JP2000143981A - Resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition having low water absorption, solder heat resistance, heat resistance and adhesiveness, bondable especially at a low temperature by mixing a specific polyimide resin with an epoxy resin. SOLUTION: This composition comprises (A) a polyimide resin obtained by reacting (i) an ester acid dianhydride of formula I (X is an aromatic ring- containing bifunctional group) with (ii) a diamine of formula II (Y is -SO2, -O- or the like; m and n are each 1-10) and (iii) a siloxanediamine of formula III (R1 and R2 are each a bifunctional 1-4C aliphatic group or bifunctional aromatic group; R3 to R6 are each a monofunctional 1-4C aliphatic group or a monofunctional aromatic group) and (B) an epoxy resin. 3,3',4,4'-Ethylene glycol benzoate tetracarboxylic dianhydride, etc., are preferable as the component (i). For example, α,ω-bis(3-aminopropyl)polydimethylsiloxane, etc., may be cited as the component (iii). The ratio of the component (iii) to the whole diamine is preferably 1-30 mol%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition which can be adhesively cured at a relatively low temperature, is soluble in an organic solvent, and has excellent heat resistance and adhesiveness. More specifically, a flexible printed circuit board, TAB (Tape Automated)
The present invention relates to a resin composition having excellent heat resistance and adhesiveness, which can be used for bonding tapes, composite lead frames, laminated materials, and the like.

[0002]

2. Description of the Related Art In recent years, electronic devices have become more sophisticated and more sophisticated.
With miniaturization progressing, there has been a demand for miniaturization and weight reduction of electronic components used accordingly. Therefore, a semiconductor element packaging method and a wiring material or a wiring component for mounting the same have been required to have higher density, higher function, and higher performance. In particular, semiconductor packages, COL and LOC packages, MCM (Mul
There is a need for a material exhibiting good adhesion that can be suitably used as a high-density packaging material such as a ti chip module), a printed wiring board material such as a multilayer FPC, and an aerospace material.

Heretofore, in semiconductor packages and other mounting materials, adhesives such as acrylic, phenolic, epoxy and polyimide have been known as adhesives exhibiting good mechanical properties, heat resistance and insulating properties. .

However, phenol-based and epoxy-based adhesives have excellent adhesiveness, but are inferior in flexibility. There has been a problem that a flexible acrylic adhesive has low heat resistance.

In order to solve these problems, polyimide is used. Polyimide is excellent in heat resistance among various organic polymers, and is therefore widely used in the fields of space and aviation to the field of electronic communication, and is also used as an adhesive material. However, a polyimide-based adhesive having high heat resistance requires a high temperature of about 300 ° C. and a high pressure for bonding, and the adhesive strength is not so high. Further, the conventional polyimide-based adhesive has a high water absorption rate. For example, when a lead frame using the polyimide-based adhesive is immersed in a solder bath, it has a problem that blisters and the like are easily generated.

[0006]

SUMMARY OF THE INVENTION Accordingly, the present inventors have solved the above-mentioned problems and have developed a resin having a low water absorption, excellent solder heat resistance, excellent heat resistance and adhesiveness, and particularly capable of bonding at a low temperature of 250 ° C. or lower. The present inventors have conducted intensive studies with the aim of providing a composition, and as a result, have completed the present invention.

[0007]

The gist of the resin composition of the present invention is that of the general formula (1).

[0008]

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An ester dianhydride represented by the formula: ## STR2 ##
Chemical 5

[0010]

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A diamine represented by the general formula (3):

[0012]

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[0013] It is intended to contain an epoxy resin and a polyimide resin obtained by reacting a siloxane diamine represented by the following formula.

In such a resin composition, the siloxane diamine may account for 1 to 30 mol% of the total diamine component.

[0015] The water absorption of the resin composition after reaction curing may be 1.5% or less, preferably 1.3% or less, more preferably 1.0% or less. Here, “after the reaction composition has been cured” means, for example, that the resin composition is formed into a sheet, dried at 100 ° C. for 10 minutes, and dried at 150 ° C. for 20 minutes, and then heat-cured at 150 ° C. for 3 hours. After. That is, the epoxy resin in the resin composition is in a cured state.

