JP4997690B2 - Resin composition, base material with resin, and laminate with conductor layer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition forming an adhesive layer with a high adhesiveness to a substrate and conductive layer, excellent in flame retardancy, and to provide a substrate with the resin and laminated board with conductive layer. <P>SOLUTION: The invention relates to the laminated board with conductive layer 20 comprising a substrate sheet 22, an adhesive layer (resin layer) 24 and the conductive layer 26 in this order. The adhesive layer 24 in the laminated board with conductive layer 20 comprises the resin composition comprising a polyamideimide containing an alicyclic hydrocarbon group and a thermosetting resin. <P>COPYRIGHT: (C)2006,JPO&amp;NCIPI

Description

  The present invention relates to a resin composition, a substrate with resin, and a conductor layer-clad laminate.

  In recent years, with the reduction in size and weight of electronic devices such as personal computers and mobile phones, printed circuit boards mounted on these devices are required to be further reduced in size and wiring density. In order to cope with such downsizing, the use of multilayer wiring boards (build-up wiring boards) and flexible wiring boards (FPC) is increasing as printed wiring boards. As a multilayer wiring board and a flexible wiring board, what has a structure provided with the sheet-like base material and conductor layer which consist of resin etc. is common. And in order to reduce peeling of the conductor layer from a base material, both layers are often bonded through an adhesive layer made of a resin material.

  Conventionally, epoxy resins, acrylic resins, and the like have been often used as resin materials for the adhesive layer. However, these resin materials tend to have low heat resistance. For this reason, the printed wiring board which applied the conventional resin material to the contact bonding layer was difficult to use for the use where severe conditions, such as high temperature, are imposed. Therefore, in order to eliminate such inconvenience, recently, polyimide having higher heat resistance has been frequently used instead of the conventional epoxy resin or the like.

  In addition, printed wiring boards mounted on electronic devices are required to have flame resistance in addition to heat resistance from the viewpoint of safety. In particular, the resin material used for the adhesive layer usually tends to have low flame retardancy as it is, and improving the flame retardancy is important for enhancing the flame retardancy of the entire printed wiring board. Thus, conventionally, for the purpose of improving the flame retardancy of the adhesive layer, a flame retardant has been applied to the resin material. As such flame retardants, halogen compounds and antimony compounds are known.

However, these flame retardants have recently been found to generate gas harmful to human bodies by combustion, and their use is being restricted. Under such circumstances, flame retardants that are less likely to generate harmful gases by combustion have been actively developed. As flame retardants having such properties, inorganic fillers such as aluminum hydroxide and magnesium hydroxide, phosphorus-containing compounds described in Patent Document 1, and the like have been proposed.
JP 2003-027028 A

  However, the conventional resin material has some disadvantages in the following points. That is, first, although polyimide has excellent heat resistance, it is extremely expensive compared to conventional resin materials. Therefore, when polyimide is used, the cost for manufacturing a printed wiring board tends to increase. For this reason, until now, polyimide has been used only for printed wiring boards and the like that particularly require high heat resistance, and has hardly been applied to printed wiring boards for normal use.

  Therefore, the present inventors have focused on polyamideimide as a resin material that replaces polyimide. Polyamideimide is obtained at a relatively low cost and has excellent heat resistance as compared with conventional epoxy resins and the like. However, polyamide imide tends to have insufficient heat resistance compared to polyimide. Therefore, it is difficult to say that the adhesive layer containing this polyamideimide is excellent in durability against a process (for example, wire bonding, solder reflow, etc.) involving a high temperature treatment when manufacturing a printed wiring board. It was found that deterioration is likely to occur due to the history. When the adhesive layer is deteriorated in this way, the adhesiveness to the base material or the conductor layer is lowered, and as a result, the conductor layer is easily peeled off from the printed wiring board.

  Further, as described above, when a flame retardant is added to a resin material for the purpose of improving flame retardancy, various characteristics of the adhesive layer made of the resin material tend to be lowered. For example, when aluminum hydroxide is added in a large amount in order to obtain sufficient flame retardancy, for example, the surface of a general polyimide film as a base material for FPC is weakened. In some cases, the adhesion of the resin was lowered. This is presumably because soluble sodium unavoidably mixed with aluminum hydroxide causes a hydrolysis reaction on the surface of the polyimide film during high-temperature treatment or the like. On the other hand, since the conventional phosphorus-containing compound functions as a plasticizer for the resin material, when a large amount of the phosphorus-containing compound is added in order to obtain sufficient flame retardancy, characteristics such as heat resistance and insulation of the adhesive layer May be reduced.

  Therefore, the present invention has been made in view of the above circumstances, a resin composition that can form an adhesive layer having high adhesion to a base material and a conductor layer, and excellent in heat resistance and flame retardancy, and a resin using the same It aims at providing a base material with a cover, and a conductor-layer-clad laminate.

  As a result of intensive studies to achieve the above object, the inventors of the present invention have excellent adhesiveness with a conductor layer, etc., due to the resin composition containing polyamideimide having a predetermined structural unit in the molecule, and It was found that an adhesive layer capable of exhibiting excellent flame retardancy was obtained, and the present invention was completed.

  That is, the resin composition of the present invention is characterized by containing a polyamideimide containing a structural unit having an aliphatic cyclic hydrocarbon group and a thermosetting resin.

  Polyamideimide containing a structural unit having an aliphatic cyclic hydrocarbon group has a high glass transition temperature (Tg) and is excellent in both heat resistance and moisture resistance characteristics. Such a resin composition containing polyamide-imide hardly deteriorates even by high-temperature treatment during the production of a printed wiring board, and can maintain excellent adhesion to a base material or a conductor layer. Moreover, this polyamideimide has the characteristic that it is excellent also in a flame retardance. For this reason, the contact bonding layer which consists of a resin composition containing this polyamideimide has the outstanding flame retardance.

  It is preferable that the resin composition of the present invention further contains a phosphorus-containing compound. The phosphorus-containing compound can enhance the flame retardancy of the resin material as described above, and the flame retardance of the adhesive layer can be further improved by containing such a phosphorus-containing compound. Further, in the resin composition of the present invention, since the polyamide-imide has excellent flame retardancy, sufficient flame retardancy can be obtained even if the amount of phosphorus-containing compound added is smaller than before. . For this reason, according to this resin composition, the above-mentioned fall of adhesiveness, heat resistance, insulation, etc. by addition of a phosphorus containing compound can be suppressed.

［式中、Ｒ^１は下記一般式（２ａ）、（２ｂ）、（２ｃ）、（２ｄ）、（２ｅ）又は（２ｆ）で表される２価の基を示す。

ただし、式（２ａ）中、Ｒ^２１は、水素原子、ヒドロキシル基、メトキシ基、メチル基又はハロゲン化メチル基、Ｒ^２２は、炭素数１〜３のアルキレン基、炭素数１〜３のハロゲン化アルキレン基、スルホニル基、オキシ基、カルボニル基又は単結合を示し、式（２ｂ）中、Ｒ^２３は、炭素数１〜３のアルキレン基、炭素数１〜３のハロゲン化アルキレン基、スルホニル基、オキシ基又はカルボニル基を示し、式（２ｆ）中、Ｒ^２４は、炭素数１〜３のアルキレン基、炭素数１〜３のハロゲン化アルキレン基、スルホニル基、オキシ基、カルボニル基又は単結合を示す。なお、複数存在するＲ^２１は、それぞれ同一でも異なっていてもよい。］ The polyamideimide is obtained by reacting a diimide dicarboxylic acid obtained by reacting a diamine compound with trimellitic anhydride and diisocyanate. As the diimide dicarboxylic acid, the following general formula (1) is used. It is preferable to contain at least the represented compound.

