KR101007914B1 - Latent Hardener, Manufacturing Method for Latent Hardener, and Adhesive - Google Patents

Abstract

It hardens | cures on condition of a short time at low temperature, and obtains the adhesive agent with high shelf life. The adhesive of the present invention includes a latent curing agent 30 coated with a capsule 33 with a curing agent particle 31 composed mainly of a silane coupling agent, an epoxy resin, and a metal chelate. Since the curing agent particles 31 are coated on the capsule at room temperature, the polymerization reaction of the epoxy resin does not occur, but when the adhesive is heated, the capsule 33 is destroyed, and the metal chelate constituting the curing agent particles 31 is a silane coupling agent. Cation is formed, the epoxy resin is polymerized by the cation (cationic polymerization), and the adhesive is cured. Since the reaction generated by the cation occurs at a lower temperature than the temperature at which the conventional adhesive is thermoset, the adhesive of the present invention is cured in a short time at a lower temperature than the conventional adhesive. Thus, the adhesive agent of this invention is low temperature hardening type, and its storage property is high.

Description

Latent Hardener, Manufacturing Method for Latent Hardener, and Adhesive

The present invention relates to an adhesive. In particular, this invention relates to the latent hardener used for the adhesive agent which connects a semiconductor chip or TCP to a board | substrate by thermocompression bonding.

Background Art Conventionally, adhesives containing epoxy resins, which are thermosetting resins, have been used in the case of connecting a semiconductor chip on a substrate or in manufacturing an electrical device by connecting a tape carrier package (TCP) and a liquid crystal display (LCD).

Reference numeral 111 in FIG. 7A denotes an LCD, and the LCD 111 includes a glass substrate 112 and an ITO electrode 113 disposed on the glass substrate 112. In order to connect LCD 111 and TCP mentioned later, an adhesive agent is first apply | coated to the surface of the side where the ITO electrode 113 of the LCD 111 is arrange | positioned. Reference numeral 125 in FIG. 7B denotes an adhesive applied to the LCD 111.

Reference numeral 115 in FIG. 7C denotes TCP, and TCP 115 includes a base film 116 and a metal wiring 117 disposed on the surface of the base film 116. The surface on which the metal wiring 117 of the TCP 115 is arranged toward the adhesive 125 on the LCD 111 and aligned, and then the surface on which the metal wiring 117 of the TCP 115 is disposed. To the adhesive (125).

When heated under pressure, the adhesive 125 softens and the metal wire 117 pushes the softened adhesive 125 to contact the surface of the ITO electrode 113.

In general, an adhesive such as electricity is added with a curing agent such as imidazole which polymerizes an epoxy resin by heating, and further heating is performed while the metal wiring 117 is in contact with the ITO electrode 113, thereby catalyzing the curing agent. The epoxy resin is polymerized to cure the adhesive 125.

Reference numeral 101 in FIG. 7C shows an electric device in a state where the adhesive 125 is cured. In this electric device 101, the TCP 115 and the LCD 111 are fixed by the adhesive 125 cured while the metal wiring 117 is in contact with the ITO electrode 113. Thus, the TCP 115 is fixed. ) And LCD 111 are electrically and mechanically connected.

However, in the case of curing the adhesive such as electricity, it is necessary to heat the adhesive to a high temperature of 180 ° C. or higher, and when the pattern of the metal wiring 117 is fine, deformation such as elongation or warping of the TCP 115 during heating is performed. This may occur. When the heating temperature is lowered, this problem is solved, but the time required for the heating treatment becomes longer, and the productivity is lowered.

As an adhesive having excellent curability at low temperatures, in recent years, adhesives containing a radical polymerizable resin such as acrylate and a radical polymerization initiator have been developed. However, such adhesives have electrical properties in a cured state compared to the case where an epoxy resin is used. Or poor heat resistance.

The present invention has been made to solve the irrationalities of the prior art, and its object is to provide an adhesive which is curable at low temperature for a short time and has excellent storage property.

