CN1506428A - Potential hardening agent, producing process and binder thereof - Google Patents
Potential hardening agent, producing process and binder thereof Download PDFInfo
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- CN1506428A CN1506428A CNA021518025A CN02151802A CN1506428A CN 1506428 A CN1506428 A CN 1506428A CN A021518025 A CNA021518025 A CN A021518025A CN 02151802 A CN02151802 A CN 02151802A CN 1506428 A CN1506428 A CN 1506428A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/01—Chemical elements
- H01L2924/01013—Aluminum [Al]
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Abstract
The latent hardening agent is for adhesive to be hardened at low temperature and in short period and to possess high storage performance. The latent hardening agent has main hardening agent particle of metal chelate as the main component and capsule coating the surface of the hardening agent particle, and the resin component of the capsule has substituent combining with the metal chelate. Owing to the high mechanical strength of the capsule, the capsule will not be damaged during the process of mixing the latent hardening agent and epoxy resin.
Description
Technical Field
The present invention relates to an adhesive, and more particularly to a latent curing agent used for an adhesive for connecting a semiconductor chip and a TCP to a substrate by thermocompression bonding.
Background
For many years, adhesives containing epoxy resins as thermosetting resins have been used for connecting semiconductor chips to substrates and for connecting tcp (tape Carrler package) and lcd (liquid Crystal display) to manufacture electrical devices.
In fig. 7(a), reference numeral 111 denotes an LCD, and the LCD 111 includes a glass substrate 112 and an ITO electrode (Indium tin oxide)113 disposed on the glass substrate 112. When the LCD 111 is connected to a TCP described below, first, an adhesive is applied to the surface of the LCD 111 on the side where the ITO electrode 113 is disposed. Reference numeral 125 in fig. 7(b) denotes an adhesive applied to the LCD 111.
In fig. 7(c), reference numeral 115 denotes a TCP, and the TCP115 includes a base film 116 and a metal wiring 117 disposed on a surface of the base film 116. The surface of the TCP115 on which the metal wiring 117 is disposed on the adhesive 125 on the LCD 111, and after the positions are aligned, the surface of the TCP115 on which the metal wiring 117 is disposed is pressed against the adhesive 125.
In this state, when the adhesive 125 is softened by heating while pressing, the metal wiring 117 is pressed into the softened adhesive 125 and contacts the surface of the ITO electrode 113.
In the above adhesive, a curing agent such as imidazole, which is polymerized by heating, is generally added, and when the heating is continued in a state where the metal wiring 117 is in contact with the ITO electrode 113, the epoxy resin is polymerized by the catalytic action of the curing agent, and the adhesive 125 is cured.
In fig. 7(c), reference numeral 101 denotes an electric device in a state where the adhesive 125 is cured. In this electric device 101, since the TCP115 and the LCD 111 are fixed by the cured adhesive 125 in a state where the metal wiring 117 is in contact with the ITO electrode 113, the TCP115 and the LCD 111 are electrically and mechanically connected.
However, when the adhesive is cured, the adhesive must be heated to a high temperature of 180 ℃ or higher, and when the pattern of the metal wiring 117 is fine, the TCP115 may be deformed such as stretched or bent by heating. Although lowering the heating temperature can eliminate such problems, the heating treatment requires a longtime and the production efficiency is lowered.
As an adhesive excellent in curability at low temperatures, in recent years, an adhesive containing a radical polymerizable resin such as an acrylate and a radical polymerization initiator has been developed, but such an adhesive is inferior in both electrical characteristics and heat resistance in a cured state as compared with the case of using an epoxy resin.
Disclosure of Invention
The present invention has been made to solve the above-mentioned problems of the prior art, and an object of the present invention is to provide an adhesive which can be cured at a low temperature in a short time and has excellent storage stability.
The present inventors have paid attention to a method of polymerizing an epoxy resin with cations without using a curing agent generally used, and as a result of intensive studies, they have found a method of adding a silane compound (silane coupling agent) having at least one alkoxy group in its structure and a metal chelate (or metal alkoxide) to an adhesive and polymerizing an epoxy resin with cations generated when the metal chelate and the silane coupling agent are reacted (cationic polymerization).
