler (Uni-Charm Co., Ltd.'s system of 1 mass parts respectively, trade(brand)name " A-187 "), the electroconductive particle of 5 mass parts mixes, and makes three kinds of caking agents.
Use three kinds of caking agents,, use the bonding film 20 of embodiment 1～3, carry out following [room temperature preservation test] and [preserving test for 40 ℃] respectively by scheming (a), scheming the bonding film 20 that (b) operation is made embodiment 1～3.
[room temperature preservation test]
With embodiment 1～3 bonding film 20, after in the operation of above-mentioned Fig. 3 (a)～(d), Fig. 4 (e), (f), connecting TCP15 and LCD11, the stripping strength (initial stage stripping strength) of mensuration when LCD11 peels off TCP15, in addition, embodiment 1～3 bonding film 20 was preserved respectively under room temperature 1 day, 3 days, 7 days, with the various bonding film 20 after preserving in above-mentioned identical operation respectively with TCP15 with after LCD11 is connected, measure the stripping strength (preservation is stripping strength afterwards) when LCD11 peels off TCP15 respectively.
Here, for TCP15, use TCP with the wide metal wiring 17 of the arranged spaced 25 μ m of 25 μ m; For LCD11, use to have formed every surface-area and be 1cm
2Sheet resistance be the LCD of the ITO electrode of 10 Ω.Apply the load limit heating 10 seconds of MPa on TCP15 and LCD11 lap limit, coating layer 25 is warming up to 130 ℃ continuously.
[preserving test for 40 ℃]
Except the temperature of preserving bonding film 20 is changed into 40 ℃ from room temperature, use the condition identical to preserve bonding film 20 with above-mentioned room temperature preservation test, behind connection TCP15 and the LCD11, measure and preserve the back stripping strength.
In above-mentioned " room temperature preservation test " and " 40 ℃ preserve test ", preserve the back stripping strength for the initial stage stripping strength be 90% estimate with ' ◎ ' when above, 80% or more less than 90% o'clock with ' zero ' evaluation, estimated with ' * ' during less than 80% o'clock more than 70% with ' △ ' evaluation, less than 70%.These evaluation results are listed in table 1.
[table 1]
Table 1 evaluation test result
In the above-mentioned table 1, used identical in comparative example 1 and first example～the 3rd example, make the stiffening agent particle of state shown in Fig. 1 (b) under the state of handling, not be directly used in caking agent with silane coupling agent and dibasic alcohol.
By above-mentioned table 1 as can be known, use the embodiment 1～3 of the stiffening agent particle 30,40,50 of the present invention's first example～the 3rd example, compare with the comparative example 1 of direct use Fig. 1 (b) stiffening agent particle, ' room temperature preservation test ' preserves test with ' 40 ℃ ' evaluation result is all high, can confirm caking agent, its keeping quality height with stiffening agent particle of the present invention.
Particularly handle the second routine stiffening agent particle 40 of the present invention's first routine stiffening agent particle 30, compared in 30,50 o'clock,, do not find almost that also bonding force reduces even 40 ℃ were preserved 7 days with the stiffening agent particle that uses first example, the 3rd example with Resins, epoxy.
More than, the situation of using caking agent, making bonding film is illustrated, but the present invention is not limited to these, the starchiness caking agent that for example also can directly use.
The middle symbol 11 of Fig. 8 (a) is represented the identical LCD with Fig. 3 (a) expression, for TCP15 is connected with this LCD11, at first, caking agent of the present invention is coated on the part of connection TCP15 on electrode 13 surfaces of LCD11, forms the coating layer 75 (Fig. 8 (b)) of caking agent.
In the operation of above-mentioned Fig. 3 (d), aim at the position of TCP15 after, in the operation of above-mentioned Fig. 4 (e), (f), LCD11 be connected with TCP15 obtain electrical means 70 (Fig. 8 (c)).
More than be illustrated using caking agent that LCD11 is connected with TCP15, but the present invention is not limited to these, also can be used for the occasion of the various electrical meanss of manufacturing such as semiconductor board is connected with substrate.
More than occasion that electroconductive particle is dispersed in the caking agent be illustrated, but the present invention is not limited to these, for example the present invention also comprises the caking agent that does not contain electroconductive particle.
Constitute the metallo-chelate of stiffening agent particle or the central metal of metal alkoxides and can use zirconium, titanium, aluminium etc., wherein particularly preferred central metal is reactive high aluminium.
The situation of Resins, epoxy as thermosetting resin of using more than has been described, but the present invention is not limited to these, cationoid polymerisation resin such as urea resin, melamine resin, resol, vinyl ether resin, oxetane resin etc. also can use, but consider intensity of caking agent after the thermofixation etc., preferably use Resins, epoxy.
The silane coupling agent that is used for caking agent of the present invention, shown in the preferably following general expression (9).
Substituent X in the above-mentioned general expression (9)
12～X
15In, at least one substituting group is an alkoxyl group.The substituent X beyond the alkoxyl group preferably
12～X
15In, at least one substituting group has oxirane ring or vinyl, and the substituting group that contains oxirane ring particularly preferably is epoxypropyl.
Thermoplastic resin for example also can use rubber-like such as vibrin, urethane resin, vinylite, ethylene vinyl acetate resin, polybutadiene rubber except phenoxy resin.And in caking agent of the present invention, also can add various additives such as anti-aging agent, weighting agent, tinting material.
