JP2005179513A - Heat resistant resin composition, adhesive film using this and polyimide film with adhesive - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a heat resistant resin composition which has thermal properties necessary for various kinds of printed wiring boards and an excellent halogen-free flame retardance, an adhesive film and a polyimide film with an adhesive. <P>SOLUTION: The heat resistant resin composition comprises (A) a modified polyamideimide resin having a micro phase separation structure, (B) a thermosetting resin and (C) an organophosphoric compound. The modified polyamideimide resin having a micro phase separation structure, The modified polyamideimide resin of component (A) is obtained by reacting an aromatic diisocyanate with a diimide carboxylic acid obtained by reacting the mixture of (a) a diamine having not less than three aromatic rings or an aliphatic diamine and (b) an alicyclic diamine and a siloxane diamine with trimellitic acid anhydride. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a heat resistant resin composition, an adhesive film using the same, and a polyimide film with an adhesive. Specifically, the thermal characteristics and non-halo flame retardancy were improved while maintaining the excellent characteristics of the heat-resistant resin composition comprising a modified polyamideimide resin having a microphase-separated structure and other thermosetting resins. The present invention relates to a heat resistant resin composition, an adhesive film using the same, and a polyimide film with an adhesive.

  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. Under such circumstances, especially in the printed wiring board, the area occupied by the wiring is reduced in size and density, and demands for multilayer wiring boards (build-up wiring boards), flexible wiring boards (FPC), and the like are increasing. These wiring boards use various adhesives or adhesive films in the manufacturing process, and examples of resins that are generally used as adhesives include epoxy resins and acrylic resins. However, in the recent enhancement of functionality in printed wiring boards, all of these resins are becoming insufficient to satisfy characteristics such as heat resistance and electrical insulation.

  In contrast, the amount of polyimide resin adhesive used has increased heat resistance and electrical insulation, but the cost of the raw material monomer composition is high, and some high value-added wiring board applications It is currently used in a limited way. Then, paying attention to the polyamide-imide resin which is excellent in the balance between the characteristics including heat resistance and the cost, an adhesive having various modifications has been studied, but the heat resistance is inferior to that of the polyimide resin. Therefore, the thermal characteristics when molded into a wiring board using a polyamideimide resin, for example, the adhesion after standing at high temperature, is inferior. In addition, the heat history (during wire bonding and solder reflow process) applied during each manufacturing process of the wiring board affects the thermal resistance of the resin, so that the high elastic modulus and low thermal expansion coefficient of the wiring board at high temperatures are inferior. was there.

Furthermore, in various printed wiring board applications, it is essential to impart flame retardancy. To date, the most commonly used flame retardants are halogens such as brominated compounds having excellent flame retardancy. And antimony compounds. However, since halogen compounds generate gas containing toxic dioxins and the like during combustion according to recent research, their use is being restricted mainly in European countries, and the demand for non-halo flame retardants is increasing. Further, as such a non-halo flame retardant that does not generate a toxic gas, specifically, inorganic fillers such as aluminum hydroxide and magnesium hydroxide, phosphorus compounds, and the like are known (for example, JP 2003-27028 A). reference).
JP 2003-27028 A

  However, these compounds need to be added in a large amount to the target resin in order to obtain sufficient flame retardancy, and the properties of the original resin may be greatly reduced. Specifically, aluminum hydroxide is generally soluble sodium that is mixed during production. For example, in FPC adhesives that are adhesives for wiring boards, polyimide films that are adherends after long-term high-temperature and high-humidity treatment It is known that a hydrolysis reaction occurs on the surface, the polyimide film surface becomes brittle, and the peel strength decreases. Further, magnesium hydroxide is generally known to reduce acid resistance. In addition, well-known phosphate esters among phosphorus compounds function as plasticizers and reduce heat resistance, insulation, etc., so it is necessary to limit the type and amount used as much as possible. It was difficult to maintain the balance.

  In order to solve the above-mentioned problems, the present invention has a thermal characteristic, that is, a heat-resistant resin composition that has less heat deterioration and moisture resistance of adhesive force, and further greatly improves non-halo flame retardancy, and various types using the same. An object of the present invention is to provide an adhesive film and a polyimide film with an adhesive suitable for printed wiring board applications.

As a result of studying to solve the above problems, the inventors of the present invention have a heat-resistant resin composition containing a modified polyamideimide resin, a thermosetting resin, and a phosphorus compound, with little adhesive deterioration due to heating, and high temperature. The present inventors have found the knowledge that the thermal expansion coefficient at the time is reduced and the non-halo flame retardancy is improved, and the present invention has been achieved.
The present invention relates to each item described below.
(1) (A) A heat-resistant resin composition containing a modified polyamideimide resin having a microphase-separated structure, (B) a thermosetting resin, and (C) an organophosphorus compound. The following general formula (1) obtained by reacting a mixture of a diamine or aliphatic diamine, alicyclic diamine and siloxane diamine having 3 or more aromatic rings with trimellitic anhydride, A modified polyamideimide resin obtained by reacting the following general formula (2) or a mixture containing a diimidecarboxylic acid represented by the following general formula (3) with an aromatic diisocyanate represented by the following general formula (4): A heat-resistant resin composition characterized by being.

（但し、一般式（１）中、Ｒ_１は、一般式（５）で示され、一般式（５）のＸは、一般式（６）で示される。）

(In the general formula (1), R ₁ is represented by the general formula (5), and X in the general formula (5) is represented by the general formula (6).)