The process of curing an epoxy resin with an adhesive to which a metal chelate compound and a silane coupling agent are added will be described with reference to the following reaction formulas (1) to (4).
[ solution 1]
… reaction formula (1)
… reaction formula (2)
… reaction formula (3)
… reaction formula (4)
The silane compound having at least one alkoxy group reacts with water in the adhesive as shown in the reaction formula (1), and the alkoxy group is hydrolyzed to form a silanol group.
When the adhesive is heated, the silanol group reacts with a metal chelate compound such as an aluminum chelate compound, and the silane compound is bonded to the aluminum chelate compound. (reaction formula (2)).
Next, as shown in reaction formula (3), the aluminum chelate compound having a silanol group bonded thereto is coordinated to another silanol group remaining in the adhesive in the equilibrium reaction to generate a brensted acid site, and as shown in reaction formula (4), the activated proton opens an epoxy ring located at the terminal of the epoxy resin, and is polymerized with an epoxy ring of another epoxy resin (cationic polymerization). Thus, when the silane coupling agent and the metal chelate compound are added to the adhesive, the thermosetting resin such as the epoxy resin undergoes cationic polymerization. Since the reactions shown in the reaction formulae (2) to (4) proceed at a temperature lower than the conventional curing temperature of the adhesive (180 ℃ or higher), the adhesive can be cured at a lower temperature and in a shorter time than the conventional adhesive.
However, when the metal chelate compound and the metal alkoxide are directly dispersed in the binder together with the silane coupling agent, the epoxy resin is polymerized even at room temperature, and thus the storage stability is poor. When the metal chelate compound isencapsulated in a capsule to form a so-called latent curing agent, although the storage stability of the adhesive is improved, when the mechanical strength of the capsule is weak, the capsule may be broken in the process of dispersing the latent curing agent in the epoxy resin.
The present inventors have further studied a method for improving the mechanical strength of capsules, and as a result, they have found that when a capsule is formed using a resin component having a substituent such as a hydroxyl group or a carboxyl group, a metal chelate complex is bonded to the substituent at the surface portion of the curing agent particle, and the mechanical strength of the capsule is improved, thereby obtaining a latent curing agent having high physical impact resistance.
The present invention has been made in view of the above-mentioned findings, and therefore according to a 1 st embodiment of the present invention, there is provided a latent hardener having hardener particles and capsules coating surfaces of the hardener particles, wherein the hardener particles are mainly composed of either one or both of a metal chelate compound and a metal alkoxide, the capsules are resin components having either one or both of a hydroxyl group and a carboxyl group, and the substituents of the resin components are reacted with the metal chelate compound at surface portions of the hardener particles.
According to the 2 nd embodiment of the present invention, there is provided a latent hardener as set forth in the 1 st embodiment, wherein said metal chelate compound comprises an aluminum chelate compound as a main component.
According to the 3 rd embodiment of the present invention, there is provided a latent hardener as set forth in the 1 st embodiment, wherein the metal alkoxide is an aluminum alkoxide as a main component.
A latent curing agent according to claim4 is characterized in that in the latent curing agent according to claim 1, the resin component contains polyvinyl alcohol as a main component.
The 5 th embodiment of the present invention is a method for producing a latent hardener, which is a method for producing a latent hardener comprising hardener particles and a latent hardener coating a surface capsule of the hardener particles, comprising the steps of: a capsule material production step of producing a powdery capsule material which is composed of a resin component having either or both of a hydroxyl group and a carboxyl group and has an average particle diameter smaller than that of the hardener particles; and an encapsulating step of adhering the capsule material to the surface of the hardening agent particle and melting the capsule material in a state of adhering to the surface of the hardening agent particle to form the capsule.
The method for producing a latent curing agent according to claim 6 of the present invention is the method for producing a latent curing agent according to claim 5, wherein the encapsulating step comprises: a mixing step of mixing the hardener particles with the capsule material to attach the capsule material to the hardener particles; and a stirring step of stirring the hardening agent particles to which the capsule material is attached, thereby melting the capsule material.
The 7 th embodiment of the present invention is a method for producing a latent hardener, characterized in that in the method for producing a latent hardener according to any one of the 5 th or 6 th embodiments, a ratio of an average particle size of the hardener particles to an average particle size of the capsule material is 100: 80 or more.