[Wherein, R ¹ represents a divalent group represented by the following general formula (2a), (2b), (2c), (2d), (2e) or (2f).

In the formula ^{(2a), R 21} represents a hydrogen atom, a hydroxyl group, a methoxy group, a methyl group or a halogenated methyl ^{group, R 22} is an alkylene group having 1 to 3 carbon atoms, a halogenated 1 to 3 carbon atoms Represents an alkylene group, a sulfonyl group, an oxy group, a carbonyl group or a single bond, and in formula (2b), R ²³ represents an alkylene group having 1 to 3 carbon atoms, a halogenated alkylene group having 1 to 3 carbon atoms, a sulfonyl group, Represents an oxy group or a carbonyl group, and in formula (2f), R ²⁴ represents an alkylene group having 1 to 3 carbon atoms, a halogenated alkylene group having 1 to 3 carbon atoms, a sulfonyl group, an oxy group, a carbonyl group or a single bond. Show. A plurality of R ²¹ may be the same or different. ]

  Such a polyamideimide preferably has an aliphatic cyclic hydrocarbon group in the molecule. Therefore, the adhesive layer containing such polyamideimide is further excellent in heat resistance and flame retardancy.

［式中、Ｒ^３は上記一般式（２ａ）、（２ｂ）、（２ｃ）、（２ｄ）、（２ｅ）又は（２ｆ）で表される２価の基を示す。］ More specifically, the diimide dicarboxylic acid represented by the general formula (1) is obtained by reacting a diamine compound represented by the following general formula (3) with trimellitic anhydride, And the amine equivalent of this diamine compound is preferable in it being 50-200 g / mol.

[Wherein R ³ represents a divalent group represented by the general formula (2a), (2b), (2c), (2d), (2e) or (2f). ]

［式（４ａ）中、Ｒ^４１は、水素原子、アルキル基、フェニル基又は置換フェニル基を示し、ｎは１〜５０の整数であり、式（４ｂ）中、Ｒ^４２は、下記一般式（５ａ）又は（５ｂ）で表される２価の基を示す。

ただし、式（５ａ）中、Ｒ^５は、炭素数１〜３のアルキレン基、炭素数１〜３のハロゲン化アルキレン基、スルホニル基、オキシ基、カルボニル基又は単結合を示す。］ Further, the polyamideimide described above further contains a compound represented by the following general formula (4a) and / or a compound represented by the following general formula (4b) as diimidedicarboxylic acid during the production thereof. It is more preferable that it is obtained.

[In the formula (4a), R ⁴¹ represents a hydrogen atom, an alkyl group, a phenyl group or a substituted phenyl group, n is an integer of 1 to 50, and in the formula (4b), R ⁴² represents the following general formula ( The divalent group represented by 5a) or (5b) is shown.

However, in formula (5a), R ⁵ represents an alkylene group having 1 to 3 carbon atoms, a halogenated alkylene group having 1 to 3 carbon atoms, a sulfonyl group, an oxy group, a carbonyl group, or a single bond. ]

  By containing these diimide dicarboxylic acids, the resulting polyamideimide contains structural units having 3 or more aromatic rings and / or structural units having an aliphatic hydrocarbon group not having a cyclic structure in the molecule. To have. The polyamideimide having the former structural unit has further excellent heat resistance. In addition, the polyamideimide having the latter structural unit is excellent in flexibility, and can relieve stress generated in the adhesive layer and suppress cracks and breaks.

［式中、Ｒ^６１は、アルキル基、フェニル基又は置換フェニル基、Ｒ^６２は、２価の有機基を示し、ｍは１〜５０の整数を示す。］ Further, the polyamideimide is preferably obtained by further containing a compound represented by the following general formula (6) as diimidedicarboxylic acid at the time of production. Such a polyamideimide has a siloxane structure in the molecule, and has excellent flexibility like the one containing the aliphatic hydrocarbon group.

[Wherein, R ⁶¹ represents an alkyl group, a phenyl group or a substituted phenyl group, R ⁶² represents a divalent organic group, and m represents an integer of 1 to 50. ]

［式中、Ｒ^７１は、アルキル基、フェニル基又は置換フェニル基、Ｒ^７２は、２価の有機基を示し、ｐは１〜５０の整数を示す。］ Specifically, the diimide dicarboxylic acid having such a siloxane structure is preferably obtained by reacting a diamine compound represented by the following general formula (7) with trimellitic anhydride, The amine equivalent of the diamine compound is more preferably 200 to 2500 g / mol.

[Wherein, R ⁷¹ represents an alkyl group, a phenyl group or a substituted phenyl group, R ⁷² represents a divalent organic group, and p represents an integer of 1 to 50. ]

［式（８ａ）中、ｑは１０〜５０の整数であり、式（８ｂ）中、Ｒ^８は単結合、炭素数１〜５のアルキレン基、スルフィド基、スルホニル基、オキシ基、又はアゾ基を示し、ｒは１０〜５０の整数である。］ Furthermore, as the phosphorus-containing compound, a phosphate ester compound is preferable, and a compound represented by the following general formula (8a) and / or a compound represented by the following general formula (8b) is particularly preferable. These phosphorus-containing compounds can impart extremely excellent flame retardancy to a resin composition containing polyamideimide.

Wherein (8a), q is an integer of 10 to 50, wherein (8b), ^{R 8} represents a single bond, an alkylene group having 1 to 5 carbon atoms, a sulfide group, a sulfonyl group, aryloxy group, or an azo group R is an integer of 10-50. ]

  Moreover, the base material with a resin of this invention is equipped with the resin layer which consists of a sheet-like base material and the resin composition of the said this invention formed on this base material, It is characterized by the above-mentioned. Since the resin layer is composed of the resin composition of the present invention, it has excellent adhesion to the substrate, and also has excellent adhesion to conductor foils such as metal foil, Furthermore, it has excellent flame retardancy.

  A polyimide film is mentioned as said sheet-like base material. Such a polyamide film is effective as a substrate such as a flexible wiring board because it is thin and has high strength. Even for such a polyimide film, the resin layer made of the resin composition of the present invention can exhibit excellent adhesiveness.

  The present invention further includes a conductor layer-clad laminate comprising a sheet-like base material, a resin layer comprising the resin composition of the present invention provided on the base material, and a conductor layer provided on the resin layer. Provide a board. Such a laminate also has excellent heat resistance and flame retardancy because the resin layer of the present invention is used for the resin layer that is an adhesive layer.

  ADVANTAGE OF THE INVENTION According to this invention, the resin composition which can form the contact bonding layer which has high adhesiveness with respect to a base material or a conductor layer, and is excellent also in heat resistance and a flame retardance, the base material with resin using this, and a conductor layer tension lamination | stacking A board can be provided.

Hereinafter, preferred embodiments of the present invention will be described in detail.
[Resin composition]

The resin composition which concerns on suitable embodiment contains the polyamideimide containing the structural unit which has an aliphatic cyclic hydrocarbon group in a molecule | numerator, and a thermosetting resin. Hereinafter, suitable components contained in the resin composition will be described.
(Polyamideimide)

  The polyamideimide contained in the resin composition includes the structural unit having the above-described aliphatic cyclic hydrocarbon group. Such a polyamide-imide imide preferably has the above structural unit at a position where nitrogen atoms in adjacent imide groups are bonded to each other. Examples of such a structural unit include a divalent group represented by the general formula (2a), (2b), (2c), (2d), (2e), or (2f).

