JPH0860133A - Reactional hot-melt adhesive - Google Patents

Abstract

PURPOSE: To obtain the adhesive, containing a polycarbodiimide comprising a specific recurring unit and a polyhydric phenol compound, excellent in shelf life, operating efficiency, curability and flexibility, (wet) heat resistance and adhesive strength of a cured product and useful for assembling electronic parts, etc. CONSTITUTION: This adhesive contains (A) 100 pts.wt. polycarbodiimide comprising 50-100mol% recurring unit of formula I [X, Y and Z are each H or CH3 ) and 50-0mol% recurring unit of formula II (R is a bivalent organic group) different from the recurring unit of formula I and (B) 1-100 pts.wt. polyhydric phenol compound having >=2 phenolic OH groups. Furthermore, the adhesive contains 100 pts.wt. component (A), 1-100 pts.wt. component (B) and further (C) 0.1-80 pts.wt. epoxy resin.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a reactive hot melt adhesive which is useful for assembling electronic parts, particularly for assembling semiconductor devices, and which has excellent resistance to heat and moisture.

[0002]

2. Description of the Related Art In the assembly of electronic parts, particularly in the assembly of semiconductor devices, adhesive materials having excellent heat resistance, moisture resistance, moist heat resistance, adhesive strength, storage stability and workability are required. Conventionally, epoxy-based, rubber-modified epoxy-based, phenol-based, acrylic-based, and other resins have been used for these applications. These resins show excellent adhesion, but workability,
It has the drawback of being inferior in moist heat resistance. On the other hand, a composition containing polycarbodiimide as a heat-resistant adhesive is known. For example, JP-A-5-239427 discloses an aromatic polycarbodiimide, an epoxy resin, a curing agent for an aromatic carbodiimide, and a curing agent for an epoxy resin. A paste-like or powder-like adhesive composition containing an agent has been proposed. However, this composition is inferior in workability because it is necessary to add the respective curing agents immediately before bonding when thermally curing the aromatic polycarbodiimide and the epoxy resin. In addition, in order to improve the workability, when pre-mixing the polycarbodiimide, the epoxy resin and the respective curing agents, in order to ensure storage stability, the amount of the curing agent must be significantly reduced, There is a problem that it takes time to heat cure.

[0003]

The object of the present invention is to provide excellent storage stability and workability in bonding and assembling precision parts such as electronic parts, and to cure and react at a low temperature in a short time. It is an object of the present invention to provide a reactive hot melt adhesive which has a high softening temperature of a cured product afterwards, is excellent in heat resistance, moisture resistance and wet heat resistance, has flexibility, and has good adhesive strength.

[0004]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that a specific polycarbodiimide easily reacts with a carboxylic acid at room temperature like ordinary polycarbodiimides. It forms an isourea bond, but does not react with a phenolic hydroxyl group whose acidity is weaker than that of a carboxylic acid at room temperature, but first reacts at 150 ° C. or higher, and completed the present invention.
That is, the object of the present invention is the first invention, (A)
50-100 repeating units represented by the following general formula (1)
Mol%, and

[0005]

[Chemical 1]

(In the formula, X, Y and Z are the same or different groups selected from hydrogen or a methyl group.) A repeating unit represented by the following general formula (2) (provided that the general formula (1 ) Is different from the general formula (2)) in an amount of 50 to 0 mol%, and -RNN = C = N- (2) (wherein, R is a divalent organic group). Hereinafter, 100 parts by weight of "polycarbodiimide (A)" and 1 to 100 parts by weight of (B) a polyhydric phenol compound having two or more phenolic hydroxyl groups (hereinafter referred to as "polyhydric phenol compound (B)"). It can be achieved by a reactive hot melt adhesive characterized by containing parts.

A further object of the present invention is (C) with respect to 100 parts by weight of the polycarbodiimide (A) and 1 to 100 parts by weight of the polyhydric phenol compound (B), which is the second invention.
It can be achieved by the reactive hot melt adhesive according to claim 1, which contains 0.1 to 80 parts by weight of an epoxy resin (hereinafter referred to as "epoxy resin (C)") as a component.

