JP5103928B2 - Adhesive composition and adhesive film using the same - Google Patents

Description

  The present invention relates to an adhesive composition and an adhesive film using the same.

  In recent years, with the rapid progress of miniaturization and weight reduction of various electronic devices, the mounting density of electronic components has increased, and the characteristics required for various electronic components and materials used therefor have also diversified. In particular, a printed wiring board has a small wiring occupation area and a high wiring density, and demands for multilayer wiring boards (build-up wiring boards), flexible wiring boards (FPC), and the like are increasing. These printed wiring boards are manufactured using various adhesives or adhesive films. Resins used as adhesives mainly include epoxy resins and acrylic resins. However, all of these resins are insufficient to satisfy characteristics such as heat resistance, moisture resistance and electrical insulation.

  On the other hand, an adhesive using a polyimide resin as a constituent material, which is intended to provide an adhesive having excellent heat resistance, moisture resistance, and electrical insulation, is known. However, this adhesive is presently used in a limited manner for wiring boards having high added value due to the high cost of the adhesive composition. Therefore, recently, an adhesive having a polyamide-imide resin as a constituent material is known as an adhesive having a good balance between characteristics such as heat resistance, moisture resistance and electrical insulation and low cost.

On the other hand, imparting flame retardancy is essential for adhesives for various printed wiring boards, but halogen-based compounds such as bromine-containing compounds and antimony compounds having an excellent flame-retardant effect have been used as flame retardants. However, recent research has revealed that halogen-based flame retardants generate gases containing dioxins and the like that are toxic to the human body during combustion, and their use is being restricted mainly in European countries. Therefore, there is an increasing demand for so-called non-halo flame retardants that do not contain halogen atoms. As non-halogen flame retardants, inorganic fillers such as aluminum hydroxide and magnesium hydroxide, phosphorus-containing compounds and the like are known. (See Patent Document 1)
JP 2003-238806 A

  However, although conventional adhesives using polyamide-imide resin have sufficient adhesiveness and heat resistance in normal conditions, sufficient adhesiveness and heat resistance can be obtained after leaving in a high temperature or high temperature and high humidity environment. I couldn't.

  Furthermore, when a polyamide-imide resin and a conventionally known non-halo flame retardant are combined, it is necessary to add a large amount of the flame retardant to the adhesive composition in order to obtain sufficient flame retardancy. The properties inherent to the resin may be significantly impaired due to the flame retardant. For example, when aluminum hydroxide is used as a flame retardant for an FPC adhesive having a polyimide film or the like as a substrate, the adhesive strength with the substrate is lowered after being subjected to a high temperature and high humidity treatment for a long time. Magnesium hydroxide also reduces the acid resistance of the adhesive. Moreover, since the phosphoric ester compound which is a phosphorus flame retardant acts as a plasticizer for the adhesive composition, it is necessary to limit the type and amount of use as much as possible in order to prevent deterioration of heat resistance, insulation and the like. Yes, it was difficult to maintain a balance between these properties and flame retardancy when used alone.

  The present invention has been made in view of the above circumstances, has a sufficiently excellent adhesiveness and heat resistance in a normal state, has sufficient flame retardancy, and is left in a high temperature or high temperature and high humidity environment. An object of the present invention is to provide an adhesive composition capable of maintaining sufficiently excellent adhesion and heat resistance even afterward.

  The adhesive composition of the present invention is represented by a diimide dicarboxylic acid represented by the following general formula (1a) or (1b), a diimide dicarboxylic acid represented by the following general formula (1c), and the following general formula (1d). A modified polyamideimide resin obtained by reacting a diimidedicarboxylic acid mixture containing diimidedicarboxylic acid with an aromatic diisocyanate, a thermosetting resin, and an organic phosphorus compound.

In formula (1a), Z ¹ represents a divalent organic group having an aromatic ring, in formula (1b), Z ² represents a divalent aliphatic group, and in formula (1c), Z ³ represents an alicyclic ring. A divalent organic group having a structure is shown, and in formula (1d), Z ⁴ represents a divalent organic group having a siloxane bond.

  The adhesive composition of the present invention can solve the problems of the present invention by including components obtained from the compound having the above structure. By using the compound having the above structure as the diimide dicarboxylic acid, the adhesive composition containing the compound can form a microphase-separated structure after being cured or at least partially formed with a crosslinked structure. The present inventors speculate that a specific stress relaxation action in the adhesive composition is exhibited by the presence of the microphase separation structure. It is considered that due to the stress relaxation action, it is possible to have not only a normal state but also a sufficiently excellent adhesive property even after being left at high temperature or high temperature and high pressure.

  The diimide dicarboxylic acid mixture includes, for example, a diamine represented by the following general formula (4a) or (4b), a diamine represented by the following general formula (4c), and a diamine represented by the following general formula (4d). It can be obtained by reacting the mixture with cyclohexanetricarboxylic anhydride.

In formula (4a), Z ¹ represents a divalent organic group having an aromatic ring, in formula (4b), Z ² represents a divalent aliphatic group, and in formula (4c), Z ³ represents an alicyclic ring. A divalent organic group having a structure is shown, and in formula (4d), Z ⁴ represents a divalent organic group having a siloxane bond.

Z ¹ in the formulas (1a) and (4a) is a divalent organic group represented by the following general formula (2a), and Z ² in the formulas (1b) and (4b) is represented by the following general formula (2b) Z ³ in the formulas (1c) and (4c) is represented by the following general formula (21), (22), (23), (24), (25) or (26 ) is a divalent organic group represented by, Z ⁴ in the formula (1d) and (4d) is a divalent organic group represented by the following general formula (2d), an aromatic diisocyanate represented by the following general A compound represented by the formula (3a), (3b), (3c), (3d) or (3e) is preferable.