[0016]

DETAILED DESCRIPTION OF THE INVENTION General formula (1)

[0017]

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(In the formula, X represents a divalent group containing an aromatic ring.) The resin composition of the present invention containing an ester dianhydride represented by the formula (1) as a component has excellent low water absorption. Therefore, it has characteristics excellent in solder heat resistance. Preferred examples of the ester dianhydride used in the present invention include 2,2
-Bis (4-hydroxyphenyl) propanedibenzoate-3,3 ', 4,4'-tetracarboxylic dianhydride, p-phenylenebis (trimellitic acid monoester anhydride), 3,3', 4 4,4'-ethylene glycol benzoate tetracarboxylic dianhydride, 4,4'-biphenylene bis (trimellitic acid monoester acid anhydride), 1,4-naphthalene bis (trimellitic acid monoester acid anhydride), 1 1,2-ethylenebis (trimellitic acid monoester anhydride), 1,3-trimethylenebis (trimellitic acid monoester anhydride), 1,4-
Tetramethylene bis (trimellitic acid monoester anhydride), 1,5-pentamethylene bis (trimellitic acid monoester anhydride) and 1,6-hexamethylene bis (trimellitic acid monoester anhydride) No. One or more of these may be used in combination.

Formula (2) 8

[0020]

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As a preferred example of the diamine represented by the formula, in the formula, Y is -C (= O)-, -SO _2- , -O
-, - S -, - ( CH 2) m -, - NHCO -, - C
_{(CH 3) 2 -, -} C (CF 3) 2 -, - C (= O) O
— Or a bond, and a compound in which m and n are integers of 1 or more and 10 or less.

In the general formula (2), a plurality of Y
May be the same or two or more substituents. Further, hydrogen of each benzene ring can be appropriately substituted with various substituents within a range that can be considered by those skilled in the art. Examples thereof include a halogen group such as a methyl group, an ethyl group, and Br and Cl, but are not limited to these substituents.

Furthermore, the present inventors have found that, since the amino group of the diamine represented by the general formula (2) is bonded to the meta position, the solubility of the polyimide composition using the same in a solvent is increased. And paid attention to exhibiting excellent usefulness when used as an adhesive.

Specifically, as the diamine, in the general formula (2), particularly, the amino group is a compound represented by the general formula (2) ′

[0025]

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(Where Y is -C (= O)-, -SO
_{2 -, - O -, -} S -, - (CH 2) m -, - NHCO
_{-, - C (CH 3)} 2 -, - C (CF 3) 2 -, - C
(= O) O- or a bond. m and n are 1 or more and 5
It is the following integer. As shown in ()), it is preferably in the meta position. By having an amino group at the meta position,
The solubility of the resulting polyimide in an organic solvent is better, and the processability is excellent.

The diamine represented by the general formula (2) or (2) ′ can be used alone or in combination of two or more.

Next, the general formula (3)

[0029]

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As a preferred example of the siloxane diamine represented by the formula, in the formula, R ₁ and R ₂ are divalent carbon atoms having 1 carbon atom.
To 4 aliphatic groups or divalent aromatic groups, and R ₃ ,
Compounds in which R ₄ , R ₅ and R ₆ are monovalent aliphatic groups having 1 to 4 carbon atoms or monovalent aromatic groups, and m and n are integers of 1 or more and 10 or less. Can be Specifically, α, ω-bis (3-aminopropyl) polydimethylsiloxane, ω, ω′-bis (2-aminoethyl) polydimethylsiloxane, ω, ω′-bis (3-aminopropyl) polydimethylsiloxane, ω, ω '-Bis (4-aminophenyl) polydimethylsiloxane,
ω, ω′-bis (4-amino-3-methylphenyl) polydimethylsiloxane, ω, ω′-bis (3-aminopropyl) polydiphenylsiloxane, etc.
It is not limited to this.

The polyimide resin contained in the resin composition according to the present invention can be obtained by subjecting a polyamic acid polymer as a precursor thereof to dehydration and ring closure. The polyamic acid solution comprises an ester dianhydride represented by the above general formula (1), one or more diamine components represented by the above general formula (2) or (2) ′, and the above formula (3) The siloxane diamine represented by the formula (1) is used so that the ester dianhydride and all the diamine components are substantially equimolar, and is obtained by polymerization in an organic polar solvent.

