JP4639752B2 - Circuit board with adhesive layer, method for producing multilayer printed wiring board, and multilayer printed wiring board - Google Patents

Description

  The present invention relates to a circuit board with an adhesive layer, a method for producing a multilayer printed wiring board, and a multilayer printed wiring board.

  Mobile communication devices such as mobile phones, base station equipment, network-related electronic devices such as servers and routers, and large computers are required to transmit and process large amounts of information with low loss and high speed. Yes. In order to meet such demands, the frequency of electrical signals handled on the multilayer printed wiring board mounted on the apparatus as described above is increasing. However, the higher the frequency is, the more easily the electric signal is attenuated. Therefore, the printed wiring board used in these fields needs to further reduce the transmission loss.

  In order to obtain a multilayer printed wiring board with low transmission loss, conventionally, a fluorine resin having a low relative dielectric constant and dielectric loss tangent was included as a dielectric material of an insulating board such as a laminated board or an electrical insulating layer in the multilayer printed wiring board. A thermoplastic resin material is used. However, since a fluorine-based resin generally has a high melt viscosity and a relatively low fluidity, it is necessary to set high-temperature and high-pressure conditions during press molding. Moreover, as a printed wiring board material used for the above-mentioned communication equipment, network-related electronic equipment, large computers, etc., processability, dimensional stability, and adhesion to metal plating are insufficient.

Therefore, resin compositions containing triallyl cyanurate and triallyl isocyanurate shown in Patent Documents 1 to 3, which are thermosetting resin compositions having a low relative dielectric constant and dielectric loss tangent, Patent Documents 1 and 2 Resin composition containing polybutadiene shown in 4 and 5, thermosetting polyphenylene ether provided with radical crosslinkable functional group such as allyl group shown in Patent Document 6 and triallyl cyanurate And a method of using a resin composition containing triallyl isocyanurate as a raw material for dielectric materials such as the above-mentioned electronic devices has been proposed. According to these patent documents, generally, the cured resin does not have many polar groups, so that it is possible to reduce transmission loss.
Japanese Examined Patent Publication No. 6-69746 Japanese Patent Publication No. 7-47689 JP 2002-265777 A Japanese Patent Publication No.58-21925 JP-A-10-117052 Japanese Patent Publication No. 6-92533

  However, when a printed wiring board using a low dielectric constant, low dielectric loss tangent resin, such as those described in Patent Documents 1 to 6, which are cured by polymerization of vinyl groups or allyl groups, is examined in detail, such a method is required. In the multilayer printed wiring board, since the polarity of the electric insulating layer is low, the adhesive force (bonding force) between the conductor circuit (wiring circuit) and the electric insulating layer is weak, and the present inventors have a tendency to cause peeling between these layers. Found. Such peeling becomes significant when the multilayer printed wiring board is heated (particularly when heated after moisture absorption).

  Therefore, when such a low dielectric constant and low dielectric loss tangent resin is used for a multilayer printed wiring board by a conventional method, the surface of the conductor circuit is subjected to a roughening treatment, and the adhesive force (bonding force) between the conductor circuit and the electrically insulating layer. Need to be reinforced. Examples of such surface roughening treatment include oxidation treatment (blackening treatment), oxidation-reduction treatment, etching treatment, and metal plating treatment.

  By the way, in recent years, merely reducing the transmission loss of an electric signal in an insulating plate such as a laminated plate or an electric insulating layer is insufficient as a measure for further increasing the frequency of the electric signal. In other words, transmission loss of electrical signals includes loss (dielectric loss) caused by insulating plates and electrical insulation layers, and loss caused by conductor circuits such as signal layers, ground layers (earth layers, shield layers, etc.) and power supply layers. In the category of (conductor loss), recently, not only the reduction of dielectric loss but also the reduction of conductor loss cannot be ignored. In particular, in most multilayer printed wiring boards that have been put to practical use in recent years, the thickness of the electrical insulation layer is relatively thin, such as 200 μm or less, so that the material of the electrical insulation layer has a somewhat low dielectric constant and dielectric loss tangent. When the resin shown is adopted, the conductor loss rather than the dielectric loss is dominant as the transmission loss of the entire wiring board.

  The conductor loss is mainly attributed to the size of the surface roughness of the conductor circuit. From such a viewpoint, the metal foil having a small maximum value of the ten-point average roughness (Rz) of the surface is small. (Hereinafter referred to as “low profile metal foil”) is said to be effective. In the case where a low dielectric constant, low dielectric loss tangent resin that is cured by polymerization of vinyl group or allyl group, including those described in Patent Documents 1 to 6, is used for the dielectric material of the multilayer printed wiring board, the above-mentioned As described above, since the adhesive force (bonding force) between the conductor circuit and the electrically insulating layer is weak, it is difficult to reduce the surface roughness of the conductor circuit using such a low profile metal foil, and a sufficiently low transmission loss is achieved. Can be said to have limitations.

  The present invention has been made in view of the above circumstances, and can form a multilayer printed wiring board that can sufficiently reduce transmission loss particularly in a high-frequency band and that has a sufficiently strong adhesive force between a conductor circuit and an electrical insulating layer. It is an object of the present invention to provide a circuit board with an adhesive layer, a method for producing a multilayer printed wiring board, and a multilayer printed wiring board.

  The present inventors can solve the above-mentioned problem even when a low dielectric constant thermosetting resin such as polybutadiene, triallyl isocyanurate and polyphenylene ether is used as a dielectric material for an electrically insulating layer in combination with a metal foil having a small surface roughness. As a result of intensive studies to solve this problem, the present invention has been completed.

  That is, the circuit board with an adhesive layer of the present invention comprises an adhesive layer comprising a circuit board on which a conductor circuit is formed on one or both main surfaces of an insulating plate, and an adhesive layer provided on at least the surface of the conductor circuit. A circuit board with an adhesive layer comprising: (A) component; polyamideimide; and (B) component; a compound having a functional group capable of reacting with an amide group of the polyamideimide and having an ethylenically unsaturated bond It consists of curable resin composition containing these.

  The circuit board with an adhesive layer of the present invention is an adhesive layer comprising a circuit board having a conductor circuit formed on one or both main surfaces of an insulating plate, and an adhesive layer provided at least on the surface of the conductor circuit. The adhesive layer comprises: (A) component; polyamideimide, (C) component; compound having two or more functional groups capable of reacting with the amide group of the polyamideimide, and (D) component; It comprises a curable resin composition containing a functional group capable of reacting with the component (C) and a compound having an ethylenically unsaturated bond.

  When the adhesive layer according to the present invention is used, even if the above-described dielectric material is used in combination with the surface roughness of the conductor circuit being small, it can be sufficiently adhered. Therefore, when the circuit board with an adhesive layer of the present invention is used, it is possible to sufficiently reduce transmission loss in a high frequency band and to form a multilayer printed wiring board with sufficiently strong adhesive force between a conductor circuit and an electrically insulating layer. .

  The layer obtained by curing the adhesive layer according to the present invention (hereinafter referred to as “cured layer”) also functions as a part of the electrical insulating layer of the printed wiring board. The portion constituting the electrical insulating layer other than the cured layer is expressed as “insulating resin layer” and is distinguished from the cured layer.

  The reason why the circuit board with an adhesive layer of the present invention can achieve the above-mentioned object has not been clarified in detail at present, but the present inventors presume as follows. However, the factor is not limited to this.

  Polyamideimide is generally known as a compound having high adhesive strength with a conductor. Therefore, when polyamideimide is used as the material for the adhesive layer, the peel strength between the conductor circuit of the circuit board and the cured layer obtained by curing the adhesive layer is improved. However, polyamideimide has low compatibility and extremely low reactivity with low dielectric constant resins such as the above-mentioned vinyl curing type and allyl curing type. For this reason, a cured layer made of only polyamideimide cannot exhibit sufficient peel strength between the layer using these resins (insulating resin layer).

  In the multilayer printed wiring board manufactured using the circuit board with an adhesive layer of the present invention, the (B) component, or the (C) component and the (D) component enhance the compatibility with the low dielectric constant resin. Furthermore, the polyamideimide as component (A) undergoes a crosslinking reaction by radical polymerization with a low dielectric constant resin that is a constituent material of the adjacent insulating resin layer simultaneously with the polymerization reaction in the adhesive layer. Thereby, the hardened layer obtained from the adhesive layer and the insulating resin layer are almost integrated. As a result, this hardened layer not only has a sufficiently high adhesive force with the conductor layer, but also can improve the breaking strength inside the hardened layer and in the vicinity of the interface between the hardened layer and the insulating resin layer. Even with the resin layer, it has a sufficiently high adhesive force. In addition, due to the improvement in breaking strength, such a multilayer printed wiring board tends to improve heat resistance.

  In the circuit board with an adhesive layer of the present invention, the polyamideimide as the component (A) preferably has a structural unit composed of a saturated hydrocarbon. A multilayer printed wiring board formed using such a circuit board with an adhesive layer can further enhance the adhesive force between the conductor circuit and the electrically insulating layer, and can maintain a high adhesive force even during moisture absorption. Moisture and heat resistance can be expressed.

The circuit board with an adhesive layer of the present invention preferably has a component (B) having an oxirane ring represented by the following formula (I) or an oxetane ring represented by the following formula (II) from the viewpoint of enhancing curability. More preferably, it has an oxirane ring.

Moreover, the circuit board with an adhesive layer of the present invention has a vinyl group, an allyl group, an acrylic group (CH ₂ ═CHCOO—) and a methacryl group (CH ₂ ═) as the functional group having an ethylenically unsaturated bond in the component (B). It is preferred to have one or more groups selected from the group consisting of C (CH ₃ ) COO—.

  From the same viewpoint, the component (C) preferably has two or more oxirane rings or oxetane rings, and more preferably has two or more oxirane rings.

The circuit board with an adhesive layer of the present invention is curable when the component (B) is an epoxy compound having a polybutadiene structure and an oxirane ring, that is, an epoxy compound having an oxirane ring and further having a polybutadiene structure. From the viewpoint of further improvement and compatibility with the insulating resin layer, it is preferable. Such component (B) is, for example, from the group consisting of phenolic hydroxyl groups, alcoholic hydroxyl groups, carboxyl groups, amide groups, amino groups, imino groups (—NH—) and groups represented by the following formula (III). It can be obtained by reacting a modified polybutadiene having one or more selected groups with a compound having two or more oxirane rings.

  In the circuit board with an adhesive layer of the present invention, the epoxy compound in the curable resin composition constituting the adhesive layer preferably has a vinyl group at its side chain or terminal.

Moreover, it is preferable that the said epoxy compound has a structural unit represented by the following general formula (1), (2) or (3), or the following general formula (5).

Here, in Formula (1), n shows the integer of 2-8, and the sum total of n and m shows the integer of 10-10000. In Formula (2), R ¹ and R ² each independently represent a hydrogen atom or a hydroxyl group, and R ³ represents an acrylic group or an oxiranyl group.

In formula (3), R ⁴ represents a group represented by the following formula (4), i represents an integer of 0 to 100, and the sum of i and j represents an integer of 10 to 10,000.

  In formula (5), p and u each independently represent an integer of 1 to 10,000, q represents an integer of 1 to 100, r and s each independently represents an integer of 0 to 100, and t represents An integer of 1 to 10,000 is shown. However, either r or s represents an integer of 1 or more.

  In the circuit board with an adhesive layer of the present invention, the component (D) has a vinyl group at its side chain or terminal, and has a phenolic hydroxyl group, an alcoholic hydroxyl group, a carboxyl group, an amide group, an amino group, an imino group, and A modified polybutadiene having one or more groups selected from the group consisting of the above formula (III) is preferred. Here, the “modified polybutadiene” refers to a polybutadiene having a part of the structure of the polybutadiene added with another atom or functional group, or a part of the structure of the polybutadiene substituted with another atom or functional group.

  In the circuit board with an adhesive layer of the present invention, the blending ratio of the component (B) is 5 to 200 parts by mass with respect to 100 parts by mass of the component (A) from the viewpoint of further exerting the effects of the present invention described above. Preferably, the total blending ratio of component (C) and component (D) is 5 to 200 parts by weight with respect to 100 parts by weight of component (A), and the blending ratio of component (D) is 100 parts by weight of component (C). It is preferable that it is 5-1000 mass parts with respect to a part.

  In the circuit board with an adhesive layer of the present invention, when the adhesive layer is made of a curable resin composition containing the component (A) and the component (B), the circuit board is provided between the insulating plate and the conductor circuit. It is preferable that a layer formed by curing the curable resin composition containing the component (A) and the component (B) is provided. Moreover, when an adhesive layer consists of curable resin composition containing (A) component, (C) component, and (D) component, a circuit board is (A) between an insulating board and a conductor circuit. ) Component, (C) component, and (D) It is preferable when the layer formed by hardening | curing the curable resin composition containing a component is provided.

  When such a circuit board is used for the circuit board with an adhesive layer of the present invention, a sufficient adhesive force is obtained between the insulating plate and the conductor circuit even if a resin having a low dielectric constant and a low dielectric loss tangent is used for the insulating plate. be able to. For this reason, the adhesive force (bonding force) is increased between the insulating plate and the conductor circuit, and the conductor loss between the insulating plate and the conductor circuit is sufficiently reduced by reducing the surface roughness of the conductor circuit on the insulating plate side. It is possible.

  Moreover, in the circuit board with an adhesive layer of the present invention, when the curable resin composition further contains the component (E); a radical polymerization initiator, a cured layer can be formed more quickly, and the storage stability of the adhesive layer portion can be increased. This is preferable because the property tends to be improved.

  The adhesive layer according to the present invention is obtained, for example, by applying a resin varnish containing a curable resin composition and a solvent on the surface of the conductor circuit and then volatilizing the solvent. It is preferable in it being 1-10 micrometers.

  Further, in the conductor circuit of the circuit board according to the present invention, when the ten-point average roughness (Rz) of the surface is 2 μm or less, the transmission loss can be further reduced, and between the conductor circuit and the hardened layer. Adhesive strength can be maintained in a sufficiently high state. Here, the ten-point average roughness Rz is a surface roughness in accordance with JIS-B0601-1994.

  The adhesive layer according to the present invention is preferably provided on one or both main surfaces of the insulating plate and on the surface of the conductor circuit. In this case, since the adhesive layer is formed on the entire surface of the circuit board having the conductor circuit, the manufacture of the circuit board with the adhesive layer of the present invention can be facilitated.

  In addition, the circuit board according to the present invention may be a board in which a conductor circuit is formed on the main surface of an insulating plate that is an electrical insulating layer located in the outermost layer of the laminate, or may be a core board. Good. Here, the “core substrate” refers to a circuit board that is first prepared for manufacturing a multilayer printed wiring board, and may be one in which conductor circuits are provided on both surfaces of a single insulating board. In addition, a conductor circuit may be provided on one surface of a single insulating plate. When the circuit board according to the present invention is a core board, when a multilayer printed wiring board is formed, sufficient adhesive force is obtained between the innermost conductor circuit and the electrical insulating layer formed thereon. Can do.

  In the method for producing a multilayer printed wiring board of the present invention, an insulating resin sheet containing an insulating resin and a metal foil are laminated in this order on at least the surface of the adhesive layer of the circuit board with the adhesive layer. It has the process of obtaining a multilayer body, and the process of heating and pressurizing this multilayer body, It is characterized by the above-mentioned.