An 8 th embodiment of the present invention is a method for producing a latent hardener, wherein in the method for producing a latent hardener according to anyone of the 5 th or 6 th embodiments, a ratio of an average particle size of the hardener particles to an average particle size of the capsule material is 100: 50 or more.
The 9 th embodiment of the present invention is a method for producing a latent hardener, characterized in that in the method for producing a latent hardener according to the 5 th embodiment, after the capsule is formed, the capsule and the hardener particle are heated.
The 10 th embodiment of the present invention is an adhesive comprising a thermosetting resin, a silane coupling agent, and the latent curing agent according to any one of embodiments 1 to 4.
In the present invention, the powdery capsule material and the curing agent particles are mixed and stirred, and the capsule material is electrostatically attached to the surfaces of the curing agent particles. The hardening agent particles in this state are stirred at a high speed, and the capsule material is melted in a state of being electrostatically attached to the surfaces of the hardening agent particles, and the capsule material is integrated into a capsule (encapsulated).
When the reactivity of the substituent of the resin component with respect to the hardener particles is particularly high, in the encapsulation step, the substituent of the resin component reacts with the metal chelate or metal alkoxide on the surface of the hardener particles, and the substituent is bonded to the central metal of the metal chelate or metal alkoxide.
When the reactivity of the substituent of the resin component to the hardener particle is low, the hardener particle and the capsule are heated together after the encapsulation process, and the substituent and the metal chelate or metal alkoxide on the surface of the hardener particle can react.
The following reaction formula (5) shows a binding reaction between a substituent of the resin component and an aluminum chelate compound when the aluminum chelate compound is used as the metal chelate compound.
[ solution 2]
… reaction formula (5)
The reaction formula (5) shows that the aluminum chelate complex is bonded to a hydroxyl group, and a proton (hydrogen atom) is separated from the hydroxyl group to form a bond with aluminum. When the substituent is a carboxyl group, the hydroxyl group in the carboxyl group undergoes the same reaction as in the above reaction formula (5), and forms a bond with aluminum.
As described above, in the latent curing agent of the present invention, the substituent of the resin component constituting the capsule is bonded to the metal chelate on the surface of the curing agent particle, and therefore the mechanical strength of the capsule is high. Therefore, in the adhesive production process in which the latent curing agent of the present invention is dispersed in an epoxy resin, the capsule is not broken by physical impact.
When the latent curing agent, the silane coupling agent and the epoxy resin are mixed to prepare an adhesive, the surface of the powdery curing agent particles is entirely covered with the capsule at normal temperature, so that the epoxy resin does not cause a polymerization reaction, but when the adhesive is heated, the metal chelate compound constituting the curing agent particles is thermally expanded to rupture the capsule.
When the capsule is broken, the curing agent particles are mixed with the epoxy resin and the silane coupling agent in the adhesive, the metal chelate compound constituting the curing agent particles reacts with the silane coupling agent, cations are released in the adhesive, and the cations cause the polymerization reaction of the epoxy resin to proceed rapidly (cationic polymerization), and as a result, the adhesive is cured.
The average particle size of the hardener particles is preferably 0.5 to 50 μm, because the difference in particle size between the hardener particles and the capsule material becomes small and the capsule is difficult to form over a long period of time.
In the mixing step and the stirring step, a hybrid mixer device (for example, a trade name "NHS-0" manufactured by naxa mechanical products) having a mixing device for mixing the hardener particles and the capsule material and a stirring device for stirring the hardener particles in a state where the capsule material is adhered can be used. In this case, the mixing ratio of the curing agent particles and the capsule material can be determined by the following formula (1).
Formula (1) M/M ═ D × F/(4 × D × F)
In the above formula (1):
m represents the compounding amount (g) of hardener particles
m represents the compounding amount (g) of the capsule material
D represents the average particle diameter (. mu.m) of the powder-form hardener particles
d represents the average particle diameter (. mu.m) of the capsule material
F represents the specific gravity of the hardener particles
f represents the specific gravity of the capsule material
The specific gravity is a ratio of the density of each substance to the density of water at 4 ℃ as a standard substance. However, the above formula (1) is a theoretical formula, and the optimum compounding ratio of the hardener particles and the capsule material should be determined on a case-by-case basis.