The inventors of the present invention have focused on the method of cationic polymerization of epoxy resins without using a curing agent generally used, and as a result, a silane compound (silane coupling agent) containing at least one alkoxy group in the structure is studied. And a method in which an epoxy resin is polymerized (cationic polymerization) by a cation generated when a metal chelate (or metal alcoholate) is added to an adhesive to react the metal chelate with a silane coupling agent.

Since the adhesive agent of this invention is coat | covered with the hardening agent particle | grains whose metal chelate is a main component by the capsule, the polymerization reaction of an epoxy resin does not occur at normal temperature, and the storage property of an adhesive agent is high. In addition, the adhesive of the present invention is cured by the cation polymerization reaction of the epoxy resin. Since the cationic polymerization reaction occurs at a lower temperature than the polymerization reaction in the case of using a conventional curing agent, the adhesive of the present invention is cured in a short time at a low temperature compared with the conventional adhesive.

1A, 1B and 1C are views for explaining an example of a process for producing a latent curing agent of the present invention.
2A and 2B are views for explaining an example of a process of manufacturing an adhesive film using the adhesive of the present invention.
3A, 3B, 3C, and 3D are views for explaining the overall process of connecting an LCD and a TCP using the adhesive of the present invention.
4 is a diagram for explaining the second half of the process of connecting the TCP and the LCD.
5 is a plan view for explaining a state in which TCP is aligned on an LCD.
6A, 6B and 6C are views for explaining another example of the process of connecting the TCP and the LCD using the adhesive of the present invention.
7A, 7B, and 7C are diagrams for explaining the first half of a process of connecting a TCP and an LCD using a conventional adhesive.

The process of hardening an epoxy resin with the adhesive which added the metal chelate and a silane coupling agent is demonstrated by following Reaction Formula (1)-(4).

.... Scheme (1)

.... Scheme (2)

.... Scheme (3)

.... Reaction Scheme (4)

The silane compound which has at least one alkoxy group reacts with the water in an adhesive agent as shown in Reaction formula (1), and alkoxy group hydrolyzes and becomes a silanol group.

When the adhesive is heated, the silanol group reacts with a metal chelate such as aluminum chelate to bind the silane compound to the aluminum chelate (Scheme (2)).

Subsequently, as shown in Scheme (3), the Brünsted acid point is generated by coordinating the other silanol groups remaining in the adhesive by equilibrium reaction to the aluminum chelate to which the silanol groups are bonded, and as shown in Scheme (4), The epoxy ring located at the terminal of the epoxy resin is opened by the activated hydrogen group and polymerized with the epoxy ring of another epoxy resin (hydrogen group polymerization). In this way, when the silane coupling agent and the metal chelate are added to the adhesive, a thermosetting resin such as an epoxy resin is hydrogenated. Since the reactions shown in Schemes (2) to (4) proceed at a temperature lower than the temperature at which the conventional adhesive is cured (180 ° C. or more), the adhesive such as electricity is cured in a short time at a low temperature as compared with the conventional one.

However, when the same metal chelate or metal alcoholate as described above is added directly to the adhesive together with the silane coupling agent, the polymerization reaction of the epoxy resin proceeds at room temperature and the viscosity of the adhesive may increase.

As a result of further studies by the present inventors, the present inventors have found a method of encapsulating the metal chelate in a capsule that is a main component of a resin component that does not react with an epoxy resin at room temperature, and adding it to the adhesive as a latent curing agent.

This invention is comprised based on electric discovery, and when a resin particle and a hardening | curing agent particle are mixed and stirred, many resin particles are electrostatically attached to the surface of one hardening | curing agent particle. When the curing agent particles in this state are stirred at a high speed in the stirring apparatus, the resin particles that have been electrostatically attached to the surface of the curing agent particles collide with the blades or inner walls of the stirring apparatus and the resin particles on the surface of the other curing agent particles, and the energy generated by the physical impact. As a result, the resin particles are melted or become core materials (hardener particles). The molten resin particles are integrated to form a capsule covering the surface of the curing agent particles.