Polyamideimide can be obtained by reacting diimide dicarboxylic acid obtained by reacting a diamine compound and trimellitic anhydride with diisocyanate. Hereinafter, diimide dicarboxylic acid suitable for obtaining the polyamideimide according to the embodiment and a method for producing the polyamideimide using these will be described.
<Diimide dicarboxylic acid containing a structural unit having an aliphatic cyclic hydrocarbon group>

  As diimide dicarboxylic acid, in order to introduce a structural unit having an aliphatic cyclic hydrocarbon group into polyamideimide, at least diimide dicarboxylic acid containing such a structural unit (hereinafter abbreviated as “alicyclic diimide dicarboxylic acid”) is used. It is desirable to contain. Examples of the alicyclic diimide dicarboxylic acid include compounds represented by the general formula (1).

  This alicyclic diimide dicarboxylic acid is preferably obtained by reacting a diamine compound containing a structural unit having an aliphatic cyclic hydrocarbon group (hereinafter abbreviated as “alicyclic diamine”) with trimellitic anhydride. Can do. As alicyclic diamine, the diamine compound represented by the said General formula (3) is mentioned, for example.

  Specific examples of the diamine compound represented by the general formula (3) 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-aminosi (Rohexyloxy) benzene, 1,4-bis (4-aminocyclohexyloxy) benzene, 2,2-dimethyldicyclohexyl-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) dicyclohexylmethane, (4,4'-diamino) dicyclohexyl ether, (4,4'-diamino) dicyclohexylsulfone, (4,4'- Diamino) dicyclohexyl ketone, (3,3'-diamino) dicyclohexyl ether, 2,2-bis (4-aminocyclohexyl) E) Propane and the like. These diamine compounds may be used alone or in combination.

  The diamine compound described above can be obtained, for example, by hydrogen reduction of an aromatic diamine compound having a corresponding structure. Such aromatic diamine compounds include 2,2-bis [4- (4-aminophenoxy) phenyl] propane (BAPP), bis [4- (3-aminophenoxy) phenyl] sulfone, 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, Examples thereof include (3,3′-diamino) benzophenone, (4,4′-diamino) diphenylmethane, (4,4′-diamino) diphenyl ether, (3,3′-diamino) diphenyl ether, and the like.

  Hydrogen reduction of these aromatic diamine compounds can be suitably performed by a known reduction method. For example, the method of processing in presence of various catalysts in presence of hydrogen is mentioned. Such catalysts include Raney nickel, platinum oxide (D. Varech et al., Tetrahedron Letters 26, 61 (1985), RH Baker et al., J. Am. Chem. Soc., 69, 1250 (1947), Rhodium-aluminum oxide (JC Sircar et al., J. Org. Chem., 30, 3206 (1965), AI Meyers et al., Organic Synthesis, Collective Volume VI, 371 (1988), A. w. Burgstahler, organic Synthesis, Collective Volume V, 591 (1973), AJ Briggs, Synthesis, 19880, 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), charcoal-supported rhodium (K. Chebaane et al., Bull. Soc. Chim. Fr., 244 (1975)), etc. In addition to hydrogen reduction such as these, sodium borohydride-rhodium chloride system (PG Gassman et al., Organic Synthesis Collective Volume VI, 581 (1988), PG Gassman et al., Organic Synthesis Collective Volume VI, 601 ( 1988)) example It can be.

  As such alicyclic diamine, that whose amine equivalent is 50-200 g / mol is preferable, and what is 50-120 g / mol is more preferable. Here, the amine equivalent means a weight (g) including 1 mol of an amino group in the compound. When the amine equivalent of the alicyclic diamine is in the above range, a microphase separation structure is favorably formed in the polyamideimide, and as a result, the adhesiveness and toughness of the cured product of the resin composition are improved.

＜脂肪族炭化水素から構成される構造単位を有するジイミドジカルボン酸＞ Among the diamine compounds described above, a compound in which R ³ in the compound represented by the general formula (3) is the general formula (2a) is preferable, and particularly, the compound represented by the following chemical formula (9) (4, 4 '-Diamino) dicyclohexylmethane is preferred. Such a compound is commercially available, for example, as Wandamine HM (amine equivalent 105, trade name, manufactured by Shin Nippon Rika Co., Ltd.).

<Diimide dicarboxylic acid having a structural unit composed of aliphatic hydrocarbon>

  The diimide dicarboxylic acid is a diimide dicarboxylic acid having a structural unit composed of an aliphatic hydrocarbon and having no aliphatic cyclic hydrocarbon group (hereinafter abbreviated as “aliphatic diimide dicarboxylic acid”). Is further preferably contained. By containing the aliphatic diimide dicarboxylic acid, a structural unit composed of an aliphatic hydrocarbon is introduced into the polyamideimide, and the polyamideimide has more excellent stress relaxation characteristics. As a result, a sheet-like molded product such as an adhesive layer made of a resin composition is excellent in flexibility and adhesion to a metal foil or the like.

Specific examples of the aliphatic diimide dicarboxylic acid include compounds represented by the general formula (4a). The compound represented by the general formula (4a) is suitably obtained by reacting a diamine compound represented by the following general formula (10) (hereinafter abbreviated as “aliphatic diamine”) with trimellitic anhydride. be able to. In the formula, R ⁴¹ and n are as defined above.

Among the diamine compounds represented by the general formula (10), those in which R ⁴¹ is an alkyl group are preferable, and in particular, the diamine compounds represented by the following chemical formula (11) in which R ⁴¹ is a methyl group are preferable. In the formula, n is as defined above.

Examples of such a diamine compound include Jeffamine D-230 (amine equivalent 115), Jeffamine D-400 (amine equivalent 200), Jeffamine D-2000 (amine equivalent 1000), and Jeffamine D-4000 (amine equivalent 2000). As mentioned above, the product name of Sun Techno Chemical Co., Ltd.) is commercially available and suitable. These can be contained alone or in combination.
<Diimide dicarboxylic acid having three or more aromatic rings>

  As the diimide dicarboxylic acid, a diimide dicarboxylic acid having three or more aromatic rings (hereinafter abbreviated as “aromatic diimide dicarboxylic acid”) instead of the aliphatic diimide dicarboxylic acid described above or together with the aliphatic diimide dicarboxylic acid. It is preferable to contain. By containing this aromatic diimide dicarboxylic acid, a structural unit having three or more aromatic rings in the polyamideimide is introduced. Since such a structural unit improves the strength and heat resistance of the polyamideimide, the adhesive layer made of the resin composition has excellent characteristics.

Examples of the aromatic diimide dicarboxylic acid include compounds represented by the general formula (4b). The compound represented by the general formula (4b) can be suitably obtained by reacting a diamine compound (hereinafter abbreviated as aromatic diamine) represented by the following general formula (12) with trimellitic anhydride. it can. In the formula, R ⁴² has the same meaning as described above.

Examples of the diamine compound represented by the general formula (12) include 2,2-bis [4- (4-aminophenoxy) phenyl] propane (BAPP) and bis [4- (3-aminophenoxy) phenyl] sulfone. 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-amino) Examples thereof include phenoxy) benzene and 1,4-bis (aminophenoxy) benzene. Among these, BAPP in which R ⁴² is a divalent group represented by the general formula (5a) and R ^{5 in} the group is a divalent group represented by —C (CH ₃ ) ₂ —. preferable.
<Diimide dicarboxylic acid having a siloxane structure>

  The diimide dicarboxylic acid preferably contains a diimide dicarboxylic acid having a siloxane structure (hereinafter abbreviated as “siloxane diimide dicarboxylic acid”) in addition to the above-described compounds. By including siloxane diimide dicarboxylic acid, a siloxane structure is introduced into the polyamideimide. Polyamideimide having such a structural unit has excellent stress relaxation properties as well as those having a structural unit composed of an aliphatic hydrocarbon introduced, and also tends to cause volatilization of a solvent, etc. Processing and the like can be facilitated.