（一般式（２）中のＲ_２は、一般式（７）で示され、ｎ₁は１〜７０の整数を、Ｘ_１は炭素数１〜３の脂肪族炭化水素基、炭素数１〜３のハロゲン化脂肪族炭化水素基、スルホニル基、エーテル基、カルボニル基、単結合を、Ｒ_１、Ｒ_２、Ｒ_３は同じでも異なっていてもよく、水素原子、水酸基、メトキシ基、メチル基、ハロゲン化メチル基を、Ｙ_１は炭素数１〜３の脂肪族炭化水素基、炭素数１〜３のハロゲン化脂肪族炭化水素基、スルホニル基、エーテル基、カルボニル基を、Ｚ_１は、炭素数１〜３の脂肪族炭化水素基、炭素数１〜３のハロゲン化脂肪族炭化水素基、スルホニル基、エーテル基、カルボニル基又は単結合を示す。）

(R ₂ in the general formula (2) is represented by the general formula (7), n ₁ is an integer of ₁ to 70, X ₁ is an aliphatic hydrocarbon group having 1 to 3 carbon atoms, 3 halogenated aliphatic hydrocarbon group, sulfonyl group, ether group, carbonyl group, single bond, R ₁ , R ₂ , R ₃ may be the same or different, hydrogen atom, hydroxyl group, methoxy group, methyl group , A halogenated methyl group, Y ₁ is 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 ether group, a carbonyl group, Z ₁ is A C1-C3 aliphatic hydrocarbon group, a C1-C3 halogenated aliphatic hydrocarbon group, a sulfonyl group, an ether group, a carbonyl group, or a single bond is shown.)

（一般式（３）中のＲ_３は、一般式（８）で示され、一般式（８）中、Ｒ_４及びＲ_５は各々独立に２価の有機基を、Ｒ_６〜Ｒ_９は各々独立に炭素数１〜２０のアルキル基又は炭素数６〜１８のアリール基を示し、ｎ_２は１〜５０の整数である。）

(R ₃ in the general formula (3) is represented by the general formula (8). In the general formula (8), R ₄ and R ₅ are each independently a divalent organic group, and R _{6 to} R ₉ are each independently represents an alkyl group or an aryl group having 6 to 18 carbon atoms having 1 to 20 carbon atoms, _{n 2} is an integer of 1 to 50.)

（一般式（４）中、Ｒ_１０は、一般式（９）で示される。）
（２）（Ａ）ミクロ相分離構造を有する変性ポリアミドイミド樹脂１００重量部に対して、（Ｂ）熱硬化性樹脂５〜１００重量部及び（Ｃ）有機リン系化合物２〜１０重量部を含有する（１）に記載の耐熱性樹脂組成物。
（３）前記（Ａ）成分のミクロ相分離構造を有する変性ポリアミドイミド樹脂の脂肪族ジアミンのアミン当量が２００〜２５００ｇ／ｍｏｌ、脂環式ジアミンのアミン当量が５０〜１００ｇ／ｍｏｌである（１）又は（２）に記載された耐熱性樹脂組成物。
（４）前記（Ａ）成分のミクロ相分離構造を有する変性ポリアミドイミド樹脂のシロキサンジアミンのアミン当量が２００〜２５００ｇ／ｍｏｌである（１）〜（３）いずれかに記載耐熱性樹脂組成物。
（５）前記（Ｂ）成分の熱硬化性樹脂が、エポキシ樹脂とその硬化促進剤又は硬化剤を含む熱硬化性樹脂である（１）〜（４）いずれかに記載された耐熱性樹脂組成物。
（６）前記（Ｃ）成分の有機リン系化合物が下記一般式（１０）で示されるリン酸エステル系化合物、又は下記一般式（１１）で示されるリン酸エステル系化合物を含む有機リン系化合物である（1）〜（５）いずれかに記載された耐熱性樹脂組成物。

(In General Formula (4), R ₁₀ is represented by General Formula (9).)
(2) (A) 5-100 parts by weight of thermosetting resin and (C) 2-10 parts by weight of organophosphorus compound with respect to 100 parts by weight of modified polyamideimide resin having a microphase separation structure The heat resistant resin composition according to (1).
(3) The amine equivalent of the aliphatic diamine of the modified polyamideimide resin having a microphase separation structure of the component (A) is 200 to 2500 g / mol, and the amine equivalent of the alicyclic diamine is 50 to 100 g / mol (1 ) Or the heat resistant resin composition described in (2).
(4) The heat resistant resin composition according to any one of (1) to (3), wherein the amine equivalent of the siloxane diamine of the modified polyamideimide resin having a microphase separation structure of the component (A) is 200 to 2500 g / mol.
(5) The thermosetting resin as described in any one of (1) to (4), wherein the thermosetting resin of the component (B) is a thermosetting resin containing an epoxy resin and its curing accelerator or curing agent. Stuff.
(6) The organophosphorus compound including the phosphoric acid ester compound represented by the following general formula (10) or the phosphoric acid ester compound represented by the following general formula (11) as the organophosphorus compound of the component (C) The heat resistant resin composition described in any one of (1) to (5).

（但し、一般式（１０）中、ｎ_４は１０〜５０の整数である。）

(However, in the general formula (10), _{n 4} is an integer of 10 to 50.)

（但し、一般式（１１）中、Ｗは単結合、炭素数１〜５のアルキレン基、−Ｓ−、−ＳＯ_２−、−Ｏ−、又は−Ｎ＝Ｎ−である結合基を示し、ｎ_３は１０〜５０の整数である。）
（７）（1）〜（６）いずれかに記載された耐熱性樹脂組成物を含む接着層を有する接着フィルム。
（８）ポリイミドフィルムの片面または両面に、（1）〜（６）いずれかに記載された耐熱性樹脂組成物を含む接着層を有する接着剤付きポリイミドフィルム。

(In the general formula (11), W represents a single bond, an alkylene group having 1 to 5 carbon atoms, —S—, —SO ₂ —, —O—, or —N═N—; n ₃ is an integer of 10 to 50.)
(7) An adhesive film having an adhesive layer containing the heat-resistant resin composition described in any one of (1) to (6).
(8) A polyimide film with an adhesive having an adhesive layer containing the heat-resistant resin composition described in any one of (1) to (6) on one side or both sides of the polyimide film.