When the adhesive is prepared by mixing a latent curing agent, a silane coupling agent, and an epoxy resin such as electricity, since the surface of the curing agent particle is covered with a capsule at room temperature, the polymerization reaction of the epoxy resin does not occur. When the adhesive is heated, the capsule softens or melts, which significantly lowers the mechanical strength of the capsule. Therefore, in the state in which the adhesive is heated, the capsule is easily broken by physical impact caused by thermal expansion of the curing agent particles, pressurization during thermocompression bonding, and the like, and the curing agent particles are released into the adhesive.

If the heating is continued in this state, the silane coupling agent reacts with the metal chelate, which is the main component of the curing agent particles, and the adhesive reacts with each other to produce a hydrogen group, and the epoxy resin polymerizes with the hydrogen group (hydrogen group polymerization) to cure the adhesive. do.

Since the reaction between the curing agent particles and the silane coupling agent occurs at a temperature lower than the temperature at which the conventional adhesive is thermally cured (180 ° C. or higher), the adhesive of the present invention is cured in a short time at a lower temperature than the conventional adhesive.

In order to increase the contact area with the epoxy resin, it is preferable to decrease the average particle diameter of the curing agent particles, but when the average particle diameter of the curing agent particles is too small, the particle diameter difference with the resin particles becomes small, which makes it difficult to form capsules. The average particle diameter of the curing agent particles is preferably 0.5 µm or more and 50 µm or less.

In addition, when manufacturing a latent hardening | curing agent by mixing and stirring a resin particle and a hardening | curing agent particle as mentioned above, a hybridizer apparatus (For example, brand name "NHS-0" made by Nari Machinery Co., Ltd.) Can be used. In this case, the compounding ratio of a hardening | curing agent particle and resin particle can be calculated | required by following formula (1).

(1). M / m = D × F / (4 × d × f)

In the formula (1), M is the compounding amount (g) of the curing agent particles, m is the compounding amount (g) of the resin particles, D is the average particle diameter (μm) of the powdery curing agent particles, d is the average particle of the capsule material Diameter (micrometer), F has specific gravity of hardening | curing agent particle, f has shown the specific gravity of capsule material, respectively. In addition, specific gravity shows the ratio of the density of each substance with respect to the density of 4 degreeC water which is a standard substance. However, Equation (1) is the theoretical formula and the optimum mixing ratio of the hardener particles and the resin particles is determined depending on the situation.

In addition, when the thermoplastic resin is added to the adhesive, the cohesive force of the adhesive increases from the properties of the thermoplastic resin, so that the adhesiveness of the adhesive is higher. In the case where a thermoplastic resin having a high polarity is used, the thermoplastic resin synchronizes with the curing reaction of the epoxy resin and bonds with the inorganic material through the silane coupling agent, thereby increasing the curing property of the adhesive and being compatible with the adherend made of the inorganic material. The castle is even higher.

Hereinafter, the adhesive agent of this invention is demonstrated in detail.

First, aluminum chelate, which is a metal chelate, was dissolved in an organic solvent, a metal chelate solution was prepared, and then the metal chelate solution was spray-dried using a spray drying apparatus to obtain hardener particles (spray dryer method). Reference numeral 31 in Fig. 1 (a) represents the hardener particles.

Next, powders having a melting point of 30 ° C to 350 ° C, pyrolysis temperature of 50 ° C to 500 ° C, softening temperature of 0 ° C to 300 ° C, and glass transition temperature of -40 ° C to 300 ° C. The resin (resin particle) of the phase is prepared. The ratio of the average particle diameter of the curing agent particles to the average particle diameter of the resin particles is 100: 80 or more.