In the formula (2a), X ¹ is a divalent compound represented by the following general formula (11), (12), (13), (14), (15), (16), (17) or (18). In the formula (2b), n ₁ represents an integer of ₁ to 70, and in the formula (23), X ³ represents an aliphatic hydrocarbon group having 1 to 3 carbon atoms or a halogen having 1 to 3 carbon atoms. Represents a halogenated aliphatic hydrocarbon group, a sulfonyl group, an oxy group, a carbonyl group or a single bond, and R ⁷ , R ⁸ and R ⁹ each independently represent a hydrogen atom, a hydroxyl group, a methoxy group, a methyl group or a halogenated methyl group. In the formula (24), X ⁴ represents an aliphatic hydrocarbon group having 1 to 3 carbon atoms, a halogenated aliphatic hydrocarbon group having 1 to 3 carbon atoms, a sulfonyl group, an oxy group, or a carbonyl group. ) in, X ⁵ is an aliphatic hydrocarbon group having 1 to 3 carbon atoms, halogenated aliphatic hydrocarbons having 1 to 3 carbon atoms , A sulfonyl group, an oxy group, a carbonyl group or a single bond, wherein (2d), ^{R 1} and ^{R 2} each independently represent a divalent organic ^{group, R 3, R 4, R} 5 and ^{R 6} Each independently represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 18 carbon atoms, and n ₂ represents an integer of 1 to 50.

  The amine equivalent of the diamine represented by the general formula (4c) is 50 to 200 g / mol, the amine equivalent of the diamine represented by the general formula (4d) is 200 to 2500 g / mol, and is represented by the general formula (4b). It is preferable that the amine equivalent of the diamine made is 200 to 2500 g / mol.

  The adhesive composition preferably contains 5 to 100 parts by mass of the thermosetting resin and 1 to 50 parts by mass of the organic phosphorus compound with respect to 100 parts by mass of the modified polyamideimide resin.

  The thermosetting resin preferably contains an epoxy resin and a curing agent.

  The organic phosphorus compound of the present invention is preferably a phosphate compound represented by the following general formula (5a) or (5b).

In formula (5a), n ₃ represents an integer of 10 to 50, and in formula (5b), W represents a single bond, an alkylene group having 1 to 5 carbon atoms, a thio group, a sulfonyl group, an oxy group or an azo group. , N ₄ represents an integer of 10 to 50.

  The adhesive composition of the present invention preferably has a storage elastic modulus in the temperature range of 25 ° C. to 250 ° C. of 2000 MPa or less, a thermal expansion coefficient of 2000 ppm or less, and a glass transition temperature of 100 to 230 ° C.

  The adhesive film of this invention is equipped with a support body and the contact bonding layer which consists of an adhesive composition formed on the support body.

  According to the present invention, there is provided an adhesive composition having sufficiently excellent adhesiveness and heat resistance in a normal state and sufficiently excellent adhesiveness and heat resistance even after being left in a high temperature or high temperature and high humidity environment. Is done.

  Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. In the description of the drawings, the same elements are denoted by the same reference numerals, and redundant description is omitted. For the convenience of illustration, the dimensional ratios in the drawings do not necessarily match those described.

  The adhesive composition of the present invention is represented by a diimide dicarboxylic acid represented by the following general formula (1a) or (1b), a diimide dicarboxylic acid represented by the following general formula (1c), and the following general formula (1d). A modified polyamideimide resin obtained by reacting an aromatic diisocyanate with a diimidedicarboxylic acid mixture containing diimidedicarboxylic acid, a thermosetting resin, and an organic phosphorus compound.

In formula (1a), Z ¹ represents a divalent organic group having an aromatic ring, in formula (1b), Z ² represents a divalent aliphatic group, and in formula (1c), Z ³ represents an alicyclic ring. A divalent organic group having a structure is shown, and in formula (1d), Z ⁴ represents a divalent organic group having a siloxane bond.

  Each of the diimidedicarboxylic acids represented by the general formulas (1a) to (1d) has an alicyclic structure, and each has an aromatic ring, an aliphatic group, an alicyclic structure, or a siloxane bond. . Accordingly, the polyamideimide resin skeleton has a certain combination of an aliphatic unit, an alicyclic unit, or a siloxane unit that is a soft segment and an aromatic unit that is a hard segment derived from an aromatic diisocyanate. Thereby, the adhesive composition containing the polyamide-imide resin can form a microphase separation structure after being cured or at least partially formed with a crosslinked structure, and due to the presence of the microphase separation structure. The present inventors speculate that a specific stress relaxation action is exhibited in the adhesive composition. By this stress relaxation action, it is considered that excellent adhesiveness can be obtained even after standing for a long time in a normal state and in a high temperature or high temperature and high humidity environment.

The diimide dicarboxylic acid mixture is, for example, a diamine mixture containing a diamine represented by the following general formula (4a) or (4b), a diamine represented by the following general formula (4c), and a diamine represented by the following general formula (4d). And cyclohexanetricarboxylic acid anhydride. Note ^Z 1 to Z ⁴ in (1a) ~ (1d) is derived from ^Z 1 to Z ⁴ in (4a) ~ (4d).

In formula (4a), Z ¹ represents a divalent organic group having an aromatic ring, in formula (4b), Z ² represents a divalent aliphatic group, and in formula (4c), Z ³ represents an alicyclic ring. A divalent organic group having a structure is shown, and in formula (4d), Z ⁴ represents a divalent organic group having a siloxane bond.

Z ¹ in the general formulas (1a) and (4a) is a divalent organic group represented by the following general formula (2a), and Z ² in the general formulas (1b) and (4b) is It is a divalent organic group represented by the formula (2b), and Z ³ in the general formulas (1c) and (4c) is represented by the following general formulas (21), (22), (23), (24), (25) or (26) is a divalent organic group, and Z ⁴ in the general formulas (1d) and (4d) is a divalent organic group represented by the following general formula (2d). Preferably there is.

In the formula (2a), X ¹ is a divalent compound represented by the following general formula (11), (12), (13), (14), (15), (16), (17) or (18). In the formula (2b), n ₁ represents an integer of ₁ to 70, and in the formula (23), X ³ represents an aliphatic hydrocarbon group having 1 to 3 carbon atoms or a halogen having 1 to 3 carbon atoms. An aliphatic hydrocarbon group, a sulfonyl group, an oxy group, a carbonyl group or a single bond, and R ⁷ , R ⁸ and R ⁹ each independently represent a hydrogen atom, a hydroxyl group, a methoxy group, a methyl group or a halogenated methyl group. In the formula (24), X ⁴ represents an aliphatic hydrocarbon group having 1 to 3 carbon atoms, a halogenated aliphatic hydrocarbon group having 1 to 3 carbon atoms, a sulfonyl group, an oxy group, or a carbonyl group. ) in, X ⁵ is an aliphatic hydrocarbon group having 1 to 3 carbon atoms, a halogenated aliphatic hydrocarbon having 1 to 3 carbon atoms Group, a sulfonyl group, an oxy group, a carbonyl group or a single bond, wherein (2d), ^{R 1} and ^{R 2} each independently represents a divalent organic ^{group, R 3, R 4, R} 5 and ^{R 6} Each independently represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 18 carbon atoms, and n ₂ represents an integer of 1 to 50.