The ratio of each diamine at this time is not particularly limited, but the ratio of siloxane diamine to all diamines is preferably 1 to 30 mol%.
The resin composition of the present invention containing siloxane diamine has increased solubility in low-boiling solvents and is easy to handle when used as an adhesive. The ratio of siloxane diamine is 1
When the amount is less than mol%, the solubility of the obtained resin composition in a low boiling point solvent is poor, and when it is more than 30 mol%, the heat resistance of the obtained resin composition is inferior.

This polyamic acid or polyimide is firstly prepared by reacting a compound represented by the general formula (2) and / or the general formula (2) ′ in an inert atmosphere such as argon or nitrogen.
One or more acid dianhydrides selected from at least one diamine, a siloxane diamine represented by the general formula (3), and an ester dianhydride represented by the general formula (1) in an organic polar solvent. It is obtained from a polyamic acid polymer obtained by dissolving or diffusing.

The order of addition of each monomer is not particularly limited.
The acid dianhydride is first added to the organic polar solvent, the above-mentioned general formula (2) and / or the general formula (2) ′, which is a diamine component, is added, and siloxane diamine is further added. The solution may be a combined solution, or an appropriate amount of a diamine component is first added to an organic polar solvent, then an acid dianhydride is added, and finally, the remaining diamine component is added to obtain a solution of a polyamic acid polymer. In addition, there are various addition methods known to those skilled in the art.

Examples of the organic polar solvent used in the reaction for producing the polyamic acid solution include sulfoxide solvents such as dimethyl sulfoxide and diethyl sulfoxide;
Formamide solvents such as N, N-dimethylformamide and N, N-diethylformamide; acetamide solvents such as N, N-dimethylacetamide and N, N-diethylacetamide; pyrrolidone solvents such as N-methyl-2-pyrrolidone; phenol , O-, p-, m-, or p-cresol, xinol, halogenated phenol,
Examples include phenol-based solvents such as catechol, and hexamethylphosphoramide and γ-butyrolactone. Further, if necessary, these organic polar solvents can be used in combination with an aromatic hydrocarbon such as xylene or toluene.

The polyamic acid polymer obtained above is dehydrated and ring-closed by a thermal or chemical method to obtain a polyimide resin. As the imidation method, any of a thermal method of dehydrating the polyamic acid solution by heat treatment and a chemical method of dehydrating using a dehydrating agent are used.

In the method of thermally dehydrating and cyclizing the polyamic acid polymer, the polyimide resin of the present invention can be obtained by imidizing the solvent of the solution by thermally evaporating the solvent. Thus, a polyimide resin in a solution state can be obtained. In the method of chemically dehydrating and ring-closing a polyamic acid polymer, a stoichiometric or more dehydrating agent and a catalyst are added to a solution, an organic solvent is evaporated, and imidation is advanced while heating and drying. In addition, a polyimide resin solution can be obtained by adding a dehydrating agent and a catalyst in a solution state to imidize the solution. The evaporation of the organic solvent is preferably performed at a temperature of 150 ° C. or less for a time period of about 5 minutes to 90 minutes. In addition, the heating temperature for imidization is appropriately selected within a range from room temperature to about 250 ° C.,
It is better to employ a heating method that is performed gradually. Examples of the dehydrating agent by a chemical method include aliphatic acid anhydrides such as acetic anhydride, and aromatic acid anhydrides. As a catalyst, an aliphatic tertiary amine such as triethylamine is used.
And aromatic tertiary amines such as tertiary amines and dimethylaniline, and heterocyclic tertiary amines such as pyridine and isoquinoline.

Of these, the chemical method is preferable because the heating temperature can be lowered, the time required for imidization can be shortened, and mechanical properties such as elongation or tensile strength of the produced polyimide become favorable. Combinations with thermal and chemical methods can also be used.

The polyimide resin thus obtained has a low water absorption and a relatively low glass transition temperature, so that it can be an excellent adhesive material which enables low water absorption and low temperature bonding. . Since the resin composition of the present invention contains such an excellent polyimide resin, after curing,
An excellent low water absorption of 1.5% or less, preferably 1.3% or less, particularly preferably 1.0% or less can be exhibited.