  Examples of the siloxane diimide dicarboxylic acid include compounds represented by the general formula (6). Such a siloxane diimide dicarboxylic acid can be preferably obtained by reacting a diamine compound represented by the general formula (7) (hereinafter abbreviated as “siloxane diamine”) with trimellitic anhydride. . The siloxane diamine is preferably one having an amine equivalent of 200 to 2500 g / mol, more preferably 400 to 2500 g / mol, and still more preferably 700 to 2000 g / mol. By using a siloxane diamine having an amine equivalent in the above range, a microphase-separated structure is easily formed in the polyamideimide. As a result, the adhesiveness and toughness of the cured product of the resin composition are improved, and excellent flame retardancy. Sex is also gained.

More specifically, as the siloxane diamine represented by the general formula (7), R ⁷² is an alkylene group having 1 to 3 carbon atoms (for example, a methylene group, an ethylene group or a propylene group) or 6 to 9 carbon atoms. Are preferably arylene groups (for example, a phenylene group, a tolylene group or a xylylene group). As such siloxane diamine, amino-modified silicone oil X-22-161AS (amine equivalent 450), X-22-161A (amine equivalent 840), X-22-161B (amine equivalent 1500) (Shin-Etsu Chemical Co., Ltd.) BY16-853 (amine equivalent 650), BY-16-853B (amine equivalent 2200) (above, manufactured by Toray Dow Corning Silicone), etc. are commercially available and suitable.

＜ポリアミドイミドの製造方法＞ Among these siloxane diamines, a compound represented by the following general formula (13) in which R ⁷¹ is a methyl group and R ⁷² is a propylene group is particularly preferable. In the formula, p is as defined above.

<Production method of polyamideimide>

  The polyamideimide according to a preferred embodiment can be obtained by reacting diimide dicarboxylic acid with diisocyanate as described above. Hereinafter, as an example of a preferable method for producing polyamideimide, a case where all of the above-described alicyclic diimide dicarboxylic acid, aliphatic diimide dicarboxylic acid, aromatic diimide dicarboxylic acid and siloxane diimide dicarboxylic acid are contained as diimide dicarboxylic acid will be described. To do.

  In the production of such polyamideimide, first, the various diimidedicarboxylic acids described above are synthesized by reacting a diamine compound corresponding to each diimidedicarboxylic acid with trimellitic anhydride. In this case, various diimide dicarboxylic acids can be synthesized individually, but after mixing a diamine compound corresponding to the desired diimide dicarboxylic acid to form a diamine mixture, this mixture is reacted with trimellitic anhydride. Thus, it is preferable to synthesize a plurality of types of diimidedicarboxylic acids all at once.

  In the latter case, first, alicyclic diamine, aliphatic diamine, aromatic diamine and siloxane diamine corresponding to each diimide dicarboxylic acid are mixed to form a diamine mixture. Thereafter, the diamine mixture and trimellitic anhydride are dissolved or dispersed in an aprotic polar solvent, and then reacted at 50 to 90 ° C. for 0.2 to 1.5 hours. Then, an aromatic hydrocarbon which can be azeotroped with water is added to the solution after the reaction, and further reacted at 120 to 180 ° C. to cause a dehydration cyclization reaction, thereby obtaining the various diimide dicarboxylic acids.

  As the aprotic polar solvent used in the above reaction, those having low reactivity with the diamine mixture and capable of dissolving or dispersing each component well are preferable. Examples thereof include dimethylacetamide, dimethylformamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, 4-butyrolactone, sulfolane and the like. Of these, N-methyl-2-pyrrolidone is preferred. In addition, these may be used independently and may be used in mixture of 2 or more types.

  The aprotic polar solvent preferably has a water content of 0.2% by weight or less, specifically about 0.1 to 0.2% by weight. When the water content exceeds 0.2% by weight, trimellitic anhydride is hydrated to form trimellitic acid, which makes it difficult to produce diimide dicarboxylic acid having a desired structure. It tends to be difficult to obtain a polyamideimide.

  The amount of the aprotic polar solvent used is preferably 10 to 80% by mass, more preferably 50 to 80% by mass, based on the total amount of the diamine mixture and trimellitic anhydride. When the amount of the solvent used is less than 10% by mass, the trimellitic anhydride is not sufficiently dissolved and the production of diimide dicarboxylic acid tends to be disadvantageous. On the other hand, when it exceeds 80 mass%, there is too much solvent usage-amount and it exists in the tendency for cost to become disadvantageous.

  Examples of the aromatic hydrocarbon azeotropic with water include toluene, benzene, xylene, and ethylbenzene, and toluene is preferable. The aromatic hydrocarbon is preferably added in an amount of 0.1 to 0.5 by weight with respect to the aprotic polar solvent. In addition, it is preferable to raise the temperature of a solution to about 190 degreeC after completion | finish of this spin-drying | dehydration ring-closing reaction and before performing reaction with diisocyanate mentioned later, and to remove the said aromatic hydrocarbon.

  When preparing what contains the said 4 types of diamine compound as a diamine mixture, it is preferable that the compounding quantity of each component shall be as showing below. That is, aromatic diamine / aliphatic diamine / alicyclic diamine / siloxane diamine are preferably 10 to 79/10 to 50/1 to 20/10 to 30 in molar ratio, and 25 to 60/20 to 40. It is more preferable that it is / 5-10 / 20-30. By making the molar ratio of each diamine compound in this way, the resulting polyamideimide is derived from a flexible structural unit (soft segment) derived from aliphatic diamine, alicyclic diamine and siloxane diamine, and aromatic diamine. It has a microphase separation structure in which hard structural units (hard segments) are introduced in a balanced manner. According to such a polyamideimide, it has excellent heat resistance and strength, and has an excellent stress relaxation action, so that an adhesive layer or the like that can exhibit excellent adhesion to a metal foil or the like can be obtained. become.

  In addition, in the production of the diimide dicarboxylic acid, the blending amount of the diamine mixture and trimellitic anhydride is 2.05 to 2.20 times the molar amount of trimellitic anhydride with respect to the total molar amount of the diamine mixture. Preferably, it is more preferable that the molar amount is 2.10 to 2.15 times. When the blending amount of trimellitic anhydride exceeds 2.20 times the molar amount with respect to the diamine mixture, trimellitic anhydride remains and inhibits the reaction with diisocyanate described later. It may be difficult to obtain. On the other hand, if the amount is less than 2.05 times the molar amount, diimide dicarboxylic acid is hardly generated sufficiently, and it may be difficult to obtain a high molecular weight polyamideimide.

  And polyamidoimide can be obtained by making the diimide dicarboxylic acid mixture and diisocyanate containing various diimide dicarboxylic acid obtained by the reaction mentioned above react.

Here, as the diisocyanate, both aromatic diisocyanates and aliphatic diisocyanates can be applied. For example, what is represented by the following general formula (14) is suitable. In the following formula, R ¹⁴ includes a group represented by -Ph-CH ₂ -Ph-, a tolylene group, a naphthylene group, a hexamethylene group, or an isophorone group.