  Specific examples of the diamine represented by the general formula (4a) include 2,2-bis [4- (4-aminophenoxy) phenyl] propane (hereinafter abbreviated as “BAPP”), bis [4- ( 3-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, bis [4- (4-aminophenoxy) phenyl] methane, 4,4′-bis ( 4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] ketone, 1,3-bis (4-aminophenoxy) benzene, 1, 4-bis (4-aminophenoxy) benzene and the like can be mentioned. These may be used alone or in combination of two or more. Among these, BAPP is particularly preferable from the viewpoint of maintaining the property balance of the modified polyamideimide resin and from the viewpoint of cost reduction.

Z ² in the general formulas (1b) and (4b) may be a polyoxyalkylene group such as a polyoxypropylene group or a polyoxyethylene group, or an alkylene group such as a propylene group or a hexamethylene group. Among them, the polyoxypropylene group represented by the general formula (2b) is particularly preferable from the viewpoint of improving the adhesiveness and toughness of the adhesive composition.

  Specific examples of the diamine represented by the general formula (4b) include polyoxyalkylene diamines such as polyoxypropylene diamine and polyoxyethylene diamine, and alkylene diamines such as propylene diamine and hexamethylene diamine. These may be used alone or in combination of two or more.

  From the viewpoint of easily forming a microphase separation structure, the amine equivalent of the diamine represented by the general formula (4b) is preferably 200 to 2500 g / mol, and more preferably 400 to 2000 g / mol. , 1000 to 2000 g / mol is particularly preferable. The amine equivalent in this embodiment is an equivalent per 1 mol of amino groups, and is a value obtained by dividing the molecular weight by the number of amino groups.

  Commercially available diamines represented by the general formula (4b) can be obtained. Examples of commercially available products include Jeffamine D-230 (trade name, manufactured by Sun Techno Chemical Co., Ltd., amine equivalent 115), Jeffamine D-400 (trade name, manufactured by Sun Techno Chemical Co., Ltd., amine) Equivalent 200), Jeffamine D-2000 (trade name, manufactured by Sun Techno Chemical Co., Ltd., amine equivalent 1000), Jeffamine D-4000 (trade name, manufactured by Sun Techno Chemical Co., Ltd., amine equivalent 2000). . These may be used alone or in combination of two or more.

Z ³ in the above (4c) preferably has an alicyclic structure (preferably a cyclohexane ring), and the above general formula (21), (22), (23), (24), (25) or (26) It is more preferable to have a divalent organic group represented by:

  Specific examples of the diamine represented by the general formula (4c) include 2,2-bis [4- (4-aminocyclohexyloxy) cyclohexyl] propane, bis [4- (3-aminocyclohexyloxy) cyclohexyl] sulfone. Bis [4- (4-aminocyclohexyloxy) cyclohexyl] sulfone, 2,2-bis [4- (4-aminocyclohexyloxy) cyclohexyl] hexafluoropropane, bis [4- (4-aminocyclohexyloxy) cyclohexyl] Methane, 4,4′-bis (4-aminocyclohexyloxy) dicyclohexyl, bis [4- (4-aminocyclohexyloxy) cyclohexyl] ether, bis [4- (4-aminocyclohexyloxy) cyclohexyl] ketone, 1,3 -Bis (4-aminocyclo Xyloxy) benzene, 1,4-bis (4-aminocyclohexyloxy) benzene, 2,2′-dimethylbicyclohexyl-4,4′-diamine, 2,2′-bis (trifluoromethyl) dicyclohexyl-4,4 '-Diamine, 2,6,2', 6'-tetramethyldicyclohexyl-4,4'-diamine, 5,5'-dimethyl-2,2'-sulfonyl-dicyclohexyl-4,4'-diamine, 3, 3'-dihydroxydicyclohexyl-4,4'-diamine, (4,4'-diamino) dicyclohexyl ether, (4,4'-diamino) dicyclohexyl sulfone, (4,4'-diaminocyclohexyl) ketone, (3,3 '-Diamino) benzophenone, (4,4'-diamino) dicyclohexylmethane, (4,4'-diamy ) Dicyclohexyl ether, (3,3'-diamino) dicyclohexylmethane ether, 2,2-bis (4-aminocyclohexyl) propane. These may be used alone or in combination of two or more. Furthermore, other diamines can be used in combination.

  From the viewpoint of easily forming a microphase separation structure, the amine equivalent of the diamine represented by the general formula (4c) is preferably 50 to 200 g / mol. Further, (4,4'-diamino) dicyclohexylmethane is preferably used from the viewpoint of facilitating the formation of a microphase separation structure. As a commercially available product of (4,4'-diamino) dicyclohexylmethane, Wandamine HM (trade name, manufactured by Shin Nippon Rika Co., Ltd., amine equivalent 105) is available.

  The diamine represented by the general formula (4c) can be easily obtained, for example, by hydrogen reduction of an aromatic diamine. Examples of the aromatic diamine include BAPP, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, and 2,2-bis [4- (4- Aminophenoxy) phenyl] hexafluoropropane, bis [4- (4-aminophenoxy) phenyl] methane, 4,4′-bis (4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] ether Bis [4- (4-aminophenoxy) phenyl] ketone, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 2,2′-dimethylbiphenyl-4 , 4′-diamine, 2,2′-bis (trifluoromethyl) biphenyl-4,4′-diamine, 2,6,2 ′, 6 ′ Tetramethylbiphenyl-4,4′-diamine, 5,5′-dimethyl-2,2′-sulfonyl-biphenyl-4,4′-diamine, 3,3′-dihydroxybiphenyl-4,4′-diamine, ( 4,4′-diamino) diphenyl ether, (4,4′-diamino) diphenylsulfone, (4,4′-diamino) benzophenone, (3,3′-diamino) benzophenone, (4,4′-diamino) diphenylmethane or (4,4′-diamino) diphenyl ether, (3,3′-diamino) diphenyl ether are mentioned.