The constituent features of the present invention will be described below. The feature of the present invention is that a composition containing a polycarbodiimide (A) containing a repeating unit represented by the general formula (1) as a main component and a polyhydric phenol compound (B) as an essential component is used as a reactive hot melt adhesive. To use. In the general formula (1) showing the repeating unit of the polycarbodiimide (A), X, Y and Z are hydrogen or a methyl group, and preferably any one of X, Y and Z is a methyl group or X, Y and Z is all hydrogen, especially X, Y
It is preferred that all of and Z are hydrogen. General formula (2) showing a repeating unit of polycarbodiimide (A)
In the above, R is a divalent organic group, and preferable examples include the following. 1) Those represented by the following structural formulas. -C _n H _2n - _(n is an integer from 2 to _{12) -C n H 2n -CH (COOCH} 3) - (n is an integer of from 2 to 6) - cycloalkyl _{C n H 2n-2 - (} n is 4 to 6 integer) - cyclo _{C n H 2n-2-m} (-CH 3) m - (n is 5, 6, m is an integer of from 0 to 3) - cyclo _{C 6 H 7 (CH 3)} 3 -CH 2 ——CH ₂ — Cyclo C ₆ H ₁₀ —CH ₂ — Here, cyclo represents a divalent saturated cyclic hydrocarbon group.

2) A compound represented by a structural formula obtained by removing two isocyanate groups from the diisocyanate compound described below. Cyclobutylene-1,3-diisocyanate, cyclopentylene-1,3-diisocyanate, cyclohexyl-1,3-diisocyanate, cyclohexyl-
1,4-diisocyanate, 1-methylcyclohexyl-2,4-diisocyanate, 1-methylcyclohexyl-2,6-diisocyanate, 1-isocyanate-
3,3,5-trimethyl-5-isocyanate methylcyclohexane, cyclohexyl-1,3-bis (methylisocyanate), cyclohexyl-1,4-bis (methylisocyanate), isophorone diisocyanate,
Dicyclohexylmethane-2,4'-diisocyanate, ethylene diisocyanate, tetramethylene-1,
4-diisocyanate, hexamethylene-1,6-diisocyanate, dodecamethylene-1,12-diisocyanate, lysine diisocyanate methyl ester. In the present invention, as the repeating unit represented by the general formula (2),
The R-containing carbodiimide structures of 1) and 2) above can be used alone or in combination of two or more, and in particular, R represented by a structural formula obtained by removing two isocyanate groups from isophorone diisocyanate is contained. Carbodiimide structure is preferred.

A repeating unit represented by the general formula (1),
The molar ratio of the repeating unit represented by the general formula (2) is 50-100 / 50-0 in the general formula (1) / general formula (2),
It is preferably 60 to 100/40 to 0, and particularly preferably 100/0. As R in the general formula (2), those described in 1) and 2) above can be preferably used.
Other than these can be used as a copolymerization component of the repeating unit represented by the general formula (1) as long as the effects of the present invention are not impaired. However, in this case, the proportion is preferably 30 mol% or less, particularly preferably 20 mol%.
It is the following. As such a polycarbodiimide (A), a polycarbodiimide obtained by a single polycondensation reaction of dicyclohexylmethane-4,4′-diisocyanate (hereinafter referred to as “hydrogenated MDI”) is preferably used. As the polycarbodiimide (A), a polyisocyanate compound or a polycarbodiimide end-modified with a compound having active hydrogen for a polymerization termination reaction during a polymerization reaction can also be used. The polycarbodiimide (A) can be easily synthesized by decarboxylation polycondensation of a corresponding diisocyanate compound. For details, see, for example, J. Am. Chem. Soc., 80, 5495 (1958) (E. Dyer et al.
), J.Appl.Polym.Sci., 21, 1999 (1977) (LM Alerino et al.
), Etc., JP-A-51-61599, and Japanese Patent Publication No. 2-
It is described in Japanese Patent Publication No. 292316, Japanese Patent Publication No. 4-279618, and the like. The polycarbodiimide (A) used in the present invention has a polystyrene reduced number average molecular weight (hereinafter,
It is called "Mn". ) Is preferably 3,000 to 50
50,000, particularly preferably 5,000 to 30
It is 10,000. If Mn is less than 3,000, the strength of the polymer tends to be low and the adhesive strength tends to be poor. On the other hand, M
When n exceeds 500,000, the softening temperature of the adhesive is 13
When it exceeds 0 ° C, it tends to be difficult to use as an adhesive. The polycarbodiimide (A) may be used alone or in combination of two or more.