  As aromatic diisocyanates, 4,4'-diphenylmethane diisocyanate (MDI), 2,4-tolylene diisocyanate (TDI), 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, 2,4-tolylene A dimer etc. can be illustrated and especially MDI is preferable. By containing MDI, the film-forming property of the resin composition containing the polyamideimide obtained is improved, and the flexibility of the adhesive layer made of the resin composition is improved. TDI is also preferable. When a combination of MDI and TDI is used, the flexibility is further improved and the effect of suppressing crystallization can be obtained. On the other hand, examples of the aliphatic diisocyanate include hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and isophorone diisocyanate.

  The diisocyanate preferably contains at least an aromatic diisocyanate, and more preferably used in combination. Thus, when using together, these compounding ratios are preferable when content of aliphatic diisocyanate becomes about 5-10 mol% with respect to aromatic diisocyanate. Thus, by using together aromatic diisocyanate and aliphatic diisocyanate, it becomes possible to further improve the heat resistance of the polyamideimide, and thus the resin composition.

  The reaction between the diimide dicarboxylic acid mixture and the diisocyanate is preferably carried out after once cooling the solution after the reaction to room temperature, for example, when the above-described aromatic hydrocarbon is removed. Polyamideimide can be suitably obtained by adding aromatic diisocyanate to the solution thus cooled, raising the temperature again to 150 to 250 ° C., and reacting for about 0.5 to 3 hours.

  In such a reaction, the blending amount of the diimide dicarboxylic acid mixture and the diisocyanate is such that the blending amount of the diisocyanate is 1.05-1.50 times the molar amount with respect to the total molar amount of the diimide dicarboxylic acid mixture. Is preferable, and it is more preferable that the molar amount is 1.1 to 1.3 times. When the blending amount of diisocyanate exceeds 1.50 times mole amount or less than 1.05 times mole amount with respect to the total mole amount of diimide dicarboxylic acid mixture, it is difficult to obtain a sufficiently high molecular weight polyamideimide. Tend to be.

  In the synthesis of polyamide-imide, in addition to diimide dicarboxylic acid and diisocyanate, another dicarboxylic acid component may be further contained. By carrying out like this, the heat resistance of a polyamideimide can also be improved further. Examples of the dicarboxylic acid component include aromatic dicarboxylic acids such as terephthalic acid, phthalic acid, and naphthalenedicarboxylic acid, and aliphatic dicarboxylic acids such as adipic acid, sebacic acid, decanedioic acid, dodecanedioic acid, and dimer acid. Such other dicarboxylic acid is preferably added in an amount of about 5 to 10 mol% based on the total amount of diimide dicarboxylic acid.

By such a production method, a polyamideimide having a structural unit represented by the following general formulas (15a), (15b), (15c), and (15d) is obtained, if preferred. Note that the symbols (R ¹ , R ¹⁴ , R ⁴¹ , R ⁴² , R ⁶¹ , R ⁶² , n, and m) in the formula are all as defined above.

The weight average molecular weight of the polyamideimide obtained by the above method is preferably 10,000 to 150,000, more preferably 30,000 to 120,000, and 50,000 to 100,000. Further preferred. If the polyamideimide is outside the above range of the weight average molecular weight, it is difficult to form a microphase separation structure in the polyamideimide, and the flame retardancy and heat resistance of the cured product of the resin composition tend to decrease. . In addition, the weight average molecular weight here is a value obtained by performing measurement by gel permeation chromatography and converting it with a calibration curve prepared using standard polystyrene.
(Thermosetting resin)

  Next, the thermosetting resin contained in the resin composition will be described. As a thermosetting resin, the compound provided with the functional group which reacts with the amide group of the polyamide imide mentioned above can be illustrated.

  Examples of such compounds (thermosetting resins) include polyfunctional epoxy compounds, polyimide resins, unsaturated polyester resins, polyurethane resins, bismaleimide resins, triazine-bismaleimide resins, and phenol resins. Especially, when it is set as a resin composition, the polyfunctional epoxy compound which can improve the adhesiveness to metal foil etc. favorably is preferable. As such a polyfunctional epoxy compound, a polyfunctional epoxy compound having two or more epoxy groups is preferable, and a polyfunctional epoxy compound having three or more epoxy groups is more preferable.

  Examples of the polyfunctional epoxy compound having two or more epoxy groups include an epoxy resin obtained by reacting a polyhydric phenol such as bisphenol A, a novolak type phenol resin, or an orthocresol novolak type phenol resin with epichlorohydrin; An epoxy resin obtained by reacting a polyhydric alcohol such as butanediol with epichlorohydrin; a polyglycidyl ester obtained by reacting a polybasic acid such as phthalic acid or hexahydrophthalic acid with epichlorohydrin; an amine, an amide or a heterocyclic type Examples thereof include N-glycidyl derivatives of compounds having a nitrogen base; alicyclic epoxy resins and the like.

  As polyfunctional epoxy compounds having 3 or more glycidyl groups, ZX-15548-2 (manufactured by Toto Kasei Co., Ltd.), DER-331L (bisphenol A type epoxy resin manufactured by Dow Chemical Co., Ltd.), YDCN-195 (Toto Kasei Co., Ltd.) A cresol novolac type epoxy resin manufactured by KK is commercially available and can be suitably used.

  As the thermosetting resin, a polyfunctional epoxy compound containing a phosphorus atom in the molecule is particularly preferable in order to impart flame retardancy to the resin composition. Specifically, as such a compound, phosphorus-containing epoxy resin ZX-1548-1 (phosphorus content: 2.0 wt%), ZX-15548-2 (phosphorus content: 2.5 wt%), ZX-1548-3 (phosphorus content: 3.0% by weight), ZX-1548-4 (phosphorus content: 4.0% by weight, above, trade name manufactured by Tohto Kasei Co., Ltd.). These can be used alone or in combination of two or more.

  The amount of the thermosetting resin is preferably 5 to 100 parts by mass, more preferably 10 to 80 parts by mass, and further preferably 20 to 65 parts by mass with respect to 100 parts by mass of the polyamideimide described above. preferable. When the blending amount is less than 5 parts by mass, when a sheet-like molded product is formed from the resin composition, the strength of the molded product becomes insufficient, and the flame retardancy tends to be insufficient. On the other hand, when it exceeds 100 parts by mass, the resin composition is excessively cross-linked, and the obtained sheet-like molded product becomes brittle, which may result in insufficient adhesion to a metal foil or the like.

  When the polyfunctional epoxy compound described above is contained as the thermosetting resin, it is preferable to further add a curing agent or a curing accelerator for the polyfunctional epoxy compound. Known curing agents and curing accelerators can be used. For example, as the curing agent, amines such as dicyandiamide, diaminodiphenylmethane, guanylurea; imidazoles; hydroquinone, resorcinol, bisphenol A and their halides, polyfunctional phenols such as novolac-type phenol resin, resole-type phenol resin; Examples thereof include acid anhydrides such as phthalic anhydride, benzophenone tetracarboxylic dianhydride, and methyl hymic acid. Examples of the curing accelerator include imidazoles such as alkyl group-substituted imidazole and benzimidazole.

The compounding quantity of this hardening | curing agent can be determined according to the epoxy equivalent in a polyfunctional epoxy compound. For example, when an amine compound is added as a curing agent, the compounding amount is preferably such that the active hydrogen equivalent of the amine is equal to the epoxy equivalent of the polyfunctional epoxy compound. For example, when the thermosetting resin is a phosphorus-containing epoxy resin and the curing agent is an imidazole, the blending amount of the curing agent is 0.1 to 2.0 parts by mass with respect to 100 parts by mass of the phosphorus-containing epoxy resin. Preferably there is. If the blending amount is less than 0.1 parts by mass, the phosphorus-containing epoxy resin tends to remain in an uncured state, and the heat resistance of the cured product tends to decrease. Moreover, when it exceeds 2.0 mass parts, it exists in the tendency for a hardening | curing agent to remain in the hardened | cured material of a resin composition, and for insulation and durability to fall.
(Phosphorus-containing compound)

  It is preferable that the resin composition of a preferred embodiment further contains a phosphorus-containing compound in addition to the above-described polyamideimide and thermosetting resin. Thus, by further containing the phosphorus-containing compound, the flame retardancy of the sheet-like molded product made of the resin composition can be further improved.

