JPH09194566A - Production of modified epoxy resin and adhesive and adhesive film using modified epoxy resin obtained by the same production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a modified epoxy resin useful as an adhesive and an adhesive film excellent in adhesion and heat resistance by reacting an acid- terminated polyamide-imide resin and/or a polyimide resin having a specific molecular structure with an epoxy resin at a specific ratio. SOLUTION: This modified epoxy resin is obtained by reacting (A) an acid- terminated polyamide-imide resin and/or a polyamide resin having either or both of (i) a polysiloxane unit and (ii) a polyalkylehe oxide unit in the molecular structure with (B) an epoxy resin at a ratio of the epoxy group/carboxylic acid group within the range of >1. Furthermore, the amount of the component (i) or (ii) is preferably 10-70wt.% in the modified epoxy resin. The modified epoxy resin adhesive is obtained by blending either or both of the resultant modified epoxy resin and an epoxy resin (curing agent) without containing either of the components (i) and (ii) as constituent components.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a modified epoxy resin, and an adhesive and an adhesive film having excellent adhesiveness and heat resistance, which uses a modified epoxy resin obtained by the method.

[0002]

2. Description of the Related Art In recent years, the area occupied by wiring in printed wiring boards has been reduced, and the demand for multilayer wiring boards and flexible wiring boards (FPC) has been increasing. Various adhesives or adhesive films are used in these manufacturing processes. Adhesives used in such electric and electronic fields are obviously required to have excellent heat resistance, chemical resistance, and workability, as well as good adhesiveness. To meet such demands,
Polyamide adhesives and polyimide adhesives have come to be used. In order to improve the properties of these adhesives, modified polyamide adhesives and polyimide adhesives have also been proposed. For example, an adhesive composed of a polyamide having an epoxy group at its end (see Japanese Patent Application Laid-Open No. 5-51447), a polyimide having a polysiloxane unit in the skeleton and an epoxy resin (Japanese Patent Application Laid-Open No. 6-200).
216) and the like. As the polyamide having an epoxy group at the terminal, a polyamide obtained by reacting an acid-terminated polyamide obtained by reacting dimer acid with isophorone diisocyanate with an epoxy resin in an approximately equivalent amount is preferable.

[0003]

However, the above-mentioned polyamide having an epoxy group at the terminal has a low glass transition point (Tg) even when combined with an epoxy resin curing agent,
The heat resistance is insufficient, and the adhesion of the copper foil to the glossy surface is not sufficient. Further, an adhesive composed of a polyimide having a polysiloxane unit in the skeleton and an epoxy resin does not have sufficient copper glossy surface, adhesiveness to polyimide, solder heat resistance and the like. The present invention is 200 ℃
Sufficient adhesive strength can be obtained even at the following low temperature pressure bonding, and an adhesive having excellent chemical resistance, solder heat resistance, and processability, a method for producing a modified epoxy resin capable of obtaining an adhesive film, and a method for producing the same can be obtained. It is an object to provide an adhesive or an adhesive film using a modified epoxy resin.

[0004]