When a thermoplastic resin is added to the adhesive, the cohesive force of the adhesive is increased by the properties of the thermoplastic resin, and thus the adhesiveness of the adhesive is higher. When a highly polar resin is used as the thermoplastic resin, the thermoplastic resin is not only incorporated into the curing reaction of the epoxy resin, but also bonded to the inorganic material via the silane coupling agent, thereby improving not only the curing property of the adhesive but also the affinity with the material to be bonded, which is made of the inorganic material.
Drawings
FIGS. 1(a) to (c) are explanatory views of an example of the process for producing a latent curing agent according to the present invention.
Fig. 2(a) and (b) are explanatory views showing an example of a process for producing an adhesive film using the adhesive of the present invention.
Fig. 3(a) to (d) are explanatory views of a first half step of connecting an LCD and a TCP by using the adhesive of the present invention.
Fig. 4(e) and (f) are explanatory views of the latter half of the process of connecting the TCP and the LCD.
Fig. 5 is a plan view illustrating a state in which TCP is aligned on the LCD.
Fig. 6(a) to (c) are explanatory views of another example of the process of connecting TCP and LCD using the adhesive of the present invention.
Fig. 7(a) to (c) are explanatory views of a first half step of connecting the LCD and the TCP by using a conventional adhesive.
Description of the symbols
20. 45 … … adhesive (coating layer)
30 … … latent hardener
31 … … hardener particles
32 … … Capsule Material
33 … … Capsule
Modes for carrying out the invention
The process for producing the latent curing agent of the present invention will be described below.
First, a resin component having one or both of a hydroxyl group and a carboxyl group is prepared, the resin component is dispersed in a solvent to prepare a resin solution, and the resin solution is spray-dried by a spray-drying apparatus to obtain a powdery resin component (capsule material) (spray-drying method).
Next, an aluminum chelate powder as a metal chelate is prepared as a hardener particle. In FIG. 1(a), reference numeral 31 denotes hardener particles, and the ratio of the average particle diameter of the hardener particles to the average particle diameter of the capsule material is 100: 80 or more.
Next, the hardener particles 31 and the capsule material are mixed at a predetermined mixing ratio, and the capsule material having an average particle size smaller than that of the hardener particles 31 is electrostatically attached to the surfaces of the hardener particles 31 while being stirred in the mixing device (mixing step).
In fig. 1(b), reference numeral 32 denotes a capsule material in this state, and the surface of one hardener particle 31 is covered with a plurality of capsule materials 32.
The hardening agent particles 31 having the capsule material 32 electrostatically attached to the surface thereof are charged into a stirring device and stirred at a high speed, so that the capsule material 32 on the surface of the hardening agent particles 31 collides or rubs with the capsule material 32 on the surface of the other hardening agent particles 31 and the rotating blade or the inner wall of the stirring device, the capsule material 32 is melted by the generated heat, and the melted capsule materials 32 are integrated with each other (stirring step).
At this time, the melted capsule material 32 comes into contact with the surface of the hardener particle 31, and the substituent of the resin component constituting the capsule material 32 is bonded to the metal chelate at the surface portion of the hardener particle 31.
In fig. 1(c), reference numeral 33 denotes a capsule integrally formed from a capsule material 32. The capsule 33 is formed to cover the entire surface of the hardener particle 31, and the latent hardener 30 is constituted by the hardener particle 31 and the capsule 33.
The substituent of the resin component of the capsule material 32 and the metal chelate are continuously reacted by contact, and when the latent hardener 30 forming the capsule 33 is heated, the substituent and the metal chelate are rapidly reacted.
The adhesive of the present invention using the latent curing agent 30 and a process for producing an electric device using the adhesive of the present invention will be described below.
An epoxy resin as a thermosetting resin, a thermoplastic resin, a silane coupling agent, the latent curing agent 30, conductive particles, and a solvent are mixed and stirred at a predetermined mixing ratio to prepare an adhesive. In this state, the adhesive is in the form of a paste. Since the capsules 33 of the latent hardener 30 have high mechanical strength, the capsules 33 are not broken during the stirring process.