  According to the present invention, while maintaining the excellent characteristics of a heat-resistant resin composition containing a modified polyamideimide resin having a microphase-separated structure, a thermosetting resin, and an organophosphorus compound, the thermal characteristics that have been a problem, namely adhesion The heat deterioration and moisture resistance of the force and the non-halo flame retardancy can be greatly improved. The heat-resistant resin composition of the present invention, an adhesive film using the same, and a polyimide film with an adhesive have excellent thermal characteristics, non-halo flame resistance, and flammability. It can be applied to possible multilayer FPC and semiconductor mounting substrate applications, and can be an interlayer insulating material or base material useful as an adhesive or an adhesive film.

Hereinafter, the present invention will be described in detail.
The modified polyamideimide resin having a microphase separation structure of the component (A) used in the present invention is a diamine having 3 or more aromatic rings or a mixture of aliphatic diamine, alicyclic diamine and siloxane diamine and trimellitic anhydride And a mixture of diimide dicarboxylic acids represented by the general formula (1) or the general formula (2) or the general formula (3) obtained by reacting with an aromatic diisocyanate represented by the general formula (4); Is a modified polyamideimide resin obtained by reacting Therefore, when synthesizing diimide dicarboxylic acid, alicyclic diamine and siloxane diamine are essential, and at least one or both of diamine having 3 or more aromatic rings and aliphatic diamine are included in the mixture. That's fine. The modified polyamideimide resin used in the present invention has a microphase separation structure (sea-island structure of submicron to micron order), and becomes a microphase separation structure after drying or curing. Examples of such a modified polyamideimide resin include a modified polyamideimide resin comprising an aliphatic unit that is a soft segment, an alicyclic unit, and a siloxane unit and an aromatic unit that is a hard segment. By having this microphase-separated structure, the stress relaxation action is expressed specifically, and excellent adhesiveness can be obtained while maintaining high heat resistance.

  In the general formula (2), examples of the alkyl group having 1 to 20 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, and a tert-butyl group. Butyl, pentyl, isopentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl , Nonadecyl group, icosyl group, and structural isomers thereof. In the general formula (2), examples of the aryl group having 6 to 18 carbon atoms include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, and the like, and include a halogen atom, an amino group, a nitro group, a cyano group, and a mercapto group. May be substituted with a group, an allyl group, an alkyl group having 1 to 20 carbon atoms, or the like.

  Examples of the diamine having three or more aromatic rings 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. From the viewpoint of balance of properties and cost of the modified polyamideimide resin, 2,2-bis [4- (4 -Aminophenoxy) phenyl] propane is particularly preferred. These may be used alone or in combination of two or more.

  As the aliphatic diamine used in the present invention, known diamines can be used. For example, those represented by the following general formula (12) are preferable.

  Further, commercially available aliphatic diamines include Jeffamine D-230 (amine equivalent 115), Jeffamine D-400 (amine equivalent 200), Jeffamine D-2000 (amine equivalent 1,000), Jeffer Min D-4000 (amine equivalent of 2,000), trade names made by Sun Techno Chemical Co., Ltd. and the like. These may be used alone or in combination of two or more.

  Here, in order to form a microphase-separated structure that improves the properties of the modified polyamideimide resin of the component (A), in particular, improved adhesion and toughness, the aliphatic diamine of the general formula (12), that is, polyoxypropylene The amine equivalent of diamine is preferably 200 to 2500 / mol, more preferably 400 to 2000 g / mol, and particularly preferably 1000 to 2000 g / mol. Examples of these include Jeffamine D-2000 (amine equivalent 1000), Jeffamine D-4000 (amine equivalent 2000), and trade names made by San Techno Chemical Co., Ltd. These may be used alone or in combination of two or more. In addition, in this invention, an amine equivalent is a gram number of resin containing 1 mol of amino groups.

  The saturated hydrocarbon component having an alicyclic hydrocarbon group of the diimidedicarboxylic acid represented by the general formula (2) used in the present invention is a diamine compound comprising a saturated hydrocarbon having an alicyclic hydrocarbon group as a raw material. Derived from. Such a diamine can be represented by the following general formula (13) which is a part of the general formula (7).

（一般式（１３）中、Ｘ_１は炭素数１〜３の脂肪族炭化水素基、炭素数１〜３のハロゲン化脂肪族炭化水素基、スルホニル基、エーテル基、カルボニル基、単結合を、Ｒ_１、Ｒ_２、Ｒ_３は同じでも異なっていてもよく、水素原子、水酸基、メトキシ基、メチル基、ハロゲン化メチル基を、Ｙ_１は炭素数１〜３の脂肪族炭化水素基、炭素数１〜３のハロゲン化脂肪族炭化水素基、スルホニル基、エーテル基、カルボニル基を、Ｚ_１は、炭素数１〜３の脂肪族炭化水素基、炭素数１〜３のハロゲン化脂肪族炭化水素基、スルホニル基、エーテル基、カルボニル基又は単結合を示す。）

(In the general formula (13), X ₁ 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 ether group, a carbonyl group, a single bond, R ₁ , R ₂ and R ₃ may be the same or different, and each represents a hydrogen atom, a hydroxyl group, a methoxy group, a methyl group or a halogenated methyl group, Y ₁ represents an aliphatic hydrocarbon group having 1 to 3 carbon atoms, carbon A halogenated aliphatic hydrocarbon group having 1 to 3 carbon atoms, a sulfonyl group, an ether group and a carbonyl group, Z ₁ is an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and a halogenated aliphatic carbon atom having 1 to 3 carbon atoms A hydrogen group, a sulfonyl group, an ether group, a carbonyl group or a single bond is shown.)

  Examples of the diamine compound composed of a saturated hydrocarbon having an alicyclic hydrocarbon group include 2,2-bis [4- (4-aminocyclohexyloxy) cyclohexyl] propane and 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- Aminocyclohexyloxy) 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'-tetramethyl-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) dicyclohexylsulfone, (4,4′-diaminocyclohexyl) ketone, (3,3 '-Diamino) benzophenone, (4,4'-diamino) dicyclohexylmethane, (4,4'-diamino) dicyclohexyle Ter, (3,3′-diamino) dicyclohexyl ether, (4,4′-diamino) dicyclohexyl methane, (3,3′-diamino) dicyclohexyl ether, 2,2-bis (4-aminocyclohexyl) propane, etc. it can. Two or more of these diamine compounds may be used in combination, and other diamine compounds may be used in combination.