  Here, as the insulating resin sheet, at least one material selected from the group consisting of E glass, S glass, NE glass, D glass, Q glass, paper material, aramid, fluororesin, polyester, and liquid crystalline polymer. A prepreg obtained by impregnating an insulating resin into a fiber base material containing bismuth is preferably used. Of these materials, materials other than the liquid crystalline polymer do not exhibit liquid crystallinity.

  Further, from the viewpoint of sufficiently reducing the relative permittivity and dielectric loss tangent, it is preferable that the insulating resin contains a resin having an ethylenically unsaturated bond, and the resin having an ethylenically unsaturated bond is polybutadiene, polytrimethyl. More preferably, it is at least one resin selected from the group consisting of allyl cyanurate, polytriallyl isocyanurate and polyphenylene ether. In particular, it is most preferable that the insulating resin contains polyphenylene ether.

  The multilayer printed wiring board of the present invention is obtained by such a method for producing a multilayer printed wiring board.

  According to the present invention, a circuit board with an adhesive layer capable of sufficiently reducing transmission loss particularly in a high frequency band and capable of forming a multilayer printed wiring board with sufficiently strong adhesive force between a conductor circuit and an electrically insulating layer, Moreover, the manufacturing method of a multilayer printed wiring board and a multilayer printed wiring board can be provided.

  Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings as necessary. In the drawings, the same elements are denoted by the same reference numerals, and redundant description is omitted. Further, the positional relationship such as up, down, left and right is based on the positional relationship shown in the drawings unless otherwise specified. Further, the dimensional ratios in the drawings are not limited to the illustrated ratios.

(First embodiment)
As shown in FIG. 1, the circuit board 100 with an adhesive layer according to the first embodiment of the present invention is used as a core substrate, and is composed of a circuit board 10 and an adhesive layer 20. More specifically, the circuit board 10 includes a laminated plate 12 that is an insulating plate, and a conductor circuit 14 having a predetermined shape formed on both surfaces (both main surfaces) of the laminated plate 12, An adhesive layer 20 is formed on the surface 14 a of the conductor circuit 14 and on the surface 12 a of the laminate 12. The circuit board 10 may be provided with a reference hole or the like by a known method.

  As the laminated board 12, what is obtained by laminating several known prepregs and subjecting them to pressure heat treatment can be used. As such a prepreg, those prepared by a known method by impregnating a prepared resin varnish into a fiber base material (reinforced fiber) such as glass fiber or organic fiber can be used. In particular, it is preferable to use the same base material as the insulating resin sheet (insulating resin layer) for manufacturing the multilayer printed wiring board described later for the laminate 12.

  The conductor circuit 14 is formed by performing a known patterning process such as a photolithography method on the metal foil adhered on the laminated plate 12. Although the metal foil used for the conductor circuit 14 is not specifically limited, Although copper foil, nickel foil, and aluminum foil are mentioned, Usually, it is preferable when electric field copper foil or rolled copper foil is used. Such a metal foil is preferably subjected to a barrier layer forming treatment with nickel, tin, zinc, chromium, molybdenum, cobalt or the like on the entire surface from the viewpoint of improving its rust resistance, chemical resistance and heat resistance. Such a metal foil may be a single layer made of one kind of metal material or a single layer made of a plurality of metal materials, and is formed by laminating a plurality of metal layers of different materials. May be. Moreover, the thickness is not specifically limited. Among these metal foils, as copper foil, F2-WS (Furukawa Circuit Foil, Rz = 3.0 μm), F0-WS (Furukawa Circuit Foil, trade name, Rz = 1.2 μm), 3EC- VLP (made by Mitsui Kinzoku Co., Ltd., trade name, Rz = 3.0 μm) and the like are commercially available.

  In addition, the surface 14a of the conductor circuit 14 may be subjected to a surface roughening treatment, a treatment with a silane coupling agent, or the like. However, with respect to the surface roughening treatment, the surface roughness (Rz) of the conductor circuit 14 is When the roughening treatment is performed so that the thickness is preferably 2 μm or less, more preferably 1 μm or less, the high-frequency transmission characteristics can be further improved. Examples of the silane coupling agent include epoxy silane, amino silane, cationic silane, vinyl silane, acryloxy silane, methacryloxy silane, ureido silane, mercapto silane, sulfide silane, and isocyanate silane.

  The adhesive layer 20 is composed of (A) component; polyamideimide, (B) component; a compound having a functional group capable of reacting with the amide group of the polyamideimide and having an ethylenically unsaturated bond (hereinafter referred to as necessary). A curable resin composition containing an “amide-reactive unsaturated compound”). Hereinafter, the curable resin composition and its components constituting the adhesive layer 20 will be described.

<(A) component>
The polyamideimide as the component (A) is not particularly limited, and examples thereof include polyamideimide synthesized by a so-called isocyanate method by reaction between trimellitic anhydride and aromatic diisocyanate. As a specific example of the isocyanate method for synthesizing a polyamideimide, a method in which an aromatic tricarboxylic acid anhydride and a diamine compound having an ether bond are reacted in the presence of an excess of a diamine compound and then a diisocyanate is reacted (for example, Japanese Patent No. 2897186). And a method of reacting an aromatic diamine compound and trimellitic anhydride (for example, a method described in JP-A No. 04-182466).

  A siloxane structure may be introduced into the main chain of polyamideimide. Thereby, the characteristics such as the elastic modulus and flexibility of the cured layer obtained by curing the adhesive layer 20 can be improved, and the drying efficiency and the like can be further improved. Polyamideimide having a siloxane structure in the main chain can be synthesized according to the isocyanate method. Specific examples of the synthesis method include a method of polycondensing an aromatic tricarboxylic acid anhydride, an aromatic diisocyanate and a siloxane diamine compound (for example, a method described in JP-A No. 05-009254), an aromatic dicarboxylic acid or A method of polycondensing an aromatic tricarboxylic acid and a siloxane diamine compound (for example, a method described in JP-A-06-116517), a diamine compound having three or more aromatic rings and a mixture containing siloxane diamine and trimellitic anhydride Examples include a method of reacting a mixture containing diimide dicarboxylic acid obtained by reacting with an acid with an aromatic diisocyanate (for example, a method described in JP-A-06-116517). In this embodiment, even if the polyamideimide synthesized by the above-described known method is used, sufficiently high adhesiveness with the conductor can be expressed.

  Furthermore, use of polyamideimide having a structural unit composed of saturated hydrocarbons further improves the adhesion to the conductor and also improves the moisture resistance, so that it maintains a high adhesion even after moisture absorption, and has a higher moisture and heat resistance. Sex is obtained. From the same viewpoint, the structural unit is more preferably a saturated alicyclic hydrocarbon group. Polyamideimides containing saturated alicyclic hydrocarbon groups are more excellent in moisture and heat resistance and exhibit higher Tg.

  Polyamideimide having a structural unit consisting of a saturated hydrocarbon is, for example, derived from an acid halide derived from an imide group-containing dicarboxylic acid obtained by reacting a diamine compound having a saturated hydrocarbon group with trimellitic anhydride, or It can be obtained by reacting with a diamine compound using a condensing agent. Alternatively, a polyamideimide having a structural unit composed of a saturated hydrocarbon can also be obtained by reacting a diisocyanate with an imide group-containing dicarboxylic acid obtained by reacting a diamine compound having a saturated hydrocarbon group with trimellitic anhydride. It is done. Similarly, the polyamide having a structural unit composed of a saturated alicyclic hydrocarbon may be one having a saturated alicyclic hydrocarbon group as the diamine compound in the above synthesis method.

式（６ａ）、（６ｂ）中、Ｌ^１はハロゲン置換されていてもよい炭素数１〜３の２価の脂肪族炭化水素基、スルホニル基、オキシ基、カルボニル基、単結合又は下記式（７ａ）又は（７ｂ）で表される２価の基を示し、Ｌ^２はハロゲン置換されていてもよい炭素数１〜３の２価の脂肪族炭化水素基、スルホニル基、オキシ基又はカルボニル基を示し、Ｒ^５、Ｒ^６及びＲ^７は、それぞれ独立に水素原子、水酸基、メトキシ基、ハロゲン置換されていてもよいメチル基を示す。

式（７ａ）中、Ｌ^３はハロゲン置換されていてもよい炭素数１〜３の２価の脂肪族炭化水素基、スルホニル基、オキシ基、カルボニル基又は単結合を示す。 As said diamine compound, what is represented by the following general formula (6a) or (6b) is mentioned, for example.

In the formulas (6a) and (6b), L ¹ is an optionally halogenated divalent aliphatic hydrocarbon group having 1 to 3 carbon atoms, a sulfonyl group, an oxy group, a carbonyl group, a single bond, or the following formula ( A divalent group represented by 7a) or (7b), wherein L ² is a halogenated halogenated divalent aliphatic hydrocarbon group having 1 to 3 carbon atoms, a sulfonyl group, an oxy group or a carbonyl group; R ⁵ , R ⁶ and R ⁷ each independently represent a hydrogen atom, a hydroxyl group, a methoxy group, or a methyl group optionally substituted with halogen.

In formula (7a), L ³ represents a C 1-3 divalent aliphatic hydrocarbon group, sulfonyl group, oxy group, carbonyl group or single bond which may be halogen-substituted.

  Examples of the diamine compound having a saturated alicyclic hydrocarbon group include 2,2-bis [4- (4-aminocyclohexyloxy) cyclohexyl] propane, bis [4- (3-aminocyclohexyloxy) cyclohexyl] sulfone, and 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-aminocyclohe Siloxy) 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'-sulfonyldicyclohexyl-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) dicyclohexyl Examples include ether, (3,3′-diamino) dicyclohexyl ether, (4,4′-diamino) dicyclohexyl methane, (3,3′-diamino) dicyclohexyl ether, 2,2-bis (4-aminocyclohexyl) propane and the like. it can. These diamine compounds may be used individually by 1 type, or may be used in combination of 2 or more type. Further, other diamine compounds, that is, diamine compounds having no saturated hydrocarbon group can be used in combination.

  A diamine compound having a saturated alicyclic hydrocarbon group can be easily obtained, for example, by hydrogen reduction of an aromatic diamine compound. Examples of such aromatic diamine compounds include 2,2-bis [4- (4-aminophenoxy) phenyl] propane (hereinafter referred to as “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 (trifluoromethyl) biphenyl-4,4′-diamine, 2,6,2 ′, 6′-tetramethyl-4,4′-diamine, 5,5′-dimethyl-2 , 2′-sulfonylbiphenyl-4,4′-diamine, 3,3′-dihydroxybiphenyl-4,4′-diamine, (4,4′-diamino) diphenyl ether, (4,4′-diamino) diphenylsulfone, (4,4′-diamino) benzophenone, (3,3′-diamino) benzophenone, (4,4′-diamino) diphenylmethane, (4,4′-diamino) diphenyl ether, (3,3′-diamino) diphenyl ether, etc. Can be illustrated.

  Hydrogen reduction of an aromatic diamine compound can be performed by a general method for reducing an aromatic ring. Examples of such reduction methods include Raney nickel catalysts and platinum oxide catalysts (D. Varech et al., Tetrahedron Letter 26, 61 (1985), RH Baker et al., J. Am. Chem. Soc., 69, 1250. (1947)), rhodium-aluminum oxide catalyst (JC Sircar et al., J. Org. Chem., 30, 3206 (1965), AI Meyers et al., Organic Synthesis Volume VI, 371 (1988), A. W. Burgstahler, Organic Synthesis Collective Volume V, 591 (1973), A. J. Briggs, Synthesis, 1988, 66), Rozi oxide. -Platinum oxide catalyst (S. Nishimura, Bull. Chem. Soc. Jpn., 34, 32 (1961), EJ Corey et al., J. Am. Chem. Soc. 101, 1608 (1979)), charcoal supported Rhodium catalyst (K. Chebaane et al., Bull. Soc. Chim. Fr., 1975, 244), sodium borohydride-rhodium chloride catalyst (PG Gasman et al., Organic Synthesis Volume VI, 581 (1988), P. G. Gassman et al., Organic Synthesis Collective Volume VI, 601 (1988)) and the like.

式（８）中、Ｌ^４はメチレン基、スルホニル基、オキソ基、カルボニル基又は単結合を示し、Ｒ^８及びＲ^９はそれぞれ独立に、水素原子、アルキル基又は置換していてもよいフェニル基を示し、ｋは１〜５０の整数を示す。 The polyamideimide suitably used in the present invention can be synthesized by using a diamine compound represented by the following general formula (8) in addition to the diamine compound described above as a diamine compound.

In the formula (8), L ⁴ represents a methylene group, a sulfonyl group, an oxo group, a carbonyl group or a single bond, and R ⁸ and R ⁹ each independently represent a hydrogen atom, an alkyl group or an optionally substituted phenyl group. K represents an integer of 1 to 50.

R ⁸ and R ⁹ are each independently preferably a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an optionally substituted phenyl group. Examples of the substituent which may be bonded to the phenyl group include an alkyl group having 1 to 3 carbon atoms and a halogen atom. In the diamine compound represented by the general formula (8), L ⁴ is particularly preferably an oxy group from the viewpoint of achieving both a low elastic modulus and a high Tg. Examples of such a diamine compound include Jeffamine D-400, Jeffamine D-2000 (manufactured by Sun Techno Chemical Co., Ltd., trade name), and the like.

  The polyamideimide suitably used in the present invention is extremely superior in water absorption resistance or water repellency compared to conventional polyamideimides because it is obtained from a diamine compound having a specific saturated hydrocarbon group as described above. Get higher. In particular, this embodiment uses a polyamideimide having a structural unit made of an alicyclic saturated hydrocarbon, obtained from a diamine compound having an alicyclic saturated hydrocarbon group, as a constituent material of a thermosetting resin composition described later. When the circuit board with an adhesive layer is formed, the multilayer printed wiring board obtained from the inner layer copper foil circuit board with the adhesive layer is, for example, compared with the case where a resin composition containing a polyamideimide having an aromatic ring is used as a constituent material. Thus, the adhesiveness at the time of moisture absorption is difficult to be lowered.

More preferably, the polyamideimide according to the present invention can be synthesized by using an aromatic diamine compound in combination with a diamine compound having a saturated hydrocarbon group. Examples of such aromatic diamine compounds include those represented by the following general formulas (9a) and (9b).

式（１０ａ）中、Ｌ^７はハロゲン置換されていてもよい炭素数１〜３の２価の脂肪族炭化水素基、スルホニル基、オキシ基、カルボニル基又は単結合を示す。 In the formulas (9a) and (9b), L ⁵ is an optionally halogenated divalent aliphatic hydrocarbon group having 1 to 3 carbon atoms, a sulfonyl group, an oxy group, a carbonyl group, a single bond, or the following formula ( 10a) or a divalent group represented by (10b), wherein L ⁶ is a halogenated halogenated divalent aliphatic hydrocarbon group having 1 to 3 carbon atoms, a sulfonyl group, an oxy group or a carbonyl group R ¹⁰ , R ¹¹ and R ¹² each independently represent a hydrogen atom, a hydroxyl group, a methoxy group or a halogen-substituted methyl group.

In formula (10a), L ⁷ represents an optionally substituted divalent aliphatic hydrocarbon group having 1 to 3 carbon atoms, a sulfonyl group, an oxy group, a carbonyl group or a single bond.