Since the resin composition according to the present invention further contains an epoxy resin, further excellent adhesiveness is imparted to the properties of polyimide such as excellent heat resistance and low water absorption.

The epoxy resins used in the present invention include bisphenol epoxy resins, halogenated bisphenol epoxy resins, phenol novolak epoxy resins, halogenated phenol novolak epoxy resins, alkylphenol novolak epoxy resins,
Polyphenol-based epoxy resin, polyglycol-based epoxy resin, cycloaliphatic epoxy resin, cresol novolak-based epoxy resin, glycidylamine-based epoxy resin, urethane-modified epoxy resin, rubber-modified epoxy resin, epoxy-modified polysiloxane, and the like can be used.

The mixing ratio of the epoxy resin is polyimide 1
1 to 50 parts by weight, preferably 5 to 3 parts by weight, per 100 parts by weight
It is desirable to add 0 parts by weight. If the amount is too small, the adhesive strength is low, and if it is too large, the flexibility and heat resistance are poor.

The resin composition of the present invention may further contain, if necessary, a commonly used epoxy such as acid dianhydride, amine or imidazole in order to improve water absorption, heat resistance and adhesiveness. Curing agents, accelerators and various coupling agents can be used in combination. In addition, thermosetting resins other than epoxy resins,
The resin composition of the present invention can be obtained by further adding a phenol resin, a cyanate resin or the like.

The resin composition of the present invention comprises a polyimide resin,
It is obtained by uniformly stirring and mixing an epoxy resin, an epoxy curing agent, and other components. At this time,
An epoxy compound, an epoxy curing agent, and other components are directly added to the polyimide solution to obtain a resin composition solution. Alternatively, a resin composition of the present invention can be prepared by adding a low boiling point solvent to a polyimide solution, further adding an epoxy resin, an epoxy curing agent, and the like, and stirring and mixing. In addition to this, the solvent used for the polymerization of polyamic acid is dissolved well, but in a poor solvent in which the polyimide is difficult to dissolve, the polyimide solution is added to precipitate the polyimide resin, the unreacted monomer is removed, purified, and dried. From the solid polyimide resin, the resin composition of the present invention can be appropriately formed. Examples of the poor solvent include, but are not limited to, acetone, methanol, ethanol, isopropanol, benzene, methyl cellosolve, and methyl ethyl ketone.

In this case, although not particularly limited, the purified polyimide resin thus obtained may be dissolved again in an organic solvent together with another epoxy resin or the like to obtain a filtered and purified varnish. The organic solvent used at this time is not particularly limited, and any organic solvent known to those skilled in the art can be used. Since the polyimide resin of the present invention is easily dissolved in a low boiling point solvent due to its composition, a low boiling point organic solvent can be used as the organic solvent.

Here, the low-boiling organic solvent is a solvent having a boiling point of 20
A solvent having a temperature of 0 ° C. or lower, for example, dimethylformamide, dimethylacetamide, tetrahydrofuran and the like.

Conventional polyimide-based adhesives do not have sufficient adhesiveness to metals such as copper foil and resin films such as polyimide, and are difficult to mix with epoxy resins due to their poor solubility. The resin composition according to the present invention has good adhesiveness with a metal foil such as a copper foil or a polyimide film, and also has a property that its solubility in an organic solvent is good, and is excellent in workability in use. . The resin composition of the present invention is particularly suitable for use as an adhesive,
There are various methods for the specific usage within a range that can be carried out by those skilled in the art. For example, the adhesive may be formed into a sheet in advance and used as a sheet adhesive. Further, the resin composition of the present invention is impregnated as a varnish in glass cloth, glass mat, aromatic polyamide fiber cloth, aromatic polyamide fiber mat, etc., semi-cured resin, and used as a fiber-reinforced sheet adhesive. It is also possible.

