KR101065444B1 - Hardener Particle, Manufacturing Method for Hardener Particle, and Adhesive - Google Patents

Abstract

It hardens on condition of a short time at low temperature, and the adhesive agent with high shelf life is obtained. Since the siloxane or alkoxy group is bonded to the central metal located on the surface of the curing agent particles of the present invention, in the adhesive obtained by dispersing the curing agent particles in the epoxy resin together with the silane coupling agent, the curing agent particles and the silane coupling agent do not react at room temperature. , The preservation of the adhesive is high. In addition, since the siloxane is not bound to the metal chelate or metal alcoholate at the portion other than the surface of the hardener particles, when the adhesive is heated, the hardener particles are cracked, and the metal chelate or metal alcoholate at the portion other than the surface of the hardener particles is silane coupler. Reaction with the ring agent generates a cation, the cation polymerizes the epoxy resin, and the adhesive cures. Since the reaction between the silane coupling agent and the metal chelate proceeds at a low temperature, the adhesive of the present invention cures in a short time at a low temperature than the conventional one.

Core Metal, Hardener Particle, Silane Coupling Agent

Description

Hardener Particles, Manufacturing Method for Hardener Particles, and Adhesives             

 1A, 1B, 1C, and 1D are diagrams for explaining a step of producing the curing agent particles of the first example of the present invention.

Figure 2a and 2b is a view for explaining an example of a process for producing an adhesive film using the curing agent particles 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 and 6B are views for explaining a step of producing the curing agent particles of the second example of the present invention.

7A and 7B are views for explaining a step of producing the curing agent particles of the third example of the present invention.

8A, 8B and 8C are views for explaining another example of the process of connecting the TCP and the LCD using the adhesive of the present invention.                 

9A, 9B, 9C, and 9D are views for explaining a process of connecting a TCP and an LCD using a conventional adhesive.

<Description of Symbols for Main Parts of Drawings>

25, 75. Adhesive (coating layer)

30, 40, 50. Hardener particles

34, 44, 54. Core metal

32, 45.siloxanes (polysiloxanes)

The present invention relates to an adhesive. In particular, it is related with the hardening | curing agent particle used for the adhesive agent which connects a semiconductor chip and 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 the case of connecting a TCP (tape carrier package) and an LCD (liquid crystal display) to manufacture an electric device.

Reference numeral 111 in FIG. 9A 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 the LCD 111 and TCP described later, an adhesive is first applied to the surface of the LCD 111 on which the ITO electrode 113 is disposed. Reference numeral 125 in FIG. 9B denotes an adhesive applied to the LCD 111.

Reference numeral 115 in FIG. 9C denotes TCP, and TCP 115 includes a base film 116 and 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). In this state, when heated under pressure, the adhesive 125 softens, and the metal wiring 117 pushes the softened adhesive 125 to contact the surface of the ITO electrode 113.

The above adhesive is generally added with a curing agent such as imidazole which polymerizes an epoxy resin by heating. If the metal wiring 117 continues to be heated in contact with the ITO electrode 113, the curing agent is catalyzed. The epoxy resin is polymerized to cure the adhesive 125.

Reference numeral 101 in FIG. 9 (d) 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 hardened adhesive 125 in a state where 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, when curing the adhesive as described above, it is necessary to heat the adhesive to a high temperature of 180 ℃ or more, and when the pattern of the metal wiring 117 is fine, deformation such as elongation or distortion in the TCP 115 at the time of heating. This may occur. When the heating temperature is lowered, this problem is solved, but the time required for the heat treatment is longer, and the productivity is lowered.

As an adhesive having excellent curability at low temperatures, in recent years, adhesives containing radical polymerizable resins such as acrylates and radical polymerization initiators have been developed. Heat resistance is inferior.

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 focus on the method of cationic polymerization of epoxy resins without using a curing agent which is generally used, and as a result of repeated studies, silane compounds having at least one alkoxy group in the structure (silane coupling agent) When the metal chelate (or metal alcoholate) was added to the adhesive, it was found that silanol formed by hydrolysis of the silane coupling agent and the metal chelate reacted with cations to form an epoxy resin.

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 (5)-(8).

.... Scheme (5)

.... Scheme (6)

.... Scheme (7)

.... Scheme (8)

As shown in Scheme (5), the silane compound having at least one alkoxy group reacts with water in the adhesive to hydrolyze the alkoxy group to form a silanol group.