That is, according to the present invention, an acid-terminated polyamide-imide resin and / or a polyimide resin and an epoxy resin having one or both of a polysiloxane unit and a polyalkylene oxide unit in a molecular structure are combined with an epoxy group. In the method for producing a modified epoxy resin, the reaction is carried out at a ratio of / carboxylic acid group is larger than 1. The polyalkylene oxide unit is a reaction product of a polyalkylene oxide, for example, polytetramethylene ether glycol, polypropylene glycol, polyethylene glycol, etc. and a dicarboxylic acid, and a polyamide imide or polyimide is formed from this reaction product, and further reacted with an epoxy resin. Thus, it is introduced into the modified epoxy resin. Among them, polytetramethylene ether glycol is preferable from the viewpoint of adhesiveness and water absorption resistance, and the usable polytetramethylene ether glycol has a molecular weight of 200 to 3000. Further, the polysiloxane unit is introduced into the modified epoxy resin by using the polysiloxane containing amino groups at both ends or the polysiloxane containing carboxylic acid groups at both ends when synthesizing the polyamideimide or the polyimide. The resulting modified epoxy resin is an adhesive prepared by blending one or both of an epoxy resin or an epoxy resin curing agent containing neither a polysiloxane unit nor a polyalkylene oxide unit as a constituent, and further forming a film if necessary. It is formed and used.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION A modified epoxy resin has an epoxy equivalent of 1 because of its heat resistance, coatability, flexibility, and ease of synthesis.
It is preferably in the range of 000 to 40,000. The epoxy equivalent of the target modified epoxy resin is set to 10 by selecting the type of each material used and the usage ratio (molar ratio).
It can be set in the range of 00 to 40,000. The amount of one or both of the polysiloxane unit and the polyalkylene oxide unit in the modified epoxy resin is 10% by weight to 70% by weight in the modified epoxy resin in terms of adhesiveness, solubility, heat resistance, glass transition point and the like. It is preferably set to wt%. Polysiloxane unit has a molecular weight of 400
A polydimethylsiloxane containing 0 or less amino groups at both ends or a polydimethylsiloxane containing 4,000 or less molecular weight carboxylic acid groups at both ends is preferable. Examples of commercially available polydimethylsiloxane containing amino groups at both ends include TSL9306 (trade name, the symbols following the company name in this paragraph are trade names), TSL9346, and TSL manufactured by Toshiba Silicone Co., Ltd.
9386, Shin-Etsu Silicone Co., Ltd., X-
22-161AS, X-22-161A, X-22-1
61B etc. are mentioned. Further, as the polydimethylsiloxane containing carboxylic acid groups at both ends, BY16-750, BY manufactured by Toray Dow Corning Silicone Co., Ltd.
16-750C and the like.

Polyamideimide can be synthesized by condensation reaction from dicarboxylic acid, tricarboxylic acid or tetracarboxylic dianhydride and diamine or diisocyanate.
In addition, polyimide can be synthesized from tetracarboxylic dianhydride and diamine or diisocyanate by a condensation reaction.

Examples of the polycarboxylic acid used include aliphatic dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, decanedioic acid, dodecanedioic acid and dimer acid, isophthalic acid, terephthalic acid, Aromatic dicarboxylic acids such as phthalic acid, naphthalenedicarboxylic acid, oxydibenzoic acid, trimellitic anhydride, pyromellitic dianhydride, diphenylsulfone tetracarboxylic dianhydride, diphenyl ether tetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride And aromatic carboxylic acid anhydrides such as biphenyl tetracarboxylic acid dianhydride and naphthalene tetracarboxylic acid dianhydride. These may be used alone or in combination of two or more in the polyamide-imide resin or polyimide resin 5-4.
0% by weight is used.

Examples of the diamine to be used include phenylenediamine, diaminodiphenylpropane, diaminodiphenylmethane, benzidine, 4,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfide and diaminodiphenylether. In order to improve the solubility in organic solvents, 2,2-bis (3-aminophenoxyphenyl) propane, 2,2-
Bis (4-aminophenoxyphenyl) propane, 3,
3-bis (3-aminophenoxyphenyl) sulfone,
4,4-bis (3-aminophenoxyphenyl) sulfone, 3,3-bis (4-aminophenoxyphenyl) sulfone, 4,4-bis (4-aminophenoxyphenyl) sulfone, 2,2-bis (3- Aminophenoxyphenyl) hexafluoropropane, 2,2-bis (4-
Aminophenoxyphenyl) hexafluoropropane,
1,4-bis (4-aminophenoxy) benzene, 1,
3-bis (4-aminophenoxy) benzene, 4,4-
(P-phenylenediisopropylidene) bisaniline,
It is useful to use diamines such as 4,4- (m-phenylenediisopropylidene) bisaniline.

Organic diisocyanates can be used instead of the diamines. As the organic diisocyanate,
4,4'-diphenylmethane diisocyanate, 2,4
-Tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,5-naphthalene diisocyanate,
3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, p-phenylene diisocyanate, m-
Aromatic isocyanates such as xylene diisocyanate and m-tetramethyl xylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, transcyclohexane-1,4- Aliphatic isocyanates such as diisocyanate, hydrogenated m-xylene diisocyanate, lysine diisocyanate and the like can be mentioned. Of these, aromatic isocyanates are preferable from the viewpoint of heat resistance, and 4,4′-diphenylmethane diisocyanate and tolylene diisocyanate are particularly preferable. These diamines and isocyanates may be used alone or in combination of two or more. However, diamine and diisocyanate are not preferable because they react with each other to form a urea bond having poor heat resistance. These diamines and isocyanates are (carboxylic acid group + acid anhydride group) / (amino group + isocyanate group)>
20 to 60% by weight is used in the polyamide-imide or polyimide so as to be 1.