  A diamine compound composed of a saturated hydrocarbon having such an alicyclic hydrocarbon group can be easily obtained by hydrogen reduction of an aromatic diamine compound. Examples of such aromatic diamine compounds include 2,2-bis [4- (4-aminophenoxy) phenyl] propane (BAPP), bis [4- (3-aminophenoxy) phenyl] sulfone, and bis [4- ( 4-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, 2,2′-dimethylbiphenyl-4,4′-diamine, 2,2′-bis (tri Fluoromethyl) biphenyl-4,4′-diamine, 2,6,2 ′, 6′-tetramethyl-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) diphenyl sulfone, (4,4'-diamino) benzophenone (3,3′-diamino) benzophenone, (4,4′-diamino) diphenylmethane, (4,4′-diamino) diphenyl ether, (3,3′-diamino) diphenyl ether, and the like.

  Hydrogen reduction of an aromatic diamine compound can be performed by a general method for reducing an aromatic ring. For example, Raney nickel or platinum oxide (D. Varech et al., Tetrahedron Letter 26, 61 (1985), R. H. Baker et al., J. Am. Chem. Soc., 69, 1250 (1947)), rhodium-aluminum oxide (JC. Sircar et al., J. Org. Chem., 30, 3206 (1965)). I. Meyers et al., Organic Synthesis Collective Volume VI, 371 (1988), A. W. Burgstahler, Organic Synthesis Volume V, 591 (1973), AJ. nthesis, 1988, 66), rhodium oxide-platinum oxide (S. Nishimura, Bull. Chem. Soc. Jpn., 34, 32 (1961), EJ Corey et al., J. Am. Chem. Soc. 101, 1608 (1979)), a catalytic system of charcoal-supported rhodium (K. Chebaane et al., Bull. Soc. Chim. Fr., 1975, 244) and sodium borohydride-rhodium chloride system (PG Gasman et al., Organic Synthesis). Collective Volume VI, 581 (1988), PG Gassman et al., Organic Synthesis Volume VI, 601 (1988)).

  As the alicyclic diamine used in the present invention, known alicyclic diamines can be used, but for example, those represented by the following general formula (14) are preferable.

  Examples of commercially available alicyclic diamines include Wandamine HM (amine equivalent of 100) or more and trade names manufactured by Shin Nippon Chemical Co., Ltd. This is used alone. Here, in order to form a micro phase separation structure that improves the properties of the modified polyamideimide resin of the component (A), in particular, the adhesion and toughness, this alicyclic diamine, that is, 4,4'-diaminodi (cyclohexyl) It is particularly preferred to use methane. Similarly, the amine equivalent of the alicyclic diamine is preferably 50 to 100 g / mol.

  As the siloxane diamine used in the present invention, publicly known ones can be used, but for example, those represented by the following general formula (15) are preferable.

（一般式（１５）中Ｒ_１１、Ｒ_１２は各々独立に２価の有機基を示し、Ｒ_１３〜Ｒ_１６は各々独立に一般式（８）におけるＲ_６〜Ｒ_９と同意義であり、ｎは１〜５０の整数を示す。）

(In the general formula (15), R ₁₁ and R ₁₂ each independently represent a divalent organic group, and R _{13 to} R ₁₆ are each independently the same as R _{6 to} R ₉ in the general formula (8); n represents an integer of 1 to 50.)

  In the general formula (15), examples of the divalent organic group include alkylene groups such as methylene group, ethylene group and propylene group, and arylene groups such as phenylene group, tolylene group and xylylene group. Examples of such siloxane diamine include those represented by the following general formula (16).

（一般式（１６）中、ｎは１〜５０の整数を示す。）

(In general formula (16), n represents an integer of 1 to 50.)

  Commercially available amino-modified silicone oils X-22-9362 (amine equivalent 700), X-22-9415 (amine equivalent 1100), X-22-9405 (amine equivalent) which are siloxane-based both-end amines 1900) and above, trade names manufactured by Shin-Etsu Chemical Co., Ltd., and the like. These may be used alone or in combination of two or more.

  Here, the amine equivalent of siloxane diamine is used to improve the properties of the modified polyamideimide resin of component (A), in particular to impart adhesion and toughness, and to form a microphase-separated structure that improves non-halo flame retardancy. Is preferably 200 to 2,500 g / mol, more preferably 400 to 2,500 g / mol, and particularly preferably 700 to 2,000 g / mol. Examples of these include X-22-9415 (amine equivalent 1100), X-22-9405 (amine equivalent 1900) or more, trade names manufactured by Shin-Etsu Chemical Co., Ltd., and the like. These may be used alone or in combination of two or more.

  Examples of the aromatic diisocyanate represented by the general formula (4) used in the present invention include 4,4′-diphenylmethane diisocyanate (hereinafter abbreviated as MDI) and 2,4-tolylene diisocyanate (hereinafter abbreviated as TDI). 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, 2,4-tolylene dimer, and the like. These may be used alone or in combination of two or more. In particular, from the standpoint of imparting flexibility and preventing crystallinity, the combined use of MDI and TDI is particularly preferred. As the mixing weight ratio, MDI / TDI is preferably 90/10 to 10/90, and 80/20 to 20 / 80 is more preferable, and 70/30 to 30/70 is particularly preferable. From the viewpoint of heat resistance, aliphatic diisocyanates such as hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate should be used in an amount of 5 to 10 mol% with respect to the aromatic diisocyanate. Is preferred.

  From the viewpoint of heat resistance, in addition to the imide dicarboxylic acid, aromatic dicarboxylic acids such as terephthalic acid, phthalic acid, naphthalenedicarboxylic acid, adipic acid, sebacic acid, decanedioic acid, dodecanedioic acid, dimer acid, etc. The aliphatic dicarboxylic acid is also preferably used in an amount of 5 to 10 mol% with respect to the imide dicarboxylic acid.