When the adhesive is heated, the silanol groups react with metal chelates such as aluminum chelates and the silane compound binds to the aluminum chelate (Scheme 6).

Subsequently, as shown in Scheme (7), by coordinating the other silanol groups remaining in the adhesive by equilibrium reaction to the aluminum chelate to which the silanol groups are bonded, a Brönsted acid point is generated, and as shown in Scheme (8), the activated The epoxy ring located at the terminal of the epoxy resin is ring-opened by a hydrogen atom and polymerized with the epoxy ring of another epoxy resin (cationic 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 cationicly polymerized.

Since the reaction shown in Reaction Formulas (6) to (8) proceeds at a temperature lower than the temperature at which the conventional adhesive is cured (180 ° C or more), the adhesive as described above is cured in a short time at a low temperature compared with the conventional one.

However, the silane coupling agent is easily hydrolyzed and has a high reactivity between the silanol and the metal chelate or metal alcoholate. Therefore, when the powdered metal chelate or metal alcoholate is dispersed in the adhesive directly as a hardener particle, even at room temperature The polymerization reaction of the epoxy resin proceeds and the preservation of the adhesive is inferior.

As a result of further investigation by the present inventors, before adding hardening | curing agent particle to an adhesive agent, the surface of hardening | curing agent particle is made to contact the compound containing hydroxyl groups, such as a silane coupling agent (silanol) and an alcohol, and the compound is made into the hardening agent particle | grain. It has been found that the shelf life of the adhesive is increased when it is reacted with the central metal on the surface.

The present invention is constructed on the basis of electric discovery, and the invention described in claim 1 is a metal chelate formed by coordinating at least one ligand to a central metal, or a metal alcohol formed by bonding at least one alkoxy group to a central metal. Or it is a hardening | curing agent particle which silicon couple | bonded via oxygen to the electric center metal located on both surfaces as a main component.

Invention of Claim 2 is the hardening | curing agent particle of Claim 1, Comprising: The silicon | silicone agent couple | bonded with the other silicon couple | bonded with the said core metal through oxygen interposed with one silicon couple | bonded with the said core metal.

Invention of Claim 3 is a hardening | curing agent particle in any one of Claim 1 or 2, Comprising: The hardening | curing agent particle | grains which the substituent represented by following General formula (1) couple | bonded with the said silicon.

.... General Formula (1)

In the above formula,

Substituent X ¹ is bonded to the silicon.

Invention of Claim 4 is a hardening | curing agent particle in any one of Claim 1 or 2, Comprising: The hardening | curing agent particle | grains which the substituent represented by following General formula (2) couple | bonded with electric silicon.

.... General Formula (2)

Where

The substituent X ² ~X ⁴ of at least one of the substituents X ² ~X ⁴ a is bonded to the silicon.

Here, as substituent X ¹ , -CH ₂ CH ₂ CH _2- , CH ₂ CH ₂ CH ₂ NHCH ₂ CH _2- , -CH ₂ CH ₂ CH ₂ NHC (= O), etc. may be mentioned. Examples of the substituents X ^{2 to} X ⁴ include a phenyl group, H, and-(CH) n- (n is an integer), and among these, the substituents X ^{2 to} X ⁴ bonded to silicon are -CH ₂ CH ₂ CH ₂ NHCH ₂ CH _2- , -CH ₂ CH ₂ CH ₂ NHC (= O) or the like.

The invention as set forth in claim 5 is composed of a metal chelate obtained by coordinating at least one ligand to a central metal or a metal alcohol formed by binding at least one alkoxy group to a central metal. It is a hardening agent particle | grain which carbon couple | bonded through oxygen to the center metal.

According to the sixth aspect of the present invention, there is provided a method for producing a curing agent particle, wherein the silane coupling agent represented by the following general formula (3) is hydrolyzed to form silanol and at least one ligand bonds to the central metal, or a central metal. Contacting an electric silanol with a curing agent particle composed mainly of one or both of the metal alcoholates to which at least one alkoxy group is bonded to the electrical curing agent particle, and reacting the central metal located on the surface of the curing agent particle with the electrical silanol. It is a manufacturing method of the hardening | curing agent particle which forms the siloxane represented by Formula (4).

.... General Formula (3)
Where

At least one substituent of the substituents X ^{5 to} X ⁸ is an alkoxy group.

.... General Formula (4)

Where

Oxygen that binds to silicon binds to the core metal.