  More specifically, the compound is not particularly limited as long as it is a compound in which two amino groups are directly bonded to an aromatic ring, and a diamine in which two or more aromatic rings are bonded directly or via one group. For example, 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) , 1,4-bis (4-aminophenoxy) benzene, 2,2′-dimethylbiphenyl-4,4′-diamine, 2,2′-bis (trifluoromethyl) biphenyl-4,4′-diamine, 2,6,2 ′, 6′-tetramethyl-4,4′-diamine, 5,5′-dimethyl-2,2′-sulfonylbiphenyl-4,4′-diamine, 3,3′-dihydroxybiphenyl- 4,4′-diamine, (4,4′-diamino) diphenyl ether, (4,4′-diamino) diphenylsulfone, (4,4′-diamino) benzophenone, (3,3′-diamino) benzophenone, (4 , 4′-diamino) diphenylmethane, (4,4′-diamino) diphenyl ether, (3,3′-diamino) diphenyl ether, and the like. These aromatic diamine compounds may be used individually by 1 type, and may be used in combination of 2 or more type. The thermosetting resin composition of the adhesive layer obtained by using these aromatic diamine compounds in combination with the above-described diamine compound can further improve Tg and improve heat resistance.

式（１１）中、Ｒ^１３、Ｒ^１４、Ｒ^１５、Ｒ^１６、Ｒ^１７及びＲ^１８（以下、「Ｒ^１３〜Ｒ^１８」のように表記する。）は、それぞれ独立に、炭素数１〜３のアルキル基又は置換していてもよいフェニル基であると好ましい。フェニル基に結合していてもよい置換基としては、炭素数１〜３のアルキル基又はハロゲン原子が好ましい。Ｒ^１９及びＲ^２０は、それぞれ独立に、炭素数１〜６のアルキレン基又は置換していてもよいアリーレン基が好ましく、該アリーレン基としては置換していてもよいフェニレン基又は置換していてもよいナフタレン基が好ましい。アリーレン基に結合していてもよい置換基としては、炭素数１〜３のアルキル基又はハロゲン原子が好ましい。また、ａ及びｂはそれぞれ１〜１５の整数を示す。 Furthermore, you may use together the siloxane diamine represented by following General formula (11) as a diamine compound.

In formula (11), R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ (hereinafter referred to as “R ^{13 to} R ¹⁸ ”) are each independently represented by 1 to 1 carbon atoms. 3 alkyl groups or optionally substituted phenyl groups are preferred. The substituent that may be bonded to the phenyl group is preferably an alkyl group having 1 to 3 carbon atoms or a halogen atom. R ¹⁹ and R ²⁰ are each independently preferably an alkylene group having 1 to 6 carbon atoms or an optionally substituted arylene group, and the arylene group may be an optionally substituted phenylene group or an optionally substituted phenylene group. Good naphthalene groups are preferred. The substituent which may be bonded to the arylene group is preferably an alkyl group having 1 to 3 carbon atoms or a halogen atom. A and b each represent an integer of 1 to 15.

  As such a siloxane diamine, it is particularly preferable to use one having amino groups bonded to both ends of dimethylsiloxane. These siloxane diamines may be used alone or in combination of two or more. Siloxane diamines represented by general formula (11) are silicone oil X-22-161AS (amine equivalent 450), X-22-161A (amine equivalent 840), X-22-161B (amine equivalent 1500), X- 22-9409 (amine equivalent 700), X-22-1660B-3 (amine equivalent 2200) (above, manufactured by Shin-Etsu Chemical Co., Ltd., trade name), BY16-853 (amine equivalent 650), BY16-853B (amine equivalent 2200) ), (Above, manufactured by Toray Dow Corning Silicone Co., Ltd., trade name) and the like.

  Polyamideimide obtained by using the above-mentioned siloxane diamine as a raw material has a siloxane structure in the main chain, so the flexibility is improved and the occurrence of swelling and the like under high temperature conditions is greatly reduced. be able to.

  In order to obtain the polyamideimide according to the present embodiment, for example, first, the amino group of the diamine compound is reacted with the carboxyl group or the anhydrous carboxyl group of trimellitic anhydride. At this time, it is preferable that the amino group reacts with an anhydrous carboxyl group. Such a reaction can be carried out at 70 to 100 ° C. by dissolving or dispersing both compounds in an aprotic polar solvent. Examples of the aprotic polar solvent include N-methyl-2-pyrrolidone (NMP), γ-butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, sulfolane, and cyclohexanone. Of these, NMP is particularly preferable. These aprotic polar solvents may be used alone or in combination of two or more.

  The aprotic polar solvent described above is preferably an amount such that the solid content is 10 to 70% by mass with respect to the total weight of the solution containing the aprotic polar solvent, the diamine compound and trimellitic anhydride, It is more preferable in it being the quantity used as -60 mass%. When the solid content in the solution is less than 10% by mass, the amount of the solvent used tends to be industrially disadvantageous, and when it exceeds 70% by mass, the solubility of trimellitic anhydride decreases, It tends to be difficult to perform a sufficient reaction.

  Subsequently, an imide group-containing dicarboxylic acid can be obtained by adding an aromatic hydrocarbon azeotropic with water to the solution after the above reaction and further reacting at 150 to 200 ° C. to cause a dehydration cyclization reaction. it can. Examples of aromatic hydrocarbons that can be azeotroped with water include toluene, benzene, xylene, and ethylbenzene, and it is preferable to use toluene. The aromatic hydrocarbon is preferably added in an amount corresponding to 10 to 50 parts by mass with respect to 100 parts by mass of the aprotic polar solvent. When the addition amount of the aromatic hydrocarbon is less than 10 parts by mass with respect to 100 parts by mass of the aprotic polar solvent, the water removal effect tends to be insufficient, and the amount of imide group-containing dicarboxylic acid produced is small. It tends to decrease. Moreover, when it exceeds 50 mass parts, reaction temperature will fall and it exists in the tendency for the production amount of imide group containing dicarboxylic acid to reduce.

  Further, during the dehydration and ring closure reaction, the aromatic hydrocarbon in the solution is distilled off simultaneously with water, so that the amount of the aromatic hydrocarbon may be less than the above preferred range. It is preferable to keep the amount of aromatic hydrocarbons at a constant ratio, for example, by separating the aromatic hydrocarbons distilled in the moisture determination receiver into water and then returning them to the reaction solution. In addition, after completion | finish of a spin-drying | dehydration ring-closing reaction, it is preferable to remove the aromatic hydrocarbon which can be azeotroped with water, keeping the temperature of a solution at about 150-200 degreeC.

式中、Ｌ^８は上記一般式（６ａ）、（６ｂ）、（８）、（９ａ）、（９ｂ）又は（１１）で表されるジアミン化合物のアミノ基を除いた残基を示す。ここで、Ｒ^５〜Ｒ^２０及びｋ、ａ、ｂは上記と同義である。 As the imide group-containing dicarboxylic acid obtained as described above, for example, a compound represented by the following general formula (12) is suitable.

Wherein, ^{L 8} is the general formula (6a), a residue formed by removing (6b), (8), (9a), amino groups of the diamine compound represented by (9b) or (11). Here, R ^{5 to} R ²⁰ and k, a, and b are as defined above.

  The polyamideimide suitably used in the present embodiment can be produced by inducing an imide group-containing dicarboxylic acid as described above into an acid halide and copolymerizing it with the diamine compound. The imide group-containing dicarboxylic acid is easily derived into an acid halide by reaction with thionyl chloride, phosphorus trichloride, phosphorus pentachloride, or dichloromethyl methyl ether, and the resulting imide group-containing dicarboxylic acid halide is at room temperature or under heating conditions. It can be easily copolymerized with the diamine compound below.

  Moreover, the polyamideimide suitably used in this embodiment can be produced by copolymerizing the imide group-containing dicarboxylic acid as described above with the diamine compound in the presence of a condensing agent. In such a reaction, a general condensing agent that forms an amide bond can be used as the condensing agent, and in particular, dicyclohexylcarbodiimide, diisopropylcarbodiimide, or N-ethyl-N′-3-dimethylaminopropylcarbodiimide alone. Or it is preferable to use together with N-hydroxysuccinimide or 1-hydroxybenzotriazole.

  Furthermore, as described above, the polyamideimide of this embodiment can be obtained by reacting diisocyanate after derivatizing the imide group-containing dicarboxylic acid into an acid halide. When going through such a reaction, (diamine compound: trimellitic anhydride: diisocyanate) is in the range of 1.0: (2.0-2.2) :( 1.0-1.5) in molar ratio. It is preferable that the ratio is in the range of 1.0: (2.0 to 2.2) :( 1.0 to 1.3). In the reaction, by setting the molar ratio of these compounds within the above range, it is possible to obtain a polyamideimide having a higher molecular weight and advantageous for film formation.

As a diisocyanate used in the synthesis | combination of a polyamideimide, the compound represented by following General formula (13) can be illustrated.

In the formula (13), L ⁹ is a divalent organic group having one or more aromatic rings or a divalent aliphatic hydrocarbon group, a group represented by the following formula (14a), It is preferably a group selected from the group consisting of a group represented by 14b), a tolylene group, a naphthylene group, a hexamethylene group and a 2,2,4-trimethylhexamethylene group.

  As the diisocyanate represented by the general formula (13), aliphatic diisocyanate or aromatic diisocyanate can be used, but it is preferable to use aromatic diisocyanate, and it is particularly preferable to use both in combination. Aromatic diisocyanates include 4,4′-diphenylmethane diisocyanate (MDI), 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, 2,4-tolylene dimer, and the like. As an example, it is particularly preferable to use MDI. By using MDI as the aromatic diisocyanate, the flexibility of the resulting polyamideimide can be improved and the crystallinity can be reduced, so that the film formability of the polyamideimide can be improved. Examples of the aliphatic diisocyanate include hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and isophorone diisocyanate.

  When aromatic diisocyanate and aliphatic diisocyanate are used in combination, it is preferable to add aliphatic diisocyanate in an amount of about 5 to 10 parts by mole with respect to 100 parts by mole of aromatic diisocyanate, thereby further improving the heat resistance of the resulting polyamideimide. Can be improved.

  The reaction between the imide group-containing dicarboxylic acid and the diisocyanate can be performed at a reaction temperature of 130 to 200 ° C. by adding the diisocyanate to a solution containing the imide group-containing dicarboxylic acid. When a basic catalyst is used, this reaction is preferably performed at 70 to 180 ° C, more preferably 120 to 150 ° C. When such a reaction is performed in the presence of a basic catalyst, the reaction can proceed at a lower temperature than when the reaction is performed in the absence of a basic catalyst. The progress of side reactions such as reaction between each other can be suppressed, and a high molecular weight polyamideimide compound can be obtained.

  Examples of such basic catalysts include trialkylamines such as trimethylamine, triethylamine, tripropylamine, tri (2-ethylhexyl) amine, and trioctylamine. Among these, triethylamine is particularly preferable because it is a suitable basic catalyst capable of promoting the above-described reaction and can be easily removed from the system after the reaction.

The polyamideimide obtained by the above reaction has a structural unit represented by the following general formula (15). In the formula, L ⁸ and L ⁹ have the same meanings as L ⁸ and L ⁹ described above.

  The weight average molecular weight (Mw) of the polyamideimide obtained as described above is preferably 20000 to 300000, more preferably 30000 to 200000, and particularly preferably 40000 to 150,000. In addition, Mw here is measured by gel permeation chromatography and converted by a calibration curve created using standard polystyrene.

<(B) component>
The amide-reactive unsaturated compound (B) has a functional group that can react with the amide group of the polyamide-imide (A) by applying heat or the like, and has an ethylenically unsaturated bond. If it does, it will not specifically limit. Specific examples include an epoxy compound having an ethylenically unsaturated bond, an oxetane compound having an ethylenically unsaturated bond, and the like, and an epoxy compound having an ethylenically unsaturated bond is preferably used.

  The epoxy compound having such an ethylenically unsaturated bond is not particularly limited as long as it is an epoxy resin having one or more ethylenically unsaturated groups such as a vinyl group, an allyl group, an acrylic group, and a methacryl group. Specifically, a polybutadiene-modified epoxy compound having an ethylenically unsaturated group, an alicyclic epoxy resin having a vinyl group such as 1,2-epoxy-4-vinylcyclohexane, glycidyl methacrylate (GMA), methyl glycidyl methacrylate (M -GMA), 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, and other epoxy compounds having an acrylic group or a methacryl group. Among these, a polybutadiene-modified epoxy compound having an ethylenically unsaturated group is preferably used.

  Examples of the polybutadiene-modified epoxy compound include a polybutadiene-modified epoxy compound obtained by epoxidizing a part of an ethylenically unsaturated group of a compound having a 1,2-polybutadiene structure and / or a 1,4-polybutadiene structure (hereinafter referred to as “ A first modified epoxy compound "), or a phenolic hydroxyl group, an alcoholic hydroxyl group, a carboxyl group, an amide group, an amino group, an imino group, or a group represented by the above formula (III), which reacts with an oxirane ring. And a polybutadiene-modified epoxy compound (hereinafter referred to as “second modified epoxy compound”) obtained by reacting a modified polybutadiene having the above group with a polyfunctional epoxy compound having two or more oxirane rings. Among such compounds, it is particularly preferable to use a polybutadiene-modified epoxy compound having one or more vinyl groups at the terminal or side chain in the molecule.

  Specific examples of the first modified epoxy compound include a compound represented by the general formula (1) or (2) or a compound having a structural unit represented by the general formula (5). Examples of the epoxy compound represented by the formula (1) include BF-1000 (trade name, manufactured by Nippon Soda Co., Ltd.). Examples of the epoxy compound represented by the formula (2) include PB3600 (trade name, manufactured by Daicel Chemical Industries, Ltd.). As the epoxy compound having the structural unit represented by the formula (5), A1005, A1010, A1020 (above, manufactured by Daicel Chemical Industries, Ltd., trade name) and the like are commercially available.

  Specific examples of the second modified epoxy compound include an epoxy compound obtained by reacting a polybutadiene having a carboxyl group and a bisphenol A type epoxy resin as represented by the general formula (3). As such a second modified epoxy compound, EPB-13 (trade name, manufactured by Nippon Soda Co., Ltd.) is commercially available.

  The second modified epoxy compound is a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, a brominated bisphenol A type epoxy resin, a biphenyl type epoxy resin or a phenol novolac type as a polyfunctional epoxy compound. Epoxy resin, cresol novolak type epoxy resin, brominated phenol novolak type epoxy resin, bisphenol A novolak type epoxy resin, naphthalene skeleton containing epoxy resin, aralkylene skeleton containing epoxy resin, biphenyl-aralkylene skeleton epoxy resin, phenol salicylaldehyde novolak type epoxy resin , Lower alkyl group-substituted phenol salicylaldehyde novolak type epoxy resin, dicyclopentadiene skeleton-containing epoxy resin, polyfunctional glycidyl Amine type epoxy resin and a polyfunctional alicyclic epoxy resin may be a polybutadiene-modified epoxy compound obtained by using the.

  Moreover, the amide reactive unsaturated compound which concerns on this embodiment may be used individually by 1 type, and may be used in combination of 2 or more type.