Subsequently, when the curing agent particles 31 and the resin particles are mixed at a predetermined mixing ratio and stirred in the mixing apparatus, resin particles having a smaller average particle diameter than the curing agent particles 31 are electrostatically attached to the surface of the curing agent particles 31. (Mixing process). Reference numeral 32 in Fig. 1 (b) denotes resin particles, and the surface of one curing agent particle 31 is covered with a plurality of resin particles 32.

When the hardener particles 31 in which the resin particles 32 are electrostatically attached to the surface are put into a stirring device (not shown) and stirred at a high speed, the resin particles 32 on the hardener particles 31 surface are rotated by the blade of the stirring device. The resin particles 32 are melted by heat generated by collision or friction with the inner wall, and the melted resin particles 32 are integrated with each other (stirring step).

Reference numeral 33 in FIG. 1C indicates a capsule in which the resin particles 32 are integrally formed. The capsule 33 is formed to cover the entire surface of the hardener particles 31, and the latent hardener 30 is formed from the hardener particles 31 and the capsule 33.

Next, the process of manufacturing an electric apparatus using the adhesive agent of this invention using the said latent hardening | curing agent 30, and the adhesive agent of this invention is demonstrated.

An epoxy resin, a thermoplastic resin, a silane coupling agent, the latent curing agent 30, conductive particles, and a solvent were mixed and stirred at a predetermined blending ratio to prepare an adhesive. In this state, the adhesive is a paste.

Reference numeral 21 in FIG. 2 (a) denotes a release film. When the adhesive is applied and dried in a predetermined amount on the surface of the release film 21, the solvent in the adhesive is evaporated to form the coating layer 25 of the adhesive (Fig. 2 (b)).

Reference numeral 20 in FIG. 2B denotes an adhesive film in a state where the coating layer 25 is formed. Reference numeral 27 in the same figure represents 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 and the curing agent particles 30 in the adhesive constituting the coating layer 25 do not contact each other. In this case, the curing reaction of the coating layer 25 does not occur.

Reference numeral 11 in FIG. 3A denotes an LCD, which includes a plurality of ITO electrodes 13 (indium tin oxide) formed in a narrow width on one surface of the glass substrate 12 and the glass substrate 12. It includes. Here, five ITO electrodes 13 are shown.

On the surface where the ITO electrode 13 of the LCD 11 is formed, the application layer 25 of the adhesive film 20 shown in FIG. . Since the adhesive force 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 is separated by the LCD when the release film 21 is peeled off. It remains on (11) (FIG. 3 (c)). The code | symbol 15 of FIG. 5 has shown TCP. The TCP 15 includes a long-sized base film 16, and one side of the base film 16 has a narrow metal wiring 17 along the longitudinal direction of the base film 16. Plural numbers (here, five metal wires 17 are shown) are arranged. The terminal portions in the longitudinal direction of the metal wiring 17 are positioned in the terminal portions in the longitudinal direction of the base film 16, respectively.

FIG. 3 (d) shows a cross-sectional view along the AA line of FIG. 5, with the surface on the side where the metal wiring 17 of the TCP 15 is arranged toward the surface where the ITO electrode 13 of the LCD 11 is arranged. One end of the (15) is opposed to the coating layer 25 on the surface of the ITO electrode 13 so that the ITO electrode 13 of the LCD 11 and the metal wiring 17 of the TCP 15 face each other. .

In this state, if the surface where the metal wiring 17 of the TCP 15 is disposed is abutted against the coating layer 25, the entire heating is performed while applying pressure to the overlapped portion of the TCP 15 and the LCD 11, The coating layer 25 is softened, and by applying pressure, the conductive layer 27 in the coating layer 25 remaining by pushing out the coating layer 25 softened by the metal wiring 17 is separated from the metal wiring 17. It is sandwiched between the ITO electrode 13 (Fig. 4 (e)).

 Further heating in this state and the application of pressure continue to significantly weaken the mechanical strength of the capsule 33 by heating. At this time, since the hardening agent particle 31 thermally expands by heating, the capsule 33 whose mechanical strength is weakened by heating is cracked, and the hardening agent particle 31 is mixed with the epoxy resin or silane coupling agent in the coating layer 25. do.