The invention according to claim 7 is a curing agent particle according to claim 6, wherein the curing agent particles are reacted with an epoxy resin with at least one of substituents X ^{9 to} X ¹¹ bonded to the silicon of the siloxane represented by the general formula (4). It is a way.

Invention of Claim 8 is a manufacturing method of the hardening | curing agent particle of Claim 7, The manufacturing method of the hardening | curing agent particle whose substituent which reacts with the said epoxy resin contains an amino group in the structure.

The invention according to claim 9 is a method for producing a curing agent particle, wherein the curing agent is composed mainly of one or both of a metal chelate formed by coordinating at least one ligand to a central metal or a metal alcohol formed by bonding at least one alkoxy group to a central metal. It is a manufacturing method of the hardening | curing agent particle which makes particle and the compound containing a hydroxyl group contact, and makes the compound containing an electric center metal and an electric hydroxyl group located on the surface of an electrohardening agent particle react.

Invention of Claim 10 is a manufacturing method of the hardening | curing agent particle of Claim 9, The compound containing the said hydroxyl group is a manufacturing method of the hardening | curing agent particle which consists of alcohol.

Invention of Claim 11 is a manufacturing method of the hardening | curing agent particle of Claim 10, The said alcohol is a manufacturing method of the hardening | curing agent particle which consists of tripropylene glycol.

Invention of Claim 12 is an adhesive agent containing a thermosetting resin, a silane coupling agent, and the hardening | curing agent particle in any one of Claims 1-5 as an adhesive agent.

The present invention is constructed as described above, and when the silane coupling agent represented by the general formula (3) is brought into contact with the surface of the curing agent particle, first, an alkoxy group of the silane coupling agent is hydrolyzed to silanol, and the silanol and the curing agent particle The metal chelate or metal alcoholate located on the surface is dehydrated and condensed, and the core metal of the metal chelate or metal alcoholate and the silicon of silanol are bonded (siloxane bond) via oxygen to obtain the curing agent particles of the present invention.

The silane coupling agent is also hydrolyzed by the moisture adhering to the surface of the curing agent particles or the moisture in the air.However, in order to perform the treatment more quickly, the silanolated agent is added to the silane coupling agent to react with the curing agent particles. You can use

Since the siloxane is bonded to the central metal located on the surface of the curing agent particles of the present invention, when the curing agent particles of the present invention are added to the adhesive, the silane coupling agent and the curing agent particles in the adhesive do not react at room temperature and the adhesive does not cure. However, when the adhesive is thermocompressed, the curing agent particles are thermally expanded by heating, and the curing agent particles thermally expanded are cracked due to physical impact such as pressure to expose portions other than the surface of the curing agent particles.

Since no siloxane is bound to the central metal located at the portion other than the surface of the curing agent particle, when the central metal and the silane coupling agent in the adhesive react by heating to generate a cation, the epoxy resin is polymerized by the cation ( Cationic polymerization), the adhesive is cured. Thus, the hardening | curing agent particle of this invention contains the function as what is called a latent hardening | curing agent.

Moreover, since the temperature at which a metal alcoholate, a metal chelate, and a silane coupling agent react is lower than the temperature (180 degreeC or more) which thermosets a conventional adhesive agent, the adhesive agent of this invention hardens in a short time at low temperature compared with a conventional adhesive agent.

In addition, since cations are also generated in the process of reacting the central metal on the surface of the hardener particles with the silane coupling agent, when the hardener particles immediately after the siloxane is formed on the surface are added to the adhesive, the adhesive is kept at room temperature by the cation remaining on the surface of the hardener particles. Although it may be cured, the residual cation or excess silane coupling agent may be removed from the curing agent particles by washing with water or an organic solvent before adding the curing agent particles to the adhesive.

In addition, when the substituent other than an alkoxy group uses the aminosilane coupling agent containing an amino group, the siloxane containing an amino group is formed. When the epoxy resin is further brought into contact with the curing agent particles in that state, the amino group of the siloxane and the epoxy ring of the epoxy resin react to bind the epoxy resin to the siloxane. Therefore, since the structure of the siloxane on the surface of the hardener particles becomes more complicated, the mechanical strength of the hardener particles becomes higher.