As the polyhydric phenol compound (B) used in the present invention, dithiobisphenol, 4,4'-
(Dichloroethenylidene) bisphenol (also known as bisphenol C2), 4,4 '-(1,2-ethanediyl)
Bisphenol (also known as bisphenol E), 4,4'-
(1-Methylethylidene) bis (2,6-dimethyl-phenol) (alias bisxylenol A), 4,4′-methylenebisphenol (alias bisphenol F), 4,
4 '-(1,4-phenylenebis (1-methylethylidene)) bisphenol (also known as bisphenol P), 4,
4 '-(diphenylmethylene) bisphenol (alias bisphenol TP), 4,4'-(1-phenylethylidene) bisphenol (alias bisphenol ACP),
4,4 '-[2,2,2-Trifluoro-1- (trifluoromethyl) ethylidene] bisphenol (alias bisphenol AF), 4,4'-cyclohexylidene bisphenol (alias bisphenol Z), 4,4'- Sulfonyl bisphenol (also known as bisphenol S), 4,
4 '-(1-methylethylidene) bisphenol (alias bisphenol A), 4,4'-(1-methylethylidene) bis (2-methylphenol) (alias bisphenol C), 4,4 '-(1-methylpropyiene) Redene) bisphenol (also known as bisphenol B), 4,4 '-[1-
[4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol (also known as trisphenol PA) 4,4 ′, 4 ″-(1-phenyl-1-ethanyl-2)
-Ylidene) tris (3-methyl-phenol), 2,
4-bis [1- (4-hydroxyphenyl) -1-methylethyl] -phenol (also known as trisphenol), phenol novolac resin, phenol terpene resin, cresol novolac resin and the like can be mentioned. These can be used alone or as a mixture of two or more kinds.

The polyhydric phenol compound (B) used in the present invention acts as a curing agent for the polycarbodiimide (A) and the epoxy resin (C). The polyhydric phenol compound (B) is used in an amount of 1 to 100 parts by weight, preferably 5 to 80 parts by weight, based on 100 parts by weight of the polycarbodiimide (A). If the blending amount of the polyhydric phenol compound (B) is less than 1 part by weight, it is difficult to raise the softening temperature of the cured product because of insufficient crosslinking during heating, resulting in poor heat resistance. On the other hand, when the polyhydric phenol compound (B) is blended in an amount of more than 100 parts by weight, the crosslink density becomes high, and
The Young's modulus becomes high, the cured product becomes brittle, and the adhesive strength decreases.

Examples of the epoxy resin (C) include glycidyl ether type epoxy resins, alicyclic epoxy resins and glycidyl ester type epoxy resins represented by bisphenol A type epoxy resin, novolac type epoxy resin, cresol novolac type epoxy resin and the like. An epoxy resin such as a heterocyclic epoxy resin, an amine type epoxy resin, or a liquid rubber-modified epoxy resin can be used alone or as a mixture of two or more kinds. These epoxy resins may be liquid or solid at room temperature, but when they are solid, their softening temperature is 15
It is preferably 0 ° C. or lower. The compounding amount of the epoxy resin (C) is 0.1 to 80 parts by weight, preferably 1 to 50 parts by weight, based on 100 parts by weight of the polycarbodiimide (A). The three-component system in which the epoxy resin (C) is blended has a carbodiimide (A) and a polyhydric phenol compound (B).
Although the adhesive strength is relatively lower than that of the component system, 1
Even when cured at a temperature of 50 ° C. to 200 ° C., the curing reaction sufficiently proceeds, so the difference in adhesive strength between when cured at 200 ° C. or higher is small, and the adhesive strength is unlikely to be affected by the curing temperature. There is a feature called.

