WO2006109831A1 - Processes for production of adhesives - Google Patents

Abstract

A process for the production of adhesives curable at a thermocompression temperature which comprises preparing a composition by mixing a silane coupling agent capable of giving the first and second products through hydrolysis with a curing agent capable of reacting with the first product at the thermocompression temperature to give a reactive species and the first raw material for resin capable of polymerizing by the action of the reactive pieces and heating the composition to the first elevated temperature lower than the thermocompression temperature to make the hydrolysis proceed. A process for the production of adhesives curable at a thermocompression temperature which comprises heating the above composition to the first elevated temperature, adding a diluent to the resulting composition, and heating the obtained mixture to the second elevated temperature which exceeds the first elevated temperature but is lower than the thermocompression temperature to evaporate the second product. The curing agent can be prepared by subjecting a metal chelate and a polyfunctional isocyanate to interfacial polymerization and comprises a porous resin and a metal chelate supported on the porous resin.

Description

 Specification

 Manufacturing method of adhesive

 Technical field

 [0001] The present invention relates to a technical field of manufacturing an adhesive.

 Background art

 [0002] Conventionally, thermosetting adhesives that are cured by heating have been widely used. Such adhesives include thermosetting resins such as epoxy resin and curing that cures the resin. In general, a method of producing a composition containing an agent is included.

 However, when an adhesive is sandwiched between objects to be adhered such as a wiring board or an electrical component and the adhesive is thermally cured, voids (voids) are generated in the adhesive at the time of thermal curing. If voids occur, the mechanical strength of the adhesive cured product will be weakened, and the connection reliability of electrical devices that can be obtained will also be lowered.

 Patent Document 1: JP 2002-212537

 Patent Document 2: JP 2002-363255 A

 Disclosure of the invention

 Problems to be solved by the invention

[0004] The present invention was created to solve the above-mentioned disadvantages of the prior art, and an object of the present invention is to provide an adhesive that hardly causes voids when thermally cured.

 Means for solving the problem

[0005] The inventors have investigated the cause of the generation of voids, and in particular, in a reaction system in which a silane coupling agent and an aluminum chelate are reacted to cure a thermosetting resin, in a short time. High! When heat-cured at a temperature (eg 150 ° C), a large amount of alcohol, which is a by-product of the heat-curing reaction, is generated in a short time, and when the alcohol evaporates, voids are formed in the adhesive. I was able to do it.

The present invention based on such knowledge is an adhesive manufacturing method for manufacturing an adhesive that cures when heated to a thermocompression bonding temperature, and generates a first product and a second product by hydrolysis. Reacts with the first product at the thermocompression bonding temperature with the silane coupling agent A curing agent that generates seeds and a first resin raw material that is polymerized by the reactive species are mixed to create a composition, and the composition is lower than the thermocompression bonding temperature! This is a method for producing an adhesive in which the hydrolysis proceeds by raising the temperature.

 The present invention is a method for producing an adhesive, wherein after the composition is heated to the first heating temperature, a diluent is added to the composition to create a mixture, and the mixture It is a manufacturing method of the adhesive which heats to the 2nd heating temperature exceeding one heating temperature and less than the said thermocompression bonding temperature, and evaporates a said 2nd product.

 The present invention is a method for producing an adhesive, wherein the first product is silanol.

 The present invention is a method for producing an adhesive, wherein the second product is an alcohol.

 The present invention is a method for producing an adhesive, wherein the first heating temperature is 60 ° C. or more and less than 70 ° C.

 The present invention is a method for producing an adhesive, wherein the first resin material is an epoxy resin.

 The present invention is a method for producing an adhesive, wherein the heating of the mixture is a method for producing an adhesive in which the mixture is formed into a film.

 The present invention is a method for producing an adhesive, wherein the diluent is a method for producing an adhesive containing an organic solvent.

 The present invention is a method for producing an adhesive, wherein the second heating temperature is 70 ° C or higher and 80 ° C or lower.

 The present invention is a method for producing an adhesive, wherein the conductive agent is added to the diluent.

 This invention is a manufacturing method of an adhesive agent, Comprising: The said diluent is a manufacturing method of the adhesive agent containing a 2nd resin material.

 The present invention is a method for producing an adhesive, wherein the second resin material is a thermoplastic resin.

The present invention is a method for producing an adhesive, wherein the curing agent comprises a porous resin and the porous It is a manufacturing method of the adhesive agent which has the metal chelate hold | maintained at the coffin.

 The present invention is a method for producing an adhesive, wherein the curing agent is a method for producing an adhesive formed by interfacial polymerization of the metal chelate and a multifunctional isocyanate compound.

 [0006] The silane coupling agent is, for example, a compound represented by XSiOR, wherein R is an alkyl group, X is 1 to 3 substituents that can be bonded to Si, and these substituents Is not particularly limited, but specific examples include an epoxy group, a vinyl group, an alkyl group, and an alkoxy group.

 The invention's effect

 [0007] In the present invention, since the composition (first composition) is heated in advance before thermosetting to generate alcohol in advance, a large amount of alcohol is not generated when the adhesive is thermoset. Also, the adhesive is heated between the process of generating alcohol and the process of thermosetting the adhesive.

Since the generated alcohol is removed in advance, a large amount of alcohol is not released when the adhesive is thermally cured, and no void is formed in the cured adhesive. Brief Description of Drawings

[0008] FIG. 1 is a diagram for explaining the difference in methanol generation amount depending on heating temperature and heating time.

 [Figure 2] Diagram for explaining the difference in the amount of methanol generated with and without a curing agent

 [Figure 3] Diagram for explaining the difference in the amount of methanol detected before thermosetting

 [Figure 4] Diagram for explaining the difference in the amount of methanol detected after thermosetting

 [Figure 5] Electron micrograph of latent hardener particles

 [Figure 6] Magnified electron micrograph near the center of the latent hardener particle in Figure 1A

 [Figure 7] DSC measurement diagram of an example of adhesive

 [Figure 8] DSC measurement diagram of the adhesive using the latent curing agent of the ninth example

 [Figure 9] DSC measurement diagram of another example of adhesive

 [Fig. 10] Experimental example l Particle size distribution chart of latent curing agent prepared by ib

 [FIG. 11] Particle size distribution chart of the latent curing agent prepared in Experimental Example 11c

 [Fig. 12] Experimental example l Particle size distribution chart of latent curing agent prepared by id

 [Fig. 13] Experimental example l Size distribution chart of latent curing agent prepared in ie

[Fig.14] Experimental example l Electron micrograph of ib latent curing agent [Figure 15] Experimental example l An electron micrograph of the latent curing agent of ie

 [Fig.16] Electron micrograph of the latent curing agent of Experimental Example 12a

 [FIG. 17] Electron micrograph of the latent curing agent of Experimental Example 12b

 [Figure 18] Electron micrograph of the latent curing agent of Experimental Example 12c

 [FIG. 19] Electron micrograph of the latent curing agent of Experimental Example 12d

 [Fig. 20] Electron micrograph of the latent curing agent of Experimental Example 12e.