The above-mentioned polyamide-imide or polyimide is
50 ° C. to 250 using lactones such as γ-butyrolactone, amide solvents such as N-methylpyrrolidone (NMP) and dimethylformamide (DMF), sulfones such as tetramethylene sulfone and ethers such as diethylene glycol dimethyl ether. It is synthesized by reacting at ℃.

The epoxy resin which is reacted with the polyamide-imide or polyimide having a polysiloxane unit or polyalkylene oxide unit in the structure is
Bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin,
Aromatic epoxy resins such as cresol novolac type epoxy resins and naphthalene type epoxy resins, aliphatic type epoxy resins such as neopentyl glycol diglycidyl ether, polypropylene glycol diglycidyl ether, tetrahydrophthalic acid diglycidyl ester, triglycidyl isocyanate, etc. Examples thereof include heterocyclic epoxy compounds. Among these, 2 from the viewpoint of reaction control
A functional epoxy resin is preferable, and an aromatic epoxy resin is preferable from the viewpoint of heat resistance. A brominated epoxy resin is useful for imparting flame retardancy. These are single or 2
Used in combination with more than one type. Further, these epoxy resins are reacted with 5 to 100% by weight with respect to 100% by weight of acid-terminated polyamideimide or polyimide under the condition of epoxy group / carboxylic acid group ≧ 1. If the number of epoxy groups / carboxylic acid groups is less than 1, a terminal epoxy resin cannot be obtained. On the other hand, if it is less than 5%, a resin having an epoxy terminal cannot be obtained, and if it exceeds 100% by weight, the adhesiveness is poor. The modified epoxy resin thus obtained has an epoxy equivalent of 1
It is preferably 000 to 40,000. When it is less than 1000, the molecular weight is low and the adhesiveness is poor, and when it exceeds 40,000, the molecular weight is too high and the workability is poor.

The epoxy resin containing neither the polysiloxane unit nor the polyalkylene oxide unit used in combination with the obtained modified epoxy resin is not particularly limited as long as it can be mixed with the modified epoxy resin. One or more of the epoxy resins listed above can be used in combination regardless of the number of functional groups. The compounding ratio is preferably 5 to 60% by weight of epoxy resin with respect to 95 to 40% by weight of modified epoxy resin.

The epoxy resin curing agent used in combination with the obtained modified epoxy resin is not particularly limited, and examples thereof include aliphatic polyamines, aromatic polyamines, and 2
Examples include primary or tertiary amines, organic acids, imidazoles, dicyandiamide, polymercaptans, and phenol resins. These are used in an appropriate amount depending on the type of the curing agent from the viewpoint of adhesiveness, heat resistance and other properties.

In the present invention, conventionally known curing accelerators, coupling agents, fillers, pigments and the like may be appropriately blended in addition to the above components.

The resin of the present invention comprising the above components is dissolved in a solvent and used as an adhesive. In addition, the resin solution, the surface of the peeled metal foil, polyester film,
An adhesive film can be obtained by coating a substrate such as a polyimide film or paper by a conventionally known method, then drying and peeling from the substrate. As the solvent, the solvent used in the production of the above-mentioned polyamide-imide or polyimide may be used as it is. Other solvents that can be used include various solvents such as tetrahydrofuran, dioxane, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene, ethyl acetate, butyl cellosolve, and chlorophenol.

The modified epoxy resin obtained is a glass fiber-epoxy wiring board, paper-phenol wiring board, flexible wiring board, flex-rigid wiring board, metal core wiring board, TAB (tape automated bonding).
It can be used as an adhesive, an adhesive film, a cover lay, a sealant, a coating material, a conductive paste, and a conductive film used for a substrate for mounting electric and electronic components such as. Also, it can be used as a coating material for high-density mounting parts such as BGA (ball grid array) and MCM (multi-chip module), an adhesive, a sealant, a liquid crystal-related coating material such as a liquid crystal sealant, and an adhesive. Further, it can be used as a resin for paints for metals such as iron, stainless steel, tin plate, copper or the like, or a resin for heat resistant paints. It can also be used as a matrix resin for fiber reinforced plastics having inorganic fibers such as glass fibers and carbon fibers as a reinforcing material.