Further, the resin composition of the present invention can be used as a varnish as it is. Specifically, on one or both sides of the film, a varnish in which the resin composition of the present invention is dissolved is applied and dried, and copper foil, aluminum foil, metal foil such as 42 alloy foil or another film, a printed circuit board, etc. Adhesion may be performed by applying heat and pressure. The type of the film in this case is not particularly limited, and examples thereof include a polyimide film and a polyethylene film. The bonding condition in this case may be any bonding condition that is necessary and sufficient for bonding and curing, and specifically, a heating temperature of 150 ° C. to 250 ° C.
It is preferable to heat and press at a temperature of about 0.1 to 10 MPa and a heating time of about 5 to 20 minutes.

The resin composition according to the present invention obtained as described above has characteristics that can be suitably used for electronic devices, particularly flexible printed circuit boards, TAB tapes, composite lead frames, laminated materials, and the like. That is, specifically, the water absorption after reaction curing shows an excellent low water absorption of 1.5% or less, preferably 1.3% or less, particularly preferably 1.0% or less. It is excellent in heat resistance, heat resistance and adhesiveness, and can be bonded at a temperature of about 250 ° C. or less when used as an adhesive.

[0050]

EXAMPLES Hereinafter, the present invention will be described in detail with reference to Examples, but these Examples illustrate the present invention.
It is not meant to be limiting. Those skilled in the art can make various changes, modifications, and alterations without departing from the scope of the present invention.

Example 1 In a glass flask having a capacity of 500 ml, 280 g of dimethylformamide (hereinafter referred to as DMF) and 3,3'-bis (aminophenoxyphenyl) propane (meta type: hereinafter referred to as BAPP-M). 0.1338 mol and α, ω-bis (3-aminopropyl) polydimethylsiloxane (APPS).
01487 mol was charged and dissolved under a nitrogen atmosphere.
Further, 2,2-bis (4-hydroxyphenyl) propanedibenzoate-3,3 ′, 4, while cooling the solution with ice water and replacing the atmosphere in the flask with nitrogen.
0.1487 mol of 4'-tetracarboxylic dianhydride (hereinafter referred to as ESDA) was gradually added while paying attention to the viscosity. When the viscosity reaches 1000poise, ES
The addition of DA was stopped to obtain a polyamic acid polymer solution.

To this polyamic acid solution were added 150 g of DMF,
After adding 35 g of β-picoline and 60 g of acetic anhydride and stirring for 1 hour, the mixture was further stirred at 100 ° C. for 1 hour and imidized. The solution was then dripped little by little into methanol stirred at high speed. The filamentous polyimide precipitated in methanol was dried at 100 ° C. for 30 minutes, pulverized with a mixer, washed with Soxhlet with methanol, and dried at 100 ° C. for 2 hours to obtain a polyimide powder.

20 g of the polyimide powder thus obtained, 5 g of Epicoat 828 (manufactured by Yuka Shell Co., Ltd.), a bisphenol A-based epoxy resin, and 2-ethyl-
0.015 g of 4-methylimidazole was dissolved and mixed in 83 g of tetrahydrofuran (hereinafter referred to as THF) to obtain a varnish. The resulting varnish was cast on a glass plate, dried at 100 ° C. for 10 minutes, peeled off from the glass plate, fixed on an iron frame, and dried at 150 ° C. for 20 minutes to obtain a sheet having a thickness of 25 μm. The obtained sheet was mixed with a polyimide film (Apical 50AH, manufactured by Kaneka Corporation)
Sandwiched by 5μm copper foil, temperature 200 ℃, pressure 3MPa
For 20 minutes to obtain a copper-clad flexible laminate.

(Example 2) The varnish obtained in Example 1 was applied on a polyimide film (Apical 50AH, manufactured by Kanegabuchi Chemical Industry Co., Ltd.), and then 100 ° C for 10 minutes and further 150 ° C.
For 20 minutes to form an adhesive layer having a thickness of 25 μm. Single-sided polyimide film with adhesive layer obtained and 2
The 5 μm copper foil was heated at a temperature of 200 ° C. and a pressure of 3 MPa for 20 minutes to obtain a copper-clad flexible laminate.