The adhesive of the present invention contains, as its constituent components, components other than the polycarbodiimide (A), the polyhydric phenol compound (B) and the epoxy resin (C) within a range that does not impair the wet heat resistance and the adhesiveness. Can be added at. For example, addition of a thermoplastic elastomer or a petroleum resin is effective for imparting flexibility to an adhesive, particularly a film-shaped adhesive. Further, in order to reduce the viscosity of the adhesive when it is melted, it is effective to add a coumarone resin or the like.

The adhesive of the present invention is prepared by dissolving polycarbodiimide (A), polyhydric phenol compound (B) and epoxy resin (C) in a solvent. Examples of the solvent used at that time include 1,1-dichloroethane, 1,
2-dichloroethane, 1,1,1-trichloroethane,
1,1,2-trichloroethane, 1,1,1,2-tetrachloroethane, 1,1,2,2-tetrachloroethane, pentachloroethane, hexachloroethane, 1,1
-Dichloroethylene, 1,2-dichloroethylene, trichloroethylene, tetrachloroethylene, chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, p
-Halogenated hydrocarbon solvents such as dichlorobenzene, 1,2,4-trichlorobenzene, trichloromethylbenzene;

Dioxane, tetrahydrofuran, tetrahydropyran, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether,
Ether solvents such as diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether;

N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N-benzyl-2-pyrrolidone,
N-methyl-3-pyrrolidone, N-acetyl-3-pyrrolidone, N-benzyl-3-pyrrolidone, formamide, N-methylformamide, N, N-dimethylformamide, N-ethylformamide, N, N-diethylformamide, Acetamide, N-methylacetamide,
Amide solvents such as N, N-dimethylacetamide and N-methylpropionamide; aprotic polar solvents such as dimethylsulfoxide;

2-methoxyethyl acetate, 2-ethoxyethyl acetate, 2-propoxyethyl acetate, 2-butoxyethyl acetate, 2-phenoxyethyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monopropyl ether acetate, Acetate solvents such as diethylene glycol monobutyl ether acetate may be mentioned.

The adhesive of the present invention has a softening temperature of 50-13.
It is preferably 0 ° C. When the softening temperature is less than 50 ° C, it becomes a paste even at room temperature, and it is difficult to obtain good workability as a hot melt adhesive. Also, the softening temperature is 1
If it exceeds 30 ° C., it takes time to heat for melting, and the viscosity at the time of melting tends to be high, so that the adhesiveness tends to deteriorate. In order to set the softening temperature to 50 to 130 ° C., Mn of the polycarbodiimide (A) should be 3,000.
The range is 0 to 500,000, and the polyphenol compound (B) and the epoxy resin (C) are mixed according to the type and blending ratio. As described above, the polycarbodiimide (A) / polyphenol compound (B) weight ratio in the first invention of the present application is 100/1 to 100, preferably 100/5 to 80, as described above. The weight ratio of polycarbodiimide (A) / polyhydric phenol compound (B) / epoxy resin (C) in the second invention is 100/1 to 100/0.
It is 1 to 80, preferably 100/5 to 80/1 to 50.

The adhesive of the present invention is reactively cured when heated at 150 ° C. or higher, and the composition after curing has a softening temperature of 1 or less.
High as 70 ° C or higher and Young's modulus at room temperature is, for example, 3 GPa
It has flexibility below, and is further excellent in wet heat resistance and adhesive strength.