  Hydrogen reduction of an aromatic diamine can be performed by a conventionally known method. For example, a method using Raney nickel or platinum oxide in the presence of hydrogen (D. Varech et al., “Tetrahedron Letter”, Vol. 26, p. 61 (1985), RH Baker et al., “J. Am. Chem. Soc. 69, p. 1250 (1947), etc.), a method using rhodium-aluminum oxide (JC Sircar et al., “J. Org. Chem.”, 30, p. 3206 (1965)). , AI Meyers et al., "Organic Synthesis Collective Volume", Volume VI, p.371 (1988), A. W. Burgstahler, "Organic Synthesis Collective Volume", Volume V, p. J. Briggs, “Sy thesis ”, p. 66 (1988), etc.), a method using rhodium oxide-platinum oxide (S. Nishimura,“ Bull. Chem. Soc. Jpn. ”, 34, p. 32 (1961), E. et al. J. Corey et al., “J. Am. Chem. Soc.”, 101, p. 1608 (1979), etc.), a method using charcoal-supported rhodium (K. Chebaane et al., “Bull. Soc. Chim. Fr. ”, P. 244 (1975), etc.) and a method using sodium borohydride and rhodium chloride (PG Gassman et al.,“ Organic Synthesis Collective Volume ”, Volume VI, p. 581 (1988), PG Gassman et al., “Organic Synthesis”. Ollective Volume ", VI winding, p.601 (1988), etc. See.) and the like.

Z ⁴ in the general formula (4d) is a divalent organic group represented by the general formula (2d). Examples of the divalent organic group represented by R ¹ and R ² in the formula (2d) include an alkylene group such as a methylene group, an ethylene group, and a propylene group, and an arylene group such as a phenylene group, a tolylene group, and a xylylene group. Is mentioned. Examples of the alkyl group having 1 to 20 carbon atoms in the general formula (2d) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, An octadecyl group, a nonadecyl group, an icosyl group, or these structural isomers is mentioned. Examples of the aryl group having 6 to 18 carbon atoms in the general formula (2d) include a phenyl group, a naphthyl group, an anthryl group, and a phenanthryl group, and further a halogen atom, an amino group, a nitro group, a cyano group, and a mercapto group. It may be substituted with a group, an allyl group, an alkyl group having 1 to 20 carbon atoms, or the like.

  Among the diamines represented by the general formula (4d), diamines represented by the following formula (4d ′) are preferably used.

式（４ｄ’）中、ｎ_２は１〜５０の整数を示す。

Wherein (4d '), _{n 2} is an integer of 1 to 50.

  The amine equivalent of the diamine represented by the general formula (4d) is preferably 200 to 2500 g / mol, more preferably 400 to 2500 g / mol, and still more preferably 700 to 2000 g / mol. . When the amine equivalent is in the above range, the adhesiveness and toughness of the adhesive composition can be improved, and a micro phase separation structure can be easily formed. Moreover, it is thought that non-halo flame retardance improves by forming a micro phase separation structure.

  As the diamine represented by the general formula (4d), commercially available products can be obtained. Examples of commercially available products include amino-modified silicone oils X-22-9362 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., amine equivalent 700), X-22-9415 (trade name, Shin-Etsu Chemical ( Co., Ltd., amine equivalent 1100), X-22-9405 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., amine equivalent 1900). These may be used alone or in combination of two or more.

  Examples of the aromatic diisocyanate include 4,4′-diphenylmethane diisocyanate (hereinafter abbreviated as “MDI”) represented by the following general formula (3a), and 2,4 represented by the following general formula (3b). -Tolylene diisocyanate, 2,6-tolylene diisocyanate represented by the following general formula (3c) (hereinafter, the diamine represented by the following general formula (3b) or (3c) is abbreviated as "TDI"), Examples include 2,4-tolylene dimer represented by the general formula (3d) and naphthalene-1,5-diisocyanate represented by the following general formula (3e). These may be used alone or in combination of two or more.

  Among these, MDI and TDI are preferably used in combination from the viewpoint of imparting appropriate flexibility to the adhesive composition or preventing crystallization. The mixing ratio (mass ratio) of MDI and TDI is preferably 90/10 to 10/90, more preferably 80/20 to 20/80, and 70/30 to 30/70. Further preferred. In addition to the aromatic diisocyanate, aliphatic diisocyanates such as hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and isophorone diisocyanate can be contained. From the viewpoint of improving heat resistance, the aliphatic diisocyanate is preferably contained in an amount of about 5 to 10 mol with respect to 100 mol of the aromatic diisocyanate.

  Next, a preferred production method for obtaining a modified polyamideimide resin using the above-described raw materials will be described. First, a diamine mixture containing at least one of the diamines represented by the general formulas (4a) and (4b), the diamine represented by the general formula (4c) and the diamine represented by the general formula (4d), and cyclohexane Tricarboxylic acid anhydride (hereinafter referred to as “H-TMAn”) is mixed, and an aprotic polar solvent is further added.

  At that time, the mixing ratio of the diamine mixture is preferably (4a) / (4b) / (4c) / (4d) (molar ratio) of 10 to 79/10 to 50/1 to 20/10 to 30, It is more preferable that it is 25-60 / 20-40 / 5-5 / 10 / 20-30. If the diamine is not mixed at the above mixing ratio, the microphase separation structure in the adhesive composition cannot be obtained, or the molecular weight of the polyamideimide resin is lowered, and the adhesiveness and toughness of the obtained adhesive film are lowered. Tend.

  The amount of H-TMAn is preferably 2.05-2.20 mol, more preferably 2.10-2.15 mol, per 1 mol of the diamine mixture. When the blending amount of H-TMAn is not within this range, the amine mixture or H-TMAn remains after the reaction, and the molecular weight of the resulting polyamideimide resin tends to decrease.

  The aprotic polar solvent is preferably an organic solvent that does not react with the diamine mixture and H-TMAn. Specific examples include dimethylacetamide, dimethylformamide, dimethylsulfoxide, N-methyl-2-pyrrolidone, γ-butyrolactone, sulfolane, and cyclohexanone. These may be used alone or in combination of two or more. The above reaction is often carried out under high temperature conditions, and among these, N-methyl-2-pyrrolidone having a high boiling point is preferably used.