[0017]

EXAMPLES The present invention will be further described with reference to Examples and Comparative Examples. The reactions described below were all carried out in an inert gas atmosphere in a flask equipped with a stirrer, a reflux condenser, an inert gas inlet and a thermometer.

Example 1 1000 g of polytetramethylene ether glycol having an average molecular weight of 1000 (hereinafter polytetramethylene ether glycol is referred to as PTG) and 405 g of sebacic acid were charged, and the temperature was raised to 200 ° C. over 2 hours, and the reaction was continued for 3 hours. After cooling, PT with acid value 81.9 and molecular weight 1370
G-terminal carboxylic acid product of G was obtained. Next, 50 g of N-methylpyrrolidone (hereinafter referred to as NMP) and 2,2-bis (4
-Aminophenoxyphenyl) propane (hereinafter BAP
P) (12.4 g, 0.030 mol) and trimellitic anhydride (11.6 g, 0.060 mol) were charged and kept at 200 ° C. for 2.5 hours. To this, 45.5 g (0.033 mol) of PTG at both ends of carboxylic acid, adipic acid of 4.
3 g (0.029 mol), sebacic acid 5.9 g (0.0
29 mol), 4.9 g (0.029 mol) of isophthalic acid, 4,4'-diphenylmethane diisocyanate (MDI) 18.9 g (0.075 mol), tolylene diisocyanate (TDI, Coronate T80 manufactured by Nippon Polyurethane Industry Co., Ltd.) 8.8 g (using (trade name))
(0.050 mol) and 100 g of γ-butyrolactone were charged, the temperature was raised to 200 ° C., the temperature was kept for 4 hours, and then cooled. The obtained polyamideimide had a heating residue of 40% (weight%, the same applies hereinafter) and an acid value (solid content) of 33.2.
In addition to this polyamide-imide, 1.2 carboxylic acid groups
56.8 g of a brominated bisphenol type epoxy resin (using a product name Platherm EP16 manufactured by Dainippon Ink and Chemicals, Inc.) was charged in a double amount, and after keeping the temperature at 150 ° C. for 3 hours, dimethylformamide (DMF) was added. Addition heating residue to 35%, epoxy equivalent (solid content conversion) 950
A modified epoxy resin of 0 was obtained.

Example 2 1000 g of PTG having an average molecular weight of 1000 was changed to 2000 g of PTG having an average molecular weight of 2000, and 405 g of sebacic acid was changed to 292 g of adipic acid. Others were the same as in Example 1, except that the acid value was 49.6 and the molecular weight was 2260. A carboxylic acid product at both ends of PTG was obtained. Next, 20 g of NMP and polydimethylsiloxane containing amino groups at both ends (using TSL9386, trade name, manufactured by Toshiba Silicone Co., Ltd.) 20.
6 g (0.024 mol), trimellitic anhydride 9.3 g
(0.048 mol) was charged and kept at 200 ° C. for 2.5 hours. 20.9 g (0.0092 mol) of both-end carboxylic acid product of PTG having the above-mentioned molecular weight of 2260, 4.4 g (0.030 mol) of adipic acid, 6.1 g of sebacic acid
(0.030 mol), 12.6 g of isophthalic acid (0.0
76 mol), 7.0 g (0.012 mol) of dimer acid,
MDI22.7g (0.091mol), TDI10.6
g (0.061 mol) and 100 g of γ-butyrolactone were charged, and the mixture was kept at 200 ° C. for 4 hours and then cooled. The obtained polyamideimide has a heating residue of 40% and an acid value (solid content).
Was 48.5. In addition to this polyamide-imide,
Epoxy resin (trade name: EPOMIK manufactured by Mitsui Petrochemical Co., Ltd.) so that the amount is 1.2 times the amount of carboxylic acid groups.
R1 was used) (19.5 g) and charged at 150 ° C for 3
After keeping the temperature for a while, DMF was added to make the heating residue 35% to obtain a modified epoxy resin having an epoxy equivalent (solid content conversion) of 9,300.