The adhesive of the present invention can be made into a fiber-reinforced sheet-like product by impregnating the solution with a thin cloth mat of fibers having excellent heat resistance such as glass fibers and drying. A film with a heat-resistant hot-melt adhesive can be obtained by applying a solution of this adhesive to one or both sides of a supporting film such as a polyimide film, a polyester film, or a polycarbonate film and drying. The adhesive solution is used as it is by applying it to an adherend as it is, drying it, and heating, melting, and pressing with another adherend. Further, the adhesive of the present invention can be obtained as a film by casting on a glass plate or a stainless plate, drying and peeling. The drying temperature of the adhesive solution is 150 ° C
The following is preferable. If the drying temperature exceeds 150 ° C., a crosslinking reaction between the polycarbodiimide (A) and the polyhydric phenol (B) occurs, the viscosity of the solution increases, stable film processing becomes difficult, and the adhesiveness also decreases.

The adhesive of the present invention is solid at room temperature,
It can be used in any shape such as powder, flakes, pellets, crumbs and films. However, if importance is attached to workability in assembling electronic components, especially semiconductor devices, it is preferably used in the form of film or tape.

[0023]

The present invention will be further described below with reference to examples and comparative examples, but the present invention is not limited to these examples.

Example 1 100 g of hydrogenated MDI was added to 1-phenyl-3-methyl-
180 ° C. in the presence of 4 g of 2-phospholen-1-oxide
After reacting for 4 hours, Mn is 10,000 and softening point is 7
Polycarbodiimide (A) at 0 ° C. (hereinafter, referred to as “polycarbodiimide (A-1)”) was obtained. Next, 5 g of polycarbodiimide (A-1) was dissolved in 15 g of chlorobenzene. On the other hand, 4,4 '-[1- [4- [1-
2.5 g of (4-hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol (hereinafter referred to as “trisphenol PA”) was dissolved in 5 g of tetrahydrofuran (hereinafter referred to as “THF”).
Both solutions were mixed well and coated on a stainless steel plate. 8
After drying at 0 ° C. for 20 minutes, the film was peeled off from the stainless plate to obtain an adhesive film having a thickness of 50 μm.

Example 2 5 g of polycarbodiimide (A-1) was dissolved in 15 g of chlorobenzene. On the other hand, trisphenol PA
Both solutions obtained by dissolving 0.75 g in 2 g of THF were sufficiently mixed and coated on a stainless plate. 20 at 80 ° C
After drying for a minute, the film was peeled from the stainless plate to obtain an adhesive film having a thickness of 50 μm.

Example 3 80 g of hydrogenated MDI, 20 of isophorone diisocyanate
g to 1-phenyl-3-methyl-2-phosphorene-1-
Polycarbodiimide (A) having a Mn of 18,000 and a softening point of 60 ° C. was reacted in the presence of 2.5 g of oxide at 180 ° C. for 4 hours (hereinafter referred to as “polycarbodiimide (A-
2) ”. ) Got. Polycarbodiimide (A-
2) 5 g was dissolved in 15 g of anisole. On the other hand, 0.25 g of trisphenol PA was dissolved in 1 g of THF. Both solutions were mixed well and coated on a stainless steel plate. After drying at 100 ° C. for 20 minutes, the film was peeled off from the stainless plate to obtain an adhesive film having a thickness of 50 μm.

Example 4 5 g of polycarbodiimide (A-1) and bisphenol A
1.5 g was dissolved in 15 g anisole. The obtained solution was applied onto a stainless plate and dried at 100 ° C. for 20 minutes, and then the film was peeled from the stainless plate to obtain an adhesive film having a thickness of 50 μm.

Example 5 5 g of polycarbodiimide (A-1) and a phenol terpene resin (manufactured by Sumitomo Chemical Co., Ltd .; tacky roll 160)
0.75 g was dissolved in 15 g anisole. The obtained solution was applied onto a stainless plate and dried at 80 ° C. for 20 minutes, and then the film was peeled from the stainless plate to obtain an adhesive film having a thickness of 50 μm.