In addition, when a compound containing a hydroxyl group such as an alcohol in place of the silane coupling agent is brought into contact with the surface of the curing agent particle, the metal chelate or metal alcoholate on the surface of the curing agent particle and the hydroxyl group of the compound are dehydrated and condensed on the surface of the curing agent particle. The central metal bonds through the compound and oxygen. The hardening agent particle obtained in this way contains the function as a latent hardening | curing agent similarly to the case where siloxane is formed.

When alcohol is used as the compound containing a hydroxyl group, the type of alcohol is not particularly limited, but when monohydric alcohol is used as the alcohol, it is difficult to form a crosslinked structure on the surface of the curing agent particle, and the molecule that binds to the central metal is one-dimensional. Becomes a straight chain. In such a case, the rigidity of the film-like molecule covering the surface of the curing agent is lowered. However, when a monohydric alcohol containing a highly reactive functional group is used, the rigidity of the film-like molecule on the surface of the curing agent particle can be increased by reacting the functional group with another substance.

Moreover, as a compound containing a hydroxyl group, carboxylic acid can also be used, for example.

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, since the thermoplastic resin synchronizes with the curing reaction of the resin component and binds to the inorganic material through the silane coupling agent, the curing property is high and the affinity with the adherend made of the inorganic material is high. This high adhesive is obtained.

EMBODIMENT OF THE INVENTION Hereinafter, the adhesive agent of this invention is demonstrated in detail.

The left side of the chemical formula shown in Fig. 1 (a) shows an example of a silane coupling agent used in the present invention. The silane coupling agent contains four substituents X ^{a to} X ^d , and three of these substituents X ^{b to} X ^d are bonded to silicon of the silane coupling agent via oxygen. Therefore, this silane coupling agent contains three alkoxy groups.

After heating this silane coupling agent to a predetermined temperature, the hardening agent particle | grains of powdered metal chelate or metal alcoholate (here, a core metal becomes aluminum) is disperse | distributed in a silane coupling agent, and the silane coupling agent is prescribed | regulated. Stir while keeping warm to temperature.

When moisture in air or moisture adhering to the surface of the hardener particles and the silane coupling agent come into contact with each other, three alkoxy groups of the silane coupling agent are hydrolyzed to form hydroxyl groups. The right side of the formula of FIG. 1 (a) shows silanol formed by hydrolysis of a silane coupling agent.

Reference numeral 31 in Fig. 1 (b) denotes hardener particles dispersed in the silane coupling agent. Reference numeral 34 in the same figure denotes a center metal (here, aluminum) located on the surface of the curing agent particle 31, and the substituent X ⁰ is bonded to the center metal 34. When the hardener particles 31 are made of aluminum chelate, the substituent X ⁰ is a ligand and when the hardener particles 31 are made of aluminum alcoholate, the substituent X ⁰ is an alkoxy group.

When the stirring is continued while maintaining the silane coupling agent at a predetermined temperature, silanol reaction generated by hydrolysis of the central metal 34 on the surface 31 of the curing agent particle and the silane coupling agent is reacted, and silicon of the silanol reacts with oxygen. The siloxane is formed by bonding to the central metal 34 through the intermetallic. At this time, silanol reacts with other silanol to form polysiloxane on the surface of the curing agent particle 31.

1 (c) shows the state, and reference numeral 32 in the same figure shows a polysiloxane formed on the surface of the hardener particles 31. Each silicon in the polysiloxane 32 is bonded to the central metal 34 located on the surface of the hardener particles 31, respectively, and as a result, siloxane, which is a structural unit of the polysiloxane 32, is formed on the surface of the hardener particles 31. It is arrange | positioned on a monolayer. In addition, since the silicon of the polysiloxane 32 is mutually bonded through oxygen, the mechanical strength of the polysiloxane 32 is high.

Next, the hardening agent particle 31 of the state in which the polysiloxane 32 was formed is pulled up from a silane coupling agent. In this state, the cation 36 (hydrogen ion) generated when the silane coupling agent reacts with the central metal 34 and the excess silane coupling agent (including silanol) not bonded to the central metal surface of the polysiloxane 32 Residing in

When the hardener particles 31 in this state are washed with water, the remaining cation 36 and the silane coupling agent are removed to obtain the hardener particles 30 of the first example of the present invention (Fig. 1 (d)).

Next, the process of manufacturing an electric device using the adhesive agent of this invention using the hardening | curing agent particle 30 of 1st example of this invention, and the adhesive agent of this invention is demonstrated.