 [Fig.21] Electron micrograph of latent curing agent in Experimental Example 12f

 [Figure 22] Electron micrograph of conventional latent hardener particles using partially saponified PVA

 [Fig. 23] Electron micrograph of conventional latent hardener particles using fully saponified PVA

 [Fig.24] Diagram showing manufacturing process of adhesive film

 [Fig.25] Diagram showing the object to be attached fixed with adhesive

 Explanation of symbols

 [0009] 1 ... Latent curing agent 2 ... Porous resin matrix 3 ... Hole 20 ... Adhesive 21, 22 ... Object to be adhered

 BEST MODE FOR CARRYING OUT THE INVENTION

 [0010] The method for producing the adhesive of the present invention will be described in detail below.

 A first composition is prepared by mixing a first resin material, which is a thermosetting resin, a liquid silane coupling agent, and a curing agent to be described later. Heat to a first heating temperature of less than 70 ° C and maintain that temperature (first heating step).

 [0011] The silane coupling agent has a chemical structure represented by XSiOR. When the first composition is heated, the silane coupling agent is hydrolyzed as shown in the reaction formula (1). The first product, silanol (XSiOH), and the second product, alcohol (ROH) are produced.

 [0012] [Chemical 1]

XS i OR + H ₂ 0 —— ^ XS i OH + R0H …… Reaction formula (1) [0013] When a latent curing agent in which a metal chelate is microcapsulated is used as the curing agent, when the first composition is heated at the first heating temperature, a part of the microcapsule is dissolved or broken. And the metal chelate is released into the first composition.

 The microcapsule includes a porous resin described later in addition to a simple structure such as a resin film covering the periphery of the metal chelate which is a core material.

 [0014] The released metal chelate (here, the aluminum chelate) reacts with the silanol produced in the reaction formula (1), and the silanol coordinates to the metal chelate as shown in the following reaction formula (2). The silanol is reduced.

 [0015] [Chemical 2]

I \

 A l + XS i OH —— ^ A l—OS i X + RH …… Reaction formula (2) / \ /

 R

 [0016] When free silanol is reduced, the chemical equilibrium of the above reaction formula (1) is lost, so that the hydrolysis reaction proceeds and the silane coupling agent is consumed, and the amount of alcohol generated by the reaction formula (1) is The hydrolysis reaction does not proceed!

 [0017] A second composition (diluent) is prepared by dispersing conductive particles in an organic solvent in which the second raw material of the resin, which is thermoplastic resin, is dissolved. Mix with the first composition after heating for a predetermined time at one heating temperature.

 [0018] Since the mixture contains an organic solvent and has fluidity, the mixture is applied to the surface of a peeling film (not shown) and the surface of the applied mixture is exposed to the first heating temperature. When heated to a higher second heating temperature (for example, 70 ° C or higher and 80 ° C or lower), the alcohol generated in the first heating step evaporates and is released from the inside of the mixture (second heating Process).

 The organic solvent is also released by the heating, and the mixture loses fluidity to form a film, whereby a film-like adhesive (adhesive film) is obtained. The manufacturing process of the adhesive film detailed above is shown in FIG.

Even if the adhesive is not formed into a film, if the mixture is heated to the second heating temperature with the surface exposed, alcohol is released from the mixture. Further, if the viscosity of the mixture heated to the second heating temperature is lower than the viscosity of the first composition, the alcohol is more easily released.

 [0020] When using the adhesive film manufactured by the manufacturing method of the present invention, an adhesive film is disposed between two objects to be adhered, and one object to be adhered is brought into contact with the surface of the adhesive film, and the other The adhesive film is heated to a thermocompression bonding temperature higher than the first and second heating temperatures while pressing the whole with the object to be adhered in contact with the back surface of the adhesive film (thermocompression bonding step).

 [0021] When the adhesive film is heated to the thermocompression bonding temperature, as shown in the following reaction formula (3), other silanols further coordinate to the metal chelate coordinated with silanol, and the Bronsted acid point is increased. Arise.

 [0022] [Chemical 3]

 +

 XSiO -H

 \

 Al -OSiX + XSiOH

 / \

 I Al-OSiX

 /

 Reaction formula (3)

Here, epoxy resin is used as the first resin material, and when active protons (reactive species) are donated from the Bronsted acid point, the epoxy resin is expressed as shown in the following reaction formula (4). The ring is polymerized (cation polymerization), and the adhesive film is cured in a state of being in close contact with the object to be adhered.

 [0024] [Chemical 4]

 +

R-CH—CH ₂ CH 1 CH ₂

R-CH-CH ₂ OH— Reaction formula (4) [0025] As described above, in the adhesive of the present invention, alcohol is generated in the first heating process before thermosetting, and the alcohol is removed between the first heating process and the thermocompression bonding process. Therefore, no alcohol is generated or released in the adhesive film during thermocompression bonding, and no voids are formed in the adhesive due to alcohol release.

 FIG. 25 shows a state in which the two adhesive objects 21 and 22 are fixed with the cured adhesive 20, and since no voids are present in the adhesive 20, the adhesive objects 21 and 22 are firmly attached. It is fixed.

 [0026] The silane coupling agent of the present invention not only contributes to the reaction of the first resin raw material, but also serves to improve the affinity with the adhesive by adsorbing to the inorganic material.

 [0027] For example, when the adhesive contains conductive particles whose surface is exposed to an inorganic material such as a metal, the silane coupling agent is adsorbed on the surface of the conductive particles, and the conductive particles are contained in the adhesive. It will be dispersed without settling. Further, when the adhesive contains an inorganic filler, the coupling agent is adsorbed on the surface of the inorganic filler, and the inorganic filler is dispersed in the adhesive as in the case of the conductive particles.

 [0028] Furthermore, when an inorganic material is exposed on the surface of the object to be adhered, such as a glass substrate or a ceramic plate, the silane coupling agent is adsorbed on the surface of the object to be adhered, and the adhesive is adhered to the object to be adhered. Adhesiveness is improved.

 [0029] The type of silane coupling agent is not particularly limited, and X can use a silicate having three alkoxy (OR) forces. X is a substituent that is incorporated into the polymerization reaction of the first resin material. If at least one is present, a silane coupling agent is incorporated into the curing reaction of the first resin material, increasing the strength of the cured adhesive.