Example 6 5 g of polycarbodiimide (A-1) was dissolved in 15 g of chlorobenzene. On the other hand, trisphenol PA
0.75 g was dissolved in 2 g THF. Both solutions were sufficiently mixed, cast on a polyimide film having a thickness of 50 μm (manufactured by Ube Industries, Ltd .; Upilex S) to a thickness of 50 μm, and dried at 80 ° C. for 20 minutes. Further, similarly, on the opposite surface of the polyimide film, a mixed solution of both solutions was cast and dried to obtain a polyimide film with an adhesive having a thickness of 10 μm on each of the front and back sides.

Example 7 Polycarbodiimide (A-1) 5 g, trisphenol PA 1.5 g, and coumarone resin (Nippon Steel Chemical Co., Ltd.)
Exxon G-90) (2 g) was dissolved in 20 g of anisole. Apply the obtained solution on a stainless steel plate,
After drying at 100 ° C. for 20 minutes, the film was peeled off from the stainless plate to obtain an adhesive film having a thickness of 50 μm.

Example 8 5 g of polycarbodiimide (A-1) was dissolved in 15 g of chlorobenzene. On the other hand, trisphenol PA2.
5g was dissolved in 5g THF. Both solutions and bisphenol A type epoxy resin (Okaka Shell Epoxy Co., Ltd.)
Manufactured: Epicoat 828) (2.5 g) was sufficiently mixed and coated on a stainless steel plate. After drying at 80 ° C for 20 minutes, the film is peeled off from the stainless steel plate and the thickness is 50 μm.
The adhesive film of was obtained.

Example 9 5 g of polycarbodiimide (A-1) was dissolved in 15 g of chlorobenzene. On the other hand, trisphenol PA0.
75 g was dissolved in 2 g THF. Both solutions and amine type epoxy resin (manufactured by Tohto Kasei Co., Ltd .; YH-434)
L) 1 g was sufficiently mixed and coated on a stainless plate.
After drying at 80 ° C. for 20 minutes, the film was peeled off from the stainless steel plate to obtain an adhesive film having a thickness of 50 μm.

Example 10 Polycarbodiimide (A-2) (5 g) and bisphenol A type epoxy resin (Yukaka Shell Epoxy Co., Ltd .; Epicoat 1001) (2 g) were dissolved in 15 g of anisole. On the other hand, 0.25 g of trisphenol PA was dissolved in 1 g of THF. Both solutions were mixed well and coated on a stainless steel plate. After drying at 100 ° C for 20 minutes,
The film was peeled off from the stainless plate to obtain an adhesive film having a thickness of 50 μm.

Example 11 Polycarbodiimide (A-1) 5 g, bisphenol A
1.5 g and 2.2 g of a novolac type epoxy resin (Toto Kasei Co., Ltd .; YDCN-704) were dissolved in 15 g of anisole. The obtained solution was applied onto a stainless plate and dried at 100 ° C. for 20 minutes, and then the film was peeled from the stainless plate to obtain an adhesive film having a thickness of 50 μm.

Example 12 Polycarbodiimide (A-1) (5 g) and phenol terpene resin (Sumitomo Chemical Co., Ltd .; Tuck roll 160)
0.75 g and 1 g of a glycidyl ester type epoxy resin (manufactured by Nippon Kayaku Co., Ltd .; AK-601) were dissolved in 15 g of anisole. The obtained solution was applied onto a stainless plate and dried at 80 ° C. for 20 minutes, and then the film was peeled from the stainless plate to obtain an adhesive film having a thickness of 50 μm.