In fig. 2(a), reference numeral 21 denotes a release film. The adhesive is appliedto the surface of the release film 21 in a predetermined amount, dried, and the solvent in the adhesive is evaporated to form an adhesive coating layer 25 (fig. 2 (b)).
In fig. 2(b), reference numeral 20 denotes an adhesive film on which a coating layer 25 is formed. In the same drawing, reference numeral 27 denotes conductive particles dispersed in the adhesive together with the latent curing agent 30. In this state, the curing agent particles 31 of the latent curing agent 30 are encapsulated in the capsule 33, and the silane coupling agent in the adhesive constituting the coating layer 25 and the curing agent particles 31 do not come into contact with each other, so that the curing reaction of the coating layer 25 does not occur at normal temperature.
In fig. 3(a), reference numeral 11 denotes an LCD, and the LCD11 has a glass substrate 12 and a plurality of ITO electrodes 13(Indium tin oxides) having a narrow width formed on one surface of the glass substrate 12, and 5 ITO electrodes 13 are shown in the drawing.
The coating layer 25 of the adhesive film 20 shown in fig. 2(b) is pressure-bonded to a portion to which a TCP described below is connected, on the surface of the LCD11 on which the ITO electrode 13 is formed (fig. 3 (b)). Since the adhesion between the release film 21 and the coating layer 25 is smaller than the adhesion between the coating layer 25 and the ITO electrode 13, the coating layer 25 does not remain on the LCD11 when the release film 21 is released (fig. 3 (c)).
Fig. 3(d) is a cross-sectional view taken along line a-a in fig. 5, in which the surface of the TCP15 on which the metal wiring 17 is disposed faces the surface of the LCD11 on which the ITO electrode 13 is disposed, one end of the TCP15 is opposed to the coating layer 25 on the surface of the ITO electrode 13, and the ITO electrode 13 of the LCD11 and the metal wiring 17 of the TCP15 are opposed to each other and are aligned.
In this state, the surface of the TCP15 on which the metal wiring 17 is disposed is pressed against the coating layer 25, the entire body is heated while pressing the overlapping portion of the TCP15 and the LCD11, the coating layer 25 is softened by heating, and the metal wiring 17 is pressed into the softened coating layer 25 by pressing, and the conductive particles 27 in the remaining coating layer 25 are sandwiched between the metal wiring 17 and the IT electrode 13 (fig. 4 (e)).
In this state, the heating and pressing are continued, and the hardening agent particles 31 expand by heat, and the capsules 33 are broken. After the capsules 33 are broken, the curing agent particles 31 are mixed with the epoxy resin and the silane coupling agent in the coating layer 25, the aluminum chelate compound constituting the curing agent particles 31 reacts with the silane coupling agent, cations are released in the coating layer 25, and the coating layer is cured in a state where the conductive particles 27 are sandwiched between the metal wiring 17 and the ITO electrode 13 by the rapid polymerization reaction (cationic polymerization) of the epoxy resin by the cations (fig. 4 (f)).
In FIG. 4(f), reference numeral 10 denotes an electric device after the coating layer 25 is cured. In the electric device 10, the metal wiring 17 and the ITO electrode 13 are electrically connected not only by the conductive particles 27, but also the LCD11 andthe TCP15 are mechanically connected by the hardened coating layer 25.
As described above, the adhesive of the present invention is excellent in storage stability, and can be cured at a lower temperature in a shorter time than a conventional curing agent by curing an epoxy resin by cationic polymerization.
Example for the following
10 parts by weight of a resin component composed of polyvinyl alcohol (trade name "PVA 205" manufactured by クラレ K.) was dissolved in 90 parts by weight of water to prepare a 10% by weight aqueous solution of the resin component. Subsequently, a 10 wt% aqueous solution of the resin component was sprayed from a nozzle into nitrogen (temperature 160 ℃ C.) and dried to prepare a powdery capsule material 32 (average particle size 0.8 μm) (spray drying method).
As the hardener particles 31, fine powder of aluminum chelate as a metal chelate (aluminum triacetoacetate manufactured by kawa フアィンケミカル, ltd.) and fine powder of aluminum alkoxide as a metal alkoxide (aluminum isopropionate manufactured by kawa フアィンケミカル, ltd.) were prepared, respectively. The 2 hardener particles 31 each had an average particle diameter of 5 μm. Therefore, the ratio of the average particle diameter of the hardener particles 31 to the average particle diameter of the capsule material 32 is 5: 0.8.