 [0030] The type of metal chelate used for the curing agent is not particularly limited. In addition to aluminum chelate, the ability to use zirconium chelate, titanium chelate, etc. Among these, the reactivity with silanol is high, and aluminum chelate is used. Most preferred. One of these metal chelates may be used alone as a curing agent, or two or more thereof may be used as a curing agent.

[0031] The second resin material is not particularly limited as long as it is a different type of resin than the first resin material, but if thermoplastic resin is used as the second resin material, For sticking objects The adhesion is improved. Further, when the second resin material is incorporated into the curing reaction with the first resin material, the mechanical strength of the adhesive after thermocompression bonding is improved.

 [0032] Specific examples of the resin used as the second resin raw material include rubbers such as phenoxy resin, polyester resin, polyurethane resin, polybutacetal, ethylene butyl acetate, and polybutadiene rubber. These resins can be used alone for the second resin, or two or more can be mixed and used for the second resin.

[0033] The solvent for dissolving the second resin material is not particularly limited, and for example, PGMAC (propylene glycol monomethyl ether acetate), toluene, ethyl acetate, MEK (methyl ethyl ketone) and the like can be used. These solvents can be used alone.

Two or more types may be mixed and used.

[0034] The adhesive may be an anti-aging agent as long as it does not hinder the reactions of the above reaction formulas (1) to (4).

Other additives such as coloring agents and fillers can also be added.

[0035] The first heating step may be performed after mixing the first and second compositions, but the higher the silane coupling concentration in the composition, the faster the reaction to produce alcohol. Therefore, in order not to lower the concentration of the silane coupling agent, it is preferable that the first heating step is performed only with the first composition.

[0036] In the first composition, the curing agent, the silane coupling agent, and the first resin material are present in a high concentration, so that the first composition is added without adding the second composition. When the second heating step is performed by heating to the second heating temperature, the reactions of the above reaction formulas (3) and (4) proceed, and the first composition is cured.

 Accordingly, in the second heating step, the second composition is added to the first composition, and the concentrations of the curing agent, the silane coupling agent, and the first greave material are determined at the time of the first heating step. It is desirable that the force be applied at a lower level. The second composition is not particularly limited as long as the concentration of the curing agent, the silane coupling agent, and the first resin material can be diluted, and the second composition may be composed of only a solvent. However, it may be composed of only the second raw material of rosin.

Instead of the second heating step, the adhesive may be defoamed to remove alcohol, and both the vacuum defoaming and the second heating step may be performed. When performing vacuum defoaming, the adhesive may be diluted with an organic solvent before defoaming to increase defoaming efficiency. [0037] It is possible to use a metal chelate as it is, which is microencapsulated as a curing agent!ヽ. However, if the concentration of the metal chelate is increased in order to enhance the curability of the adhesive, the above reaction formulas (3) and (4) can be used during the first and second heating steps and during storage of the obtained adhesive. ) Progresses.

 In that case, if the latent curing agent in which the metal chelate is microencapsulated as described above is used so that part of the metal chelate remains in a microencapsulated state after the first and second heating steps, In addition, the reaction of the above reaction formulas (3) and (4) does not proceed during the second heating step or during storage of the adhesive, and the adhesive is not cured, so that the storage of the adhesive is improved.

 Since the porous resin described later is melted or broken at the above-mentioned thermocompression bonding temperature, the metal chelate is released into the adhesive during the hot-pressing step, and the reactions of the reaction formulas (3) and (4) occur. It progresses rapidly and the adhesive hardens.

 Example

 [0038] <Heating test 1>

 Epoxy resin (trade name “2021P” manufactured by Hitachi Chemical Co., Ltd.) A first composition was prepared by mixing 8 parts by weight and 15 parts by weight of a latent curing agent in which an aluminum chelate was microencapsulated. Here, a latent curing agent in which an aluminum chelate was held in a porous resin described later was used.

 [0039] Put 0.05 g of the first yarn and composite into a sample tube and heat at 50 ° C, 60 ° C for 5 minutes, or 40 ° C, 50 ° C, 60 ° C, 70 A heated sample was prepared by heating for 10 minutes at a heating temperature of ° C. Separately, the first composition was left unheated at room temperature (25 ° C) for 5 minutes and 10 minutes to prepare an unheated sample. During heating, the sample tube was heated with the lid removed.

 [0040] The heated sample and the unheated sample were heated at 80 ° C for 10 minutes, and from the components captured by the purge and trap method, the amount of alcohol (here, the amount of methanol) was determined by gas chromatography mass spectrometry. Was quantified.

[0041] The amount of methanol detected when heated for 10 minutes is shown in Table 1 below, and the amount of methanol detected when heated for 5 minutes is shown in Table 2 below. [0042] [Table 1]

 [0043] [Table 2]

[0044] In Tables 1 and 2 and Tables 3 and 4 below, “heating condition, none” indicates the case where the sample is left at room temperature.

 Furthermore, FIG. 1 shows the relationship between the detected amount of methanol detected (ppm) and the heating time (minutes).

 [0046] As can be seen from FIG. 1 and Tables 1 and 2, the unheated sample has a detected methanol level of 620 ppm, whereas the heated sample has a detected methanol level higher than that of the unheated sample. It can be seen that the detected amount of methanol is greater for 10 minutes than for the same heating temperature.

 [0047] The higher the heating temperature, the more the detected amount of methanol tends to increase. With a heating time of 10 minutes, the detected temperature reached its maximum value (4540ppm) at a heating temperature of 60 ° C. The first composition was heated to 70 ° C and heated for 10 minutes to prepare a heated sample. As the heated sample had cured the first resin material, the heating temperature of the adhesive was 70 Less than ° C is suitable for the present invention.

 [0048] <Heating test 2>

 Heat the first composition under the same conditions as in Heat Test 1 above, except that the first composition is the same as Heat Test 1 except that the heating temperature is 60 ° C and the heating time is 5 minutes, 10 minutes, and 15 minutes. Thus, a heated sample was prepared.

[0049] Separately, the first composition containing no curing agent is heated under the same conditions, and then cured. An agent was added to prepare a heated sample of a comparative example. The amount of methanol in these heated samples was quantified under the same conditions as in Heating Test 1 above.

[0050] The amount of methanol of the heated sample heated after the addition of the curing agent is shown in Table 3 below, and the amount of methanol of the heated sample heated without adding the hardener is shown in Table 4 below.

[0051] [Table 3]

[0052] [Table 4]

[0053] Further, FIG. 2 shows the relationship between the detected amount of methanol (ppm) and the heating time (minutes). The composition of the comparative example containing no curing agent showed little increase in the detected amount of methanol even when the heating time was prolonged. When no curing agent was contained, the composition of the silane coupling agent was used at a low temperature of 60 ° C. It can be seen that the hydrolysis of the glue is very slow.