  As the phosphorus-containing compound, a phosphoric acid ester compound is preferable. Specifically, trimethyl phosphate, triethyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl phenyl phosphate, cresyl-di-2,6-xylenyl phosphate, 2- (meth) acryloxy Examples thereof include xylethyl acid phosphate and diphenyl-2- (meth) acryloyloxyethyl phosphate.

  As the phosphorus-containing compound, an aromatic condensed phosphate ester compound is also applicable. Examples of such a compound include a compound represented by the general formula (8a) and a compound represented by the general formula (8b). These may be contained alone or in combination.

  The compound represented by the general formula (8a) or (8b) may have an aromatic ring having an alkyl group having 1 to 5 carbon atoms as a substituent. Examples of the alkyl group having 1 to 5 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, And neopentyl group.

  Examples of the phosphoric acid ester compounds mentioned above include Leophos 35, Leophos 50, Leophos 65, Leophos 95, Leophos 110 (above, trade name of Ajinomoto Fine Techno Co., Ltd.) and the like. Moreover, as aromatic condensed phosphate ester compounds, CR-733S, CR-741, CR-747, PX-200 (above, trade names manufactured by Daihachi Chemical Industry Co., Ltd.), SP-703, SP601 (above, Shikoku) Kasei Co., Ltd. trade name) etc. are commercially available.

The compounding amount of the phosphorus-containing compound is preferably 2 to 10 parts by mass and more preferably 2 to 5 parts by mass with respect to 100 parts by mass of the polyamideimide. When the compounding amount of the phosphorus-containing compound is less than 2 parts by mass, the flame retardancy of the sheet-like molded product made of the resin composition tends to be insufficient. On the other hand, when it exceeds 10 parts by mass, the adhesiveness of the molded product to the metal foil is lowered, and the properties such as heat resistance and insulation tend to be lowered.
(Other ingredients)

In addition to the components described above, the resin composition of the embodiment may further contain other components for adjusting the properties of the resin composition. Examples of such other components include a filler and a coupling agent.
[Substrate with resin]

  Next, the substrate with resin according to a preferred embodiment will be described. FIG. 1 is a schematic cross-sectional view showing an example of a substrate with resin. The base material with resin 10 includes a sheet-like base material 12 and a resin layer 14 formed thereon and made of the resin composition of the above-described embodiment. Such a substrate 10 with resin can be used as an adhesive film or the like.

  As the sheet-like substrate 12 in the substrate 10 with resin, a known resin material, metal foil, release paper, or the like can be applied. The substrate 12 is preferably made of a resin material, and examples of the resin material include polyolefins such as polyethylene and polypropylene, polyesters such as polyethylene terephthalate, polycarbonate, polyimide, and tetrafluoroethylene. Especially, as the base material 12, since it is excellent in characteristics, such as intensity | strength and heat resistance, the film which consists of polyimides is especially preferable. The thickness of the base 12 in the base 10 with resin is preferably 10 to 150 μm. Further, such a base material 12 may be appropriately subjected to mud treatment, corona treatment, mold release treatment and the like.

  The base material with resin 10 having such a configuration is, for example, after applying a varnish containing the above-described resin composition on the base material 12 and then volatilizing the solvent by heating or spraying hot air to apply the resin composition. It can be manufactured by drying the physical layer to form the resin layer 14. Here, as a varnish containing a resin composition, what a resin composition melt | dissolves or disperse | distributes to a predetermined organic solvent is suitable. The content of the resin composition in the varnish is preferably about 20 to 40% by mass in the total mass of the varnish.

  The organic solvent used for the varnish can be applied without particular limitation as long as it can disperse or dissolve the resin composition satisfactorily. For example, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl isobutyl ketone, and cyclohexanone; Esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl acetate, carbitol acetate, and γ-butyrolactone; cellosolves such as cellosolve and butylcellosolve; carbitols such as carbitol and butylcarbitol; toluene, xylene and the like Aromatic hydrocarbons; dimethyl sulfoxide, dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, sulfolane and the like.

  The thickness of the resin layer 14 in the substrate 10 with resin is preferably 5 to 50 μm, and more preferably 10 to 40 μm. Such a substrate 10 with resin may be stored in the form of a sheet cut by a predetermined length, or may be wound up and stored in the form of a roll. From the viewpoint of improving storability, productivity, and workability, the latter roll form is more preferable.

Moreover, the protective film for protecting the said layer 14 may be further laminated | stacked on the surface of the resin layer 14 in the base material 10 with resin. As such a protective film, what consists of the material similar to the base material 12 can be applied, and especially the thing with the adhesiveness with respect to the resin layer 14 small compared with the base material 12 is preferable. The thickness of the protective film 14 is preferably about 20 to 100 μm, and the surface thereof may be subjected to mud treatment, corona treatment, and mold release treatment.
[Conductor layer laminate]

  Next, a conductor layer-clad laminate according to a preferred embodiment will be described. FIG. 2 is a schematic cross-sectional view showing an example of a conductor layer-clad laminate. The conductor layer-clad laminate 20 has a configuration in which the adhesive layer 24 (resin layer) made of the above-described resin composition and the conductor layer 26 are sequentially laminated on both surfaces of the base material 22. Here, as the base material 22, the thing similar to the base material 12 in the base material 10 with a resin mentioned above can be applied, and a polyimide film is especially suitable.

  The conductor layer 26 is not particularly limited as long as it is made of a conductive material, but is preferably made of a metal foil from the viewpoint of obtaining better conductivity. Examples of the metal foil include copper foil, and electrolytic copper foil, rolled copper foil, and the like can be applied. As will be described later, since the adhesive layer 24 has excellent adhesion to a copper foil or the like, the copper foil is subjected to a roughening treatment or the like on the surface that is generally used. It is also possible to use one having a smooth surface.

  Moreover, metal foils other than copper foil are also applicable. As metal foil other than copper foil, an intermediate layer made of nickel, nickel-phosphorus, nickel-tin alloy, nickel-iron alloy, lead, lead-tin alloy, etc. is provided between the aluminum foil and the two copper foil layers. Examples thereof include a composite foil having a three-layer structure and a composite foil having a two-layer structure in which aluminum and a copper foil are combined.

  The conductor layer-clad laminate 20 can be manufactured as follows, for example. That is, first, the base material 22 is prepared, and a varnish containing a resin composition is applied to both surfaces thereof, and then dried by heating or spraying with hot air. Thereafter, a metal foil or the like for forming the conductor layer 26 is bonded to the outside of the applied resin layer. And the obtained laminated body is heated, pressing as needed using a heating press apparatus or a heating roll apparatus, and, thereby, each layer is closely_contact | adhered and the conductor layer-clad laminated board 20 is obtained. In this heating, the resin composition in the resin layer is cured and the adhesive layer 24 is formed.

  The conductor layer-clad laminate of the present invention does not have to have the form in which the adhesive layer 24 and the conductor layer 26 are laminated on both surfaces of the base material 22 as described above, but has a form in which these are laminated only on one side. May be.