First, an epoxy resin, a thermoplastic resin, a silane coupling agent, the curing agent particles 30 of the first example of the present invention, conductive particles, and a solvent were mixed and stirred at a predetermined compounding ratio to prepare a paste adhesive.

In this state, since the polysiloxane 32 is bonded to the central metal 34 on the surface of the curing agent particle 30, the reaction between the silane coupling agent in the adhesive and the central metal 34 does not occur and no cation is produced. In addition, cations remaining in the polysiloxane 32 are also removed. Therefore, since the cationic polymerization of the epoxy resin does not occur in the adhesive, the adhesive does not cure at room temperature.

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 is evaporated in the adhesive 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 indicates conductive particles dispersed in the adhesive together with the curing agent particles 30.

Reference numeral 11 in FIG. 3A denotes an LCD, and the LCD 11 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 is included. Here, five ITO electrodes 13 are shown.

The coating layer 25 of the adhesive film 20 shown in FIG. 2 (b) is pressed and covered in the part which connects TCP mentioned later among the surfaces in which the ITO electrode 13 of the LCD 11 was formed (FIG. 3 (b). )). Since the adhesive force between the release film 21 and the coating layer 25 is smaller than the adhesive force between the coating layer 25 and the ITO electrode 13, when the release film 21 is peeled off, the coating layer 25 becomes the LCD ( 11) (FIG. 3 (c)).

The code | symbol 15 of FIG. 5 has shown TCP. TCP 15 includes a long-sized base film 16, and one side of the base film 16 has a plurality of narrow metal wires 17 along the longitudinal direction of the base film 16 (here In the drawing, five metal wires 17 are shown). 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. 3D shows a cross-sectional view taken along the line A-A of FIG. 5. The surface of the side on which the metal wiring 17 of the TCP 15 is arranged is directed toward the surface on which the ITO electrode 13 of the LCD 11 is arranged, and one end of the TCP 15 is coated on the surface of the ITO electrode 13. Positioning is performed so that the ITO electrode 13 of the LCD 11 and the metal wiring 17 of the TCP 15 face each other so as to face (25).

In this state, if the surface where the metal wiring 17 of the TCP 15 is disposed is abutted against the coating layer 25 and the whole is heated while applying pressure to the overlapped portion of the TCP 15 and the LCD 11, As a result, the coating layer 25 is softened, and the conductive particles 27 in the coating layer 25 in which the metal layer 17 is softened by the pressure are pushed out, and the conductive particles 27 remain in the metal layer 17 and the ITO. It is sandwiched between the electrodes 13 (Fig. 4 (e)).

 When further heating and pressure are continued in this state, the hardening agent particle 30 thermally expanded by heating cracks by pressurization and expansion, and the part other than the surface of the hardening agent particle 30 is exposed. Since the siloxane is not bonded to the metal chelate or the metal alcohol in the portion other than the surface of the hardener particle 31, the cracked hardener particles shown by reference numeral 35 in FIG. 4 (f) are silane couplers of the coating layer 25. In contact with the ring agent, the silane coupling agent in the coating layer 25 reacts with the metal chelate or metal alcoholate to generate cations.

The epoxy resin in the coating layer 25 is polymerized by cation (cationic polymerization), and the coating layer 25 is cured while the metal wiring 17 and the ITO electrode 13 sandwich the conductive particles 27 ( 4 (f)).

Reference numeral 10 in Fig. 4F shows the electric device in a state where the coating layer 25 is cured. In the electric device 10, the metal wiring 17 and the ITO electrode 13 are not only electrically connected to each other by interfering with the conductive particles 27, but also the coating layer hardened by the LCD 11 and the TCP 15 ( 25) is also mechanically connected.

As described above, the adhesive of the present invention not only has excellent storage properties but also cures the epoxy resin 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.

As mentioned above, although the method of disperse | distributing the hardening | curing agent particle 31 only to a silane coupling agent was described, this invention is not limited only to this.

Reference numeral 41 in FIG. 6 (a) denotes the same curing agent particles as shown in FIG. 1 (d), and the same steps as in FIGS. 1 (a) to (d) are applied to the central metal 44 on the surface of the curing agent particles 41. Polysiloxane 42 formed as is bonded. Reference numeral 43 in the same figure represents a substituent which directly bonds to silicon of the polysiloxane 42 without intervening oxygen, where the substituent 43 is a substituent X ^{a '} bonded to silicon and the terminal of the substituent X ^a' It contains the amino group couple | bonded with. Therefore, in this state, the amino group is exposed on the surface of the polysiloxane 42.