  In the thermosetting resin composition which is a constituent material of the adhesive layer 20, the blending ratio of the component (B) is preferably in the range of 5 to 200 parts by mass with respect to 100 parts by mass of the component (A), and 7 to 80 More preferably, it is more preferably 10 to 50 parts by mass. When the blending ratio of the amide-reactive unsaturated compound as the component (B) is less than 5 parts by mass, in the circuit board 100 with the adhesive layer obtained by employing the blending component (B), the adhesive layer 20 Since the thermosetting property and the reactivity between the adhesive layer 20 and the insulating resin layer are lowered, in the obtained multilayer printed wiring board, the heat resistance and resistance in the cured layer and in the vicinity of the interface between the insulating resin layer and the cured layer are reduced. Chemical properties and breaking strength tend to decrease. Moreover, when it exceeds 200 mass parts, it exists in the tendency for the adhesiveness of the contact bonding layer 20 and the conductor circuit 14 to fall, and also in the multilayer printed wiring board obtained, it exists in the tendency for the toughness of a hardened layer to fall.

  In the circuit board 100 with an adhesive layer of the present embodiment, the thermosetting resin composition that is a constituent material of the adhesive layer 20 includes an amide group of (A) component polyamideimide and an amide reactive unsaturated compound (B) component. It is preferable to further contain a curing accelerator having a catalytic function that promotes the reaction with. Specifically, examples of the curing accelerator include amine compounds, imidazole compounds, organic phosphorus compounds, alkali metal compounds, alkaline earth metal compounds, quaternary ammonium salts, and the like, but are not limited thereto. Moreover, these hardening accelerators may be used individually by 1 type, and may be used in combination of 2 or more type.

  The blending ratio of the curing accelerator in the thermosetting resin composition can be determined according to the blending ratio of the amide-reactive unsaturated compound that is the component (B), and with respect to 100 parts by weight of the component (B), It is preferable to set it as 0.05-10 mass parts. When a curing accelerator is blended within this numerical range, an appropriate reaction rate can be obtained, and the thermosetting resin composition of the adhesive layer 20 becomes more excellent in reactivity and curability. , It has better chemical resistance, heat resistance and / or moisture heat resistance.

  In addition, the thermosetting resin composition, which is a constituent material of the adhesive layer 20, promotes the crosslinking reaction between the components (B) in the adhesive layer 20 and on the adhesive layer 20 when producing a multilayer printed wiring board. In order to promote the crosslinking reaction between the compound having an unsaturated bond in the formed insulating resin layer and the component (B) in the adhesive layer 20, the component (E) further contains a radical polymerization initiator. And preferred.

  Specifically, as a radical polymerization initiator, dicumyl peroxide, t-butylcumyl peroxide, benzoyl peroxide, cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 2, 5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3, di-t-butyl peroxide, α, α′-bis (t-butylperoxy) diisopropylbenzene, 2,5-dimethyl- 2,5-bis (t-butylperoxy) hexane, di-t-butylperoxyisophthalate, t-butylperoxybenzoate, 2,2-bis (t-butylperoxy) butane, 2,2-bis (T-butylperoxy) octane, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, bis (t -Butylperoxy) isophthalate, isobutyryl peroxide, di (trimethylsilyl) peroxide, trimethylsilyltriphenylsilyl peroxide and other peroxides, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, Examples include, but are not limited to, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, benzoin methyl ether, methyl-o-benzoylbenzoate, and the like. Moreover, these radical polymerization initiators may be used individually by 1 type, and may be used in combination of 2 or more type.

  The blending ratio of the radical polymerization initiator in the thermosetting resin composition can be determined according to the blending ratio of the component (B), and 0.5 to 10 parts by mass with respect to 100 parts by mass of the component (B). It is preferable that When a radical polymerization initiator is blended within this numerical range, an appropriate reaction rate is obtained, and the thermosetting resin composition of the adhesive layer 20 becomes more excellent in reactivity and curability. The breaking strength and the peel strength of the metal foil are increased, and the chemical resistance, heat resistance and moisture heat resistance are improved.

  In addition, the thermosetting resin composition that is a constituent component of the adhesive layer 20 has heat resistance, adhesiveness, and moisture absorption resistance when various additives such as a flame retardant and a filler are used as a multilayer printed wiring board as necessary. You may mix | blend further by the compounding quantity of the range which does not deteriorate characteristics, such as property.

  Although it does not specifically limit as said flame retardant, Flame retardants, such as a bromine type | system | group, a phosphorus type | system | group, and a metal hydroxide, are used suitably. More specifically, brominated flame retardants include brominated epoxy resins such as brominated bisphenol A type epoxy resin and brominated phenol novolac type epoxy resin, hexabromobenzene, pentabromotoluene, ethylenebis (pentabromophenyl). , Ethylenebistetrabromophthalimide, 1,2-dibromo-4- (1,2-dibromoethyl) cyclohexane, tetrabromocyclooctane, hexabromocyclododecane, bis (tribromophenoxy) ethane, brominated polyphenylene ether, brominated Brominated flame retardants such as polystyrene and 2,4,6-tris (tribromophenoxy) -1,3,5-triazine, tribromophenyl maleimide, tribromophenyl acrylate, tribromophenyl methacrylate, tetrabromide Bisphenol A dimethacrylate, unsaturated double bonds brominated reactive flame retardants containing such pentabromobenzylacrylate and brominated styrene.

  Phosphorus flame retardants include aromatic phosphorus such as triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, cresyl di-2,6-xylenyl phosphate and resorcinol bis (diphenyl phosphate) Acid esters, phosphonic acid esters such as divinyl phenylphosphonate, diallyl phenylphosphonate and bis (1-butenyl) phenylphosphonate, phenyl diphenylphosphinate, methyl diphenylphosphinate, 9,10-dihydro-9-oxa-10- Phosphinates such as phosphaphenanthrene-10-oxide derivatives, phosphazene compounds such as bis (2-allylphenoxy) phosphazene and dicresylphosphazene, melamine phosphate, melamine pyrophosphate, Melamine phosphate, melam polyphosphate, phosphorus-based flame retardant ammonium polyphosphate and red phosphorus and the like. Examples of the metal hydroxide flame retardant include magnesium hydroxide and aluminum hydroxide.

  The above flame retardants may be used alone or in combination of two or more.

  The blending ratio of the flame retardant in the thermosetting resin composition according to the present embodiment is not particularly limited, but is 5 to 150 mass with respect to 100 mass parts of the total amount of the (A) component and the (B) component. Parts, preferably 5 to 80 parts by mass, more preferably 5 to 60 parts by mass. When the blending ratio of the flame retardant is less than 5 parts by mass, the flame resistance tends to be insufficient, and when it exceeds 100 parts by mass, the heat resistance of the cured adhesive layer tends to decrease.

  The above-mentioned filler is not particularly limited, but usually an inorganic filler is preferably used. Examples of the inorganic filler include alumina, titanium oxide, mica, silica, beryllia, barium titanate, titanate. Potassium, strontium titanate, calcium titanate, aluminum carbonate, magnesium hydroxide, aluminum hydroxide, aluminum silicate, calcium carbonate, calcium silicate, magnesium silicate, silicon nitride, boron nitride, baked clay clay, talc, Examples thereof include aluminum borate, aluminum borate, and silicon carbide. These fillers may be used individually by 1 type, and may be used in combination of 2 or more type. Moreover, there is no restriction | limiting in particular also about the shape of a filler, and a particle size, Usually, the particle size of 0.01-50 micrometers, Preferably 0.1-15 micrometers is used suitably.

  The blending ratio of the filler in the thermosetting resin composition according to the present embodiment is not particularly limited, but is 1 to 1000 parts by mass with respect to 100 parts by mass of the total amount of the component (A) and the component (B). Is preferable, and 1-800 mass parts is more preferable.

  The thermosetting resin composition that is a constituent material of the adhesive layer 20 is composed of (A) component, (B) component, a curing accelerator, a radical polymerization initiator, and other additives as required by a known method. , And can be produced by mixing.

  The film thickness (thickness) of the adhesive layer 20 is preferably 0.1 to 10.0 μm, and more preferably 0.5 to 5.0 μm. If the film thickness is less than 0.1 μm, the multilayer printed wiring board having a cured layer obtained by curing the adhesive layer 20 tends to have difficulty in improving the metal foil peeling strength. When a low dielectric constant resin as described later is used for the insulating resin layer of the printed wiring board, the high-frequency transmission characteristics tend to deteriorate.

  As a manufacturing method of the circuit board 100 with an adhesive layer, the thermosetting resin composition according to the preferred embodiment of the present invention described above or the resin composition is applied to the surface 12a of the insulating plate 12 and the surface 14a of the conductor circuit 14. The resin varnish dissolved or dispersed in a solvent is applied, dried and semi-cured (B-stage), and the adhesive layer 20 is formed on the circuit board 10 to be manufactured.

  The application of the resin varnish can be performed by a known method, for example, using a kiss coater, a roll coater, a comma coater, or the like. Moreover, the drying of the applied resin varnish includes a method of drying at a temperature of usually 70 to 250 ° C., preferably 100 to 200 ° C. for 1 to 30 minutes, preferably 3 to 15 minutes in a heat drying oven or the like. . The drying temperature at this time is preferably equal to or higher than the temperature at which the solvent can be volatilized when a solvent is used to dissolve the thermosetting resin composition.

  The solvent used when varnishing the thermosetting resin composition described above is not particularly limited, but specific examples include alcohols such as methanol, ethanol, butanol, ethyl cellosolve, butyl cellosolve, ethylene glycol monomethyl ether. , Ethers such as carbitol and butyl carbitol, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene, xylene and mesitylene, methoxyethyl acetate, ethoxyethyl acetate, butoxyethyl acetate And solvents such as esters such as ethyl acetate, nitrogen-containing compounds such as N, N-dimethylformamide, N, N-dimethylacetamide, and N-methyl-2-pyrrolidone. These may be used individually by 1 type and may be used in combination of 2 or more type.

  Among these solvents, the blending ratio in the case of using aromatic hydrocarbons and ketones is preferably 30 to 300 parts by mass of ketones with respect to 100 parts by mass of aromatic hydrocarbons, and 30 to 250 parts by mass. Parts, more preferably 30 to 220 parts by mass. In addition, when the varnish is formed, it is preferable to adjust the amount of the solvent so that the solid content (nonvolatile content) concentration in the varnish is usually 5 to 80% by mass, but the circuit board 100 with an adhesive layer is manufactured. In this case, by adjusting the amount of the solvent, the solid content concentration and the varnish viscosity can be adjusted so that the adhesive layer 20 has a desired film thickness, particularly the above-described preferable film thickness.

  When the circuit board 100 with an adhesive layer described above is used, a multilayer printed laminate obtained from the above is obtained by using polytriallyl cyanurate or triallyl isocyanurate which is a polymer of polybutadiene and triallyl cyanurate as a constituent material of an insulating resin layer. When a low dielectric constant resin such as polytriallyl isocyanurate or polyphenylene ether, which is a polymer of the above, is used, not only can a high metal foil peel strength be exhibited, but also a high adhesive force can be maintained during moisture absorption. As a result, such a multilayer printed wiring board has sufficiently high heat resistance and moisture heat resistance.

  Furthermore, since these excellent characteristics are sufficiently expressed even when the surface roughness of the conductor circuit 14 is relatively small, it is possible to achieve both excellent high frequency characteristics and high adhesion and heat resistance. Become. For these reasons, the circuit board 100 with an adhesive layer is effective as a member / part application such as a multilayer printed wiring board provided in various electric / electronic devices that handle high-frequency signals.

  In addition, when the circuit board 10 which concerns on 1st Embodiment is provided with the layer (not shown) which hardens the above-mentioned curable resin composition between the laminated board 12 and the conductor circuit 14, it is provided. Even more preferred. Thereby, in addition to the above-mentioned effect, it is possible to achieve both excellent high-frequency characteristics and high adhesiveness and heat resistance between the laminate 12 and the conductor circuit 14.

  As a manufacturing method of the circuit board 10 provided with such a layer, first, the above-described curable resin composition is applied to a metal foil (not shown), and the laminate 12 is laminated to the application surface side of the metal foil. To form a laminate (not shown). Next, a metal-clad laminate (not shown) is formed by heating and / or pressurizing the laminate under predetermined conditions, and finally, a known patterning process is performed on the metal foil side of the metal-clad laminate. To complete the conductor circuit 14. The heating in this case can be carried out preferably at a temperature of 150 to 250 ° C., and the pressurization can be carried out preferably at a pressure of 0.5 to 10.0 MPa. In particular, when the surface roughness of the metal foil on the side on which the curable resin composition is applied is 4 μm or less, preferably 2 μm or less, the high-frequency transmission characteristics can be further improved.

(Second Embodiment)
The circuit board with an adhesive layer according to the present embodiment is the same as the circuit board with the adhesive layer according to the first embodiment, and the adhesive layer reacts with the (A) component; polyamideimide, and (C) component; the amide group of the polyamideimide. A compound having two or more functional groups (hereinafter referred to as “amide-reactive compound” if necessary), a component (D); a functional group capable of reacting with the component (C), and ethylenic It differs in that it is composed of a curable resin composition containing a compound having an unsaturated bond (hereinafter referred to as “reactive unsaturated compound” if necessary), but the other points are the first implementation. It is the same as that of the circuit board with an adhesive layer which concerns on a form. Hereinafter, the curable resin composition constituting the adhesive layer and its components will be described.

  As (A) component which concerns on this embodiment, the thing similar to (A) component which concerns on 1st Embodiment can be used.

<(C) component>
The amide-reactive compound as the component (C) is not particularly limited as long as it has two or more functional groups that can react with the amide group of the polyamideimide as the component (A) by applying heat or the like. Specific examples include compounds having two or more oxirane rings or oxetane rings, that is, polyfunctional epoxy compounds (oxirane compounds) or oxetane compounds, and polyfunctional epoxy compounds are more preferred. Polyfunctional epoxy compounds include bisphenol F type epoxy resin, bisphenol S type epoxy resin, brominated bisphenol A type epoxy resin, biphenyl type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, brominated phenol novolak type Epoxy resin, bisphenol A novolac epoxy resin, naphthalene skeleton-containing epoxy resin, aralkylene skeleton-containing epoxy resin, biphenyl-aralkylene skeleton epoxy resin, phenol salicylaldehyde novolak epoxy resin, lower alkyl group-substituted phenol salicylaldehyde novolak epoxy resin, di Examples include cyclopentadiene skeleton-containing epoxy resins, polyfunctional glycidylamine type epoxy resins, and polyfunctional alicyclic epoxy resins. That. As the component (C), the amide reactive compound may be used alone or in combination of two or more.

<(D) component>
The reactive unsaturated compound as component (D) has one or more ethylenically unsaturated bonds in the molecule, and is functionally reactive with the amide reactive compound as component (C) by applying heat or the like. If it is a compound which has group, it will not specifically limit. Specifically, for example, a modification having an ethylenically unsaturated bond and having a phenolic hydroxyl group, an alcoholic hydroxyl group, a carboxyl group, an amide group, an amino group, an imino group, or a group represented by the above formula (III) Polybutadiene is mentioned. In particular, modified polybutadiene in which an ethylenically unsaturated group is a vinyl group present at the terminal and / or side chain is preferably used.