Next, using a trade name "hybrid mixer-NHS-0" manufactured by neilin mechanical products, in the steps of fig. 1(a) and (b), after the capsule material 32 was electrostatically adhered to the surface of the hardener particle 31, the mixture was stirred at 16200rpm (peripheral speed 100 m/sec) for 5 minutes to form a capsule 33, and 2 kinds of latent hardeners 30 were obtained, and then these latent hardeners 30 were heated at 40 ℃ for 48 hours.
2 kinds of adhesive pastes were prepared by mixing the 2 kinds of latent curing agents 30, phenoxy resin (product name "PKHH" manufactured by フュノキシアソシェ - ツ, Inc.), bisphenol A type epoxy resin (product name "EP 828" manufactured by Takara シュルェボキシ, Inc.), silane coupling agent (product name "A-187" manufactured by Nippon ュニカ, Inc.), and conductive particles at the mixing ratios shown in Table 1 below, and the adhesive films 20 of examples 1 and 2 were prepared by the steps shown in FIGS. 2(a) and (b) using these adhesives.
TABLE 1
Table 1: composition of adhesive
| Composition of adhesive | Example 1 | Example 2 | Comparative example 1 | Comparative example 2 |
| Phenoxy resin | 50 | 50 | 50 | 50 |
| Bisphenol A epoxy resin | 50 | 50 | 50 | 50 |
| Latent hardener A | 1 | - | - | - |
| Latent hardener B | - | 1 | - | - |
| Aluminium triacetyl acetate salt | - | - | 1 | - |
| Aluminum isopropoxide | - | - | - | 1 |
| Silane coupling agent | 1 | 1 | 1 | 1 |
| Conductive particles | 5 | 5 | 5 | 5 |
*Latent hardener a: altriacetoacetate + capsule
*Latent hardener B: aluminum isopropoxide + capsule
*The numerical values in the above tables are expressed in parts by weight, respectively
Comparative examples 1 and 2 in table 1 above were prepared by adding 2 kinds of hardener particles used in examples 1 and 2 to an adhesive without forming capsules.
The adhesive films 20 of examples 1 and 2 and comparative examples 1 and 2 were used to perform the following "room temperature storage test" and "storage test at 40 ℃.
[ Room temperature storage test]
Using the adhesive films 20 of examples 1 and 2 and comparative examples 1 and 2, the TCP15 and the LCD11 were connected in accordance with the steps of fig. 3(a) to (d), fig. 4(e), and (f), and then the peel strength (initial peel strength) when the TCP15 was peeled from the LCD11 was measured.
Except for this, the adhesive films 20 of examples 1 and 2 and comparative examples 1 and 2 were stored at room temperature (25 ℃) for 1 day, 3 days, and 7 days, respectively, and the TCP15 and the LCD11 were connected to each other by the same procedure as described above using the adhesive films 20 after storage, and then the peel strength (peel strength after storage) when the TCP15 was peeled from the LCD11 was measured.
[ storage test at 40 ℃]
The adhesive film 20 was stored under the same conditions as in the "room temperature storage test" described above except that the temperature at which the adhesive film 20 was stored was changed from room temperature to 40 ℃, and after connecting the TCP15 and the LCD11, the peel strength after storage was measured.
In the "room temperature storage test" and the "40 ℃ storage test", the magnitude of peel strength after storage was "◎" when the magnitude of initial peel strength was 90% or more, and "○" when 80% or more and less than 90%, and "△" when70% or more and "x" when less than 70%, and the evaluation results are shown in table 2 below.
TABLE 2
Table 2: evaluation of the results of the test
| Storing at room temperature | Storing at 40 deg.C | |||||
| 1 day | 3 days | 7 days | 1 day | 3 days | 7 days | |
| Example 1 | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ |
| Example 2 | ◎ | ◎ | ◎ | ◎ | ◎ | ○ |
| Comparative example 1 | ○ | △ | × | × | × | × |
| Comparative example 2 | - | - | - | - | - | - |
*-: the adhesive is cured in the process of manufacturing the adhesive film.