After heating a liquid epoxy resin at normal temperature, it heats at predetermined temperature and disperse | distributes the hardening | curing agent particle of the state shown to FIG. 6 (a) in the epoxy resin.

Reference numeral 46 in Fig. 6A shows the chemical formula of the epoxy resin. When the epoxy resin 46 has the main skeleton R ^a and state, and contains the epoxy ring bonded to the terminal of the backbone R ^a, curing agent with the amino group of an epoxy resin (46) of the polysiloxane (42) of the surface of the particle 41 is in contact The amino group and the epoxy resin 46 react to obtain the curing agent particles 40 of the second example of the present invention. Here, two epoxy rings of the epoxy resin 46 react with one amino group.

Reference numeral 45 in Fig. 6 (b) shows polysiloxane in a state where the epoxy resin 46 is bonded. Since the structure of this polysiloxane 45 becomes more complicated than the polysiloxane 42 shown to Fig.6 (a), the mechanical strength of the hardening | curing agent particle 40 of the 2nd example of this invention is high.

As mentioned above, although the case where the silane coupling agent reacts with the center metal on the surface of hardening | curing agent particle was demonstrated, this invention is not limited only to this, If it contains the functional group which reacts with the metal chelate or metal alcoholate which comprises hardening agent particle | grains, , Alcohols, carboxylic acids, and various resins (polymers, monomers, oligomers, etc.) can be used.                     

Reference numeral 56 in FIG. 7A represents an alcohol (diol) including two hydroxyl groups, and diol 56 includes two hydroxyl groups bonded to the main skeleton R ^b and the main skeleton R ^b . When the hardener particles 51 in the same state as shown in Fig. 1 (b) are dispersed and stirred in the diol 56 kept at a predetermined temperature, the diol 56 is as shown in Figs. 1 (b) to (c). The hydroxyl group of one of the two hydroxyl groups of N 2) reacts with the central metal 54 located on the surface of the curing agent particle 51.

Reference numeral 50 in FIG. 7 (b) denotes hardener particles in a state in which the alkoxy group 52 is bonded to the central metal 54 by reaction with the diol 56.

Example

The hardener particles 31 were used as the hardener particles 31 by using aluminum acetylacetonate manufactured by Kawaken Fine Chemicals Co., Ltd. (trade name "Aluminum Chelate A (W)", average particle diameter of 5 µm). After disperse | distributing to the aminosilane coupling agent (brand name "A-1100" made by Nippon Unicar) heated at 40 degreeC, and making the aminosilane coupling agent heat-retain at 40 degreeC for 24 hours, it was made to react, and then it hardened | cured particle ( 31) was pulled up, and it washed with water and dried, and obtained the hardening | curing agent particle 30 of the 1st example of this invention shown to FIG. 1 (d).

Subsequently, the hardening | curing agent particle 30 of the said 1st example was disperse | distributed in the bisphenol-A epoxy resin (trade name "EP828" made from Yugase Chemical Co., Ltd.) heated at 40 degreeC, and it stirred, keeping the epoxy resin at 40 degreeC, stirring. After that, the curing agent particles 51 were pulled up, the curing agent particles 41 were dispersed in toluene which is an organic solvent, and then filtered to obtain the curing agent particles 40 of the second example of the present invention.

Separately, TPG (tripropylene manufactured by Asahi Kaishi Co., Ltd.) was insulated at 40 ° C using the same powdery metal chelate as that used for the curing agent particles 30 of the first example as the curing agent particles 51. Glycol)), and after stirring for 24 hours, the curing agent particles 51 were pulled up and washed to obtain the curing agent particles 50 of the third example of the present invention.

Next, 2 parts by weight of the curing agent particles 30, 40, and 50 of each of the first to third examples, 50 parts by weight of a phenoxy resin (manufactured by phenoxy succinate), which is a thermoplastic resin, and a bisphenol A type epoxy resin, which is a thermosetting resin ( 50 parts by weight of a trade name "EP828" manufactured by Yugasheru Epoxy Co., Ltd., 1 part by weight of an epoxy silane coupling agent (trade name "A-187" manufactured by Unika Japan Co., Ltd.) and 3 parts by weight of conductive particles, respectively, Adhesive was prepared.