式（１６）中、Ｒ^２１は水素原子又は炭素数１〜４のアルキル基を示し、ｃ及びｄはそれぞれ独立に０〜１００の整数を示し、ｃ及びｄのうちいずれかは１以上の整数を示し、ｅは１〜１０００の整数を示す。

式（１７）中、Ｒ^２２は、ヒドロキシエチル基、カルボキシル基又は下記一般式（１８）で表される基を示し、ｆは０〜１００の整数を示し、ｆ及びｇの合計は１０〜１００００の整数を示す。

式（１８）中、Ｒ^２３は水素原子又はメチル基を示す。

式（１９）中、Ｒ^２４は下記一般式（２０ａ）又は（２０ｂ）で表される基を示し、ｖ、ｗ及びｘはそれぞれ独立に０〜１００の整数を示し、ｖ及びｗのうちいずれかは１以上の整数を示し、ｈは１〜１００００の整数を示す。

式（２０ａ）、（２０ｂ）中、Ｒ^２５、Ｒ^２６は、単結合、炭素数１〜６の２価の脂肪族炭化水素基、置換していてもよいフェニレン基、スルホニル基、オキシ基又はカルボニル基を示す。

式（２１）中、ｙは１〜８の整数を示し、ｙ及びｚの合計は１０〜１００００の整数を示す。 Specific examples of such modified polybutadiene include compounds represented by the following general formula (16), (17), (19) or (21).

In formula (16), R ²¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, c and d each independently represents an integer of 0 to 100, and either c or d is an integer of 1 or more. E represents an integer of 1 to 1000.

In the formula (17), R ²² represents a hydroxyethyl group, a carboxyl group or a group represented by the following general formula (18), f represents an integer of 0 to 100, and the sum of f and g is 10 to 10,000. Indicates an integer.

In the formula (18), R ²³ represents a hydrogen atom or a methyl group.

In the formula (19), R ²⁴ represents a group represented by the following general formula (20a) or (20b), v, w and x each independently represent an integer of 0 to 100, and any of v and w Or represents an integer of 1 or more, and h represents an integer of 1 to 10,000.

In formulas (20a) and (20b), R ²⁵ and R ²⁶ are a single bond, a divalent aliphatic hydrocarbon group having 1 to 6 carbon atoms, an optionally substituted phenylene group, a sulfonyl group, an oxy group, or A carbonyl group is shown.

In formula (21), y represents an integer of 1 to 8, and the sum of y and z represents an integer of 10 to 10,000.

  Examples of the modified polybutadiene represented by the general formula (16) include PP700-300, PP1000-180, PP1000-240 (above, trade name, manufactured by Shin Nippon Petrochemical Co., Ltd.) and the like, which are represented by the general formula (17). Examples of the polybutadiene include G-1000, G-2000, G-3000, C-1000, TEA-1000, TEA-2000 (above, Nippon Soda Co., Ltd., trade name) and other modified compounds represented by the general formula (19). As the polybutadiene, ATBN1300 (manufactured by Ube Industries, trade name) and the like, and as the modified polybutadiene represented by the general formula (21), BN-1015 (manufactured by Nippon Soda Co., Ltd., trade name) are commercially available. is there. Moreover, the reactive unsaturated compound of (D) component may be used individually by 1 type, and may be used in combination of 2 or more type.

  The total blending ratio of the component (C) and the component (D) in the thermosetting resin composition that is a constituent component of the adhesive layer according to this embodiment is 5 to 200 parts by mass with respect to 100 parts by mass of the component (A). Preferably, it is 7-80 parts by mass, more preferably 10-50 parts by mass. In the circuit board with an adhesive layer obtained by employing the (C) component and the (D) component having such a blending ratio, the total blending ratio of the (C) component and the (D) component is less than 5 parts by mass. Because the thermosetting property of the layer and the reactivity between the adhesive layer and the insulating resin layer are reduced, in the resulting multilayer printed wiring board, heat resistance in the cured layer and in the vicinity of the interface between the insulating resin layer and the cured layer, Chemical resistance and breaking strength tend to decrease. Moreover, when it exceeds 200 mass parts, it exists in the tendency for the adhesiveness of an adhesive layer and a conductor circuit to fall, and also in the multilayer printed wiring board obtained, it exists in the tendency for the toughness of a hardened layer to fall.

  Moreover, it is preferable to set it as the range of 5-1000 weight part with respect to 100 mass parts of (C) component, and, as for the mixture ratio of (D) component, it is more preferable to set it as 20-500 mass part, 50-150. It is still more preferable to set it as a mass part. When the blending ratio of the component (D) is less than 5 parts by mass, in the circuit board with an adhesive layer obtained by employing the blending ratio of the component (D), the thermosetting of the adhesive layer, and the adhesive layer and the insulating resin Since the reactivity with the layer is lowered, in the obtained multilayer printed wiring board, the heat resistance and the breaking strength in the cured layer and in the vicinity of the interface between the insulating resin layer and the cured layer tend to be lowered. Moreover, when it exceeds 1000 parts by mass, the thermosetting property of the adhesive layer is lowered, and the heat resistance and chemical resistance of the cured layer of the resulting multilayer printed wiring board tend to be lowered.

  In the circuit board with an adhesive layer of the present embodiment, the thermosetting resin composition that is a constituent material of the adhesive layer includes a reaction between the amide group of the polyamideimide (A) and the amide reactive compound (C). It is preferable to further contain a curing accelerator having a catalytic function that promotes the curing reaction between the amide-reactive group of component (C) and component (D). Specific examples of the curing accelerator include those exemplified and listed in the first embodiment, and these may be used alone or in combination of two or more.

  In addition, the thermosetting resin composition, which is a constituent material of the adhesive layer according to the present embodiment, includes (E) component; radical polymerization initiator in order to promote the crosslinking reaction of the unsaturated bond group of component (D). Is further preferably contained. Specific examples of the radical polymerization initiator include those listed and exemplified in the first embodiment, and these may be used alone or in combination of two or more.

  In the thermosetting resin composition, the blending ratio of the curing accelerator can be determined according to the blending ratio of the component (C), and the blending ratio of the radical polymerization initiator can be determined according to the blending ratio of the component (D). It is preferable from the same viewpoint that the numerical range is the same as the blending ratio with respect to the component (B) in the first embodiment.

  In addition, the thermosetting resin composition, which is a constituent component of the adhesive layer according to the present embodiment, has heat resistance and adhesiveness when various additives such as flame retardants and fillers are used as printed wiring boards as necessary. Further, it may be further blended in a blending amount within a range that does not deteriorate the properties such as moisture absorption resistance. Specific examples, shapes, and particle sizes of these additives are the same as those described in the first embodiment. Moreover, a preferable mixture ratio is the mixture ratio with respect to the total amount of (A) component and (B) component demonstrated in 1st Embodiment with respect to the total amount of (A) component, (C) component, and (D) component. Is the same numerical range.

  A thermosetting resin composition that is a constituent material of an adhesive layer according to a preferred embodiment of the present invention includes (A) component, (C) component, (D) component, a curing accelerator, a radical polymerization initiator, and Accordingly, other additives can be produced by blending and mixing by a known method.

(Third embodiment)
In the multilayer printed wiring board 200 according to the third embodiment, a cured layer 60, an insulating resin layer 70, and a metal foil 80 are laminated in this order on both surfaces of the circuit board 50. More specifically, the circuit board 50 includes a laminated plate 52 that is an insulating plate, and a conductor circuit 54 formed on both surfaces of the laminated plate 52. Both surfaces are on the surface 54a of the conductor circuit 54 and laminated. A cured layer 60 and an insulating resin layer 70 are laminated in this order on the surface 52 a of the plate 52.

  As the circuit board 50, the thing similar to the circuit board 10 of 1st Embodiment can be handled. The cured layer 60 is obtained by curing the adhesive layer 20 of the first embodiment by heating or the like.

  As the insulating resin layer 70, a known cured prepreg can be used. In the present invention, as a prepreg, a low dielectric constant resin having polybutadiene, triallyl cyanurate, triallyl isocyanurate, polyphenylene ether or the like is used as a fiber base material (reinforced fiber) containing materials such as glass fiber, organic fiber, and paper material. Or a nonwoven fabric produced by a known method can be used. Examples of the glass fiber include E glass, S glass, NE glass, D glass, and Q glass, and examples of the organic fiber include aramid, fluororesin, polyester, and liquid crystalline polymer. An example of such a liquid crystalline polymer is a thermotropic (thermal melting type) liquid crystal polymer. Furthermore, examples of the thermotropic liquid crystal polymer include aromatic polyesters. More specifically, for example, a copolymer of parahydroxybenzoic acid (HBA), biphenol and terephthalic acid (TPA), HBA And 2-oxy-6-naphthoic acid (BON6), and those obtained by modifying polyethylene terephthalate with HBA. Examples of commercially available products include “ZAIDER” (trade name, manufactured by Nippon Petrochemical Co., Ltd.), “SUMICA SUPER LCP” (trade name, manufactured by Sumitomo Chemical Co., Ltd.), “VECTRA” (product manufactured by Polyplastics Co., Ltd. Name), “Rod Run” (trade name, manufactured by Unitika), “Ueno-LCP” (trade name, manufactured by Ueno Pharmaceutical Co., Ltd.), “Novacurate” (trade name, manufactured by Mitsubishi Engineering Plastics), and the like. As the insulating resin layer 70, a material obtained by combining the low dielectric constant resin and the fiber base material can be suitably used, but it is particularly preferable to use the same base material as the laminated plate 52.

  As the metal foil 80, the same metal foil used for the conductor circuit 14 of the first embodiment can be handled. In particular, it is preferable to use the same base material as the conductor circuit 54.

  As a suitable manufacturing method of such a multilayer printed wiring board 200, first, the circuit board 100 with an adhesive layer of the first embodiment is prepared, and an insulating resin sheet such as a prepreg and a metal foil are provided on the surface having the conductor circuit 14. Are laminated together in this order to produce a multilayer body (not shown). At this time, it adheres so that an adhesive layer may contact | connect an insulating resin sheet. Next, this multilayer body is heated and / or pressurized under predetermined conditions to complete the multilayer printed wiring board 200. The heating in this case can be carried out preferably at a temperature of 150 to 250 ° C., and the pressurization can be carried out preferably at a pressure of 0.5 to 10.0 MPa. Heating and pressing are preferably performed simultaneously using a vacuum press or the like. In this case, the adhesive layer and the insulating resin sheet are sufficiently cured by performing these treatments for 30 minutes to 10 hours.

  Even if the multilayer printed wiring board 200 described above employs a low dielectric constant resin such as polybutadiene, polytriallyl cyanurate, polytriallyl isocyanurate, polyphenylene ether or the like as the constituent material of the insulating resin layer, the conductor circuit 54 and the electric circuit 54 Since the insulating layers (cured layer 60 and insulating resin layer 70) are sufficiently adhered to each other, a high adhesive force can be maintained even during moisture absorption. As a result, such a multilayer printed wiring board has sufficiently high heat resistance and moisture heat resistance.

  Furthermore, since these excellent characteristics are sufficiently exhibited even when the surface roughness of the conductor circuit 54 is relatively small, it is possible to sufficiently reduce transmission loss particularly in the high frequency band. It can be suitably used as a member / part of various electric / electronic devices that handle high-frequency signals.

  In the obtained multilayer printed wiring board 200, the metal foil 80 may be patterned as necessary to form a conductor circuit. Also, if necessary, an adhesive layer is formed on the surface of the conductor circuit (or the surface of the metal foil 80 when no conductor circuit is formed), and the insulating resin sheet and the metal foil are laminated by the above-described method, followed by heating and pressing. Can be molded. By repeating such operations and alternately laminating insulating resin layers and metal foils (conductor circuits), a multilayer printed wiring board having a further multilayered structure can be manufactured.

  In addition, if it is after hardening | curing an insulating resin sheet, you may form a via hole (through hole) etc. in the laminated substrate which has a circuit board, an insulating resin layer, and metal foil. For forming via holes, it is necessary to make holes in the laminated substrate. However, if the metal foil on the laminated substrate is thin, it can be directly drilled by a drill or a laser. If the metal foil is thick, the conformal mask method is used. Or after forming a window hole by the large window method, it can form by drilling with a drill or a laser. After completion of drilling, if resin residues remain on the surface of the metal foil, through holes, etc., they are removed and via holes can be formed by electroless copper plating, metal deposition, sputtering, ion plating, or the like.

  Further, a protective layer may be formed on the outermost layer of the multilayer printed wiring board 200 or a multilayer printed wiring board having a multilayered structure by a tenting method using a dry film or the like.

  The preferred embodiment of the present invention has been described above, but the present invention is not limited to the above embodiment.

  For example, in the first embodiment, the adhesive layer 20 only needs to be formed on the surface 14 a of the conductor circuit 14, and may not be formed on the surface 12 a of the laminate 12. That is, in the third embodiment, the hardened layer 60 may be formed on the surface 54 a of the conductor circuit 54 and may not be formed on the surface 52 a of the laminated plate 52. The laminate 52 and the insulating resin layer 70 can be sufficiently bonded by thermocompression bonding or the like.

  In the first embodiment, the conductor circuit 14 and the adhesive layer 20 may be laminated only on one side of the laminate 12. That is, in the third embodiment, the conductor circuit 54, the cured layer 60, the insulating resin layer 70, and the metal foil 80 may be laminated only on one side of the laminated plate 52. In this case, nothing may be formed on the surface of the laminated plates 12 and 52 where the conductor circuit is not formed, or a metal foil or the like may be formed. Hereinafter, “single-sided circuit board with adhesive layer” means that the conductor circuit and the adhesive layer are laminated only on one side of the laminated board, and “double-sided circuit with adhesive layer” means that the conductor circuit and the adhesive layer are laminated on both sides of the laminated board. It will be called a “substrate”.

  Instead of the laminated plate 12 of the first embodiment or the laminated plate 52 of the third embodiment, a single-layer insulating plate may be used, or a metal core substrate having a metal plate sandwiched between electric insulating layers. A thing may be used.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples. In addition, all the surface roughness given below are based on the ten-point average roughness Rz of JIS-B0601-1994.

[Synthesis of Polyamideimide]
(Synthesis Example 1)
First, in a 1 L separable flask equipped with a Dean-Stark reflux condenser, a thermometer, and a stirrer, (4,4′-diamino) dicyclohexylmethane (Wandamine HM (as diamine compound A having a saturated alicyclic hydrocarbon group) was added. WHM), manufactured by Shin Nippon Chemical Co., Ltd., trade name) 45 mmol, reactive silicone oil as siloxane diamine compound B (X-22-161-B, manufactured by Shin-Etsu Chemical Co., Ltd., amine equivalent: 1500, trade name) 5 mmol, anhydrous tri 105 mmol of merit acid (TMA) and 145 g of N-methyl-2-pyrrolidone (NMP) as an aprotic polar solvent were added, and the temperature in the flask was set at 80 ° C. and stirred for 30 minutes.

  After completion of the stirring, 100 mL of toluene was further added as an aromatic hydrocarbon azeotropic with water, and the temperature in the flask was raised to 160 ° C. and refluxed for about 2 hours. After confirming that the theoretical amount of water was stored in the moisture meter and no water distilling was observed, the temperature in the flask was increased to 190 ° C while removing the water in the meter. The toluene in the reaction solution was removed.