When the curing agent particles 31 are mixed with the epoxy resin or the silane coupling agent, the aluminum chelate constituting the curing agent particles 31 reacts with the silane coupling agent to release cations in the coating layer 25.

Due to the cation, the polymerization reaction of the epoxy resin proceeds rapidly (cationic polymerization), and the coating layer 25 is cured while the metal wiring 17 and the ITO electrode 13 sandwich the conductive particles 27 (FIG. 4). (f)).

Reference numeral 10 in FIG. 4 (f) shows an electric device in a state where the coating layer 25 is cured. In this electric apparatus 10, the metallization wiring 17 and the ITO electrode 13 are not only electrically connected through the electroconductive particle 27, but also the coating layer 25 which the LCD 11 and the TCP 15 hardened | cured. Is also mechanically connected.

As described above, the adhesive of the present invention not only has excellent storage properties, but also the epoxy resin is cured by cationic polymerization, so that the adhesive can be cured in a short time at low temperature as compared with the case of using a conventional curing agent.

Example

Aluminum alcoholate (Aluminum acetylacetate (brand name "Aluminum Chelate A (W)" made by Kawaken Fine Chemicals)), aluminum alcoholate (Aluminum isopropylate (Kaken Fine Chemicals Co., Ltd. product) (brand name "AIPD") )) Were each dispersed with methyl ethyl ketone as a solvent to prepare a metal chelate solution containing 10% by weight of aluminum chelate and a metal alcohol solution solution containing 10% by weight of aluminum alcoholate.

Subsequently, using a spray dryer (trade name "GC-31" manufactured by Yamato Labotech Co., Ltd.), the spray inlet temperature was 80 ° C, the spray outlet temperature was 60 ° C, the spray pressure 1 kg / cm 2, and the dry nitrogen gas flow rate 0.5 m 3 /. The metal chelate dissolution solution and the metal alcohol dissolution solution were sprayed and dried under the condition of powder to form two kinds of powdery hardeners (curing agent particles) (spray dryer method). As a powder-like fluorine resin (trade name "Lebron L-5" manufactured by Daikin Industries Co., Ltd., primary particle diameter of 0.2 µm, melting point of 327 ° C) was prepared.

20 weights of the said hardening | curing agent particle 31 and the said resin particle 32 were carried out by the process of FIG. 1 (a), (b) using the brand name "Hybridizer NHS-0" of Nara Machinery Co., Ltd. After mixing by 3 parts by weight, the resin particles 32 are electrostatically bonded to the surface of the curing agent particles 31 (mixing step), and then the resin particles (at the operating conditions of the processing temperature of 50 ° C. for 5 minutes at a wind speed of 5 minutes) The hardening | curing agent particle 31 of the state which attached 32 was stirred (stirring process), the capsule 33 was formed, and two types of latent hardening | curing agent 30 were obtained.

50 parts by weight of bisphenol A type epoxy resin (trade name "EP828" made by Yucca Epoxy Co., Ltd.) which is a thermosetting resin, is a phenoxy resin (trade name and "YP50" made by Toudo Chemical Co., Ltd.) 50 1 part by weight of the silane coupling agent (trade name "A-187" manufactured by Nippon Yurika Co., Ltd.), 2.5 parts by weight of conductive particles, 10 parts by weight of each latent curing agent and an organic solvent were added and decomposed to form a paste adhesive. After the preparation, the adhesive films 20 of Examples 1 and 2 were prepared in the processes of FIGS. 2 (a) and 2 (b), respectively. Using the films 20 of Examples 1 and 2, the following room temperature storage test and 40 ° C storage test were performed, respectively.