Subsequently, the adhesive film 20 of Examples 1-3 was produced at the process of FIG. (A), (b) using three types of adhesives, and the following using the adhesive film 20 of Examples 1-3 is carried out. Room temperature preservation test and 40 degreeC preservation test were done, respectively.

Room temperature preservation test

After connecting the TCP (15) and the LCD (11) in the process of Figs. 3 (a) to (d), Fig. 4 (e), (f) using the adhesive film 20 of Examples 1-3 , Peeling strength at the time of peeling the TCP 15 from the LCD 11 was measured (initial peeling strength). Separately, the adhesive films 20 of Examples 1 to 3 are stored at room temperature for 1 day, 3 days, and 7 days, respectively, and the TCP 15 and the LCD in the same process as described above using the respective adhesive films 20 after storage. After connecting (11), respectively, the peeling strength at the time of peeling TCP15 from LCD11 was measured, respectively (peeling strength after storage).

In this case, as the TCP 15, 25 µm wide metal wirings 17 are arranged at intervals of 25 µm, and the LCD 11 is formed by using the ITO electrodes 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, connecting to the part which superimposed on (15) and the LCD 11, 3 Mpa.

40 ℃ preservation test

Except for changing the temperature for storing the adhesive film 20 from room temperature to 40 ° C., the adhesive film 20 was preserved under the same conditions as the above room temperature preservation test, and then the TCP 15 and the LCD 11 were connected. After storage, the peel strength was measured.

In the above room temperature preservation test and 40 ° C preservation test, "◎" for the case where the peel strength after storage is 90% or more of the size of initial peeling strength, "O" for the case where 80% or more and less than 90% is "O", 70% or more In the case of less than 80%, "△" and the case of less than 70% were evaluated as "x", respectively. These evaluation results are shown in Table 1 below.

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

In addition, the comparative example 1 of the said Table 1 is the same as what was used for the 1st-3rd example, and is a case where the hardening | curing agent particle | grains of the state shown in FIG. .

As shown in Table 1, Examples 1 to 3 using the curing agent particles 30, 40, and 50 of the first to third examples of the present invention are compared with Comparative Example 1 using the curing agent particles of FIG. , The room temperature storage test and the 40 degreeC storage test were all high in evaluation results, and it was confirmed that the storage property of the adhesive agent using the hardening | curing agent particle of this invention is high.

In particular, the curing agent particles 40 of the second example in which the curing agent particles 30 of the first example of the present invention were treated with an epoxy resin were used at 40 ° C. as compared with the case of using the curing agent particles 30, 50 of the first example or the third example. Even when stored for 7 days, almost no decrease in adhesive force was observed.

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 adhesive as a paste-like seal.                     

Reference numeral 11 in FIG. 8 (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 of this invention is apply | coated to the part which connects TCP15 in the middle, and the application layer 75 of an adhesive agent is formed (FIG. 8 (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). 70) is obtained (Fig. 8 (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 center metal of the metal chelate or metal alcohol constituting the hardener particles, various kinds of metals such as zirconium, titanium, and aluminum can be used. Among them, aluminum having high reactivity is particularly preferred.

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 resin is cationic polymerization, various kinds of resins such as urea resin, melamine resin, phenol resin, vinyl ether resin and oxetane resin can be used, but considering the strength of adhesive after thermal curing, epoxy resin is used. It is preferable.

Moreover, it is preferable to use what is represented by following General formula (9) as a silane coupling agent used for the adhesive agent of this invention.

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.... General Formula (9)

At least one substituent in the substituents X ^{12 to} X ¹⁵ in the general formula (9) is an alkoxy group. Further, wherein the at least one substituent of the substituents X ¹² ~X ¹⁵ other than the alkoxy group may include an epoxy ring or vinyl, a substituent containing an epoxy group is glycidyl ring is particularly preferred.

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 to the adhesive agent of this invention.                     

As mentioned above, although the case where the silane coupling agent which makes contact with a hardening | curing agent particle uses the aminosilane coupling agent in which substituents other than an alkoxy group contain an amino group was demonstrated, this invention is not limited only to this. As the silane coupling agent, those in which substituents other than the alkoxy group include various substituents such as vinyl group, epoxy group, methacryl group, mercapto group and isocyanate group can be used.