  After returning the solution in the flask to room temperature, 60 mmol of 4,4′-diphenylmethane diisocyanate (MDI) was added as a diisocyanate, the temperature in the flask was raised to 190 ° C. and reacted for 2 hours, and then diluted with NMP. Thus, an NMP solution of polyamideimide of Synthesis Example 1 (solid content concentration of 30% by mass) was obtained. It was 50000 when the weight average molecular weight (Mw) of this NMP solution was measured by the gel permeation chromatography.

(Synthesis Example 2)
First, in a 1 L separable flask equipped with a Dean-Stark reflux condenser, a thermometer, and a stirrer, (4,4′-diamino) dicyclohexylmethane (Wandamine HM (as diamine compound A having a saturated alicyclic hydrocarbon group) was added. WHM), manufactured by Shin Nippon Rika Co., Ltd., trade name) 140 mmol, as a diamine compound C having a saturated aliphatic hydrocarbon group, Jeffamine D-2000 (manufactured by Suntechno Chemical Co., trade name) 35 mmol, trimellitic anhydride (TMA) 368 mmol , 413 g of N-methyl-2-pyrrolidone (NMP) was added as an aprotic polar solvent, and the temperature in the flask was set at 80 ° C. and stirred for 30 minutes.

  After the stirring, 120 mL of toluene was further added as an aromatic hydrocarbon azeotropic with water, and the temperature in the flask was raised to 160 ° C. and refluxed for about 2 hours. After confirming that the theoretical amount of water was stored in the moisture meter and no water distilling was observed, the temperature in the flask was increased to 190 ° C while removing the water in the meter. The toluene in the reaction solution was removed.

  After returning the solution in the flask to room temperature, 210 mmol of 4,4′-diphenylmethane diisocyanate (MDI) was added as a diisocyanate, the temperature in the flask was raised to 190 ° C. and reacted for 2 hours, and then diluted with NMP. Thus, an NMP solution of polyamideimide of Synthesis Example 2 (solid content concentration of 30% by mass) was obtained. It was 64000 when Mw of this NMP solution was measured by the gel permeation chromatography.

(Synthesis Example 3)
First, in a 1 L separable flask equipped with a Dean-Stark reflux condenser, a thermometer, and a stirrer, Jeffamine D-2000 (trade name, manufactured by Sun Techno Chemical Co., Ltd.) 30 mmol as a diamine compound C having a saturated aliphatic hydrocarbon group. , Reactive silicone oil (X-22-161-B, manufactured by Shin-Etsu Chemical Co., Ltd., amine equivalent: 1500, trade name) 10 mmol as siloxane diamine compound B, (4,4′-diamino) diphenylmethane ( DDM) 60 mmol, trimellitic anhydride (TMA) 210 mmol, and 407 g of N-methyl-2-pyrrolidone (NMP) as an aprotic polar solvent were added, and the temperature in the flask was set at 80 ° C. and stirred for 30 minutes.

  After completion of the stirring, 100 mL of toluene was further added as an aromatic hydrocarbon azeotropic with water, and the temperature in the flask was raised to 160 ° C. and refluxed for about 2 hours. After confirming that the theoretical amount of water was stored in the moisture meter and no water distilling was observed, the temperature in the flask was increased to 190 ° C while removing the water in the meter. The toluene in the reaction solution was removed.

  After returning the solution in the flask to room temperature, 210 mmol of 4,4′-diphenylmethane diisocyanate (MDI) was added as a diisocyanate, the temperature in the flask was raised to 190 ° C. and reacted for 2 hours, and then diluted with NMP. Thus, an NMP solution of polyamideimide of Synthesis Example 3 (solid content concentration of 30% by mass) was obtained. It was 62000 when Mw of this NMP solution was measured by the gel permeation chromatography.

(Synthesis Example 4)
First, in a 1 L separable flask equipped with a Dean-Stark reflux condenser, a thermometer, and a stirrer, Jeffamine D-2000 (trade name, manufactured by Sun Techno Chemical Co., Ltd.) 30 mmol as a diamine compound C having a saturated aliphatic hydrocarbon group. , 120 mmol of (4,4′-diamino) diphenylmethane (DDM) as aromatic diamine compound D, 315 mmol of trimellitic anhydride (TMA), 442 g of N-methyl-2-pyrrolidone (NMP) as an aprotic polar solvent, The temperature in the flask was set to 80 ° C. and stirred for 30 minutes.

  After completion of the stirring, 100 mL of toluene was further added as an aromatic hydrocarbon azeotropic with water, and the temperature in the flask was raised to 160 ° C. and refluxed for about 2 hours. After confirming that the theoretical amount of water was stored in the moisture meter and no water distilling was observed, the temperature in the flask was increased to 190 ° C while removing the water in the meter. The toluene in the reaction solution was removed.

  After returning the solution in the flask to room temperature, 180 mmol of 4,4′-diphenylmethane diisocyanate (MDI) was added as a diisocyanate, the temperature in the flask was raised to 190 ° C. and reacted for 2 hours, and then diluted with NMP. Thus, an NMP solution of polyamideimide of Synthesis Example 4 (solid content concentration of 30% by mass) was obtained. It was 74000 when Mw of this NMP solution was measured by the gel permeation chromatography.

(Synthesis Example 5)
First, in a 1 L separable flask equipped with a Dean-Stark reflux condenser, thermometer, and stirrer, a reactive silicone oil (X-22-161-B, manufactured by Shin-Etsu Chemical Co., Ltd., amine equivalent: 1500, trade name) 11 mmol, (4,4′-diamino) diphenylmethane (DDM) 99 mmol as aromatic diamine compound D, 231 mmol trimellitic anhydride (TMA) 231 mmol, N-methyl-2-pyrrolidone (aprotic polar solvent) NMP) 309 g was added, the temperature in the flask was set to 80 ° C., and the mixture was stirred for 30 minutes.

  After completion of the stirring, 100 mL of toluene was further added as an aromatic hydrocarbon azeotropic with water, and the temperature in the flask was raised to 160 ° C. and refluxed for about 2 hours. After confirming that the theoretical amount of water was stored in the moisture meter and no water distilling was observed, the temperature in the flask was increased to 190 ° C while removing the water in the meter. The toluene in the reaction solution was removed.

  After returning the solution in the flask to room temperature, 132 mmol of 4,4′-diphenylmethane diisocyanate (MDI) was added as a diisocyanate, the temperature in the flask was raised to 190 ° C. and reacted for 2 hours, and then diluted with NMP. Thus, an NMP solution of polyamideimide of Synthesis Example 5 (solid content concentration of 30% by mass) was obtained. It was 56000 when Mw of this NMP solution was measured by the gel permeation chromatography.

(Synthesis Example 6)
First, in a 1 L separable flask equipped with a Dean-Stark reflux condenser, a thermometer, and a stirrer, a reactive silicone oil (X-22-161-AS, manufactured by Shin-Etsu Chemical Co., Ltd., amine equivalent: 850, trade name) 24 mmol, aromatic diamine compound D (4,4′-diamino) diphenylmethane (DDM) 96 mmol, trimellitic anhydride (TMA) 252 mmol, aprotic polar solvent N-methyl-2-pyrrolidone ( NMP) 289 g was added, and the temperature in the flask was set to 80 ° C. and stirred for 30 minutes.

  After completion of the stirring, 100 mL of toluene was further added as an aromatic hydrocarbon azeotropic with water, and the temperature in the flask was raised to 160 ° C. and refluxed for about 2 hours. After confirming that the theoretical amount of water was stored in the moisture meter and no water distilling was observed, the temperature in the flask was increased to 190 ° C while removing the water in the meter. The toluene in the reaction solution was removed.

  After returning the solution in the flask to room temperature, 144 mmol of 4,4′-diphenylmethane diisocyanate (MDI) was added as a diisocyanate, the temperature in the flask was raised to 190 ° C., and the mixture was reacted for 2 hours, and then diluted with NMP. Thus, an NMP solution of polyamideimide of Synthesis Example 6 (solid content concentration of 30% by mass) was obtained. It was 52000 when Mw of this NMP solution was measured by the gel permeation chromatography.

Table 1 summarizes the amount of each polyamideimide raw material used in Synthesis Examples 1-6.

[Preparation of resin varnish (curable resin composition)]
(Preparation Example 1)
To 100 g of the polyamideimide NMP solution obtained in Synthesis Example 1 as the component (A), the modified epoxy compound as the component (B) (PB3600, manufactured by Daicel Chemical Industries, Ltd., trade name, hereinafter referred to as “modified epoxy compound A”) .) 7.5 g is blended, and 2-ethyl-4-methylimidazole (2E4MZ, manufactured by Shikoku Kasei Kogyo Co., Ltd., trade name) 0.08 g as a curing accelerator, and α as a radical polymerization initiator which is a component (E). , Α′-bis (t-butylperoxy) diisopropylbenzene (perbutyl P, manufactured by NOF Corporation, trade name) 0.15 g was added, and then 265 g of N, N-dimethylacetamide was added. A resin varnish (for adhesive layer) (solid content concentration of about 10% by mass) was prepared.

(Preparation Example 2)
To 100 g of the polyamideimide NMP solution obtained in Synthesis Example 2 as the component (A), the modified epoxy compound as the component (B) (EPB-13, manufactured by Nippon Soda Co., Ltd., carboxylic acid-terminated polybutadiene and bisphenol A type epoxy resin) Product, product name, hereinafter referred to as “modified epoxy compound B”) 6.0 g, and 2-ethyl-4-methylimidazole (2E4MZ, manufactured by Shikoku Kasei Kogyo Co., Ltd., product name) as a curing accelerator. 0.06 g, after adding 0.12 g of α, α′-bis (t-butylperoxy) diisopropylbenzene (Perbutyl P, trade name, manufactured by NOF Corporation) as a radical polymerization initiator as component (E), N, N-dimethylacetamide (255 g) was blended to prepare a resin varnish (for adhesive layer) of Preparation Example 2 (solid content concentration of about 10% by mass).

(Preparation Example 3)
To 100 g of the polyamideimide NMP solution obtained in Synthesis Example 3 which is the component (A), the modified epoxy compound (A1020, manufactured by Daicel Chemical Industries, Ltd., trade name, hereinafter referred to as “modified epoxy compound C”). .) 10.0 g is blended, and 2-ethyl-4-methylimidazole (2E4MZ, manufactured by Shikoku Kasei Kogyo Co., Ltd., trade name) 0.1 g as a curing accelerator, and α as a radical polymerization initiator which is a component (E). , Α′-bis (t-butylperoxy) diisopropylbenzene (Perbutyl P, manufactured by NOF Corporation, trade name) 0.2 g was added, and then 290 g of N, N-dimethylacetamide was added. A resin varnish (for adhesive layer) (solid content concentration of about 10% by mass) was prepared.

(Preparation Example 4)
To 100 g of the polyamideimide NMP solution obtained in Synthesis Example 4 as the component (A), cresol novolac type epoxy resin (N673, manufactured by Dainippon Ink & Chemicals, trade name) 5.0 g as the component (C), And 4.0 g of modified polybutadiene (BN-1015, manufactured by Nippon Soda Co., Ltd., trade name, hereinafter referred to as “modified polybutadiene A”) as component (D), and further 2-ethyl-4-methyl as a curing accelerator. Imidazole (2E4MZ, manufactured by Shikoku Kasei Kogyo Co., Ltd., trade name) 0.05 g, α, α′-bis (t-butylperoxy) diisopropylbenzene (Perbutyl P, Nippon Oil & Fats Co., Ltd.) as a radical polymerization initiator as component (E) Product, product name) 0.08 g was added, 280 g of N, N-dimethylacetamide was added, and the resin varnish of Preparation Example 4 (for adhesive layer) (solid) It was prepared concentration of about 10 wt%).

(Preparation Example 5)
To 100 g of the polyamideimide NMP solution obtained in Synthesis Example 5 which is component (A), 5.0 g of phenol novolac epoxy resin (N770, manufactured by Dainippon Ink & Chemicals, Inc.) which is component (C), And 4.0 g of modified polybutadiene (C-1000, manufactured by Nippon Soda Co., Ltd., trade name, hereinafter referred to as “modified polybutadiene B”) as component (D), and further 2-ethyl-4-methyl as a curing accelerator. Imidazole (2E4MZ, manufactured by Shikoku Kasei Kogyo Co., Ltd., trade name) 0.05 g, α, α′-bis (t-butylperoxy) diisopropylbenzene (Perbutyl P, Nippon Oil & Fats Co., Ltd.) as a radical polymerization initiator as component (E) Product, product name) 0.08 g was added, 280 g of N, N-dimethylacetamide was added, and the resin varnish of Preparation Example 5 (for adhesive layer) (solid content) The degrees about 10 wt%) was prepared.

(Preparation Example 6)
To 100 g of the polyamideimide NMP solution obtained in Synthesis Example 6 which is component (A), bisphenol A type epoxy resin (DER-331L, manufactured by Dow Chemical Japan, trade name) 6.0 g which is component (C), And 4.0 g of modified polybutadiene (ATBN1300X42, manufactured by Ube Industries, trade name, hereinafter referred to as “modified polybutadiene C”) as component (D), and 2-ethyl-4-methylimidazole as a curing accelerator ( 2E4MZ, manufactured by Shikoku Kasei Kogyo Co., Ltd., trade name) 0.06 g, (E) α, α′-bis (t-butylperoxy) diisopropylbenzene (Perbutyl P, manufactured by NOF Corporation) as a radical polymerization initiator Product name) After adding 0.08 g, 290 g of N, N-dimethylacetamide was added, and the resin varnish of Preparation Example 6 (for adhesive layer) (Solid content concentration of about 10 wt%) was prepared.

(Preparation Example 7)
(B) Component glycidyl methacrylate (GMA, manufactured by Tokyo Chemical Industry Co., Ltd., trade name) 5.0 g is blended with 100 g of the polyamideimide NMP solution obtained in Synthesis Example 1 as component (A), and further cured. 2-ethyl-4-methylimidazole (2E4MZ, trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.) 0.05 g as an accelerator, and α, α′-bis (t-butylperoxy) as a radical polymerization initiator as component (E) ) After adding 0.10 g of diisopropylbenzene (Perbutyl P, manufactured by NOF Corporation, trade name), 245 g of N, N-dimethylacetamide was added, and the resin varnish of Preparation Example 7 (for adhesive layer) (solid content concentration) About 10% by weight) was prepared.

(Comparative Preparation Example 1)
To 100 g of the polyamideimide NMP solution obtained in Synthesis Example 1 as the component (A), 7.5 g of a cresol novolac type epoxy resin (N673, manufactured by Dainippon Ink & Chemicals, Inc.) as the component (C) Further, 0.08 g of 2-ethyl-4-methylimidazole (2E4MZ, manufactured by Shikoku Kasei Kogyo Co., Ltd., trade name) was added as a curing accelerator, and then 265 g of N, N-dimethylacetamide was added for comparative preparation. The resin varnish (for adhesive layer) of Example 1 (solid content concentration of about 10% by mass) was prepared.