  The amount of the aprotic polar solvent used is preferably 10 to 80 parts by mass and more preferably 50 to 80 parts by mass with respect to 100 parts by mass of the total amount of the diamine mixture and H-TMAn. If the amount used is less than 10 parts by mass, H-TMAn is not sufficiently dissolved and the production of diimide dicarboxylic acid tends to be disadvantageous. If it exceeds 80 parts by mass, the amount of solvent used is too large, which is disadvantageous in terms of cost. Tend. Moreover, it is preferable that the moisture content contained in an aprotic polar solvent is 0.5 mass% or less. If the water content exceeds 0.5% by mass, the molecular weight of the polyamideimide resin tends to decrease due to the presence of cyclohexanetricarboxylic acid obtained by hydrating H-TMAn.

  Next, the diamine mixture and H-TMAn were reacted over 0.2 to 1.5 hours while heating the reaction mixture obtained by mixing the raw materials to 50 to 90 ° C. Furthermore, an aromatic hydrocarbon azeotropic with water is added to the reaction mixture at a ratio of 0.1 to 0.5 mass ratio with respect to the aprotic polar solvent, and heated to 120 to 180 ° C. Examples of the aromatic hydrocarbon azeotropic with water include toluene and xylene. Among these, it is preferable to use toluene which has a relatively low boiling point and is not harmful.

  Thus, the diimide dicarboxylic acid mixture containing the diimide dicarboxylic acid represented by the general formulas (1a) to (1d) is obtained.

  Subsequently, an aromatic diisocyanate is added to the mixed solution containing the diimide dicarboxylic acid mixture, and the reaction is carried out for 0.5 to 3 hours while heating at 150 to 250 ° C. to form a polyamideimide resin. The modified polyamideimide resin is preferably a varnish containing an aprotic polar solvent. Aromatic dicarboxylic acids such as terephthalic acid, phthalic acid, naphthalenedicarboxylic acid, or aliphatic dicarboxylic acids such as adipic acid, sebacic acid, decanedioic acid, dodecanedioic acid, and dimer acid from the viewpoint of improving the heat resistance of the polyamideimide resin May be added. It is preferable that the usage-amount is 5-10 mol with respect to 100 mol of diimide dicarboxylic acid mixture total amount.

  In this reaction, the mixed solution after producing the diimide dicarboxylic acid mixture may be used as it is without any particular isolation operation as long as the performance of the obtained polyamideimide resin is not significantly impaired. However, when an aromatic hydrocarbon that can be azeotroped with water is used, it is preferable to remove this from the mixed solution after the diimide dicarboxylic acid mixture is produced. Aromatic hydrocarbons can be removed by heating and distilling the diimide dicarboxylic acid mixture to 150-250 ° C.

  The compounding amount of the aromatic diisocyanate is preferably 1.05-1.50 mol, more preferably 1.1-1.3 mol, per 1 mol of the diimide dicarboxylic acid mixture. When the blending amount of the aromatic diisocyanate is not within such a range, the molecular weight of the resulting polyamideimide resin tends to decrease.

  The weight average molecular weight of the modified polyamideimide resin is preferably 10,000 to 150,000, more preferably 30000 to 120,000, and still more preferably 50,000 to 100,000. The weight average molecular weight is measured by a gel permeation chromatography method and converted by a calibration curve prepared using standard polystyrene.

  The thermosetting resin is a component that contains a thermosetting monomer and is cured by heating or the like. The thermosetting monomer preferably has a functional group capable of reacting with the amide group in the modified polyamideimide resin skeleton by heating or the like. Specific examples include an epoxy resin, a phenol resin, a cresol novolac resin, and a bismaleimide triazine resin. Among these, an epoxy resin or the like is more preferable from the viewpoint of adhesiveness and handleability, and an epoxy resin containing a phosphorus atom in the molecule is particularly preferable from the viewpoint of non-halo flame retardancy. These may be used alone or in combination of two or more.

  Commercially available epoxy resins containing phosphorus atoms can be obtained. Examples of commercially available products include ZX-1548-1 (trade name, manufactured by Toto Kasei Co., Ltd., phosphorus content: 2.0% by mass), ZX-15548-2 (trade name, Toto Kasei ( Co., Ltd., phosphorus content: 2.5 mass%), ZX-1548-3 (trade name, manufactured by Toto Kasei Co., Ltd., phosphorus content: 3.0 mass%), ZX-1548-4 ( Trade name, manufactured by Tohto Kasei Co., Ltd., phosphorus content: 4.0% by mass). These may be used alone or in combination of two or more.

  The blending amount of the thermosetting monomer is preferably 5 to 100 parts by weight, more preferably 10 to 80 parts by weight, and more preferably 20 to 65 parts by weight with respect to 100 parts by weight of the modified polyamideimide resin. Is particularly preferred. If the blending amount is less than 5 parts by mass, the flame retardancy becomes insufficient and the curing function tends to be lowered, and if it exceeds 100 parts by mass, the cross-linked structure of the resin after curing is weakened. , The adhesive strength tends to decrease.

  Moreover, the said thermosetting resin contains a hardening | curing agent, and a hardening | curing agent will not be restrict | limited especially if it reacts with an epoxy resin, or what accelerates | stimulates hardening reaction of a modified polyamide imide resin and a thermosetting monomer. Specific examples include amines and imidazoles. These may be used alone or in combination of two or more. Examples of the amines include dicyandiamide, diaminodiphenylmethane, and guanylurea. These may be used alone or in combination of two or more. Examples of the imidazoles include alkyl group-substituted imidazoles such as 2-ethyl-4-methylimidazole and benzimidazoles. These may be used alone or in combination of two or more. When an epoxy resin containing a phosphorus atom in the molecule is used as the thermosetting monomer, it is particularly preferable to use the curing agent.

  When the curing agent is an amine, the compounding amount of the curing agent is preferably such that the equivalent of amine active hydrogen (amine equivalent) and the epoxy equivalent of an epoxy resin containing a phosphorus atom are substantially equal to each other. Moreover, when a hardening | curing agent is imidazole, it is preferable that it is 0.1-2.0 mass parts with respect to 100 mass parts of epoxy resins containing a phosphorus atom. If the blending amount is less than 0.1 parts by mass, an epoxy resin containing uncured phosphorus atoms remains, and the glass transition temperature of the resin after crosslinking tends to be low, and exceeds 2.0 parts by mass. And unreacted curing agent remains, and the pot life, insulation, and the like tend to decrease.