More than just as the silane coupling agent that contact with the stiffening agent particle, used substituting group beyond the alkoxyl group to contain the situation of the silane coupling agent of amino, but the present invention is not limited thereto.As silane coupling agent, the substituting group beyond the alkoxyl group also can use various substituent silane coupling agents such as having vinyl, epoxy group(ing), methacrylic acid group, sulfydryl, isocyanate group.
Also be not limited to Resins, epoxy with the material of the present invention's first routine stiffening agent particle reaction.The silane coupling agent that for example uses alkoxyl group substituting group in addition to have isocyanate group, when making the stiffening agent particle of first example, if change Resins, epoxy into dibasic alcohol, then isocyanate group and diol reaction form urethane resin at the stiffening agent particle surface.
So, and the material of polysiloxane reaction is not confined to the combination between various silane coupling agents especially, also can be depending on the substituent kind of silane coupling agent.
More than illustrated stiffening agent particle 31,41,51 has been scattered in silane coupling agent and the dibasic alcohol, the situation that dibasic alcohol and silane coupling agent contact with stiffening agent particle 31,41,51, but the present invention is not limited thereto, for example also can spray on the stiffening agent particle silane coupling agent, dibasic alcohol make silane coupling agent, dibasic alcohol contact with the stiffening agent particle.
The invention effect
Because siloxanes, alkoxyl are combined with the central metal of curing agent particle surface of the present invention, So curing agent particle and silane coupling agent in the bonding agent do not react. Of the present invention bonding Agent is solidified by the cationic polymerization of epoxy resin. Anti-with in the past used curing agent polymerization Should compare, cationic polymerization can carry out at low temperature, therefore, compared with former bonding agent, But bonding agent low temperature of the present invention, short time solidify.
Claims (8)
1. curing agent particle; One or both in its granulated metal alkoxide that is combined into for the granulated metal chelate, central metal and at least one alkoxyl that form take central metal and at least one coordination atom coordination is the curing agent particle of main component; Process through silane coupling agent on the surface of this curing agent particle; The silicon that comes from silane coupling agent is combined with the described central metal of described curing agent particle surface by oxygen; And the substituting group of the expression of the following general expression (1) on the described silane coupling agent is combined with aforementioned silicon
Substituent X in the above-mentioned general expression
1Combine substituent X with described silicon
1For-CH
2CH
2CH
2-,-CH
2CH
2CH
2NHCH
2CH
2-,-CH
2CH
2CH
2NHC (=O)-.
2. the stiffening agent particle of claim 1 record wherein, interosculates by oxygen with described central metal bonded silicon.
3. according to the stiffening agent particle of claim 1, wherein, the substituting group of following general expression (2) expression on the described silane coupling agent combines with aforementioned silicon,
Substituent X in the above-mentioned general expression (2)
2～X
4In, at least one substituent X
2～X
4Combine substituent X with described silicon
2-X
4Be phenyl or H.
4. stiffening agent particle, it is the stiffening agent particle of main component for the one or both in the metal alkoxide of the metallo-chelate, central metal and at least one the alkoxyl group be combined into that form with central metal and at least one ligating atom coordination, handle through alcohol on the surface of this stiffening agent particle, and the carbon that comes from alcohol combines with the described central metal of described stiffening agent particle surface by oxygen.
5. the manufacture method of stiffening agent particle, wherein, making one or both in the metal alkoxide of the metallo-chelate that forms with central metal and at least one ligating atom coordination, central metal and at least one alkoxyl group be combined into is that the stiffening agent particle of main component contacts with hydroxyl compound, makes the central metal and the reaction of described hydroxyl compound of aforementioned stiffening agent particle surface.
6. the manufacture method of the stiffening agent particle of claim 5 record, wherein, hydroxyl compound be pure.
7. the manufacture method of the stiffening agent particle of claim 6 record, wherein said alcohol is tripropylene glycol.
8. caking agent wherein contains the stiffening agent particle of any record in thermosetting resin, silane coupling agent and the claim 1～4.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031035329A CN100509933C (en) | 2003-01-14 | 2003-01-14 | Hardening particle, manufacturing method of hardening particle and binder |
| HK04109313.7A HK1066560A1 (en) | 2003-01-14 | 2004-11-25 | Hardener particle, the method for manufacturing the same and an adhesive |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031035329A CN100509933C (en) | 2003-01-14 | 2003-01-14 | Hardening particle, manufacturing method of hardening particle and binder |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1517419A CN1517419A (en) | 2004-08-04 |
| CN100509933C true CN100509933C (en) | 2009-07-08 |
Family
ID=34282041
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB031035329A Expired - Lifetime CN100509933C (en) | 2003-01-14 | 2003-01-14 | Hardening particle, manufacturing method of hardening particle and binder |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN100509933C (en) |
| HK (1) | HK1066560A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106605309B (en) * | 2014-06-19 | 2022-10-18 | 英克伦股份有限公司 | LED lamp, manufacturing method of LED lamp and sealing method of LED device |
-
2003
- 2003-01-14 CN CNB031035329A patent/CN100509933C/en not_active Expired - Lifetime
-
2004
- 2004-11-25 HK HK04109313.7A patent/HK1066560A1/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| CN1517419A (en) | 2004-08-04 |
| HK1066560A1 (en) | 2005-03-24 |
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