  The conductor layer-clad laminate 20 having the above configuration is suitable as a substrate for a flexible wiring board (FPC), for example. That is, by performing known etching or the like on the conductor layer 26 in the conductor layer-clad laminate 20 to form a conductor layer having a predetermined pattern, an FPC having a circuit pattern formed on the surface can be obtained.

  As described above, the conductor layer-clad laminate 20 includes a layer made of the resin composition in the above-described form as the adhesive layer 24. Since the adhesive layer 24 contains polyamideimide containing a structural unit having an aliphatic cyclic hydrocarbon group, the adhesive layer 24 has excellent heat resistance and adhesion to a metal foil or the like. For this reason, even when an FPC or the like formed using the conductor layer-clad laminate 20 is mounted on an electronic device, the adhesive layer 24 in the laminate 20 is deteriorated due to thermal history even if a process involving high-temperature treatment is performed. Etc. are hardly generated. Thus, in the conductor layer-clad laminate 20, the adhesive layer 24 can maintain excellent adhesion to the base material 22 and the conductor layer 24 even after high temperature treatment. As a result, even after being mounted on an electronic device or the like, the inconvenience that the conductor layer 26 is peeled off is extremely difficult to occur.

  Further, in the conductor layer-clad laminate 20, the adhesive layer 24 contains polyamideimide having excellent flame retardancy as described above, and also contains a phosphorus-containing compound when appropriate. For this reason, this conductor layer-clad laminate has excellent flame retardancy even when it is processed into, for example, FPC and mounted on an electronic device. Here, since the adhesive layer 24 itself contains polyamideimide having excellent flame retardancy, the content of the phosphorus-containing compound does not affect the properties of the adhesive layer 24 such as heat resistance and adhesiveness. Even if it is the amount, sufficient flame retardancy can be exhibited. For this reason, in this adhesive layer 24, the characteristic deterioration by addition of a phosphorus containing compound which had arisen with the conventional adhesive layer can be reduced significantly. Thus, the conductor layer-clad laminate 20 has improved flame retardancy while maintaining excellent properties such as adhesion to the conductor layer and heat resistance.

EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited to these Examples.
[Synthesis of Polyamideimide]
(Synthesis Examples 1-8)

  Select a alicyclic diamine, aliphatic diamine, aromatic diamine and siloxane diamine as appropriate in a 1 L separable flask equipped with a 25 mL moisture meter with a cock connected to a reflux condenser, a thermometer, and a stirrer. These were mixed with trimellitic anhydride (TMA) and aprotic polar solvent N-methyl-2-pyrrolidone (NMP) and stirred at 80 ° C. for 30 minutes.

  After stirring, 100 mL of toluene was added as an aromatic hydrocarbon azeotropic with water, and the temperature was raised to 160 ° C. and refluxed for 2 hours. When it was confirmed that about 3.6 mL or more of water had accumulated in the moisture determination receiver and no water distilling was observed, the temperature was increased to 190 ° C. while removing the water in the moisture determination receiver, and toluene was removed. Removed.

After returning the flask solution to room temperature (25 ° C.), aromatic isocyanate and aliphatic diisocyanate and solvent γ-butyrolactone (γ-BL) were added to the solution and reacted at 150 ° C. for 1 hour. Furthermore, it was made to react at 180 degreeC for 2 hours, and the NMP / gamma-BL solution of the polyamideimide of the synthesis examples 1-8 was obtained. In addition, the kind and compounding quantity of each component used in Synthesis Examples 1-8 were as shown in Table 1. Table 1 also shows the solid content weight of the obtained solution and the weight average molecular weight of the obtained polyamideimide.

In Table 1, BAPP is 2,2-bis [4- (4-aminophenoxy) phenyl] propane, D-2000 is Jeffamine D-2000 (trade name, manufactured by Sun Techno Chemical Co., amine equivalent 105), Wandamine HM is Wandamine HM (trade name, manufactured by Shin Nippon Chemical Co., Ltd., amine equivalent 1000), X-22-9362, X-22-9415 and X-22-9405 have amine equivalents of 700, 1100 and 1900, respectively. Reactive silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd.), MDI represents 4,4′-diphenylmethane diisocyanate, and TDI represents 2,4-tolylene diisocyanate.
[Preparation of resin composition]
(Examples 1-5, Comparative Examples 1-3)

Each component shown in Table 2 was added to the NMP solution of polyamideimide of Synthesis Examples 1 to 8 and stirred until uniform, and then allowed to stand at room temperature for 24 hours for defoaming to obtain a resin composition. In addition, the case where the NMP solution of the polyamide imide of the synthesis examples 1-5 is used corresponds to Examples 1 to 5, and the case of using the NMP solution of the polyamide imide of the synthesis examples 6 to 8 corresponds to Comparative Examples 1 to 3, respectively. . Table 2 summarizes the types and amounts (g) of each component.

In the table, ZX-1548-2 is a phosphorus-containing epoxy resin ZX-1548-2 (trade name, manufactured by Tohto Kasei Co., Ltd., methyl ethyl ketone solution with a solid content of 75% by weight), and Reofos 65 is a phosphate ester. A certain Leophos 65 (trade name, manufactured by Ajinomoto Fine Techno Co., Ltd.), 2E4MZ is 2-ethyl-4-methylimidazole, and KA-1160 is KA-1160 (trade name, manufactured by Dainippon Ink & Chemicals, Inc.) which is a cresol novolac resin. Each is shown.
[Evaluation of adhesion]

  The resin compositions of Examples 1 to 5 and Comparative Examples 1 to 3 were each applied to a polyimide film (Kapton 100V, trade name manufactured by Toray DuPont) having a thickness of 25 μm so that the thickness after drying would be 20 μm. And dried at 130 ° C. for 10 minutes to obtain a film with a resin. Next, the surface formed by applying the resin composition in each resin-attached film to the roughened surface side of a 35 μm-thick rolled copper foil (BHY-22B-T, product name manufactured by Nikko Materials) is bonded to the temperature. With a conductor layer having a polyimide film, an adhesive layer (resin layer), and a copper foil in this order, after temporarily bonding by heat pressing for 30 minutes under conditions of 160 ° C. and pressure 3 MPa, heating at 180 ° C. for 120 minutes with a dryer A laminate was obtained.

A plurality of laminates with conductor layers in the case of using the resin compositions of Examples 1 to 5 and Comparative Examples 1 to 3 were prepared, and the laminates corresponding to each Example or Comparative Example were as follows: Condition 1: Normal 10 The treatment was carried out under the following three conditions: standing for days, condition 2: heat treatment at 150 ° C. for 10 days with a dryer, or condition 3: treatment for 24 hours under high temperature and high humidity conditions (121 ° C., 2 atm, saturated state). Peeling strength (kN / m, 90 ° peel strength) when the copper foil in each laminated board after treatment is peeled in the direction of 90 ° under the conditions of a measurement temperature of 25 ° C. and a peel rate of 10 mm / min. By measuring JIS C6481, the adhesion between the copper foil and the adhesive layer was evaluated. The obtained results are shown in Table 3.
[Evaluation of solder heat resistance]

A plurality of laminated plates with conductor layers corresponding to each of the examples and comparative examples were prepared in the same manner as prepared in the above “Evaluation of adhesiveness”, and the laminated plates corresponding to each of the examples and comparative examples were prepared under the condition 1: The laminate is directly contacted with a solder bath at 300 ° C., condition 2: the laminate is heated (40 ° C., 90% RH, 8 hours) and then contacted with a solder bath at 280 ° C., condition 3: the laminate is added. After heat treatment (40 ° C., 90% RH, 8 hours), each was processed under three conditions: contact with a solder bath at 260 ° C., and each laminate was visually observed to see whether blistering or peeling occurred. . At this time, the laminated plates were brought into contact with each other so as to float in the solder bath so that the copper foil side was down. The contact time was 1 minute. The obtained results are shown in Table 3. In Table 3, those in which no blistering or peeling occurred were indicated by “◯” as those having excellent solder heat resistance, and those in which blistering or peeling occurred were indicated by “x” as inferior in solder heat resistance.
[Evaluation of flame retardancy]

  The resin compositions of Examples 1 to 5 and Comparative Examples 1 to 3 were each applied to a polyimide film (Kapton 100V) with a thickness of 25 μm so that the thickness after drying was 20 μm, and dried at 130 ° C. for 10 minutes. I let you. Next, the same resin composition is applied and dried on the uncoated surface of the polyimide film in the same manner as described above, and then heated at 180 ° C. for 120 minutes to have a resin layer, a polyimide film, and a resin layer in this order. A substrate with resin was obtained.