Here, as TCP15, TCP in which metal wirings 17 having a width of 25 μm are arranged at an interval of 25 μm was used, and TCP formed at an interval of 1cm was used2An LCD having an ITO electrode 13 with a sheet resistance of 10 Ω was connected as an LCD11 by heating the superposed part of the TCP15 and the LCD11 for 10 seconds while applying a 3MPa load to raise the temperature of the coating layer 25 to 130 ℃.
As is clear from tables 1 and 2, in examples 1 and 2 in which the curing agent particles 31 were sealed in the capsule 33, the evaluation results of the "room temperature storage test" and the "storage test at 40 ℃ were all good, and it was confirmed that the adhesive using the latent curing agent of the present invention was excellent in storage stability.
On the other hand, in comparative examples 1 and 2 in which the curing agent particles were not encapsulated, the adhesive was added, and the evaluation results in all the tests were inferior to those in examples 1 and 2. In particular, in comparative example 2 using a highly reactive aluminum alkoxide (aluminum isopropoxide), the epoxy resin was polymerized in the step of producing the adhesive and the adhesive film, and the adhesive was too viscous to produce an adhesive film by itself.
Although the case of using an adhesive to form an adhesive film has been described above, the present invention is not limited to this, and for example, the adhesive may be used as it is in the form of a paste.
In fig. 6 a, reference numeral 11 denotes the same LCD as that shown in fig. 3 a, and in order to connect the TCP15 to the LCD11, first, an adhesive is applied to a portion of the surface of the ITO electrode 13 of the LCD11 to which the TCP15 is connected, thereby forming an adhesive coating layer 45 (fig. 6 b).
Next, after the TCP15 is aligned in the step of fig. 3(d), the electrical device 40 is obtained when the TCP15 and the LCD11 are connected in the steps of fig. 4(e) and (f) (fig. 6 (c)).
Although the case where the TCP15 and the LCD11 are connected by using the adhesive has been described above, the present invention is not limited to this, and can be applied to the case where various electric devices are manufactured when a substrate and a semiconductor chip are connected.
Various conductive particles can be used for the conductive particles 27 in the adhesive of the present invention. Although the case where the conductive particles are dispersed in the adhesive has been described above, the present invention is not limited to this, and, for example, an adhesive containing no conductive particles is also included in the present invention.
As the metal chelate compound, various metal chelate compounds such as zirconium chelate compound, titanium chelate compound, and aluminum chelate compound can be used, but among these, aluminum chelate compound having high reactivity is more preferably used.
Although the case of using polyvinyl alcohol as the resin component has been described above, the present invention is not limited thereto, and various resin components may be used aslong as they have a substituent that reacts with a metal chelate and a metal alkoxide such as a hydroxyl group and a carboxyl group, and for example, various resins such as phenoxy resin, urethane resin, and polyester resin may be used.
After the capsule 33 is formed, the heating temperature for heating the latent curing agent 30 is not limited to 40 ℃, and the heating temperature is preferably not higher than the glass transition temperature of the resin component because the capsule 33 is damaged due to an excessively high heating temperature.
As the thermosetting resin, various resins such as urea resin, melamine resin, phenol resin, vinyl ether resin, oxetane resin and the like can be used in addition to the epoxy resin, but the epoxy resin is preferably used in consideration of the strength of the adhesive after heat curing and the like.
As the silane coupling agent used in the present invention, the silane coupling agent represented by the following formula (6) is preferably used.
[ solution 3]
… general formula (6)
(in the above formula (6), the substituent X1-X4Wherein at least one substituent is an alkoxy group. The alkoxy group is preferablyMethoxy or ethoxy. Substituents X other than alkoxy1～X4In (3), it is preferable that at least one substituent has an epoxy ring or a vinyl group, and particularly, it is more preferable that the substituent having an epoxy ring is a glycidyl group. Examples of the substituent having a vinyl group include a methacryloxypropyl group (メタクリロキシブロビル group). Examples of the substituent having a glycidyl group include glycidoxypropyl. Or may be a substituent X1～X4All are so-called silicates formed from alkoxy groups. )
As the thermoplastic resin, in addition to the phenoxy resin, for example, rubbers such as polyester resin, polyurethane resin, polyvinyl acetal, ethylene vinyl acetate, polybutadiene rubber, and the like can be used.