Example 3 20 g of the polyimide powder obtained in Example 1 and TE of glycidylamine type epoxy resin
5 g of TRAD-C (manufactured by Mitsubishi Gas Chemical Company) to 83 g of TH
F to give a varnish. The resulting varnish was cast on a glass plate, dried at 100 ° C. for 10 minutes, peeled off from the glass plate, fixed on an iron frame, and dried at 150 ° C. for 20 minutes to obtain a sheet having a thickness of 25 μm. The obtained sheet was sandwiched between a polyimide film (Apical 50AH, manufactured by Kanegabuchi Chemical Industry Co., Ltd.) and a copper foil of 25 μm, and heated and pressed at a temperature of 200 ° C. and a pressure of 3 MPa for 20 minutes to obtain a copper-clad flexible laminate.

Comparative Example 1 280 g of dimethylformamide (DMF) was added to a glass flask having a capacity of 500 ml.
0.1487 mol of APP-M was charged and dissolved under stirring in a nitrogen atmosphere. Further, the solution was stirred with cooling with ice water and the atmosphere in the flask was replaced with nitrogen, and 0.1487 mol of benzophenonetetracarboxylic dianhydride (hereinafter referred to as BTDA) was gradually added while paying attention to the viscosity. BT when viscosity reaches 1000poise
The addition of DA was stopped to obtain a polyamic acid polymer solution.

To this polyamic acid solution were added 150 g of DMF,
After adding 35 g of β-picoline and 60 g of acetic anhydride and stirring for 1 hour, the mixture was further stirred at 100 ° C. for 1 hour and imidized. The solution was then dripped little by little into methanol stirred at high speed. The filamentous polyimide precipitated in methanol was dried at 100 ° C. for 30 minutes, pulverized with a mixer, washed with Soxhlet with methanol, and dried at 100 ° C. for 2 hours to obtain a polyimide powder.

20 g of the polyimide powder thus obtained, 5 g of Epicoat 828 (manufactured by Yuka Shell),
0.015 g of 2-ethyl-4-methylimidazole is added to 8
The varnish was obtained by dissolving in 3 g of THF. The obtained varnish was cast on a glass plate, dried at 100 ° C. for 10 minutes, peeled off from the glass plate, fixed to an iron frame, and further fixed at 150 ° C. for 2 minutes.
After drying for 0 minutes, a sheet having a thickness of 25 μm was obtained. The obtained sheet was sandwiched between a polyimide film (Apical 50AH, manufactured by Kanegabuchi Chemical Industry Co., Ltd.) and a copper foil of 25 μm, and a temperature of 200 μm.
Heating and pressurizing was performed at a temperature of 3 ° C. and a pressure of 3 MPa for 20 minutes to obtain a copper-clad flexible laminate.

Comparative Example 2 A glass flask having a capacity of 500 ml was charged with 0.1487 mol of 3,3′-bis (aminophenoxyphenyl) propane (hereinafter, referred to as BAPP-M) in 280 g of dimethylformamide (DMF) under a nitrogen atmosphere. Dissolve with stirring. Further, while cooling the solution with ice water and stirring while replacing the atmosphere in the flask with nitrogen, 2,2-bis (4-hydroxyphenyl) propanedibenzoate-3,3 ', 4,4'-tetracarboxylic acid Anhydride (hereinafter referred to as ESDA)
1487 mol was gradually added while paying attention to the viscosity.
When the viscosity reached 1000 poise, the addition of ESDA was stopped to obtain a polyamic acid polymer solution.

To this polyamic acid solution were added 150 g of DMF,
After adding 35 g of β-picoline and 60 g of acetic anhydride and stirring for 1 hour, the mixture was further stirred at 100 ° C. for 1 hour and imidized. The solution was then dripped little by little into methanol stirred at high speed. The filamentous polyimide precipitated in methanol was dried at 100 ° C. for 30 minutes, pulverized with a mixer, washed with Soxhlet with methanol, and dried at 100 ° C. for 2 hours to obtain a polyimide powder.

20 g of the polyimide powder obtained above was added to THF
When an attempt was made to dissolve it in 83 g, it was precipitated and could not be dissolved.

Comparative Example 3 20 g of the polyimide powder obtained in Example 1 was dissolved in 83 g of THF to obtain a varnish. The resulting varnish was cast on a glass plate, dried at 100 ° C. for 10 minutes, peeled off from the glass plate, fixed on an iron frame, and dried at 150 ° C. for 20 minutes to obtain a sheet having a thickness of 25 μm. The obtained sheet is placed on a polyimide film (Apical 5).
0AH, manufactured by Kanegabuchi Chemical Industry Co., Ltd.) and a copper foil of 25 μm, and heated and pressed at a temperature of 200 ° C. and a pressure of 3 MPa for 20 minutes.
A copper-clad flexible laminate was obtained.