Room temperature preservation test

Using the adhesive films 20 of Examples 1 and 2 and Comparative Examples 1 and 2, the TCP 15 and the LCD (in the processes of FIGS. 3 (a) to (d), 4 (e) and (f)) After connecting 11), the peeling strength at the time of peeling off the TCP 15 from the LCD 11 was measured (initial peeling strength).

In addition, the adhesive films 20 of Examples 1 and 2 and Comparative Examples 1 and 2 were separately stored at room temperature (25 ° C.) for 3 days and 7 days, respectively, and then each adhesive film 20 was stored using After the TCP 15 and the LCD 11 were respectively connected in the same process, the peel strength at the time of peeling the TCP 15 from the LCD 11 was measured (peel strength after storage).

40 ℃ preservation test

In addition to changing the temperature at which the adhesive film 20 is stored from room temperature to 40 ° C., the adhesive film 20 was preserved under the same conditions as the above room temperature storage test, and the TCP 15 and the LCD 11 were connected thereto. Peel strength was measured after storage.

In the above room temperature storage test and 40 ° C storage test, when the peel strength after storage is 90% or more than the initial peel strength, " ◎ " The case of less than "(triangle | delta)" and the case of less than 70% were evaluated as "x", respectively, and the evaluation results are shown in Table 1 below.

Result of evaluation examination Room temperature storage Preservation at 40 degrees Celsius 3 days 7 days 3 days 7 days Example 1 ◎ ◎ ◎ ○ Example 2 ◎ ◎ ◎ ○ Comparative Example 1 X X X X Comparative Example 2 X X X X

The comparative examples 1 and 2 of the said Table 1 are the cases of adding two types of hardening agent particles used in Examples 1 and 2 to an adhesive agent without forming a capsule.

In this case, the TCP 15 is provided with a 25 μm wide metal wiring 17 at 25 μm intervals, and the LCD 11 uses an ITO electrode 13 having a sheet resistance of 10 μs per 1 cm 2, respectively. It heated for 10 second, heated up the coating layer 25 to 130 degreeC, applying the load of 3 MPa to the part which TCP15 and LCD11 overlapped, and connected.

As can be clearly seen from Table 1, in Examples 1 and 2 in which the curing agent particles 31 were coated in the capsule 33, the evaluation results were good for the room temperature storage test and the 40 ° C storage test. On the other hand, in Comparative Examples 1 and 2 in which the curing agent particles were added to the adhesive as it was without forming a capsule, the results of each storage test were not good. From these results, it was confirmed that the adhesive agent using the latent hardener of this invention is excellent in storageability.

As mentioned above, although the case where the adhesive film was manufactured using an adhesive agent was demonstrated, this invention is not limited only to this, For example, you may use an adhesive agent as paste.

Reference numeral 11 in FIG. 6 (a) denotes the same LCD as that shown in FIG. 3 (a). In order to connect the TCP 15 to the LCD 11, first, the surface of the ITO electrode 13 of the LCD 11 is shown. The adhesive agent is apply | coated to the part which connects TCP15 in the middle, and the application layer 45 of an adhesive agent is formed (FIG. 6 (b)).

Subsequently, after the TCP 15 is aligned in the process of FIG. 3 (d), the TCP 15 and the LCD 11 are connected in the process of FIGS. 4 (e) and (f). 40) is obtained (Fig. 6 (c)).

The above has described the case where the TCP 15 and the LCD 11 are connected by using an adhesive. However, the present invention is not limited thereto, and in the case of manufacturing various electric devices such as when connecting a substrate and a semiconductor chip. Can be used for

In addition, although the above demonstrated the case where electroconductive particle is disperse | distributed in an adhesive agent, this invention is not limited only to this, For example, the adhesive agent which does not contain electroconductive particle is also included in this invention.

As the metal chelate constituting the hardener particles, various metal chelates such as zirconium chelate, titanium chelate and aluminum chelate can be used, but among them, aluminum chelate having high reactivity is more preferable. As mentioned above, although the method of manufacturing hardening | curing agent particle | grains was demonstrated by the spray dryer method, this invention is not limited only to this.