Using the obtained substrate with resin, a flame retardancy test was performed by a method based on the UL 94 flame retardancy test, and the flame retardancy of each substrate with resin was evaluated. The obtained results are shown in Table 3. In Table 3, the evaluation results of flame retardancy are shown by grades based on UL94 standards.
[Measurement of glass transition temperature and storage modulus]

  The resin compositions of Examples 1 to 5 and Comparative Examples 1 to 3 were applied to a fluorine film having a thickness of 100 μm (Naflon tape TOMBO9001, product name manufactured by NICHIAS) so that the thickness after drying would be 40 μm. After drying by heating at 130 ° C. for 10 minutes with a dryer, the substrate was further heated at 180 ° C. for 120 minutes to obtain a resin-coated substrate having a fluorine-based film and a resin layer. Then, the fluorine-type film was peeled from the obtained base material with resin, and the sheet | seat which consists of a resin composition was obtained.

The dynamic viscoelasticity measurement was performed using the sheet | seat obtained from the resin composition of each Example and the comparative example. At this time, the glass transition temperature (Tg) was calculated using the maximum value of the tan δ peak as the measured value. The obtained results are shown in Table 3. In addition, dynamic viscoelasticity evaluation was performed on the conditions shown below.
Measuring device: RSAII (Rheometric product name)
Measurement mode: Tensile sample size: 5.0 mm x 22.5 mm
Measurement temperature: 0 to 250 ° C
Temperature increase rate: 5 ° C / min Measurement frequency: 1Hz

From Table 3, when the resin compositions of Examples 1 to 5 were used, sufficient adhesion between the copper foil and the adhesive layer was obtained, and it was excellent even after treatment under predetermined temperature and humidity conditions. It was confirmed that excellent solder heat resistance was obtained, and excellent flame retardancy was also obtained. On the other hand, when the resin compositions of Comparative Examples 1 to 3 were used, it was found that the solder heat resistance after the heating / humidifying treatment was low and the flame retardancy was insufficient.
[Observation of micro phase separation structure]

  By using the laminate obtained in the above “measurement of glass transition temperature and storage elastic modulus” and observing the resin composition layer with an electron microscope, a microphase separation structure (sea island of submicron to micron order) It was evaluated whether or not (structure) occurred. As a result, it was confirmed that a microphase separation structure was generated in the laminates obtained using the resin compositions of Examples 1 to 5.

It is a schematic cross section which shows an example of a base material with resin. It is a schematic cross section showing an example of a conductor layer-clad laminate.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 10 ... Base material with resin, 12 ... Base material, 14 ... Resin layer, 20 ... Laminate laminated conductor layer, 22 ... Base material, 24 ... Adhesive layer, 26 ... Conductor layer.

Claims (11)

Containing a polyamidoimide containing a structural unit having an aliphatic cyclic hydrocarbon group, and a polyfunctional epoxy compound containing a phosphorus atom in the molecule ,
The polyamideimide is obtained by reacting diimide dicarboxylic acid obtained by reacting a diamine compound and trimellitic anhydride and diisocyanate, and the diimide dicarboxylic acid is represented by the following general formula (1). A resin composition comprising at least the compound represented.

[Wherein, R ¹ represents a divalent group represented by the following general formula (2a) or (2b).

In the formula ^{(2a), R 21} represents a hydrogen atom, a hydroxyl group, a methoxy group, a methyl group or a halogenated methyl ^{group, R 22} is an alkylene group having 1 to 3 carbon atoms, a halogenated 1 to 3 carbon atoms Represents an alkylene group, a sulfonyl group, an oxy group, a carbonyl group or a single bond, and in formula (2b), R ²³ represents an alkylene group having 1 to 3 carbon atoms, a halogenated alkylene group having 1 to 3 carbon atoms, a sulfonyl group, An oxy group or a carbonyl group is shown. A plurality of R ²¹ may be the same or different. ]   The resin composition according to claim 1, further comprising a phosphorus-containing compound. The compound represented by the general formula (1) is obtained by reacting the diamine compound represented by the following general formula (3) with trimellitic anhydride, and the amine equivalent of the diamine compound. Is 50-200 g / mol, The resin composition of Claim 1 or 2 characterized by the above-mentioned.

[Wherein R ³ represents a divalent group represented by the general formula (2a) or (2b). ] The diimide dicarboxylic acid further comprises a compound represented by the following general formula (4a) and / or a compound represented by the following general formula (4b). The resin composition according to one item.

[In the formula (4a), R ⁴¹ represents a hydrogen atom, an alkyl group, a phenyl group or a substituted phenyl group, n is an integer of 1 to 50, and in the formula (4b), R ⁴² represents the following general formula ( The divalent group represented by 5a) or (5b) is shown.

However, in formula (5a), R ⁵ represents an alkylene group having 1 to 3 carbon atoms, a halogenated alkylene group having 1 to 3 carbon atoms, a sulfonyl group, an oxy group, a carbonyl group, or a single bond. ] The resin composition according to any one of claims 1 to 4, further comprising a compound represented by the following general formula (6) as the diimide dicarboxylic acid.

[Wherein, R ⁶¹ represents an alkyl group, a phenyl group or a substituted phenyl group, R ⁶² represents a divalent organic group, and m represents an integer of 1 to 50. ] The compound represented by the general formula (6) is obtained by reacting a diamine compound represented by the following general formula (7) with trimellitic anhydride, and the amine equivalent of the diamine compound is 200 to 2500 g / mol, The resin composition according to claim 5.

[Wherein, R ⁷¹ represents an alkyl group, a phenyl group or a substituted phenyl group, R ⁷² represents a divalent organic group, and p represents an integer of 1 to 50. ]   The resin composition according to claim 2, wherein the phosphorus-containing compound is a phosphate ester compound. The phosphorus-containing compound is a compound represented by the following general formula (8a) and / or a compound represented by the following general formula (8b). The resin composition described in 1.

Wherein (8a), q is an integer of 10 to 50, wherein (8b), ^{R 8} represents a single bond, an alkylene group having 1 to 5 carbon atoms, a sulfide group, a sulfonyl group, aryloxy group, or an azo group R is an integer of 10-50. ] A sheet-like substrate;
A resin layer made of the resin composition according to any one of claims 1 to 8 formed on the substrate;
A substrate with resin, comprising:   The substrate with resin according to claim 9, wherein the substrate is a polyimide film. A sheet-like substrate;
A resin layer comprising the resin composition according to any one of claims 1 to 8 provided on the base material,
A conductor layer provided on the resin layer;
A conductor layer-clad laminate, comprising:

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