Example 3 1000 g of PTG having an average molecular weight of 1000 was converted to 950 g of polypropylene glycol (PPG) having an average molecular weight of 950.
In the same manner as in Example 1, except that 405 g of sebacic acid was changed to 332 g of isophthalic acid, an acid value of 90.
4, a carboxylic acid product having a molecular weight of 1240 at both ends of PPG was obtained. 50 g of NMP, 12.4 g (0.030 mol) of BAPP and 11.6 g (0.060 mol) of trimellitic anhydride were charged and kept at 200 ° C. for 2.5 hours. The above-mentioned PPG having a molecular weight of 1240 has carboxylic acid 4
1.0 g (0.033 mol), adipic acid 4.3 g
(0.029 mol), sebacic acid 5.9 g (0.029
Mol), isophthalic acid 4.9 g (0.029 mol), M
DI 18.9 g (0.075 mol), TDI 8.8 g
(0.050 mol) and 100 g of γ-butyrolactone were charged, the temperature was raised to 200 ° C., the temperature was kept for 4 hours and then cooled. The obtained polyamideimide had a heating residue of 40% and an acid value (solid content) of 33.2. Thereafter, in the same manner as in Example 1, modified epoxy resins having epoxy equivalents (solid content conversion) of 9,100 were obtained.

Example 4 NMP 50 g, polydimethylsiloxane containing amino groups at both ends (trade name TSL9 manufactured by Toshiba Silicone Co., Ltd.)
386) 32.7 g (0.0385 mol), 3,3 ',
27.6 g (0.77 mol) of 4,4′-diphenylsulfone tetracarboxylic acid dianhydride (DSDA) was charged,
The temperature was kept at 200 ° C. for 2.5 hours. 4,4'-oxydibenzoic acid 19.9 g (0.077 mol), sebacic acid 5.2 g (0.026 mol), MDI 16.1 g (0.
064 mol), TDI 11.2 g (0.064 mol),
100 g of γ-butyrolactone was charged and kept at 200 ° C. for 4 hours and then cooled. The obtained polyamideimide had a heating residue of 40% and an acid value (solid content) of 20.8. In addition to this polyamideimide, 8.4 g of an epoxy resin (using a trade name EPOMIK R140 manufactured by Mitsui Petrochemical Industry Co., Ltd.) so that the amount is 1.2 times the amount of carboxylic acid groups.
Was charged, and after keeping the temperature at 150 ° C for 3 hours, DMF was added to make the heating residue 35%, and the epoxy equivalent (solid content conversion) was 1010.
A modified epoxy resin of 0 was obtained.

Example 5 50 g of NMP, 32.1 g (0.0378 mol) of polydimethylsiloxane containing amino groups at both ends, DSDA36.
Charge 1 g (0.101 mol) and keep it at 80 ° C. for 30 minutes, then charge BAPP 31.0 g (0.0756 mol) and γ-butyrolactone 100 g, keep warm at 200 ° C. for 1 hour, and then trimellitic anhydride 4. 8 g (0.025 mol) was added and the mixture was kept at 200 ° C. for 2.5 hours and then cooled. The obtained polyimide has a heating residue of 40% and an acid value (solid content)
Was 19.9. In addition to this polyimide, an epoxy resin (trade name EPOMIK R140 manufactured by Mitsui Petrochemical Industry Co., Ltd.) was used so that the amount was 1.2 times the amount of carboxylic acid groups.
Was used for 3 hours and kept at 150 ° C. for 3 hours, and DMF was added to make the heating residue 35% to obtain a modified epoxy resin having an epoxy equivalent (solid content conversion) of 9000.

Comparative Example 1 NMP (50 g), BAPP (18.5 g, 0.0451 mol) and trimellitic anhydride (17.3 g, 0.0903 mol) were charged and kept at 200 ° C. for 2.5 hours. Adipic acid 10.2 g (0.0699 mol), sebacic acid 14.2 g (0.0699 mol), isophthalic acid 1
1.6 g (0.0699 mol), MDI 33.9 g
(0.0755 mol), TDI 15.7 g (0.090
2 mol) and 100 g of γ-butyrolactone were charged 20
The temperature was raised to 0 ° C., and the temperature was kept for 4 hours and then cooled. The obtained polyamide-imide has a heating residue of 40% and an acid value (solid content) of 3
It was 9.1. In addition to this polyamideimide, brominated bisphenol type epoxy resin (Prtherm EP16) 66.
After 9 g was charged and kept at 150 ° C. for 3 hours, dimethylformamide (DMF) was added to make the heating residue 35% to obtain a modified epoxy resin having an epoxy equivalent (solid content conversion) of 9800.