  The modified polyamideimide resin having a microphase separation structure of the component (A) used in the present invention includes, for example, a diamine (1 ′) having three or more aromatic rings, a polyoxypropylene diamine (2 ′) which is an aliphatic diamine, and A mixture of siloxane diamine (3 ′) and trimellitic anhydride (hereinafter abbreviated as TMA) are reacted in the presence of an aprotic polar solvent at 50 to 90 ° C. for 0.2 to 1.5 hours, and water and Aromatic diimides represented by the above general formula (1) are prepared by adding azeotropic aromatic hydrocarbons in an aprotic polar solvent in an amount of 0.1 to 0.5 weight ratio and reacting at 120 to 180 ° C. A mixture containing a dicarboxylic acid, an aliphatic diimide dicarboxylic acid represented by the general formula (2) and a siloxane diimide dicarboxylic acid represented by the general formula (3) is produced, and this is mixed with the general formula (4). An aromatic diisocyanate represented can be prepared by reacting about 0.5 to 3 hours at about 150 to 250 ° C.. Examples of the aromatic hydrocarbon include toluene and xylene.

  Moreover, after manufacturing the mixture containing the diimide dicarboxylic acid similarly represented by the said General formula (1), the said General formula (2), or the said General formula (3), the solution is about 150-250 degreeC. Thus, the aromatic hydrocarbon can be removed from the solution, and the reaction can be carried out with the aromatic diisocyanate represented by the general formula (4). The modified polyamideimide resin is preferably a varnish containing an aprotic polar solvent.

  The mixture ratio of the diamine (1 ′), aliphatic diamine (2 ′), alicyclic diamine (2 ″) and siloxane diamine (3 ′) having three or more aromatic rings is (1 ′) / (2 ′) / (2 ″) / (3 ′) is preferably 10-79 / 10-50 / 1 to 20 / 10-30 molar ratio, preferably 25-60 / 20-40 / 5 A molar ratio of 10/20 to 30 is more preferable. Resins obtained outside these molar ratio ranges tend to lose adhesion and toughness due to loss of the microphase-separated structure or reduction in molecular weight.

  Furthermore, the said mixture and trimellitic anhydride (TMA) are made to react, and the mixture containing the diimide dicarboxylic acid represented by the said General formula (1), the said General formula (2), or the said General formula (3) is obtained. The amount of the raw material used is the total number of moles of diamine (1 ′), aliphatic diamine (2 ′), alicyclic diamine (2 ″) and siloxane diamine (3 ′) having three or more aromatic rings. And the molar ratio of the number of moles of TMA is ((1 ′) + (2 ′) + (2 ″) + (3 ′)) / TMA being 1 / 2.05 to 1 / 2.20 Is more preferable and 1 / 2.10 to 1 / 2.15 is more preferable. If this molar ratio is less than 1 / 2.20, TMA remains, and the molecular weight of the finally obtained resin tends to decrease. If it exceeds 1 / 2.05, diamine remains, and the resin finally obtained The molecular weight tends to decrease.

  Next, the mixture containing the diimide dicarboxylic acid represented by the general formula (1), the general formula (2), or the general formula (3) is reacted with the aromatic diisocyanate represented by the general formula (4). The molar ratio for obtaining a modified polyamideimide resin is more preferably a mixture containing diimidedicarboxylic acid / aromatic diisocyanate = 1 / 1.50 to 1 / 1.05, and 1 / 1.3-1 to /1.1 is more preferable. If this molar ratio is less than 1 / 1.50, the molecular weight of the resulting resin tends to decrease, and if it exceeds 1 / 1.05, the molecular weight of the resulting resin tends to decrease.

  The aprotic polar solvent is preferably an organic solvent that does not react with a diamine having 3 or more aromatic rings, an aliphatic diamine, an alicyclic diamine, a siloxane diamine, and TMA, such as dimethylacetamide, dimethylformamide, and the like. , Dimethyl sulfoxide, N-methyl-2-pyrrolidone, γ-butyrolactone, sulfolane, cyclohexanone, and the like. Since the imidization reaction requires high temperature, N-methyl-2-pyrrolidone having a high boiling point is more preferable. These may be used alone or in combination of two or more.

  The amount of water contained in these aprotic polar solvents is preferably 0.1 to 0.2% by weight. If this water content exceeds 0.2% by weight, the TMA is hydrated and the trimellitic acid produced does not allow the reaction to proceed sufficiently and the molecular weight of the polymer tends to decrease. Moreover, the usage-amount of the aprotic polar solvent used by this invention is 10-80 weight with respect to the total amount of the diamine which has three or more aromatic rings, aliphatic diamine, alicyclic diamine, siloxane diamine, and TMA. %, Preferably in the range of 50 to 80% by weight. If the amount used is less than 10%, the solubility of TMA tends to be lowered and there is a tendency that sufficient reaction cannot be performed, and if it exceeds 80% by weight, it tends to be disadvantageous as an industrial production method.

  The weight average molecular weight of the modified polyamideimide resin having a microphase separation structure as the component (A) is preferably 10,000 to 150,000, more preferably 30,000 to 120,000, It is especially preferable that it is 000-90,000. In addition, the weight average molecular weight in this invention is measured by the gel permeation chromatography method, and is converted with the analytical curve created using standard polystyrene.

  The thermosetting resin of component (B) used in the present invention is not limited as long as it reacts with the amide group in the modified polyamideimide resin skeleton having the microphase separation structure of component (A) by heat or the like. Resins, phenol resins, bismaleimide triazine resins and the like are preferable. 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.

  Examples of the epoxy resin include phosphorus-containing epoxy resins ZX-1548-1 (phosphorus content: 2.0% by weight), ZX-15548-2 (phosphorus content: 2.5% by weight), ZX-1548- 3 (phosphorus content: 3.0% by weight), ZX-1548-4 (phosphorus content: 4.0% by weight) or more, trade names of Toto Kasei Co., Ltd. and the like. These may be used alone or in combination of two or more.