  The organic phosphorus compound may be an organic compound containing a phosphorus atom. Specifically, the phosphate ester compound represented by the following general formula (5a) or (5b) is mentioned, for example.

In formula (5a), n ₃ represents an integer of 10 to 50, and in formula (5b), W represents a single bond, an alkylene group having 1 to 5 carbon atoms, a thio group, a sulfonyl group, an oxy group or an azo group. , N ₄ represents an integer of 10 to 50.

  The benzene ring in the general formula (5a) or (5b) may have a substituent such as an alkyl group having 1 to 5 carbon atoms. When there are two or more substituents, the two or more substituents may be the same or different. Examples of the alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, and an isopentyl group. Or a neopentyl group is mentioned.

  Examples of the compound represented by the general formula (5a) include aromatic condensed phosphate ester, trimethyl phosphate, triethyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl phenyl phosphate, cresyl di 2,6 -Xylenyl phosphate, 2-methacryloyloxyethyl acid phosphate or diphenyl-2-methacryloyloxyethyl phosphate. Examples of the compound represented by the general formula (5b) include biphenyl phosphates.

  The organophosphorus compound can also be obtained as a commercial product. As commercially available organic phosphorus compounds, CR-733S (trade name, manufactured by Daihachi Chemical Industry Co., Ltd.), CR-741 (trade name, manufactured by Daihachi Chemical Industry Co., Ltd.), CR- 747 (trade name, manufactured by Daihachi Chemical Industry Co., Ltd.), PX-200 (trade name, manufactured by Daihachi Chemical Industry Co., Ltd.) and the like, SP-703 (trade name, Shikoku) Kasei Kogyo Co., Ltd.), SP-601 (trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.), 35, 50, 65, 95, 110 (above, trade name, Ajinomoto Fine Techno ("Reophos" series) Etc.). These may be used alone or in combination of two or more.

  The compounding amount of the organic phosphorus compound is preferably 1 to 50 parts by mass and more preferably 2 to 40 parts by mass with respect to 100 parts by mass of the modified polyamideimide resin. If the blending amount is less than 1 part by mass, the flame retardancy tends to be insufficient, and if it exceeds 50 parts by mass, the adhesive solder heat resistance or the insulation reliability tends to decrease.

  The adhesive composition can be obtained by mixing these components with an organic solvent and then remixing the components, or combining these components together with the organic solvent. The adhesive composition can be suitably used as a varnish having a solid content of about 20 to 40% by mass. The organic solvent is not particularly limited as long as each component can be dissolved in the organic solvent. Specific examples include dimethylacetamide, dimethylformamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, γ-butyrolactone, sulfolane, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, toluene or acetone.

  A coupling agent, a pigment, a leveling agent, an antifoaming agent, an ion trap agent, etc. may be suitably mix | blended with an adhesive composition other than said each component as needed.

  The adhesive film will be described with reference to FIG. FIG. 1 is a cross-sectional view showing an embodiment of an adhesive film. The adhesive film 1 includes a support 3 and an adhesive layer 2.

  Examples of the support 3 include metal foils such as polyolefins such as polyethylene and polypropylene, polyesters such as polyethylene terephthalate, polycarbonates, Teflon (registered trademark) films, release papers, copper foils, and aluminum foils. These may be used alone or in combination of two or more. In addition, as for the thickness of the support body 3, 10-100 micrometers is preferable. Further, the support 3 may be subjected to mud treatment, corona treatment, and mold release treatment.

  The adhesive layer 2 is obtained by applying the varnish of the adhesive composition of the present invention on the support 3 and then removing the solvent by heating or hot air blowing. The thickness of the adhesive layer 2 is preferably 5 to 50 μm, and more preferably 10 to 40 μm.

  The organic solvent used in the varnish for producing the adhesive film 1 may be any organic solvent that can dissolve the adhesive composition. Examples thereof include ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, ethyl acetate, butyl acetate, and cellosolve. Acetic acid esters such as acetate, propylene glycol monomethyl acetate, carbitol acetate, cellosolves such as cellosolve and butylcellosolve, carbitols such as carbitol and butylcarbitol, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, Examples include dimethylacetamide and N-methyl-2-pyrrolidone. These may be used alone or in combination of two or more.

  Examples of the form of the adhesive film 1 include a sheet shape and a roll shape cut by a predetermined length. From the standpoint of storage stability, productivity, and workability, it is preferable to roll and store a laminate of a protective film on the surface of the adhesive film 1 in a roll shape. Examples of the protective film include polyolefins such as polyethylene and polypropylene, polyesters such as polyethylene terephthalate, polycarbonate, Teflon (registered trademark) film, and release paper, as in the case of the supporting substrate. In addition, as for the thickness of a protective film, it is more preferable that it is 20-100 micrometers. Further, the protective film may be subjected to mud treatment, corona treatment, and mold release treatment.

  As another embodiment of the adhesive film, the support may be a polyimide film, and the adhesive layer may be laminated on one or both sides of the polyimide film. This adhesive film can be used as a cover lay film for a flexible printed circuit board or a base film. Furthermore, a flexible printed circuit board substrate or the like can be formed by laminating a metal foil or the like so as to be in contact with the adhesive layer.

  The printed circuit board substrate is formed by laminating an insulating film, an adhesive layer, and a copper foil or other metal foil. After forming the adhesive layer on the insulating film, the metal foil may be laminated. An insulating film may be laminated after forming an adhesive layer on the substrate.

  As a method for forming a printed circuit board substrate using the adhesive composition of the present invention, for example, after directly applying the varnish of the adhesive composition on an insulating film, the solvent is dried by heating or hot air blowing. There is a method in which an adhesive layer is formed and a metal foil is laminated on the adhesive layer using a heating press or a heated roll device. An adhesive film may be used in place of the adhesive composition varnish. When using an adhesive film, when laminating an adhesive layer on an insulating layer, the adhesive film support may be removed and then laminated, or after lamination, the support may be removed.

  The present invention has been described in detail based on the embodiments. However, the present invention is not limited to the above embodiment. The present invention can be variously modified without departing from the gist thereof.

  Examples of the present invention will be specifically described below, but the present invention is not limited thereto.