[0054] Compared to the composition of the comparative example, the first composition containing the curing agent has a lower heating temperature if the first composition contains a curing agent having a higher methanol detection amount. Even if it exists, it turns out that hydrolysis of a silane coupling agent advances.

[0055] In the first composition, the amount of methanol detected increased as the heating time increased, and the detected amount reached its maximum at a heating time of 10 minutes. However, when the heating time reached 15 minutes, the detected amount increased. Maximum value [This is reduced to 2000ppmi!

[0056] The decrease in the detected amount is presumed to be due to the release of the first composition force of methanol during heating. For example, under the condition where the first heating temperature is 60 ° C, if the heating is performed for 10 minutes, the alcohol is sufficiently absorbed. It can be seen that a rule is generated.

[0057] <Heating test 3>

 A second resin material consisting of 65 parts by weight of a phenoxy resin solution and 10 parts by weight of epoxidized polybutadiene (trade name “PB3600” manufactured by Daicel Chemical Industries, Ltd.), and gold-coated nickel particles (trade name “ 6GNM5—Ni ”)) was mixed with 19.57 parts by weight of conductive particles to prepare a second composition.

 [0058] The phenoxy resin solution used here is a product name “YP70” manufactured by Toto Kasei Co., Ltd. Ρ 40 weight of phenoxy resin in an organic solvent mixed with equal weight (weight) of BMAC and toluene. % Dissolved.

 [0059] The first composition used in the heating test 1 was heated at a heating temperature of 60 ° C for 5 minutes, 10 minutes, and 15 minutes, respectively. The above-mentioned second composition was mixed with the product, and the coating layer of the mixture was heated at 70 ° C. for 5 minutes to produce the adhesive film of the example.

 [0060] Apart from this, a comparison was made under the same conditions as those of the adhesive film of the above example except that the first heating step was performed without adding the curing agent, and the curing agent was added after the first heating step. An example adhesive film was made.

 [0061] A 0.2 mm thick silicon rubber was placed on each adhesive film, and an MCM (Multi-chip module) bonder was pressed on the silicon rubber and heated at 150 ° C for 10 seconds to heat the adhesive film. Cured to obtain a sample piece.

[0062] For the adhesive film before thermosetting and the sample piece after thermosetting, the amount of alcohol was measured under the same conditions as in the heat test 1.

[0063] The detected amounts of alcohol (methanol) in the adhesive film before thermosetting and the sample piece after thermosetting are shown in Tables 5 and 6 below, and the relationship between the detected alcohol amount and the heating time is shown in Figs. Shown in

[0064] [Table 5] Methanol concentration [ppm] 60 ° C before heating / heating time [rain] With curing agent Without curing agent None 0 101. 14 101. 1

 60 ° C / 5min 5 151. 48 103. 32

60 ° C / 10min 10 155. 96 117. 38

60 ° C / 15min 丄 5 205. 86

 ud & 'V “Hardening agent”. r Hardening agent is less than the amount of hardening agent during heating.

[0065] [Table 6]

 Table 6: Methanol content of adhesive film after heat curing

 In the table above, “with curing agent” and “without curing agent” indicate the presence or absence of a curing agent during the first heating step.

[0066] As is clear from comparison between Tables 5 and 6 and Figs. 3 and 4, the adhesive films of the examples are of the comparative example.

 L

 The amount of methanol detected before thermosetting was larger than that of the adhesive film, but the amount of methanol detected in the adhesive film of the example decreased after thermosetting.

 [0067] Since the adhesive film of the example and the adhesive film of the comparative example have the same composition of the finished product, the total amount of methanol should be the same, and there is a difference in the detected amount of methanol before and after thermal curing. This is because the progress of the reactions in the above reaction formulas (1) to (4) is different.

 [0068] That is, in the adhesive film of the example in which the curing agent was present at the time of the first heating step, a reaction in which methanol was generated before the thermal curing progressed, and therefore, methanol was detected more than the comparative adhesive film. Although the amount is large, the methanol has been removed to some extent before thermosetting, and no new methanol is produced at the time of thermosetting! Therefore, the amount of methanol detected after thermosetting becomes small.

[0069] In contrast, since the adhesive film of the comparative example is heated at a time under higher heating conditions than in the first heating step, a large amount of methanol is generated at one time, and the methanol after the thermosetting is formed. It is estimated that the amount of detected light has increased.

 [0070] Next, an example of the curing agent used in the present invention will be described in detail.

 The latent curing agent used in the present invention is obtained by holding an aluminum chelating agent in a porous resin obtained by interfacial polymerization of a polyfunctional isocyanate compound. Since this latent curing agent uses an aluminum chelating agent capable of realizing low-temperature rapid curing, it is possible to impart good low-temperature rapid curing to an adhesive containing this latent curing agent. Since the aluminum chelating agent is retained in the porous resin obtained by interfacial polymerization, even if this latent curing agent is added to the adhesive (even when it is in one solution), the storage stability of the adhesive Can be greatly improved.

[0071] In this latent curing agent, an electron microscopic photograph of latent curing agent 1 is used instead of a microcapsule having a simple structure in which the periphery of the aluminum chelating agent core is covered with a porous resin shell (Fig. 5). ) And an enlarged electron micrograph near the center (FIG. 6), the aluminum chelating agent is held in a large number of fine pores 3 present in the porous resin matrix 2.

 [0072] Here, since this latent curing agent 1 is produced using an interfacial polymerization method, its shape is spherical, and its particle diameter is preferably 0 from the viewpoint of curability and dispersibility. 5 111 or more and 100 m or less, and the size of the hole 3 is preferably 5 m or more and 150 nm or less from the viewpoint of curability and potential.

 [0073] In addition, the latent curing agent 1 has a tendency to reduce its latency when the degree of cross-linking of the porous resin used is too small, and to decrease its thermal response when it is too large. Accordingly, it is preferable to use a porous resin whose degree of crosslinking is adjusted. Here, the degree of crosslinking of the porous resin can be measured by a micro compression test.

 The latent curing agent 1 preferably contains substantially no organic solvent used during the interfacial polymerization, specifically, 1 ppm or less from the viewpoint of curing stability.

[0075] Further, the content of the porous rosin and the aluminum chelating agent in the latent curing agent 1 is such that if the aluminum chelating agent content is too small, the thermal responsiveness is lowered, and if it is too much, the latency is lowered. Aluminum chelating agent for 100 parts by mass of porous resin, preferably 1 0 parts by mass or more and 200 parts by mass or less, more preferably 10 parts by mass or more and 150 parts by mass or less

[0076] In the latent curing agent, examples of the aluminum chelating agent include a complex compound in which three | 8-ketoenolate anions are coordinated to aluminum represented by the chemical formula (1).