  The blending amount of the thermosetting resin as the component (B) is preferably 5 to 100 parts by weight with respect to 100 parts by weight of the modified polyamideimide resin having a microphase separation structure as the component (A). More preferred are parts by weight, and particularly preferred is 20 to 65 parts by weight. When the blending amount of the thermosetting resin is less than 5 parts by weight, the flame retardancy becomes insufficient, and the function as a curing agent tends to decrease. When the blending amount exceeds 100 parts by weight, the crosslinked structure of the resin after curing Tends to become dense and brittle, resulting in reduced adhesion.

  The thermosetting resin of the component (B) used in the present invention may further use a curing accelerator in addition to the thermosetting resin. In particular, when an epoxy resin containing a phosphorus atom in the molecule is used, it is preferable to use a curing accelerator. The curing accelerator is not particularly limited as long as it reacts with the phosphorus-containing epoxy resin of the component (B) or accelerates the curing reaction between the component (A) and the component (B). , Amines and imidazoles can be used. 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.

  In the case of amines, the curing accelerator is preferably blended in such an amount that the active hydrogen equivalent of the amine and the epoxy equivalent of the phosphorus-containing epoxy resin are approximately equal. In the case of imidazole, the amount is preferably 0.1 to 2.0 parts by weight with respect to 100 parts by weight of the phosphorus-containing epoxy resin. If the blending amount is small, uncured phosphorus-containing epoxy resin remains, and the glass transition temperature of the crosslinked resin is lowered. If it is too large, unreacted curing accelerator remains, resulting in pot life, insulation properties, etc. There is a tendency to decrease.

  Examples of the organophosphorus compound of component (C) used in the present invention include a biphenyl phosphate represented by the general formula (11), an aromatic condensed phosphate represented by the general formula (10), Trimethyl phosphate, triethyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl phenyl phosphate, cresyl di-2,6-xylenyl phosphate, 2-methacryloyloxyethyl acid phosphate, diphenyl-2-methacryloyl Oxyethyl phosphate, CR-733S, CR-741, CR-747, PX-200 or higher, Daihachi Chemical Industries, Ltd. trade name, aromatic condensed phosphate ester, SP-703, SP-601 or higher, Shikoku Kasei Kogyo Product name Foz "series 35,50,65,95,110 or more, include Ajinomoto Fine-Techno Co., Ltd. trade name. These may be used alone or in combination of two or more.

  In the general formula (10) or the general formula (11), the benzene ring in the compound may have a substituent such as an alkyl group having 1 to 5 carbon atoms. When two or more substituents are used, the two or more substituents may be the same or different. Examples of the alkyl group having 1 to 5 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, and isopentyl. Group, neopentyl group and the like.

  The amount of the organophosphorus compound of component (C) is preferably 2 to 10 parts by weight with respect to 100 parts by weight of the modified polyamideimide resin having a microphase separation structure of component (A), and 2 to 5 parts. More preferred are parts by weight. When the blending amount is less than 2 parts by weight, the flame retardancy tends to be insufficient, and when it exceeds 10 parts by weight, the adhesiveness, solder heat resistance, and insulation reliability tend to decrease.

  In the present invention, these compositions are remixed after premixing each resin component or solid additive component alone in an organic solvent, or these components are mixed together in an organic solvent to obtain a solid content of 20 to 40. It is preferable to use a varnish-like heat-resistant resin composition in weight percent. The organic solvent is not particularly limited as long as it is soluble in the heat resistant resin composition. For example, dimethylacetamide, dimethylformamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, γ-butyrolactone , Sulfolane, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, toluene, acetone and the like.

  Moreover, you may mix | blend a coupling agent, a pigment, a leveling agent, an antifoamer, an ion trap agent, etc. suitably with the heat resistant resin composition of this invention other than said each component as needed.

  In order to form an adhesive layer on a printed wiring board substrate using the heat resistant resin composition of the present invention, for example, a varnish-like heat resistant resin composition is directly applied to the substrate surface to form an adhesive layer. Alternatively, an adhesive layer is formed by applying a varnish-like heat-resistant resin composition to a supporting substrate, forming an adhesive film, and laminating a layer of the heat-resistant resin composition on the substrate surface. Also good. Moreover, when using an adhesive film, you may remove a support base material after laminating | stacking, or you may remove before laminating | stacking.

  The adhesive film having the adhesive layer of the present invention is produced, for example, by applying a varnish-like heat-resistant resin composition dissolved in a predetermined organic solvent on a supporting substrate and then drying the solvent by heating or hot air blowing. be able to. Examples of the support substrate include polyolefins such as polyethylene and polypropylene, polyesters such as polyethylene terephthalate, polycarbonates, fluorine-based films, release papers, copper foils, metal foils such as aluminum foils, and the like. In addition, as for the thickness of a support base material, 10-150 micrometers is preferable, and a mud process, a corona treatment, and a mold release process may be performed to a support base material.

  The organic solvent is not particularly limited as long as it is soluble in the heat resistant resin composition. For example, ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, ethyl acetate, butyl acetate, cellosolve acetate , Acetate esters such as propylene glycol monomethyl acetate and carbitol acetate, cellosolves such as cellosolve and butyl cellosolve, carbitols such as carbitol and butylcarbitol, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethyl Examples include acetamide and N-methyl-2-pyrrolidone. These may be used alone or in combination of two or more.

  The thickness of the heat-resistant resin composition laminated on the support substrate is preferably 5 to 50 μm, and more preferably 10 to 40 μm. Examples of the form of the adhesive film include a sheet shape and a roll shape that are cut by a certain length. From the viewpoint of storage stability, productivity, and workability, it is preferable to further laminate a protective film on the surface opposite to the heat-resistant resin composition, and to take up and store in a roll shape. Examples of the protective film include polyolefins such as polyethylene and polypropylene, polyesters such as polyethylene terephthalate, polycarbonate, fluorine-based films, and release papers, as in the case of the support substrate. In addition, as for the thickness of the said protective film, it is more preferable that it is 20-100 micrometers, and a mud process, a corona treatment, and a mold release process may be performed to a protective film.