(Comparative Preparation Example 2)
To 100 g of NMP solution of polyamideimide obtained in Synthesis Example 5 which is component (A), 5.0 g of phenol novolac type epoxy resin (N770, manufactured by Dainippon Ink & Chemicals, Inc.) which is component (C). Further, 0.05 g of 2-ethyl-4-methylimidazole (2E4MZ, manufactured by Shikoku Kasei Kogyo Co., Ltd., trade name) was added as a curing accelerator, and then 265 g of N, N-dimethylacetamide was added for comparative preparation. The resin varnish (for adhesive layer) of Example 2 (solid content concentration of about 10% by mass) was prepared.

(Comparative Preparation Example 3)
To 100 g of the polyamideimide NMP solution obtained in Synthesis Example 6 as the component (A), 6.0 g of the bisphenol A type epoxy resin (DER-331L, manufactured by Dow Chemical Japan Co., Ltd.) as the component (C). Further, 0.06 g of 2-ethyl-4-methylimidazole (2E4MZ, manufactured by Shikoku Kasei Kogyo Co., Ltd., trade name) was added as a curing accelerator, and then 250 g of N, N-dimethylacetamide was added for comparison preparation. The resin varnish of Example 3 (for adhesive layer) (solid content concentration of about 10% by mass) was prepared.

Table 2 summarizes the amount of each raw material used in the resin varnishes (curable resin compositions) used in Preparation Examples 1 to 5 and Comparative Preparation Examples 1 to 3.

[Preparation of prepreg and double-sided copper-clad laminate]
(Production Example 1)
First, in a 2 L separable flask equipped with a cooling tube, a thermometer, and a stirrer, 400 g of toluene and 120 g of a polyphenylene ether resin (modified PPO-noryl PKN4752, manufactured by Nippon GE Plastics Co., Ltd., trade name) were placed. The solution was stirred and dissolved while heating the temperature to 90 ° C. Next, 80 g of triallyl isocyanurate (TAIC, manufactured by Nippon Kasei Kogyo Co., Ltd., trade name) was added to the flask while stirring, and the mixture was cooled to room temperature after confirming that it was dissolved or uniformly dispersed. Next, after adding 2.0 g of α, α′-bis (t-butylperoxy) diisopropylbenzene (Perbutyl P, trade name, manufactured by NOF Corporation) as a radical polymerization initiator, 70 g of toluene was further blended. A resin varnish (for insulating resin layer) having a solid content concentration of about 30% by mass was obtained.

  The obtained resin varnish (for insulating resin layer) was impregnated into glass fiber (E glass, manufactured by Nitto Boseki Co., Ltd.) having a thickness of 0.1 mm, and then heat-dried at 120 ° C. for 5 minutes to obtain a resin content of 50 mass % Of the prepreg of Preparation Example 1 was obtained.

  Thereafter, the four prepregs of Production Example 1 described above were placed in an overlapping manner, and on each side, 35 μm thick electrolytic copper foil (F2-WS-35, low profile copper foil, manufactured by Furukawa Electric Co., Ltd., M-plane surface) Roughness (Rz): 2 μm, S-surface roughness (Rz): 1.1 μm (hereinafter simply referred to as “low profile copper foil”) are arranged with the prepreg side as the M-plane, and these are 20 The double-sided copper-clad laminate of Production Example 1 was obtained by heating and pressing under press conditions of 2.9 MPa at 70 ° C. for 70 minutes. In addition, including the following preparation examples, the thickness of the double-sided copper-clad laminate was 0.58 mm.

(Production Example 2)
First, in a 2 L separable flask equipped with a cooling tube, a thermometer, and a stirrer, 400 g of toluene and 120 g of a polyphenylene ether resin (modified PPO-noryl PKN4752, manufactured by Nippon GE Plastics Co., Ltd., trade name) were placed. The solution was stirred and dissolved while heating the temperature to 90 ° C. Next, while stirring, 80 g of 1,2-polybutadiene (B-1000, manufactured by Nippon Soda Co., Ltd., trade name) and 10 g of divinylbenzene (DVB) as a crosslinking aid were added and dissolved or uniformly dispersed. After confirmation, it was cooled to room temperature. Next, after adding 2.0 g of α, α′-bis (t-butylperoxy) diisopropylbenzene (Perbutyl P, trade name, manufactured by NOF Corporation) as a radical polymerization initiator, 70 g of toluene was further blended. A resin varnish (for insulating resin layer) having a solid content concentration of about 30% by mass was obtained.

  The obtained resin varnish (for insulating resin layer) was impregnated into glass fiber (E glass, manufactured by Nitto Boseki Co., Ltd.) having a thickness of 0.1 mm, and then heat-dried at 120 ° C. for 5 minutes to obtain a resin content of 50 mass. % Of the prepreg of Preparation Example 2 was obtained.

  Thereafter, the four prepregs of Production Example 2 described above were placed on top of each other, and further, low profile copper foils were placed on both sides thereof with the prepreg side M side, and these were placed at 20 ° C. for 70 minutes and 2.9 MPa. The double-sided copper-clad laminate of Production Example 2 was obtained by heating and pressing under the press conditions.

(Production Example 3)
First, in a 10 L separable flask equipped with a condenser, a thermometer, and a stirrer, 5000 mL of tetrahydrofuran (THF) and 100 g of polyphenylene ether resin (Noryl PPO646-111, manufactured by Nippon GE Plastics, Inc., trade name) The temperature in the flask was stirred and dissolved while heating to 60 ° C. After returning this to room temperature, 540 mL of n-butyllithium (1.55 mol / L, hexane solution) was added under a nitrogen stream and stirred for 1 hour. Furthermore, after adding 100 g of allyl bromide and stirring for 30 minutes, an appropriate amount of methanol was blended, and the precipitated polymer was isolated to obtain an allylated polyphenylene ether.

  Next, in a 2 L separable flask equipped with a cooling tube, a thermometer, and a stirrer, 400 g of toluene and 100 g of the allylated polyphenylene ether were put and dissolved while stirring while heating the temperature in the flask to 90 ° C. Next, 100 g of triallyl isocyanurate (TAIC, manufactured by Nippon Kasei Kogyo Co., Ltd., trade name) was added to the flask while stirring, and the mixture was cooled to room temperature after confirming that it was dissolved or uniformly dispersed. Then, after adding 2.5 g of α, α′-bis (t-butylperoxy) diisopropylbenzene (Perbutyl P, trade name, manufactured by NOF Corporation) as a radical polymerization initiator, 70 g of toluene was further blended. A resin varnish (for insulating resin layer) having a solid content concentration of about 30% by mass was obtained.

  The obtained resin varnish (for insulating resin layer) was impregnated into glass fiber (E glass, manufactured by Nitto Boseki Co., Ltd.) having a thickness of 0.1 mm, and then heat-dried at 120 ° C. for 5 minutes to obtain a resin content of 50 mass. % Of the prepreg of Preparation Example 3 was obtained.

  Thereafter, the four prepregs of Production Example 3 described above were placed one on top of the other, and on both sides, low profile copper foils were placed with the prepreg side M side, and these were placed at 20 ° C. for 70 minutes, 2.9 MPa. The double-sided copper-clad laminate of Production Example 3 was obtained by heat and pressure molding under the pressing conditions described above.

[Manufacture of double-sided circuit board with adhesive layer and single-sided circuit board with adhesive layer]
(Production Example 1)
A manufacturing example in which a conductor circuit in which straight lines are arranged in stripes with a wiring width of 1 cm and a pattern width (etching width) of 1 cm is formed on both sides of the double-sided copper-clad laminate obtained in Production Example 1 by using an etching method. 1 double-sided circuit board (core board) was obtained. The surface roughness of the formed conductor circuit was 0.9 μm.

  Next, the resin varnish (for adhesive layer) obtained in Preparation Example 1 is stored in a vat (building bath), and the double-sided circuit board of Production Example 1 described above is immersed in this for 1 minute, and then taken out at 150 ° C. It was dried for 5 minutes to obtain a double-sided circuit board with an adhesive layer of Production Example 1. The thickness of the adhesive layer after drying was 2 μm, including the following production examples and comparative production examples.

  In addition, a conductor circuit in which straight wirings are arranged in stripes with a wiring width of 0.5 cm and a pattern width (etching width) of 1 cm is formed on one side of the double-sided copper-clad laminate obtained in Production Example 1 Thus, a single-sided circuit board (core board) of Production Example 1 was obtained. The surface roughness of the formed conductor circuit was 0.9 μm.

  Next, the resin varnish (for adhesive layer) obtained in Preparation Example 1 is stored in a bat (building bath), and the surface on the conductor circuit side of the single-sided circuit board of Production Example 1 described above is immersed in this for 1 minute. After taking out, it was dried at 150 ° C. for 5 minutes to obtain a single-sided circuit board with an adhesive layer of Production Example 1. The thickness of the adhesive layer after drying was 2 μm, including the following production examples and comparative production examples.

(Production Example 2)
In the same manner as in Production Example 1, a double-sided circuit board (core substrate) of Production Example 2 was obtained.

  Next, instead of the resin varnish (for adhesive layer) obtained in Preparation Example 1 for the double-sided circuit board of Production Example 2, the resin varnish (for adhesive layer) obtained in Preparation Example 2 was used. Obtained a double-sided circuit board with an adhesive layer of Production Example 2 in the same manner as in Production Example 1.

  Moreover, it carried out similarly to manufacture example 1, and obtained the single-sided circuit board (core board | substrate) of manufacture example 2.

  Next, for the single-sided circuit board of Production Example 2, instead of the resin varnish (for adhesive layer) obtained in Preparation Example 1, the resin varnish (for adhesive layer) obtained in Preparation Example 2 was used. Obtained a single-sided circuit board with an adhesive layer of Production Example 2 in the same manner as Production Example 1.

(Production Example 3)
Instead of the double-sided copper-clad laminate obtained in Preparation Example 1, the double-sided copper-clad laminate obtained in Preparation Example 2 was used in the same manner as in Production Example 1, except that the double-sided circuit board (core) Substrate).

  Next, instead of the resin varnish (for the adhesive layer) obtained in Preparation Example 1 for the double-sided circuit board of Production Example 3, the resin varnish (for the adhesive layer) obtained in Preparation Example 3 was used to produce A double-sided circuit board with an adhesive layer of Example 3 was obtained.

  Further, in place of the double-sided copper-clad laminate obtained in Production Example 1, the double-sided copper-clad laminate obtained in Production Example 2 was used in the same manner as Production Example 1, except that the single-sided circuit board of Production Example 3 was used. (Core substrate) was obtained.

  Next, instead of the resin varnish (for the adhesive layer) obtained in Preparation Example 1, the resin varnish (for the adhesive layer) obtained in Preparation Example 3 was used to manufacture the single-sided circuit board of Production Example 3 A single-sided circuit board with an adhesive layer of Example 3 was obtained.

(Production Example 4)
In place of the double-sided copper-clad laminate obtained in Production Example 1, the double-sided copper-clad laminate obtained in Production Example 2 was used except that the double-sided copper-clad laminate obtained in Production Example 2 was used. Substrate).

  Next, instead of the resin varnish (for adhesive layer) obtained in Preparation Example 1 for the double-sided circuit board of Production Example 4, the resin varnish (for adhesive layer) obtained in Preparation Example 4 was used. Obtained a double-sided circuit board with an adhesive layer of Production Example 4 in the same manner as in Production Example 1.

  Further, in place of the double-sided copper-clad laminate obtained in Production Example 1, the single-sided circuit board of Production Example 4 was produced in the same manner as Production Example 1 except that the double-sided copper-clad laminate obtained in Production Example 2 was used. (Core substrate) was obtained.

  Next, instead of the resin varnish (for the adhesive layer) obtained in Preparation Example 1 for the single-sided circuit board of Production Example 4, the resin varnish (for the adhesive layer) obtained in Preparation Example 4 was used. Obtained the single-sided circuit board with the contact bonding layer of manufacture example 4 like manufacture example 1.

(Production Example 5)
In place of the double-sided copper-clad laminate obtained in Production Example 1, the double-sided copper-clad laminate obtained in Production Example 3 was used except that the double-sided copper-clad laminate obtained in Production Example 3 was used. Substrate).

  Next, as described in JP-A No. 2000-282265, sulfuric acid 160 g / L, hydrogen peroxide 100 g / L, tolyltriazole 2 g / L, phosphorous acid 10 g / L, ion-exchanged water (remainder) A mixed solution is prepared, and this mixed solution is sprayed at 30 ° C. for 1 minute on the surface of the double-sided circuit board of Production Example 5 described above, and a roughening treatment is performed so that the surface roughness of the conductor circuit becomes 3.0 μm. It was.

  Then, instead of the resin varnish (for adhesive layer) obtained in Preparation Example 1 for the double-sided circuit board of Production Example 5 after the roughening treatment, the resin varnish (for adhesive layer) obtained in Preparation Example 5 was used. A double-sided circuit board with an adhesive layer of Production Example 5 was obtained in the same manner as Production Example 1 except that it was used.

  Further, in place of the double-sided copper-clad laminate obtained in Production Example 1, the double-sided copper-clad laminate obtained in Production Example 3 was used in the same manner as Production Example 1, except that the single-sided circuit board of Production Example 5 was used. (Core substrate) was obtained.

  Next, the surface having the conductor circuit of the single-sided circuit board of Production Example 5 was subjected to the same roughening treatment as described above, so that the surface roughness of the conductor circuit was 3.0 μm.

  Then, instead of the resin varnish (for adhesive layer) obtained in Preparation Example 1 for the single-sided circuit board of Production Example 5 after the roughening treatment, the resin varnish (for adhesive layer) obtained in Preparation Example 5 was used. A single-sided circuit board with an adhesive layer of Production Example 5 was obtained in the same manner as Production Example 1 except that it was used.

(Production Example 6)
Instead of the double-sided copper-clad laminate obtained in Preparation Example 1, the double-sided copper-clad laminate obtained in Preparation Example 3 was used in the same manner as in Production Example 1, except that the double-sided copper-clad laminate (core) Substrate).

  Next, the same roughening treatment as in Production Example 5 was performed on the double-sided circuit board of Production Example 6 so that the surface roughness of the conductor circuit was 3.0 μm.

  Thereafter, the resin varnish (for adhesive layer) obtained in Preparation Example 6 was used instead of the resin varnish (for adhesive layer) obtained in Preparation Example 1 for the double-sided circuit board of Production Example 6 after the roughening treatment. A double-sided circuit board with an adhesive layer of Production Example 6 was obtained in the same manner as Production Example 1 except that it was used.

  Further, in place of the double-sided copper-clad laminate obtained in Production Example 1, the double-sided copper-clad laminate obtained in Production Example 3 was used in the same manner as Production Example 1 except that the single-sided circuit board of Production Example 6 was used. (Core substrate) was obtained.

  Next, the roughening process similar to manufacture example 5 was performed to the single-sided circuit board of manufacture example 6, and the surface roughness of the conductor circuit was set to 3.0 micrometers.

  Then, instead of the resin varnish (for adhesive layer) obtained in Preparation Example 1 for the single-sided circuit board of Production Example 6 after the roughening treatment, the resin varnish (for adhesive layer) obtained in Preparation Example 6 was used. A single-sided circuit board with an adhesive layer of Production Example 6 was obtained in the same manner as Production Example 1 except that it was used.

(Production Example 7)
In the same manner as in Production Example 1, a double-sided circuit board (core substrate) of Production Example 7 was obtained.