Example 13 5 g of polycarbodiimide (A-1) was dissolved in 15 g of chlorobenzene. On the other hand, trisphenol PA0.
75 g was dissolved in 2 g THF. Both solutions and 0.75 g of a bisphenol A type epoxy resin (produced by Yuka Shell Epoxy Co., Ltd .; Epicoat 828) are sufficiently mixed, and 50 μm is formed on a polyimide film (produced by Ube Industries, Ltd .; Upilex S) having a thickness of 50 μm. And was dried at 80 ° C. for 20 minutes. Further, the mixed solution was cast and dried on the opposite side of the polyimide film in the same manner to obtain a polyimide film with an adhesive having a thickness of 10 μm on each of the front and back sides.

Example 14 Polycarbodiimide (A-1) 5 g and trisphenol PA 1.5 g, petroleum resin (Tosoh Corp .; Petcole LX) 2 g and bisphenol A type epoxy resin (Okaka Shell Epoxy Ltd .; Epicoat 1001) 2g
Was dissolved in 20 g of anisole. The obtained solution was applied onto a stainless plate and dried at 100 ° C. for 20 minutes, and then the film was peeled off from the stainless plate to a thickness of 50 μm.
The adhesive film of was obtained.

Comparative Example 1 When 5 g of polycarbodiimide (A-1) and 1.5 g of paraphenylenediamine were dissolved in 15 g of anisole, the solution gelled.

Comparative Example 2 5 g of polycarbodiimide (A-1) was dissolved in THF. On the other hand, 1.5 g of 1,2,3,4-tetracarboxylic acid butane was dissolved in 3 g of methanol. When both solutions were mixed, the solution gelled.

Comparative Example 3 5 g of polycarbodiimide (A-1) and 1 g of 1,4-butanediol were dissolved in 15 g of chlorobenzene. The obtained solution is coated on a stainless steel plate and heated at 80 ° C for 20
After drying for a minute, the film was peeled from the stainless plate to obtain an adhesive film having a thickness of 50 μm.

Evaluation of Adhesive Film The adhesive films obtained in the above Examples and Comparative Examples were measured for softening temperature, Young's modulus and adhesive strength by the following methods. The results are shown in Table 1.

Measurement of softening temperature and Young's modulus After the adhesive film was manufactured, it was stored for 1 hour at 20 ° C. and 60% humidity, and for 3 months at 20 ° C. and 60% humidity. The temperature showing the maximum value of tan δ when measured at a frequency of 11 Hz and a heating rate of 3 ° C./min in a tensile mode with a viscoelasticity measuring device (manufactured by Orientec Co., Ltd .; DDV-01FP) was defined as the softening temperature. . The absolute value of the complex elastic modulus was defined as Young's modulus.

Measurement of Adhesive Strength After the adhesive film is manufactured, it is kept at 20 ° C. for 1 hour or 20
After leaving it for 3 months at ℃, sandwich the adhesive film (sample) punched into 15mm square between the copper adherend and a 15mm square silicon wafer with an oxide film, and pressure is 1kgf / cm.
Primary heating was performed under ² . Then, it was transferred to an oven and subjected to secondary heating under no load to advance the curing reaction. In addition,
Primary heating was performed at 170 ° C. for 10 seconds or 260 ° C. for 5 seconds under two conditions, and secondary heating was performed at 220 ° C. for 30 minutes. In consideration of actual use, the adhesive thus obtained is left under high temperature and high humidity at a temperature of 85 ° C. and a humidity of 85% for 12 days in order to accelerate deterioration, and then at a heating condition of soldering for 10 minutes at 250 ° C. Heating was performed. The adhesive thus obtained has a temperature of 20 ° C.
At, a test was conducted at a tensile speed of 10 mm / min to determine the adhesive strength.

[0044]

[Table 1]

[0045]

According to the present invention, in adhering and assembling precision parts such as electronic parts, it has excellent storage stability and workability, and it is cured by reaction at a low temperature in a short time and a cured product after reaction. It is possible to obtain a reactive hot-melt adhesive having a high softening temperature, excellent heat resistance, moisture resistance and wet heat resistance, flexibility, and good adhesive strength. This adhesive is copper,
Metals such as gold, nickel, iron and stainless steel, inorganic materials such as glass, silicon and quartz, polyester,
Strongly adheres to resins such as polyimide. This adhesive can improve the yield of products and manufacture a highly reliable semiconductor device especially in the assembly of electronic parts, for example, the assembly of semiconductor devices.