In addition, the substance made to react with the hardening | curing agent particle of 1st example of this invention is not limited to an epoxy resin. For example, in the case where the curing agent particles of the first example were prepared using a silane coupling agent in which a substituent other than the alkoxy group contains an isocyanate group, when a diol is used instead of an epoxy resin, the isocyanate group and the diol react to form a urethane on the surface of the curing agent particle. Resin is formed.

In this manner, the combination of the kind of the substance reacted with the polysiloxane and the silane coupling agent is not particularly limited and is determined according to the type of the ring group of the silane coupling agent.

The foregoing has described the case where the curing agent particles 31, 41, 51 are brought into contact with the silane coupling agent or the diol by dispersing the curing agent particles 31, 41, 51 in the silane coupling agent or the diol, but the present invention is limited thereto. For example, the silane coupling agent or diol may be sprayed onto the curing agent particles to bring the silane coupling agent or diol into contact with the curing agent particles.

Since the siloxane and the alkoxy group are bonded to the central metal located on the surface of the curing agent particle of the present invention, the reaction between the curing agent particle and the silane coupling agent does not occur in the adhesive. In addition, the adhesive of the present invention is cured by a cationic polymerization reaction of the epoxy resin. Since the cationic polymerization reaction occurs at a lower temperature than the polymerization reaction when a conventional curing agent is used, the adhesive of the present invention is cured in a short time at a low temperature compared with the conventional adhesive.

Claims (12)

A metal chelate formed by coordinating at least one ligand to the central metal or a metal alcoholate formed by combining at least one alkoxy group to the central metal, and an electrical center metal located on the surface of which the oxygen is interposed. Hardener particles combined with silicon. The method of claim 1, One silicon bonded to the central metal is mutually bonded to another silicon bonded to the central metal with oxygen therebetween. Hardener particles. The method according to claim 1 or 2, A substituent represented by the following general formula (1) is bonded to the silicon Hardener Particles:

.... General Formula (1) Where Substituent X ¹ is —CH ₂ CH ₂ CH ₂ —, CH ₂ CH ₂ CH ₂ NHCH ₂ CH ₂ — or —CH ₂ CH ₂ CH ₂ NHC (═O), To the silicon. The method according to claim 1 or 2, A substituent represented by the following general formula (2) is bonded to the silicon Hardener Particles:

.... General Formula (2) Where At least one substituent of the substituents X ^{2 to} X ⁴ is bonded to the silicon. A metal chelate formed by coordinating at least one ligand to the central metal or a metal alcoholate formed by combining at least one alkoxy group to the central metal, and an electrical center metal located on the surface of which the oxygen is interposed. Hardener particles combined with carbon. Hydrolyzing the silane coupling agent represented by the following general formula (3) to form silanol, and any of metal chelates in which at least one ligand is bonded to the central metal or metal alcohols in which at least one alkoxy group is bonded to the central metal The curing agent particles comprising one or both of the curing agent particles and the electrical silanol are brought into contact with each other to react the central metal located on the surface of the curing agent particles with the electrical silanol to form siloxane represented by the following general formula (4). Manufacturing Method:

.... General Formula (3)

.... General Formula (4) Where At least one of the substituents X ^{5 to} X ⁸ in the general formula (3) is an alkoxy group; Substituents X ⁹ , X ¹⁰ and X ¹¹ in formula (4) are each differently selected from three substituents which do not form silanol in the substituents X ^{5 to} X ⁸ in formula (3) above; And, Oxygen bonded to silicon of the general formula (4) binds to the electric core metal. The method of claim 6, A method for producing hardener particles, comprising reacting an epoxy resin with at least one of substituents X ^{9 to} X ¹¹ bonded to silicon of siloxane represented by the general formula (4). The method of claim 7, wherein A method for producing a curing agent particle, characterized in that the substituent reacting with the epoxy resin contains an amino group in its structure. An electrocuring agent is brought into contact with a compound comprising a hydroxyl group and a curing agent particle comprising a metal chelate formed by coordinating at least one ligand to a central metal or a metal alcoholate formed by bonding at least one alkoxy group to a central metal. A method for producing a curing agent particle for reacting a compound comprising an electrical center metal and an electro hydroxyl group located on the surface of the particles. The method of claim 9, The compound containing the hydroxyl group is characterized in that the alcohol Method for producing hardener particles. The method of claim 10, Characterized in that the alcohol is tripropylene glycol Method for producing hardener particles. Adhesive containing a thermosetting resin, a silane coupling agent, and the hardening | curing agent particle in any one of Claims 1, 2, and 5.

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