Comparative Example 2 NMP 50 g, polydimethylsiloxane containing amino groups at both ends 32.1 g (0.0378 mol), DSDA 40.
6 g (0.1134 mol) was charged, the mixture was kept at 80 ° C. for 30 minutes, BAPP31.0 g (0.0756 mol) and γ-butyrolactone 100 g were charged, and the mixture was heated at 200 ° C. for 4 hours and then cooled. DMF was added to adjust the heating residue to 35% to obtain a polyimide having an acid value (solid content conversion) of 5.

217 g of each of the modified epoxy resins obtained in Examples 1 to 5 and Comparative Example 1 and the polyimide obtained in Comparative Example 2 and a brominated epoxy resin (trade name BREN-S manufactured by Nippon Kayaku Co., Ltd.). ) 20 g, tetrabromobisphenol A 4 g, 2-ethyl 4-methylimidazole 1
g, a total of 242 g, to prepare an adhesive solution. This adhesive solution was uniformly applied to a 35 μm thick electrolytic copper foil glossy surface and to a polyimide film (using Kapton, trade name of DuPont) to a dry film thickness of 30 μm.
It was dried at 00 ° C. for 5 minutes. Copper foil gloss surface, gloss surface,
The film surface was laminated so that the film surface came to the surface, and the film was cured by a hot press at 170 ° C. for 30 minutes at 3.92 MPa.

Hereinafter, the T-shaped peel strength was measured, and 2
It was immersed in a solder bath at 60 ° C. for 30 seconds, and the change in the adhesion state was observed. Further, the adhesive solution was applied to a tin plate so as to have a dry film thickness of 50 μm, cured at 170 ° C. for 30 minutes, and isolated as a film by a mercury amalgam method, and then a glass transition temperature (Tg) was measured by a TMA tensile mode. Was measured. Also, 10% NaOH, 10% H
The film produced above was immersed in a Cl aqueous solution for 1 hour, and then the appearance was observed to examine the chemical resistance. These results are shown in Table 1.
Shown in

[0027]

[Table 1]

Each of the adhesive solutions containing the modified epoxy resins obtained in Examples 1 and 2 and Comparative Example 1 was applied onto a polyester film so that the dry film thickness would be 50 μm.
After drying at 10 ° C. for 10 minutes, the film was peeled off to obtain a film. These films had excellent flexibility. These films were inserted between the electrolytic copper foil shiny side and the Kapton film, respectively, and cured by hot pressing at 170 ° C. for 30 minutes at 3.92 MPa. It was immersed in a solder bath for 30 seconds at T-peel strength and 260 ° C., and the appearance of blister, peeling, etc. was observed. The results were the same as in Table 1.

[0029]

According to the present invention, a modified epoxy resin which can be suitably used for an adhesive or an adhesive film can be produced, and the resulting adhesive or adhesive film has adhesiveness, heat resistance, workability, or the like.
Excellent chemical resistance.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Hiroaki Hirakura Inventor Hiroaki Hirakura 5-1, Sunayama, Hasaki-cho, Kashima-gun, Ibaraki Hitachi Kasei Co., Ltd. Kashima factory (72) Inventor Ken Nanami Shimodate, Ibaraki Prefecture Ogawa 1500 Address Hitachi Kasei Industry Co., Ltd. Shimodate Research Institute (72) Inventor Kiyoshi Hirosawa 1500 Ogawa, Shimodate City, Ibaraki Prefecture Hitachi Chemical Co., Ltd. Shimodate Research Institute

Claims (4)

[Claims] 1. An acid-terminated polyamide-imide resin and / or a polyimide resin having one or both of a polysiloxane unit and a polyalkylene oxide unit in the molecular structure and an epoxy resin, wherein the ratio of epoxy group / carboxylic acid group is 1 or more. A method for producing a modified epoxy resin, which comprises reacting in a large area. 2. The method for producing a modified epoxy resin according to claim 1, wherein the amount of one or both of the polysiloxane unit and the polyalkylene oxide unit is 10% by weight to 70% by weight in the modified epoxy resin. 3. One or both of a modified epoxy resin obtained by the manufacturing method according to claim 1 and an epoxy resin containing neither a polysiloxane unit nor a polyalkylene oxide unit, or an epoxy resin curing agent, as a constituent component. Modified epoxy resin adhesive compounded as. 4. A modified epoxy resin adhesive film obtained by forming the adhesive according to claim 3 into a film.