The preferred embodiments of the present invention are listed below. 1) The adhesive according to claim 1 or 2, wherein in the general formula (1) showing the repeating unit of the polycarbodiimide (A), X, Y and Z are all hydrogen. 2) In the general formula (2) showing the repeating unit of the polycarbodiimide (A), the divalent organic group -R- is selected from the following.
Adhesive described. -C _n H _2n - _(n is an integer from 2 to _{12) -C n H 2n -CH (COOCH} 3) - (n is an integer of from 2 to 6) - cycloalkyl _{C n H 2n-2 - (} n is 4 to 6 integer) - cyclo _{C n H 2n-2-m} (-CH 3) m - (n is 5, 6, m is an integer of from 0 to 3) - cyclo _{C 6 H 7 (CH 3)} 3 -CH 2 --CH ₂ --CycloC ₆ H ₁₀ --CH _2-

3) The organic group -R- in 2) above has an isocyanate group from the diisocyanate compound described below.
The adhesive according to claim 1 or 2, which is represented by a structural formula excluding one of the two. Cyclobutylene-1,3-diisocyanate, cyclopentylene-1,3-diisocyanate, cyclohexyl-1,3-diisocyanate, cyclohexyl-1,4-diisocyanate, 1-methylcyclohexyl-2,4-diisocyanate, 1-methylcyclohexyl -2,6-diisocyanate, 1-isocyanate-3,3,5-trimethyl-5-isocyanate methylcyclohexane, cyclohexyl-1,3-bis (methylisocyanate), cyclohexyl-1,4-
Bis (methylisocyanate), isophorone diisocyanate, dicyclohexylmethane-2,4'-diisocyanate, ethylene diisocyanate, tetramethylene-1,4-diisocyanate, hexamethylene-1,6
-Diisocyanate, dodecamethylene-1,12-diisocyanate, lysine diisocyanate methyl ester.

4) The polycarbodiimide (A) has the general formula (1) (wherein X, Y and Z are all hydrogen).
The adhesive agent according to claim 1 or 2, which is composed of only one. 5) Polycarbodiimide (A) has the general formula (1) (wherein X, Y and Z are all hydrogen) 60 to 100
The adhesive according to claim 1 or 2, which comprises 40 to 0 mol% of the general formula (2). 6) The adhesive according to the above 5), wherein the general formula (2) is isophoronecarbodiimide. 7) With respect to 100 parts by weight of polycarbodiimide (A),
The adhesive according to claim 2, which contains 5 to 80 parts by weight of the polyhydric phenol compound (B) and 1 to 60 parts by weight of the epoxy resin (C). 8) The polyhydric phenol compound (B) is 4,4 ′-[1-
[4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol, The adhesive according to 7) above, wherein the epoxy resin (C) is a bisphenol A type epoxy resin.

Claims (2)

[Claims] 1. (A) 50 to 100 mol% of a repeating unit represented by the following general formula (1), and: (In the formula, X, Y and Z are the same or different groups selected from hydrogen or a methyl group.) A repeating unit represented by the following general formula (2) (provided that the general formula (1) and general formula (1) Different from the formula (2)) 50 to 0 mol%, -R-N = C = N- (2) (wherein, R is a divalent organic group) 100 parts by weight of a polycarbodiimide, And (B) polyhydric phenol compounds having 2 or more phenolic hydroxyl groups 1 to 100
A reactive hot melt adhesive, characterized in that it contains 100 parts by weight. 2. The polycarbodiimide 100 of (A) above.
Parts by weight, and the (B) polyhydric phenol compound 1 to
(C) Epoxy resin 0.1-8 with respect to 100 parts by weight
The reactive hot melt adhesive according to claim 1, which contains 0 part by weight.