 [0077] [Chemical 5]

[0078] where

R ² and R ³ are each independently an alkyl group or an alkoxyl group. Examples of the alkyl group include a methyl group and an ethyl group. Examples of the alkoxyl group include a methoxy group, an ethoxy group, and an oleyloxy group.

 [0079] Specific examples of the aluminum chelating agent represented by the chemical formula (1) include aluminum tris (acetyl acetonate), aluminum tris (ethyl acetoacetate), and aluminum mono-acetyl acetonate bis (e Tylacetoacetate), aluminum monoacetylacetoate bisoleylacetoacetate, ethylacetoacetate aluminum diisopropylate, alkylacetoacetate aluminum diisopropylate and the like.

[0080] The polyfunctional isocyanate compound is preferably a compound having two or more isocyanate groups, preferably three isocyanate groups in one molecule. As a more preferred example of such a trifunctional isocyanate compound, a TMP adduct having the following chemical formula (2), which is obtained by reacting 3 mol of a diisocyanate compound with 1 mol of trimethylolpropane (TMP), a diisocyanate compound: Isocyanurate of formula (3), diisocyanate obtained by self-condensation of 3 moles of compound The biuret form of the chemical formula (4) in which the remaining 1 mol of diisocyanate is condensed to the diisocyanate urea obtained from 2 mols of the 3 molate compounds.

[0081] [Chemical 6]

0

 II

OCNH-R-NCO

 CH2 0

 I II

 C2H5 -C-CHaOCNH-R-NCO (2)

 CH2

 OCNH-R-NCO

 II

 0

OCN

[0082] In the above chemical formulas (2) to (4), the substituent R is a portion excluding the isocyanate group of the diisocyanate compound. Specific examples of such diisocyanate compounds include toluene 2,4-diisocyanate, toluene 2,6-diisocyanate, m-xylylene diisocyanate, hexamethylene diisocyanate, hexahydrohydrate. Examples include m-xylylene diisocyanate, isophorone diisocyanate, and methylene diphenyl 4,4′-diisocyanate.

 [0083] The porous resin obtained by interfacial polymerization of such a polyfunctional isocyanate compound is a part of the isocyanate group that undergoes hydrolysis during the interfacial polymerization to become an amino group. It is a porous polyurea that reacts with an isocyanate group to form a urea bond and polymerize it.

A latent curing agent composed of such porous resin and an aluminum chelating agent retained in the pores is not retained for a clear reason when heated for curing. The aluminum chelating agent coexists in the latent curing agent and the adhesive, and can come into contact with the silane coupling agent and the first resin raw material, thereby allowing the curing reaction to proceed. The

 [0084] It should be noted that due to the structure of the latent curing agent, an aluminum chelating agent is considered to be present on the outermost surface. The aluminum chelating agent present on the outermost surface is water present in the system during interfacial polymerization. As a result, only the aluminum chelating agent retained inside the porous resin retains its activity, and the resulting curing agent has acquired potential. it is conceivable that.

 [0085] The latent curing agent described above is obtained by dissolving an aluminum chelating agent and a polyfunctional isocyanate compound in a volatile organic solvent, and charging the obtained solution into an aqueous phase containing a dispersant, followed by heating and stirring. Thus, it can be produced by a production method characterized by interfacial polymerization.

 [0086] In this production method, first, an aluminum chelating agent and a polyfunctional isocyanate compound are dissolved in a volatile organic solvent to prepare a solution that becomes an oil phase in the interfacial polymerization. The reason for using is as follows. That is, when a high-boiling solvent having a boiling point exceeding 300 ° C as used in the ordinary interfacial polymerization method is used, the organic solvent does not volatilize during interfacial polymerization, and the probability of contact with isocyanate-water increases. This is because the degree of progress of interfacial polymerization between them becomes insufficient.

 For this reason, it is difficult to obtain a polymer having good shape retention even when interfacial polymerization is performed, and even when it is obtained, a high boiling point solvent remains incorporated in the polymer, and when blended in an adhesive, This is because the solvent adversely affects the physical properties of the cured product of the adhesive. For this reason, in this production method, a volatile organic solvent is used as the organic solvent used in preparing the oil phase.

[0087] Such a volatile organic solvent is a good solvent of an aluminum chelating agent and a polyfunctional isocyanate compound (the respective solubility is preferably not less than 0.1 lg / ml (organic solvent)), In particular, it is preferable that the solvent does not substantially dissolve (the solubility of water is 0.5 gZml (organic solvent) or less) and the boiling point at atmospheric pressure is 100 ° C or less. Specific examples of such volatile organic solvents include alcohols, acetate esters, ketones and the like. Of these, ethyl acetate is preferred because of its high polarity, low boiling point, and poor water solubility. [0088] If the amount of the volatile organic solvent used is too small relative to 100 parts by mass of the total amount of the aluminum chelating agent and the polyfunctional isocyanate compound, the potential decreases, and if too large, the thermal responsiveness decreases. The amount is preferably 100 parts by mass or more and 500 parts by mass or less.

 [0089] The viscosity of the oil phase solution can be lowered by using a relatively large amount of the volatile organic solvent within the range of the amount of the volatile organic solvent used. Lowering the stirring efficiency improves the oil phase droplets in the reaction system, making it possible to make the oil phase droplets finer and more uniform. The resulting latent hardener particle size is submicron to several microns (0.1). It is possible to make the particle size distribution monodisperse while controlling the size to about 10 μm or more. The viscosity of the oil phase solution is preferably set to ImPa's or more and 2.5 mPa's or less.

 [0090] Further, when emulsifying and dispersing the polyfunctional isocyanate compound, when PV A (polybulal alcohol) is used as a dispersant described later, the hydroxyl group of PVA reacts with the polyfunctional isocyanate compound, By-products may adhere around the latent curing agent particles as foreign substances (Fig. 22: When using partial ken PVA), and the particle shape itself may be deformed (Fig. 23: Complete ken-yi). (When using PVA). In order to prevent this phenomenon, the reactivity between the polyfunctional isocyanate compound and water can be promoted, or the reactivity between the polyfunctional isocyanate compound and PVA can be suppressed.

 [0091] In order to promote the reactivity between the polyfunctional isocyanate compound and water, the blending amount (weight) of the aluminum chelate agent is preferably 1Z2 or less, more preferably the weight of the polyfunctional isocyanate compound. Is 1Z3 or less. This increases the probability that the polyfunctional isocyanate compound and water are in contact with each other, and the polyfunctional isocyanate compound and water are likely to react before the PVA contacts the oil droplet surface.