As mentioned above, although the case where the fluorine resin of melting | fusing point 827 degreeC is used as a resin component was demonstrated, this invention is not limited only here, Melting | fusing point is 30 degreeC or more and 350 degrees C or less, pyrolysis temperature is 50 degreeC or more and 500 degrees C or less, As long as the softening temperature satisfies any one of 0 ° C. to 300 ° C. or a glass transition temperature of −40 ° C. to 300 ° C., various kinds of thermal accelerator resins, crosslinked resins, gel resins and the like can be used.

As resin like the above, crosslinked acrylic resin (brand name "microgel" made by Nippon Paint Co., Ltd.) polymethyl methacrylate resin ("MP series" made by Shuken Chemical Co., Ltd.), benzoguanamine resin (Trade name "Eposuta" manufactured by Nippon Shockbai Co., Ltd.), silicone resin (trade name "Tospearl" manufactured by GE Toshiba Silicone Co., Ltd.), and the like can be used.

In the capsule formed by melting the resin particles having the same characteristics as the above, the resin constituting the resin particles is chemically changed in the encapsulation process. It may become other.

As mentioned above, although the case where epoxy resin was used as a thermosetting resin was demonstrated, this invention is not limited only to this. If the cation is polymerized, for example, urea resins, melamine resins, phenol resins, vinyl ether resins, oxetane resins and the like can be used. However, epoxy resins are preferably used in consideration of the strength of the adhesive after thermal curing. Do.

In addition, it is preferable to use the thing represented by following General formula (5) in the silane coupling agent compatible with this invention.

....일반식 (5)

.... General Formula (5)

(In the general formula (5), at least one substituent of the substituents X ^{1 to} X ⁴ is an alkoxy group. It is preferable that the alkoxy group is a methoxy group or an ethoxy group. Among the substituents X ^{1 to} X ⁴ other than the alkoxy group) It is preferable that at least 1 substituent contains an epoxy ring or a vinyl group, and it is more preferable that the substituent which has an epoxy ring is especially a glycidyl group .. As a substituent containing a vinyl group, there exists a methacryloxypropyl group, for example. As a substituent having a group sidil for example, groups glycidoxypropyltrimethoxysilane Further, and may have all of the substituents X ¹ ~X ^4, even a so-called silicate alkoxy group.)

As the thermoplastic resin, various kinds of rubbers such as polyester resin, polyurethane resin, polyvinyl acetal, ethylene vinyl acetate, polybutadiene rubber and the like can be used, for example.

Moreover, various additives, such as an antioxidant, a filler, a coloring agent, can also be added with the adhesive agent of this invention.

20, 45. Adhesive (coating layer)
30. Latent Curing Agent
31. Hardener particles
32. Resin Particles
33. Capsule

Claims (5)

(Iii) preparing a curing agent particle that is a metal chelate or metal alcoholate; And,
(Ii) The resin particles in the powder form having a smaller average particle diameter than the average particle diameter of the hardener particles are attached to the surface of the electrohardener particles, and the electric resin particles adhered to the surface of the hardener particles are melted to form an electric capsule. A method for producing a latent curing agent comprising a capsule covering the surfaces of the curing agent particles and the electrical curing agent particles, including an encapsulation step of forming.
The method of claim 1,
The encapsulation step includes mixing the hardener particles and the resin particles to attach the electric resin particles to the surface of the electric hardener particles and stirring the electric hardener particles in the state where the electric resin particles are attached to melt the electric resin particles. Characterized
Process for preparing latent curing agent.
3. The method according to claim 1 or 2,
The ratio of the average particle diameter of the curing agent particles to the average particle diameter of the resin particles is characterized in that more than 100: 80
Process for preparing latent curing agent.
3. The method according to claim 1 or 2,
The ratio of the average particle diameter of the curing agent particles to the average particle diameter of the resin particles is characterized in that more than 100: 50
Process for preparing latent curing agent.
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