(Synthesis of polyamide-imide resin)
First, a 1-liter separable flask equipped with a 25 ml moisture meter with a cock connected to a reflux condenser, a thermometer, and a stirrer was prepared. There, BAPP (2,2-bis [4- (4-aminophenoxy) phenyl] propane) as the diamine represented by the general formula (4a), and Jeffamine as the diamine represented by the general formula (4b) D-2000 (manufactured by Sun Techno Chemical Co., Ltd., trade name, amine equivalent 1000), Wandamine HM (manufactured by Shin Nippon Rika Co., Ltd., trade name, amine equivalent 105) as the diamine represented by the above general formula (4c) ), Reactive diamine oil X-22-9415 (trade name, amine equivalent 1100 manufactured by Shin-Etsu Chemical Co., Ltd.) as a diamine represented by the above general formula (4d), NMP (N -Methyl-2-pyrrolidone), cyclohexanetricarboxylic anhydride (H-TMAn) and trimellitic anhydride (TMA) acid are shown in Table 1, respectively. They were charged at the mixing ratio and the reaction mixture was stirred for 30 minutes while heating it to 80 ° C.. Then, 100 ml of toluene was added as an aromatic hydrocarbon azeotropic with water, and then refluxed at a temperature of about 160 ° C. for 2 hours. After confirming that approximately 3.6 ml or more of water has accumulated in the moisture meter and that no water has flowed out, remove the spilled water from the moisture meter and remove it to approximately 190 ° C. The temperature was raised and toluene was removed from the reaction mixture.

  Then, after returning the reaction mixture to room temperature (25 ° C.), MDI (4,4′-diphenylmethane diisocyanate), TDI (2,4-tolylene diisocyanate), and γ-BL (γ-butyrolactone) are used as aromatic diisocyanates. ) Was added to the reaction mixture at the mixing ratio shown in Table 1, and reacted at 180 ° C. for 2 hours. After completion of the reaction, NMP and γ-BL were added to obtain NMP / γ-BL solutions A-1 to A-5 of modified polyamideimide resin.

  To the obtained modified polyamideimide resin solutions A1 to A5, the raw materials shown in Table 2 were mixed in the blending amounts shown therein, stirred for about 1 hour until the resin became uniform, and then allowed to stand at room temperature for 24 hours. And defoamed to obtain a solution of the adhesive composition. In addition, phosphorus-containing epoxy resin ZX-15548-2 (product name of Toto Kasei Co., Ltd., product name) as a thermosetting resin, phosphate ester Leophos 65 (product of Ajinomoto Fine Techno Co., Ltd.), product as an organic phosphorus compound Name), cresol novolak resin KA1160 (manufactured by Dainippon Ink & Chemicals, Inc., trade name, solid content 50%) was used as the other component.

  Samples A to C used for evaluation of the adhesive composition were prepared by the following procedure. Sample A was used for evaluation of adhesion and solder heat resistance, Sample B was used for evaluation of flame retardancy, and Sample C was used for evaluation of glass transition temperature and storage elastic modulus. The evaluation results are summarized in Table 3.

(Sample A)
The obtained adhesive composition solutions (Examples 1 to 3 and Comparative Examples 1 and 2) were applied onto a 25 μm-thick polyimide film (manufactured by Toray DuPont Co., Ltd., trade name: Kapton 100V) and dried. The adhesive layer which consists of an adhesive composition with a film thickness of 20 micrometers was formed by heating for 10 minutes at 130 degreeC with a machine, and removing a solvent. Subsequently, the 35 μm rolled copper foil (manufactured by Nikko Materials Co., Ltd., trade name: BHY-22B-T) was bonded so that the roughened surface side and the adhesive layer were in contact with each other, and the temperature was 180 ° C. / It was temporarily bonded by hot pressing at a time of 30 minutes / pressure of 3 MPa. Furthermore, it was heat-cured at 200 ° C. for 120 minutes with a drier to obtain a laminate in which polyimide film / adhesive layer / rolled copper foil was laminated in this order.

(Sample B)
The obtained adhesive composition solutions (Examples 1 to 3 and Comparative Examples 1 and 2) were applied on one side of a polyimide film (product name: Kapton 100V, manufactured by Toray DuPont Co., Ltd.) having a thickness of 25 μm, The solvent was removed by heating at 130 ° C. for 10 minutes in a dryer, thereby forming an adhesive layer made of an adhesive composition having a thickness of 20 μm. Next, an adhesive layer made of an adhesive composition having a film pressure of 20 μm was formed on the other surface of the polyimide film in the same procedure. Thereafter, the laminate was further heat-cured at 200 ° C. for 120 minutes to obtain a laminate having an adhesive layer on both sides of the polyimide film.

(Sample C)
The obtained adhesive composition solutions (Examples 1 to 3 and Comparative Examples 1 and 2) were placed on a film having a thickness of 100 μm (Teflon (registered trademark), manufactured by Nichias Co., Ltd., trade name: Naflon tape TOMBO9001). Then, the solvent was removed by heating at 130 ° C. for 10 minutes with a dryer to form an adhesive layer made of an adhesive composition having a film thickness of 40 μm. Subsequently, this was heat-cured at 200 ° C. for 120 minutes to obtain a laminate having an adhesive layer on one side of the film, and this was designated as Sample C. In the evaluation of characteristics, the Teflon (registered trademark) film was peeled off to obtain a measurement sample.

(Adhesive evaluation)
Using sample A cut into a strip of 10 × 100 mm, a peeling test in the 90 ° direction was performed under the conditions of measurement temperature: 25 ° C. and peeling speed: 10 mm / min. / M) was measured to evaluate the adhesion of Sample A. Sample A used in the evaluation is a normal state after being left to heat at 150 for 240 hours, or after being left to stand at 121 ° C., 2 atm, in a state where steam is saturated for 30 hours.

(Evaluation of solder heat resistance)
Sample A was cut into a 20 mm square. The solder heat resistance of Sample A was evaluated after standing for 8 hours in a normal state or in a state of 90% humidity at 40 ° C. As the evaluation method, the sample A after being placed in the above environment was used for 1 minute in a solder bath heated to 280 ° C. or 300 ° C., and the sample was floated with the copper foil side down. Evaluation was made from the presence or absence of abnormal appearance such as peeling. The evaluation was as follows: ○: No abnormal appearance such as blistering, peeling, etc., X: Abnormal appearance such as blistering, peeling, etc.

(Evaluation of flame retardancy)
Using sample B, the flame retardancy grade was measured in accordance with UL94 flame retardancy standards.

It is sectional drawing which shows one Embodiment of the adhesive film of this invention.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 ... Adhesive film, 2 ... Adhesive layer, 3 ... Support body.