 [0092] In order to suppress the reactivity between the polyfunctional isocyanate compound and PVA, the amount of the aluminum chelating agent in the oil phase is increased. Specifically, the amount of the aluminum chelating agent is preferably equal to (1.0 times) or more, more preferably 1.0 to 2.0 times by weight of the polyfunctional isocyanate compound. This reduces the isocyanate concentration on the oil phase droplet surface.

Furthermore, polyfunctional isocyanate compounds are amines formed by hydrolysis rather than hydroxyl groups. The reaction rate between the polyfunctional isocyanate compound and the PVA is reduced by adding ammine to the oil phase solution together with the polyfunctional isocyanate compound because be able to.

[0093] When the aluminum chelating agent and the polyfunctional isocyanate compound are dissolved in the volatile organic solvent, they may be mixed and stirred at room temperature under atmospheric pressure, but if necessary, they may be heated.

 [0094] Next, in this production method, an oil phase solution in which an aluminum chelating agent and a polyfunctional isocyanate compound are dissolved in a volatile organic solvent is added to an aqueous phase containing a dispersant, and heated and stirred. Is interfacially polymerized. Here, as the dispersing agent, those used in a usual interfacial polymerization method such as polyvinyl alcohol, carboxymethyl cellulose, gelatin and the like can be used. The amount of the dispersant used is usually 0.1% by mass or more and 10.0% by mass or less of the aqueous phase.

 [0095] The blending amount of the oil phase solution with respect to the aqueous phase is polydispersed when the amount of the oil phase solution is too small, and agglomeration occurs when the amount is too large. Therefore, the amount is preferably 5 parts by mass with respect to 100 parts by mass of the aqueous phase. More than 50 parts by mass.

 [0096] As the emulsification conditions in the interfacial polymerization, stirring conditions (stirring device homogenizer; stirring speed of 8000 rpm or more) are usually large, preferably such that the size of the oil phase is 0.5 μm or more and 100 μm or less. The conditions of heating and stirring under atmospheric pressure, temperature of 30 ° C to 80 ° C, stirring time of 2 hours to 12 hours, and the like can be mentioned.

 [0097] After the completion of the interfacial polymerization, the resulting polymer fine particles are filtered off and air-dried to obtain a latent curing agent.

 [0098] According to the method for producing a latent curing agent described above, by changing the type and amount of the polyfunctional isocyanate compound, the type and amount of the aluminum chelating agent, and the interfacial polymerization conditions, the latent curing agent can be obtained. The curing characteristics of the curing agent can be controlled. For example, if the polymerization temperature is lowered, the curing temperature of the adhesive can be lowered. Conversely, if the polymerization temperature is raised, the curing temperature of the adhesive can be raised.

[0099] The latent curing agent can be used in the same application as the conventional imidazole-based latent curing agent. As described above, the latent curing agent includes the silane coupling agent and the thermosetting first resin raw material. Combined use By doing so, a low-temperature fast-curing adhesive can be provided.

 [0100] If the content of the latent curing agent in the adhesive is too small, it will not be cured sufficiently, and if it is too large, the resin properties (for example, flexibility) of the cured product will decrease. The first resin material (thermosetting resin) is 1 part by mass or more and 70 parts by mass or less, preferably 1 part by mass or more and 50 parts by mass or less with respect to 100 parts by mass.

[0101] As described in paragraphs 0007 to 0010 of JP-A-2002-212537, the silane coupling agent works together with an aluminum chelating agent to produce a thermosetting resin (for example, a thermosetting epoxy resin). It has a function of initiating cationic polymerization of fat.

 [0102] Such silane coupling agents have one or more and three or less lower alkoxy groups in the molecule, and are reactive to the functional groups of thermosetting resin in the molecule. For example, it may have a butyl group, a styryl group, an acryloyloxy group, a methacryloyloxy group, an epoxy group, an amino group, a mercapto group, and the like.

 A coupling agent having an amino group or mercapto group should be used when the latent curing agent is a cationic curing agent, and the amino group or mercapto group does not substantially trap the generated cationic species. Can do.

 [0103] Specific examples of such silane coupling agents include butururis (13-methoxyethoxy) silane, vinyltriethoxysilane, vinyltrimethoxysilane, γ-styryltrimethoxysilane, γ-methacryloxypropyltri Methoxysilane, γ-Ataryloxypropyltrimethoxysilane, j8 — (3,4-Epoxycyclohexyl) ethyltrimethoxysilane, γ-Glyci

-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, Ν-β- (aminoethyl) -y-aminominomethyldimethoxysilane, γ-aminopropyltriethoxysilane, Ν-phenyl γ- Examples include aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, and γ-chloropropyltrimethoxysilane.

[0104] If the content of the silane coupling agent in the adhesive is too small, the curability will be low, and if it is too large, the resin properties (eg, storage stability) of the cured product will decrease. It is 50 to 1500 parts by mass, preferably 300 to 1200 parts by mass with respect to 100 parts by mass of the curing agent. [0105] As the first resin raw material, a thermosetting epoxy resin, a thermosetting urea resin, a thermosetting melamine resin, a thermosetting phenol resin, or the like can be used. Of these, thermosetting epoxy resin can be preferably used in consideration of good adhesive strength after curing.

 [0106] Such a thermosetting epoxy resin preferably has an epoxy equivalent of 100 or more and 4000 or less, which may be liquid or solid, and has two or more epoxy groups in the molecule. For example, a bisphenol A type epoxy compound, a phenol novolak type epoxy compound, a cresol novolak type epoxy compound, an ester type epoxy compound, an alicyclic epoxy compound, etc. can be preferably used. These compounds include monomers and oligomers.

 [0107] The adhesive may contain silica, a filler such as My strength, a pigment, an antistatic agent, and the like, if necessary. Adhesives include conductive particles with a particle size on the order of several zm, metal particles, those in which the surface of the resin core is coated with a metal plating layer, and those surfaces that are further coated with an insulating thin film. It is preferable to blend in an amount of 1 to 10% by weight. This makes it possible to use the adhesive produced by the production method of the present invention as an anisotropic conductive adhesive paste or an anisotropic conductive film.

 [0108] The adhesive obtained as described above has excellent storage stability even though it is a one-component type because the curing agent becomes latent. In addition, the latent curing agent can cooperate with the silane coupling agent to cationically polymerize the thermosetting resin by low-temperature rapid curing.

 [0109] The latent curing agent used in the present invention will be described more specifically below.

 <First example of latent curing agent>

 800 parts by weight of distilled water and surfactant (Newlex RT, Nippon Oil & Fats Co., Ltd.) 0.05 part by weight and polybulu alcohol (PVA-205, Kuraray Co., Ltd.) as a dispersant 4 parts by weight Were placed in a 3 liter interfacial polymerization vessel equipped with a thermometer and mixed uniformly.