Effects of the invention
The adhesive of the present invention has improved storage stability, and the substituent of the resin component constituting the capsule is bonded to the metal chelate compound, which is the main component of the curing agent particle, on the surface of the curing agent particle. Therefore, the capsule has high mechanical strength and the latent hardener has high physical impact resistance.
Claims (10)
1. A latent hardener comprising hardener particles and a capsule covering the surface of the hardener particles,
the hardener particles contain either or both of a metal chelate and a metal alkoxide as a main component,
The capsule contains a resin component having a substituent of either or both of a hydroxyl group and a carboxyl group,
The substituent of the resin component reacts with the metal chelate compound at the surface portion of the hardener particle.
2. The latent hardener according to claim 1, wherein the metal chelate compound comprises an aluminum chelate compound as a main component.
3. The latent hardener according to claim 1, wherein the metal alkoxide comprises an aluminum alkoxide as a main component.
4. The latent curing agent according to claim 1, wherein the resin component comprises polyvinyl alcohol as a main component.
5. A method for producing a latent curing agent, which comprises a step for producing a capsule material comprising curing agent particles and a capsule covering the surfaces of the curing agent particles, characterized by comprising a capsule material production step for producing a powdery capsule material which is formed from a resin component having one or two substituents selected from a hydroxyl group and a carboxyl group and has an average particle diameter smaller than the average particle diameter of the curing agent particles, and an encapsulation step for adhering the capsule material to the surfaces of the curing agent particles and melting the capsule material in a state of adhering to the surfaces of the curing agent particles to form the capsule.
6. The method according to claim 5, wherein the encapsulating step comprises a mixing step of mixing the curing agent particles and the capsule material to attach the capsule material to the surface of the curing agent particles, and a stirring step of stirring the curing agent particles with the capsule material attached thereto to melt the capsule material.
7. The method of producing a latent curing agent according to claim 5 or 6, wherein the ratio of the average particle diameter of the curing agent particles to the average particle diameter of the capsule material is 100: 80 or more.
8. The method of producing a latent curing agent according to claim 5 or 6, wherein the ratio of the average particle diameter of the curing agent particles to the average particle diameter of the capsule material is 100: 50 or more.
9. The method of producing a latent curing agent according to claim 5, wherein the capsule and the curing agent particles are heated after the capsule is formed.
10. An adhesive comprising a thermosetting resin, a silane coupling agent, and the latent curing agent according to any one of claims 1 to 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02151802 CN1285660C (en) | 2002-12-05 | 2002-12-05 | Potential hardening agent, producing process and binder thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02151802 CN1285660C (en) | 2002-12-05 | 2002-12-05 | Potential hardening agent, producing process and binder thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1506428A true CN1506428A (en) | 2004-06-23 |
| CN1285660C CN1285660C (en) | 2006-11-22 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 02151802 Expired - Lifetime CN1285660C (en) | 2002-12-05 | 2002-12-05 | Potential hardening agent, producing process and binder thereof |
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| Country | Link |
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| CN (1) | CN1285660C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101098905B (en) * | 2005-01-12 | 2011-02-02 | 索尼化学&信息部件株式会社 | Latent curing agent |
| CN101115782B (en) * | 2006-02-07 | 2012-02-08 | 索尼化学&信息部件株式会社 | Latent curing agent |
| CN103826846A (en) * | 2011-09-28 | 2014-05-28 | 杰富意钢铁株式会社 | Resin-coated metal sheet for container |
-
2002
- 2002-12-05 CN CN 02151802 patent/CN1285660C/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101098905B (en) * | 2005-01-12 | 2011-02-02 | 索尼化学&信息部件株式会社 | Latent curing agent |
| CN101115782B (en) * | 2006-02-07 | 2012-02-08 | 索尼化学&信息部件株式会社 | Latent curing agent |
| CN103826846A (en) * | 2011-09-28 | 2014-05-28 | 杰富意钢铁株式会社 | Resin-coated metal sheet for container |
| CN103826846B (en) * | 2011-09-28 | 2016-08-17 | 杰富意钢铁株式会社 | Container resin-coated metal sheet |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1285660C (en) | 2006-11-22 |
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