Claims (9)

Diimide dicarboxylic acid containing diimide dicarboxylic acid represented by the following general formula (1a) or (1b), diimide dicarboxylic acid represented by the following general formula (1c), and diimide dicarboxylic acid represented by the following general formula (1d) A modified polyamideimide resin obtained by reacting the mixture with an aromatic diisocyanate;
A thermosetting resin;
An organophosphorus compound;
Containing, an adhesive composition,
An adhesive composition containing 5 to 100 parts by mass of the thermosetting resin and 1 to 50 parts by mass of the organophosphorus compound with respect to 100 parts by mass of the modified polyamideimide resin .

[In Formula (1a), Z ¹ represents a divalent organic group having an aromatic ring,
In the formula (1b), Z ² represents a divalent organic group represented by the following general formula (2b) . In the formula (2b), n ₁ represents an integer of ₁ to 70,

In the formula (1c), Z ³ represents a divalent organic group having an alicyclic structure,
In formula (1d), Z ⁴ represents a divalent organic group having a siloxane bond. ] Wherein ^{Z 1} is a divalent organic group represented by the following general formula (2a), before Symbol ^{Z 3} is the following general formula (21), (22), (23), (24), (25) or (26) is a divalent organic group, Z ⁴ is a divalent organic group represented by the following general formula (2d), and the aromatic diisocyanate is represented by the following general formula (3a), ( The adhesive composition according to claim 1, which is a compound represented by 3b), (3c), (3d) or (3e).

[In the formula (2a), X ¹ is a divalent compound represented by the following general formula (11), (12), (13), (14), (15), (16), (17) or (18) It shows an organic group,
In the formula (23), X ³ represents an aliphatic hydrocarbon group having 1 to 3 carbon atoms, a halogenated aliphatic hydrocarbon group having 1 to 3 carbon atoms, a sulfonyl group, an oxy group, a carbonyl group, or a single bond, and R ⁷ , R ⁸ and R ⁹ each independently represents a hydrogen atom, a hydroxyl group, a methoxy group, a methyl group or a halogenated methyl group;
In Formula (24), X ⁴ represents an aliphatic hydrocarbon group having 1 to 3 carbon atoms, a halogenated aliphatic hydrocarbon group having 1 to 3 carbon atoms, a sulfonyl group, an oxy group, or a carbonyl group.
In Formula (25), X ⁵ represents an aliphatic hydrocarbon group having 1 to 3 carbon atoms, a halogenated aliphatic hydrocarbon group having 1 to 3 carbon atoms, a sulfonyl group, an oxy group, a carbonyl group, or a single bond.
In formula (2d), R ¹ and R ² each independently represent a divalent organic group, and R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent an alkyl group having 1 to 20 carbon atoms or 6 carbon atoms. indicates to 18 aryl group, _{n 2} is an integer of 1 to 50. ]

The diimide dicarboxylic acid mixture includes a diamine represented by the following general formula (4a) or (4b), a diamine represented by the following general formula (4c), and a diamine mixture represented by the following general formula (4d): The adhesive composition according to claim 1 or 2, which is a mixture obtained by reacting with cyclohexanetricarboxylic acid anhydride.

[In formula (4a), Z ¹ represents a divalent organic group having an aromatic ring,
In the formula (4b), Z ² represents a divalent organic group represented by the following general formula (2b) . In the formula (2b), n ₁ represents an integer of ₁ to 70,

In the formula (4c), Z ³ represents a divalent organic group having an alicyclic structure,
In formula (4d), Z ⁴ represents a divalent organic group having a siloxane bond. ] Wherein ^{Z 1} is a divalent organic group represented by the following general formula (2a), before Symbol ^{Z 3} is the following general formula (21), (22), (23), (24), (25) or The adhesive composition according to claim 3, which is a divalent organic group represented by (26), wherein the Z ⁴ is a divalent organic group represented by the following general formula (2d).

[In the formula (2a), X ¹ is a divalent compound represented by the following general formula (11), (12), (13), (14), (15), (16), (17) or (18) It shows an organic group,
In the formula (23), X ³ represents an aliphatic hydrocarbon group having 1 to 3 carbon atoms, a halogenated aliphatic hydrocarbon group having 1 to 3 carbon atoms, a sulfonyl group, an oxy group, a carbonyl group, or a single bond, and R ⁷ , R ⁸ and R ⁹ each independently represents a hydrogen atom, a hydroxyl group, a methoxy group, a methyl group or a halogenated methyl group;
In Formula (24), X ⁴ represents an aliphatic hydrocarbon group having 1 to 3 carbon atoms, a halogenated aliphatic hydrocarbon group having 1 to 3 carbon atoms, a sulfonyl group, an oxy group, or a carbonyl group.
In Formula (25), X ⁵ represents an aliphatic hydrocarbon group having 1 to 3 carbon atoms, a halogenated aliphatic hydrocarbon group having 1 to 3 carbon atoms, a sulfonyl group, an oxy group, a carbonyl group, or a single bond.
In formula (2d), R ¹ and R ² each independently represent a divalent organic group, and R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent an alkyl group having 1 to 20 carbon atoms or 6 carbon atoms. indicates to 18 aryl group, _{n 2} is an integer of 1 to 50. ]

  The amine equivalent of the diamine represented by the general formula (4c) is 50 to 200 g / mol, and the amine equivalent of the diamine represented by the general formula (4d) is 200 to 2500 g / mol. 5. The adhesive composition according to 4.   The adhesive composition according to any one of claims 3 to 5, wherein an amine equivalent of the diamine represented by the general formula (4b) is 200 to 2500 g / mol. The said thermosetting resin is an adhesive composition as described in any one of Claims 1-6 containing an epoxy resin and a hardening | curing agent. The adhesive composition according to any one of claims 1 to 7 , wherein the organic phosphorus compound is a phosphate ester compound represented by the following general formula (5a) or (5b).

Wherein (5a), _{n 3} represents an integer of 10-50,
In formula (5b), W represents a single bond, an alkylene group having 1 to 5 carbon atoms, a thio group, a sulfonyl group, an oxy group, or an azo group, and n ₄ represents an integer of 10 to 50. ] An adhesive film provided with a support body and the contact bonding layer which consists of an adhesive composition as described in any one of Claims 1-8 formed on the said support body.

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