In addition to this mixed solution, 11 parts by weight of a 24% isopropanol solution (aluminum chelate D, Kawaken Fine Chemical Co., Ltd.) of aluminum monoacetylacetonate bis (ethylacetoacetate) and methylene diphenyl-4, 4, -Diisocyanate (3 mol) trimethylolpropane (1 mol) adduct (D-109, Mitsui Takeda Chemical Co., Ltd.) 11 parts by weight acetic acid An oil phase solution dissolved in 30 parts by weight of ethyl was added, emulsified and mixed with a homogenizer (11000 rpm / 10 minutes), and then subjected to interfacial polymerization at 60 ° C. overnight.

 [0110] After completion of the reaction, the polymerization reaction solution is allowed to cool to room temperature, and the interfacially polymerized particles are filtered off and dried naturally to obtain 20 parts by weight of a spherical latent curing agent having a particle size of about 10 μm. It was.

 [0111] <Second example of latent curing agent>

 Instead of methylene diphenyl 4,4, -diisocyanate (3 mol) with trimethylolpropane (1 mol), toluene diisocyanate (3 mol) and methylene diphenyl 4,4,- Except for using diisocyanate (3 mol) with trimethylolpropane (1 mol) (D-103M-2, Mitsui Takeda Chemical Co., Ltd.) Accordingly, 20 parts by weight of a spherical latent curing agent having a particle size of about 10 m was obtained.

 [0112] <Third example of latent curing agent>

 Add methylene diphenol- 4,4, -diisocyanate (3 mol) with trimethylolpropane (1 mol) in addition to toluene diisocyanate (3 mol) trimethylolpropane (1 mol) 20 parts by weight of a spherical latent curing agent having a particle size of about 10 m is used in accordance with the operation of the latent curing agent in the first example except that the product (D-103, Mitsui Takeda Chemical Co., Ltd.) is used. Obtained.

 [0113] Fourth example of latent curing agent>

 Instead of a methylene diphenol- 4,4, -diisocyanate (3 mol) with trimethylolpropane (1 mol), m-xylylene diisocyanate (3 mol) trimethylol propan (1 mol) Mole) Adhesive (D-110N, Mitsui Takeda Chemical Co., Ltd.) is used except that a spherical latent curing agent with a particle size of about 10 m is added in accordance with the operation of the latent curing agent in the first example. 0 parts by weight were obtained.

 [0114] <Fifth example of latent curing agent>

Instead of a methylene diphenol- 4,4, -diisocyanate (3 mol) with trimethylolpropane (1 mol), hexahydro-m-xylylenediisocyanate (3 mol) trimethylolpropane (1 mol) Except for using an adduct (D-120N, Mitsui Takeda Chemical Co., Ltd.) 20 parts by weight of curing agent was obtained. [0115] <Sixth example of latent curing agent>

 Addition of trimethylolpropane (1 mol) of isophorone diisocyanate (3 mol) in place of the product with methylene diphenyl-4,4-diisocyanate (3 mol) with trimethylolpropane (1 mol) 20 parts by weight of a spherical latent curing agent with a particle size of about 10 m, according to the operation of the latent curing agent in the first example, except that the product (D-140N, Mitsui Takeda Chemical Co., Ltd.) is used. Obtained.

 [0116] <Seventh example of latent curing agent>

 Isocyanurate form of isophorone diisocyanate (Z-4470, Sumitomo Bayer Urethane Co., Ltd.) 20) parts by weight of a spherical latent curing agent having a particle size of about 10 m was obtained in accordance with the operation of the latent curing agent in the first example except that (1) was used.

 [0117] <Example of adhesive>

 1st to 7th examples of latent curing agent 2 parts by weight, alicyclic epoxy resin (CEL-2021P, Daicel Chemical Industries, Ltd.) 90 parts by weight, and silane coupling agent (A-187, Japan A thermosetting adhesive having a first composition strength was prepared by uniformly mixing 8 parts by weight of Nycar Co., Ltd.

 [0118] The obtained adhesive was subjected to differential thermal analysis (DSC) (DSC6200, Seiko Instruments Inc.

 Was subjected to thermal analysis. The obtained results are shown in Table 7 and FIG. Here, regarding the curing characteristics of the latent curing agent, the exothermic start temperature means the curing start temperature of the adhesive, and the exothermic peak temperature means the temperature at which the curing of the adhesive is most active, and the end of the exotherm. The temperature means the curing end temperature of the adhesive, and the peak area means the calorific value.

[0119] [Table 7] Latent curing agent Heat generation start Glass Heat generation peak Heat generation end Peak area

 Temperature (° c) Transition point (° C) (° C) Temperature (° c) (mj / mg Curing agent 1 75 Measurement omitted 106 203-478. 425 ftlH glaze 2 103 Measurement omitted 131 2 14 -368. 224 Hardener 3 136 206 160 206

 Curing 11 4 124 122 148 232-100.666

 5 101 147 131 239 -220. 929 嫩 dispenser 6 131 203 158 228-204. 317

 1 18 Measurement omitted 149 2 18 -2 1 1. 21

[0120] As shown in Table 7 and FIG. 7, from the experimental results of the latent curing agents of the first to seventh examples, the curing characteristics of the latent curing agent were changed by changing the type of the polyfunctional isocyanate compound. It can be seen that control is possible. The latent curing agent in the first example has a curing start temperature of 10

0 ° C or less.

 [0121] In addition, as the glass transition temperature of the polyurea structure increases, the exothermic start temperature, exothermic peak temperature, and exothermic end temperature tend to shift to higher temperatures (the curing temperature tends to increase). (Latent curing agents in the third to sixth examples).

 [0122] <Ninth example of latent curing agent>

 Except that the compounding amount of 24% isopropanol solution (aluminum chelate D, Kawaken Fine Chemical Co., Ltd.) of aluminum monoacetyl acetonate bis (ethyl acetate acetate), which is an aluminum chelating agent, is changed as shown in Table 8. A latent curing agent was prepared according to the operation of the latent curing agent in the first example (Experimental Examples 9a to 9e).

 As shown in Table 8, as the amount of the aluminum chelating agent increases, the polymer particles tend to aggregate, and further increase tends to make it impossible to obtain a particulate interfacial polymer. In addition, the exothermic peak temperature tends to decrease accordingly (see Fig. 8).