  Moreover, it is preferable to make the adhesive film of this invention into a polyimide film with an adhesive by laminating on one or both sides of a polyimide film. And it can be set as the coverlay film for flexible wiring boards, and a base film. Furthermore, it can also be set as the board | substrate for flexible wiring boards by laminating | stacking metal foil.

The present invention will be specifically described below with reference to examples.
(Modified Polyamideimide Resin Synthesis Examples A1-8)
As a diamine having 3 or more aromatic rings in a 1-liter separable flask equipped with a 25 ml water quantitative receiver with a cock connected to a reflux condenser, a thermometer and a stirrer, 2,2-bis [4- (4-aminophenoxy) phenyl] propane), Jeffamine D-2000 (trade name, manufactured by Sun Techno Chemical Co., Ltd., amine equivalent 1000) as an aliphatic diamine, and Wandamine HM (trade name, manufactured by Shin Nippon Rika Co., Ltd.) as an alicyclic diamine. , Amine equivalent 100), reactive silicone oil as a siloxane diamine X-22-9362 (amine equivalent 700), X-22-9415 (amine equivalent 1100), X-22-9405 (amine equivalent 1900) (Shin-Etsu Chemical Co., Ltd.) Company name), TMA (trimellitic anhydride), aprotic polar solvent NMP (N-methyl-2-pyrrolidone), respectively, were charged in a mixing ratio shown in Table 1, was stirred at 80 ° C. 30 min. Then, 100 ml of toluene was added as an aromatic hydrocarbon azeotropic with water, and then the temperature was raised and refluxed at about 160 ° C. for 2 hours.

  Confirm that water has accumulated about 3.6 ml or more in the moisture meter and that no water has flowed out. The temperature was raised to remove toluene. Thereafter, the solution was returned to room temperature (25 ° C.), and MDI (4,4′-diphenylmethane diisocyanate), TDI (2,4-tolylene diisocyanate) and γ-BL (γ-butyrolactone) were used as aromatic diisocyanates in the following table. The compounding ratio shown in Fig. 1 was added, and after 1 hour at 150 ° C, the mixture was further reacted at 180 ° C for 2 hours. After completion of the reaction, NMP / γ-BL solutions A-1 to A-8 of modified polyamideimide resin were obtained. Table 1 below shows the weight average molecular weight of the modified polyamideimide resin synthesized and the solid content (% by weight) of the NMP / γ-BL solution of the modified polyamideimide resin. In addition, as shown in Table 1 below, in Synthesis Examples A6 to A8, alicyclic diamine (Wandamine HM) is not used.

(Examples 1-5 and Comparative Examples 1-3)
The materials shown in Table 2 below were blended with the modified polyamideimide resins of Synthesis Examples A1 to 8, and the mixture was stirred for about 1 hour until the resin became uniform, and then allowed to stand at room temperature for 24 hours for defoaming. To obtain a heat resistant resin composition. Further, phosphorus-containing epoxy resin (solid content: about 75% by weight: a product dissolved in methyl ethyl ketone) and phenol novolac resin (solid content: about 50% by weight: a product dissolved in dimethylacetamide) were used. As shown in Table 2 below, the heat-resistant resin compositions using the modified polyamideimide resins of Synthesis Examples A1 to 5 were designated as Examples 1 to 5, and the modified polyamideimide resins of Synthesis Examples A6 to 8 were used. The heat resistant resin compositions were designated as Comparative Examples 1 to 3.

(Sample A)
The obtained heat-resistant resin compositions of Examples 1 to 5 and Comparative Examples 1 to 3 were dried on a polyimide film having a thickness of 25 μm (trade name: Kapton 100V, manufactured by Toray DuPont Co., Ltd.), and the film thickness after drying was 20 μm. And then dried for 10 minutes at 130 ° C. with a dryer, and further roughened 35 μm rolled copper foil (trade name: BHY-22B-T manufactured by Nikko Materials Co., Ltd.) The samples were bonded to the surface side and temporarily bonded by hot pressing at a temperature of 160 ° C./hour 30 minutes / pressure 3 MPa, and then heated at 180 ° C. for 120 minutes in a dryer to prepare a sample.

(Sample B)
Moreover, the film thickness after drying the heat resistant resin compositions of the obtained Examples 1 to 5 and Comparative Examples 1 to 3 on one side of a polyimide film (trade name: Kapton 100V, manufactured by Toray DuPont Co., Ltd.) having a thickness of 25 μm. Was applied at a temperature of 130 ° C. for 10 minutes in a dryer, and the uncoated surface was again applied to the same dry film thickness as described above. For 120 minutes to prepare a sample.

(Sample C)
The obtained heat-resistant resin compositions of Examples 1 to 5 and Comparative Examples 1 to 3 were dried on a 100 μm-thick fluorine film (trade name: Naflon tape TOMBO9001 manufactured by NICHIAS Corporation) with a film thickness of 40 μm after drying. And dried at 130 ° C. for 10 minutes in a dryer, and then heated at 180 ° C. for 120 minutes to obtain a cured film with a fluorine-based film. In use, the fluorine-based film was peeled off to prepare a sample.

  Using these samples, adhesiveness (sample A), solder heat resistance (sample A), flame retardancy (sample B), glass transition temperature (sample C), and storage modulus (sample C) were measured. The results are shown in Table 3. Further, using (Sample C), the presence or absence of a microphase separation structure (sub-micron to micron-order sea-island structure) of the modified polyamideimide resin was confirmed by an electron microscope. The measurement methods and conditions for these characteristics are shown below.

(Adhesiveness)
When sample A (sample configuration: polyimide film / resin composition / rolled copper foil roughened surface) was left to stand for 10 days at 150 ° C. in a normal state and a drier, it was subjected to high temperature and high humidity conditions (121 ° C., 2 90 ° direction peeling test under the conditions of measurement temperature: 25 ° C. and peeling speed: 10 mm / min under the three conditions when processing at atmospheric pressure (saturated state), peel strength (kN / m) of rolled copper foil drawing Was measured.