(Comparative Example 4) Platabond M1276
A varnish was obtained by dissolving 10 g of (copolymer nylon, manufactured by Nippon Rilsan), 20 g of Epicoat 828 (manufactured by Yuka Shell) and 1 g of diaminodiphenylsulfone in 83 g of DMF. The obtained varnish is cast on a glass plate,
After drying at 100 ° C. for 10 minutes, it was peeled off from the glass plate, fixed on an iron frame, and further dried at 150 ° C. for 20 minutes to obtain a thickness of 25 μm.
m sheets were obtained. The obtained sheet was coated with a polyimide film (Apical 50AH, manufactured by Kaneka Corporation) and 25 μm thick.
At a temperature of 200 ° C and a pressure of 3MPa.
After heating and pressurizing for a minute, a copper-clad flexible laminate was obtained.

The peel strength and solder heat resistance of the flexible copper-clad laminates obtained in the above Examples and Comparative Examples were evaluated. The water absorption of each adhesive sheet was also evaluated. Table 1 shows the results.

[0065]

[Table 1]

The peeling strength was measured according to JISC 64
81. Regarding the solder heat resistance, the external appearance evaluation when immersed in a 260 ° C. solder bath for 10 seconds was evaluated as good when there was no blister.

The water absorption was calculated by measurement based on ASTM D570. A composition sheet was obtained by heating a film-shaped composition, for example, a sheet of the composition having a thickness of 25 μm as described in Example 1 at 150 ° C. for 3 hours. Such a cured sheet is further subjected to 150
The weight of the product dried at 30 ° C. for 30 minutes is defined as W _1, and the weight of the product after immersion in distilled water for 24 hours and wiping the surface is W 1
_2, and calculated by the following equation.

Water absorption (%) = (W ₂ −W ₁ ) ÷ W ₁ × 100

[0069]

The resin composition of the present invention can be bonded at a temperature of about 200 ° C. when used as an adhesive. In other words, unlike conventional heat-resistant adhesives, bonding does not require high temperatures,
Shows high adhesion to polyimide film and maintains high adhesion up to high temperatures. Further, since it is dissolved in a solvent having a low boiling point, it is excellent in handleability as an adhesive. For example, when the resin composition of the present invention is processed into a sheet, the solvent can be removed at a low temperature, so that a reaction of an epoxy resin that can occur at a high temperature can be suppressed, and a decrease in adhesiveness can be prevented. Furthermore, since it has a low water absorption, it has solder heat resistance that does not cause swelling when immersed in a solder bath.

Continued on the front page F term (reference) 4J002 CD022 CD042 CD052 CD062 CD072 CD122 CD132 CD202 CM041 CP052 GQ05 4J040 EC001 EC002 EH031 EH032 LA07 LA08 NA19 NA20

Claims (3)

[Claims] 1. A compound of the general formula (1) (Wherein X represents a divalent group containing an aromatic ring): an ester dianhydride represented by the following general formula (2): (Wherein, Y is, -C (= O) -, - SO 2 -, - O-,
_{-S -, - (CH 2)} m -, - NHCO -, - C (CH
_{3) 2 -, - C (} CF 3) 2 -, - C (= O) O-, or a bond, m and n are 1 to 10 integer. And a diamine represented by the general formula (3): (Wherein, R ₁ and R ₂ are a divalent aliphatic group having 1 to 4 carbon atoms or a divalent aromatic group, and R ₃ , R ₄ ,
R ₅ and R ₆ are a monovalent aliphatic group having 1 to 4 carbon atoms or a monovalent aromatic group, and n is an integer of 1 or more and 10 or less. A resin composition comprising a polyimide resin obtained by reacting the siloxane diamine represented by the formula (1) and an epoxy resin. 2. The resin composition according to claim 1, wherein the siloxane diamine accounts for 1 to 30 mol% of the total diamine. 3. The resin composition according to claim 1, wherein the water absorption after the reaction curing is 1.5% or less.