[0123] [Table 8] Aluminum chelating agent Particulate interface Exothermic heat

 Experimental example Compounding amount (part by weight Polymer temperature (° c)

 )

 9 a 2. 78 Acquired 134

 9 b 5. 55 Acquired 1 1 1

 9 c 1 1.10 Acquisition 103

 9 d 16. 65 ¾ collection 97

 9 e o No particles

[0124] <Other examples of adhesives>

 2 parts by weight of the latent curing agent obtained from the latent curing agent of the first example, 90 parts by weight of alicyclic epoxy resin (CEL-2021P, Daicel Engineering Co., Ltd.), and the silanes shown in Table 9 An adhesive (Experimental Example 10a-: LOh) was prepared by uniformly mixing 8 parts by weight of the coupling agent.

[0125] The obtained adhesive was subjected to thermal analysis using a differential thermal analyzer (DSC6200, Seiko Instruments Inc.). The obtained results are shown in FIG. From Fig. 9, it can be seen that the curing characteristics of the latent curing agent can be controlled by changing the type of silane coupling agent.

 [0126] [Table 9]

 [0127] <Reference example>

In order to investigate the influence of the viscosity of the oil phase solution on the particle size distribution of the latent hardener particles, aluminum monoacetyl cetate bis (ethylacetoacetate) and methylene diphenol in the latent hardener of the first example were used. -An oil phase solution of 1,4'-diisocyanate (3 mol) adducted with trimethylolpropane (1 mol) in ethyl acetate, Example 11a ~: Potential of Lie by repeating the same procedure as the latent curing agent of the first example, except that the amount of ethyl added was increased and the viscosity of the oil phase solution was changed to the value shown in Table 10. A curing agent was obtained. Experimental example l ib is a repetition of the manufacturing process of the latent curing agent of the first example.

 [0128] The viscosity of the oil phase solution was measured using a rheometer PK100 manufactured by HAAKE. The results are shown in Table 10.

[0129] [Table 10]

 [0130] Experimental example l ib-: Particle size distribution measuring device for electric resistance type particle size distribution

 (SD-2000, manufactured by Sysmex), and each particle size distribution chart (volume conversion) is shown in Figs. As can be seen from these particle size distribution charts, the particle size distribution became a normal distribution when the oil phase viscosity was about 2.5 mPa.s. Furthermore, when the oil phase viscosity was about 2.0 mPa.s, it was possible to obtain monodispersed micron-sized emulsified particles (center diameter 3 / z m).

 [0131] Further, when the oil phase viscosity was about 1.3 mPa.s, it was possible to obtain monodispersed micron-sized emulsified particles (center diameter 2 m). From the above results, it can be seen that it is effective to set the oil phase viscosity to ImPa · s or more and 2.5 mPa · s or less in order to obtain monodisperse emulsified particles. Electron micrographs of latent curing agent particles in Experimental Examples l ib and l ie are shown in FIGS. 14 and 15, respectively. The particle size distribution of the latent curing agent particles in Experimental Example l ie is shown in Experimental Example 11 It can be seen from these photos that the monodispersion is better than the latent curing agent a.

[0132] <Reference example>

In order to produce latent hardener particles with good monodispersity and good surface condition, the mixing ratio of polyfunctional isocyanate compound and aluminum chelating agent was investigated. I got it. In order to obtain monodisperse particles, the blending amount of ethyl acetate was set to be the same as in Experimental Example l ie.

 Trimethylolpropane (1 mole) of aluminum monoacetylethylacetonate bis (ethylacetoacetate), an aluminum chelator, and methylene diphenol 4,4, -diisocyanate (3 mole), a polyfunctional isocyanate compound. The amount of addition of the aluminum chelating agent and polyfunctional isocyanate compound in the oil phase solution in which the adduct was dissolved in the same amount of ethyl acetate as in Experimental Example l, is shown in Table 11 below. The latent hardeners of Experimental Examples 12a to 12f were obtained by repeating the same operation as in the case of the latent hardener of the first example except that

[0133] [Table 11]

 [0134] FIGS. 16 to 21 show electron micrographs of the obtained latent curing agents of Experimental Examples 12a to 12f. The particle size of the obtained latent curing agent particles could be reduced to a maximum particle size of 5 μm or less because the polymerization proceeds after the oil phase droplets were refined.

 In addition, these results show that no foreign matter adheres to the particles when the amount of the aluminum chelating agent is 1Z2 or less in terms of the weight of the polyfunctional isocyanate compound. It can also be seen that no foreign matter adheres to the particles even when the amount of the aluminum chelating agent is equal to or more than the weight of the polyfunctional isocyanate compound. Therefore, when producing latent hardener particles with good monodispersity and good surface condition, the amount of aluminum chelating agent is 1Z2 or less by weight of polyfunctional isocyanate compound or more. It is preferable to understand that.

Claims

 The scope of the claims

 [I] An adhesive manufacturing method for manufacturing an adhesive that cures when heated to a thermocompression bonding temperature, wherein the silane coupling agent generates a first product and a second product by hydrolysis, and thermocompression bonding. A composition is prepared by mixing a curing agent that reacts with the first product at a temperature to generate a reactive species, and a first resin raw material that is polymerized by the reactive species, and the composition is heated with the heat. A method for producing an adhesive in which the temperature is lowered to the first heating temperature and the hydrolysis proceeds.

 [2] After raising the temperature of the composition to the first heating temperature, a diluent is added to the composition to create a mixture,

 The method for producing an adhesive according to claim 1, wherein the mixture is heated to a second heating temperature that is higher than the first heating temperature and lower than the thermocompression bonding temperature to evaporate the second product.

 [3] The method for producing an adhesive according to claim 1 or 2, wherein the first product is silanol.

 [4] The method for producing an adhesive according to claim 1 or 2, wherein the second product is alcohol.

 [5] The method for producing an adhesive according to claim 1 or 2, wherein the first heating temperature is 60 ° C or higher and lower than 70 ° C.

[6] The method for producing an adhesive according to claim 1 or 2, wherein the first resin material is epoxy resin.

7. The method for producing an adhesive according to claim 2, wherein the heating of the mixture forms the mixture into a film.

 8. The method for producing an adhesive according to claim 2, wherein the diluent contains an organic solvent.

[9] The method for producing an adhesive according to [2], wherein the second heating temperature is 70 ° C or higher and 80 ° C or lower.

 10. The method for producing an adhesive according to claim 2, wherein conductive particles are added to the diluent.

 [II] The method for producing an adhesive according to claim 2, wherein the diluent contains a second resin material.

12. The method for producing an adhesive according to claim 11, wherein the second raw material of the resin is a thermoplastic resin. The method for producing an adhesive according to claim 1, wherein the curing agent includes a porous resin and a metal chelate held by the porous resin.

 14. The method for producing an adhesive according to claim 13, wherein the curing agent is formed by interfacial polymerization of the metal chelate and a polyfunctional isocyanate compound.