(Solder heat resistance)
(1) Using sample A (sample structure: polyimide film / resin composition / rolled copper foil roughened surface), solder solder resistance in the normal state is kept for 1 minute in a solder bath heated to 300 ° C. The sample was floated down and examined for the presence of abnormal appearance such as blistering and peeling.
(2) Using sample A (sample structure: polyimide film / resin composition / rolled copper foil roughened surface), after heat treatment (40 ° C., 90% RH, 8 hours), solder heat resistance was 280 and 260 ° C. The sample was floated in the solder bath heated for 1 minute with the copper foil side down, and examined for the presence of abnormal appearance such as blistering and peeling. The evaluation was as follows: ○: No abnormal appearance such as blistering, peeling, etc., X: Abnormal appearance such as blistering, peeling, etc.

(Flame retardance)
Using sample B (sample configuration: resin composition / polyimide film / resin composition), the flame retardancy grade was measured in accordance with UL94 flame retardancy standards.

(Glass transition temperature and storage modulus)
Using sample C (sample configuration: cured film only), dynamic viscoelasticity measurement (trade name: RSAII, manufactured by Rheometric Co., Ltd.) was performed under the following conditions. As the glass transition temperature (Tg), the maximum value of the tan δ peak was used as a measurement value.
Measurement mode: tensile, sample size: width 5.0 mm × 22.5 mm, measurement temperature: 0 to 250 ° C., temperature increase rate: 5 ° C./min, measurement frequency: 1 Hz

As shown in Table 3, the properties (adhesion, solder heat resistance, flame retardancy) of the adhesive films using the heat resistant resin compositions of Examples 1 to 5 are excellent, and compared with them, alicyclic The flame retardancy of the adhesive film using the heat-resistant resin composition of Comparative Examples 1 to 3 that does not use diamine and the solder heat resistance after the humidification treatment are inferior. In Examples 1 to 5, the presence of a microphase separation structure (sub-micron to micron-order sea-island structure) of the modified polyamideimide resin was confirmed. By using the heat resistant resin composition of the present invention, a flame retardant grade VTM-0 equivalent to a halogen compound is realized without using a halogen compound such as a bromine compound, and adhesion, solder heat resistance, non-halogen An adhesive film excellent in flame retardancy could be obtained.

Claims (8)

(A) A heat-resistant resin composition containing a modified polyamideimide resin having a microphase separation structure, (B) a thermosetting resin, and (C) an organophosphorus compound, a modification having a microphase separation structure of component (A) The polyamideimide resin is obtained by reacting a diamine having 3 or more aromatic rings or a mixture of an aliphatic diamine, an alicyclic diamine and a siloxane diamine with trimellitic anhydride, or the following general formula: (2) or a modified polyamideimide resin obtained by reacting a mixture containing a diimidecarboxylic acid represented by the following general formula (3) with an aromatic diisocyanate represented by the following general formula (4): A heat-resistant resin composition.

(In the general formula (1), R ₁ is represented by the general formula (5), and X in the general formula (5) is represented by the general formula (6).)

(R ₂ in the general formula (2) is represented by the general formula (7), n ₁ is an integer of ₁ to 70, X ₁ is an aliphatic hydrocarbon group having 1 to 3 carbon atoms, 3 halogenated aliphatic hydrocarbon group, sulfonyl group, ether group, carbonyl group, single bond, R ₁ , R ₂ , R ₃ may be the same or different, hydrogen atom, hydroxyl group, methoxy group, methyl group , A halogenated methyl group, Y ₁ is 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 ether group, a carbonyl group, Z ₁ is A C1-C3 aliphatic hydrocarbon group, a C1-C3 halogenated aliphatic hydrocarbon group, a sulfonyl group, an ether group, a carbonyl group, or a single bond is shown.)

(R ₃ in the general formula (3) is represented by the general formula (8). In the general formula (8), R ₄ and R ₅ are each independently a divalent organic group, and R _{6 to} R ₉ are each independently represents an alkyl group or an aryl group having 6 to 18 carbon atoms having 1 to 20 carbon atoms, _{n 2} is an integer of 1 to 50.)

(In General Formula (4), R ₁₀ is represented by General Formula (9).)   (A) 5-100 parts by weight of a thermosetting resin and (C) 2-10 parts by weight of an organophosphorus compound with respect to 100 parts by weight of a modified polyamideimide resin having a microphase separation structure. 1. The heat resistant resin composition according to 1.   The amine equivalent of the aliphatic diamine of the modified polyamideimide resin having a microphase separation structure as the component (A) is 200 to 2500 g / mol, and the amine equivalent of the alicyclic diamine is 50 to 100 g / mol. The heat resistant resin composition described in 1.   The amine equivalent of the siloxane diamine of the modified polyamideimide resin having a microphase separation structure as the component (A) is 200 to 2500 g / mol.   The heat-resistant resin composition according to any one of claims 1 to 4, wherein the thermosetting resin of the component (B) is a thermosetting resin containing an epoxy resin and a curing accelerator or a curing agent thereof. The organophosphorus compound of the component (C) is a phosphoric ester compound represented by the following general formula (10) or an organophosphorus compound containing a phosphoric ester compound represented by the following general formula (11). Item 6. The heat resistant resin composition according to any one of Items 1 to 5.

(However, in the general formula (10), _{n 4} is an integer of 10 to 50.)

(In the general formula (11), W represents a single bond, an alkylene group having 1 to 5 carbon atoms, —S—, —SO ₂ —, —O—, or —N═N—; n ₃ is an integer of 10 to 50.)   The adhesive film which has an adhesive layer containing the heat resistant resin composition in any one of Claims 1-6. The polyimide film with an adhesive which has the contact bonding layer containing the heat resistant resin composition in any one of Claims 1-6 on the single side | surface or both surfaces of a polyimide film.