  Next, the roughening process similar to the manufacture example 5 was performed to the double-sided circuit board of the manufacture example 7, and the surface roughness of the conductor circuit was set to 3.0 micrometers.

  Then, instead of the resin varnish (for adhesive layer) obtained in Preparation Example 1 for the double-sided circuit board of Production Example 7 after the roughening treatment, the resin varnish (for adhesive layer) obtained in Preparation Example 7 was used. A double-sided circuit board with an adhesive layer of Production Example 7 was obtained in the same manner as Production Example 1 except that it was used.

  Further, in the same manner as in Production Example 1, a single-sided circuit board (core substrate) of Production Example 7 was obtained.

  Next, the roughening process similar to manufacture example 5 was performed to the single-sided circuit board of manufacture example 7, and the surface roughness of the conductor circuit was set to 3.0 micrometers.

  Then, instead of the resin varnish (for the adhesive layer) obtained in Preparation Example 1 for the single-sided circuit board of Production Example 7 after the roughening treatment, the resin varnish (for the adhesive layer) obtained in Preparation Example 7 was used. A single-sided circuit board with an adhesive layer of Production Example 7 was obtained in the same manner as Production Example 1 except that it was used.

(Comparative Production Example 1)
In the same manner as in Production Example 1, a double-sided circuit board (core substrate) of Comparative Production Example 1 was obtained.

  Next, the roughening process similar to the manufacture example 5 was performed to the double-sided circuit board of the comparative manufacture example 1, and the surface roughness of the conductor circuit was set to 3.0 micrometers.

  Then, instead of the resin varnish (for adhesive layer) obtained in Preparation Example 1 for the double-sided circuit board of Comparative Production Example 1 after the roughening treatment, the resin varnish (for adhesive layer) obtained in Comparative Preparation Example 1 was used. ) Was used in the same manner as in Production Example 1 to obtain a double-sided circuit board with an adhesive layer in Comparative Production Example 1.

  Moreover, it carried out similarly to the manufacture example 1, and obtained the single-sided circuit board (core board | substrate) of the comparative manufacture example 1.

  Next, the roughening process similar to manufacture example 5 was performed to the single-sided circuit board of the comparative manufacture example 1, and the surface roughness of the conductor circuit was set to 3.0 micrometers.

  Then, instead of the resin varnish (for adhesive layer) obtained in Preparation Example 1 for the single-sided circuit board of Comparative Production Example 1 after the roughening treatment, the resin varnish (for adhesive layer) obtained in Comparative Preparation Example 1 was used. ) Was used in the same manner as in Production Example 1 to obtain a single-sided circuit board with an adhesive layer of Comparative Production Example 1.

(Comparative Production Example 2)
Instead of the double-sided copper-clad laminate obtained in Production Example 1, the double-sided circuit board of Comparative Production Example 3 was used in the same manner as Production Example 1 except that the double-sided copper-clad laminate obtained in Production Example 3 was used. A core substrate) was obtained.

  Next, the roughening process similar to the manufacture example 5 was performed to the double-sided circuit board of the comparative manufacture example 2, and the surface roughness of the conductor circuit was set to 3.0 micrometers.

  Then, instead of the resin varnish (for adhesive layer) obtained in Preparation Example 1 for the single-sided circuit board of Comparative Production Example 2 after the roughening treatment, the resin varnish (for adhesive layer) obtained in Comparative Preparation Example 2 was used. ) Was used in the same manner as in Production Example 1 to obtain a double-sided circuit board with an adhesive layer in Comparative Production Example 2.

  Moreover, it replaced with the double-sided copper clad laminated board obtained by the manufacture example 1, and carried out similarly to the manufacture example 1 except having used the double-sided copper clad laminate obtained by the manufacture example 3, and the single-sided circuit of the comparative manufacture example 3 A substrate (core substrate) was obtained.

  Next, the same roughening treatment as in Production Example 5 was performed on the single-sided circuit board of Comparative Production Example 2, and the surface roughness of the conductor circuit was set to 3.0 μm.

  Then, instead of the resin varnish (for adhesive layer) obtained in Preparation Example 1 for the single-sided circuit board of Comparative Production Example 2 after the roughening treatment, the resin varnish (for adhesive layer) obtained in Comparative Preparation Example 2 was used. ) Was used in the same manner as in Production Example 1 to obtain a single-sided circuit board with an adhesive layer in Comparative Production Example 2.

(Comparative Production Example 3)
Instead of the double-sided copper-clad laminate obtained in Production Example 1, the double-sided circuit board of Comparative Production Example 3 was prepared in the same manner as in Production Example 1 except that the double-sided copper-clad laminate obtained in Production Example 3 was used. Obtained.

  Next, the roughening process similar to the manufacture example 5 was performed to the double-sided circuit board of the comparative manufacture example 3, and the surface roughness of the conductor circuit was set to 3.0 micrometers.

  Then, instead of the resin varnish (for adhesive layer) obtained in Preparation Example 1 for the double-sided circuit board of Comparative Production Example 2 after the roughening treatment, the resin varnish (for adhesive layer) obtained in Comparative Preparation Example 3 was used. ) Was used in the same manner as in Production Example 1 to obtain a double-sided circuit board with an adhesive layer of Comparative Production Example 3.

  Moreover, it replaced with the double-sided copper clad laminated board obtained by the manufacture example 1, and carried out similarly to the manufacture example 1 except having used the double-sided copper clad laminate obtained by the manufacture example 3, and the single-sided circuit of the comparative manufacture example 3 A substrate was obtained.

  Next, the roughening process similar to the manufacture example 5 was performed to the single-sided circuit board of the comparative manufacture example 3, and the surface roughness of the conductor circuit was set to 3.0 micrometers.

  Then, instead of the resin varnish (for adhesive layer) obtained in Preparation Example 1 for the single-sided circuit board of Comparative Production Example 2 after the roughening treatment, the resin varnish (for adhesive layer) obtained in Comparative Preparation Example 3 was used. ) Was used in the same manner as in Production Example 1 to obtain a single-sided circuit board with an adhesive layer in Comparative Production Example 3.

[Manufacture of multilayer printed wiring boards (3-layer boards, 4-layer boards)]
Example 1
On both surfaces of the double-sided circuit board with the adhesive layer of Production Example 1, the prepreg for insulating resin layer and the low profile copper foil of Production Example 1 described above are arranged in this order (the M surface of the low profile copper foil is the prepreg side). The multilayer printed wiring board (four-layer board) of Example 1 was obtained by heat and pressure molding at 20 ° C. for 70 minutes under a pressing condition of 2.9 MPa.

(Example 2)
On both surfaces of the double-sided circuit board with an adhesive layer of Production Example 2, the insulating resin layer prepreg of Production Example 1 and the low profile copper foil are arranged in this order (the M surface of the low profile copper foil is the prepreg side). Then, these were subjected to heat and pressure molding at 20 ° C. for 70 minutes under a pressing condition of 2.9 MPa to obtain a multilayer printed wiring board (four-layer board) of Example 2.

(Example 3)
On both surfaces of the double-sided circuit board with adhesive layer of Production Example 3, the prepreg for insulating resin layer and Low Profile Copper Foil of Production Example 2 described above are arranged in this order (the M surface of the low profile copper foil is the prepreg side). Then, these were heated and pressed under pressure conditions of 2.9 MPa at 20 ° C. for 70 minutes to obtain a multilayer printed wiring board (four-layer board) of Example 3.

Example 4
On both surfaces of the double-sided circuit board with adhesive layer of Production Example 4, the prepreg for insulating resin layer and Low Profile Copper Foil of Production Example 2 described above are arranged in this order (the M surface of the low profile copper foil is the prepreg side). The multilayer printed wiring board (four-layer board) of Example 4 was obtained by heat and pressure molding at 20 ° C. for 70 minutes under a pressing condition of 2.9 MPa.

(Example 5)
On both surfaces of the double-sided circuit board with an adhesive layer of Production Example 5, the prepreg for insulating resin layer and Low Profile Copper Foil of Production Example 3 described above are arranged in this order (the M surface of the low profile copper foil is the prepreg side). The multilayer printed wiring board (four-layer board) of Example 5 was obtained by subjecting these to heat and pressure molding at 20 ° C. for 70 minutes under a pressing condition of 2.9 MPa.

(Example 6)
On both surfaces of the double-sided circuit board with adhesive layer of Production Example 6, the prepreg for insulating resin layer and Low Profile Copper Foil of Production Example 3 described above are arranged in this order (the M surface of the low profile copper foil is the prepreg side). The multilayer printed wiring board (four-layer board) of Example 6 was obtained by heat and pressure molding at 20 ° C. for 70 minutes under a pressing condition of 2.9 MPa.

(Example 7)
On both surfaces of the double-sided circuit board with an adhesive layer of Production Example 7, the prepreg for insulating resin layer and Low Profile Copper Foil of Production Example 3 described above are arranged in this order (the M surface of the low profile copper foil is the prepreg side). Then, these were heated and pressed under pressure of 2.9 MPa at 20 ° C. for 70 minutes to obtain a multilayer printed wiring board (four-layer board) of Example 7.

(Example 8)
The insulating resin layer prepreg and low profile copper foil of Preparation Example 1 described above are arranged in this order on the surface on the conductor circuit side of the single-sided circuit board with an adhesive layer of Production Example 1 (the M surface of the low profile copper foil is prepreg). Then, the multilayer printed wiring board (three-layer board) of Example 8 was obtained by subjecting these to heat and pressure molding at 20 ° C. for 70 minutes under a pressing condition of 2.9 MPa.

Example 9
The insulating resin layer prepreg and low profile copper foil of Preparation Example 1 described above are arranged in this order on the surface on the conductor circuit side of the single-sided circuit board with an adhesive layer of Production Example 2 (the M surface of the low profile copper foil is prepreg). Then, these were heated and pressed under pressure conditions of 2.9 MPa at 20 ° C. for 70 minutes to obtain a multilayer printed wiring board (three-layer board) of Example 9.

(Example 10)
The insulating resin layer prepreg and low profile copper foil of Preparation Example 2 described above are arranged in this order on the conductor circuit side surface of the single-sided circuit board with adhesive layer of Production Example 3 (the M surface of the low profile copper foil is prepreg). Then, these were heated and pressed under pressure conditions of 2.9 MPa at 20 ° C. for 70 minutes to obtain a multilayer printed wiring board (three-layer board) of Example 10.

(Example 11)
The insulating resin layer prepreg and low profile copper foil of Preparation Example 2 described above are arranged in this order on the conductor circuit side surface of the single-sided circuit board with an adhesive layer of Production Example 4 (the M surface of the low profile copper foil is prepreg). Then, these were heated and pressed under pressure conditions of 2.9 MPa at 20 ° C. for 70 minutes to obtain a multilayer printed wiring board (three-layer board) of Example 11.

(Example 12)
The insulating resin layer prepreg and low profile copper foil of Preparation Example 3 described above are arranged in this order on the conductor circuit side surface of the single-sided circuit board with adhesive layer of Production Example 5 (the M surface of the low profile copper foil is prepreg). Then, these were heated and pressed under pressure conditions of 2.9 MPa at 20 ° C. for 70 minutes to obtain a multilayer printed wiring board (three-layer board) of Example 12.

(Example 13)
The insulating resin layer prepreg and low profile copper foil of Preparation Example 3 described above are arranged in this order on the surface on the conductor circuit side of the single-sided circuit board with an adhesive layer of Production Example 6 (the M surface of the low profile copper foil is prepreg). Then, these were heated and pressed under pressure conditions of 2.9 MPa at 20 ° C. for 70 minutes to obtain a multilayer printed wiring board (three-layer board) of Example 13.

(Example 14)
The insulating resin layer prepreg and low profile copper foil of Preparation Example 1 described above are arranged in this order on the surface on the conductor circuit side of the single-sided circuit board with an adhesive layer of Production Example 7 (the M surface of the low profile copper foil is prepreg). Then, these were heated and pressed under pressure of 2.9 MPa at 20 ° C. for 70 minutes to obtain a multilayer printed wiring board (three-layer board) of Example 14.

(Comparative Example 1)
On both surfaces of the double-sided circuit board with the adhesive layer of Comparative Production Example 1, the prepreg for insulating resin layer and the low profile copper foil of Production Example 1 described above are arranged in this order (the M surface of the low profile copper foil is the prepreg side). Then, these were heated and pressed under pressure of 2.9 MPa at 20 ° C. for 70 minutes to obtain a multilayer printed wiring board (four-layer board) of Comparative Example 1.

(Comparative Example 2)
On both surfaces of the double-sided circuit board with an adhesive layer of Comparative Production Example 2, the prepreg for insulating resin layer and low profile copper foil of Production Example 3 described above are arranged in this order (the M surface of the low profile copper foil is the prepreg side). Then, the multilayer printed wiring board (four-layer board) of Comparative Example 2 was obtained by heating and pressing at 20 ° C. for 70 minutes under a pressing condition of 2.9 MPa.

(Comparative Example 3)
On both surfaces of the double-sided circuit board with an adhesive layer of Comparative Production Example 3, the prepreg for insulating resin layer and low profile copper foil of Production Example 3 described above are arranged in this order (the M surface of the low profile copper foil is the prepreg side). The multilayer printed wiring board (4-layer board) of Comparative Example 3 was obtained by heat and pressure molding at 20 ° C. for 70 minutes under a pressing condition of 2.9 MPa.

(Comparative Example 4)
Without forming an adhesive layer on the double-sided circuit board obtained in Production Example 1, the prepreg for insulating resin layer and low profile copper foil of Production Example 1 described above are arranged in this order on both sides (low profile copper foil) The M surface of the prepreg side is heated and pressed under pressure of 2.9 MPa at 20 ° C. for 70 minutes to obtain the multilayer printed wiring board (four-layer board) of Comparative Example 4. Obtained.

(Comparative Example 5)
The double-sided circuit board obtained in Production Example 1 was subjected to the same roughening treatment as in Production Example 5, so that the surface roughness of the conductor circuit was 3.0 μm.

  Thereafter, the adhesive layer is not formed on the double-sided circuit board after the roughening treatment, and the prepreg for insulating resin layer and low profile copper foil of Production Example 1 described above are arranged in this order on both sides (low profile). The M surface of the copper foil is the prepreg side.) These are heated and pressed under pressure conditions of 2.9 MPa at 20 ° C. for 70 minutes to obtain a multilayer printed wiring board (four-layer board) of Comparative Example 5 )

(Comparative Example 6)
On the conductor circuit side surface of the single-sided circuit board with the adhesive layer of Comparative Production Example 1, the prepreg for insulating resin layer and the low profile copper foil of Production Example 1 described above are arranged in this order (the M surface of the low profile copper foil is Then, the multilayer printed wiring board (three-layer board) of Comparative Example 6 was obtained by heating and pressing under pressure conditions of 2.9 MPa at 20 ° C. for 70 minutes.

(Comparative Example 7)
The insulating resin layer prepreg and low profile copper foil of Production Example 3 described above are arranged in this order on the surface on the conductor circuit side of the single-sided circuit board with an adhesive layer of Comparative Production Example 2 (the M surface of the low profile copper foil is arranged in this order). Then, the multilayer printed wiring board (three-layer board) of Comparative Example 7 was obtained by heating and pressing under pressure conditions of 2.9 MPa at 20 ° C. for 70 minutes.

(Comparative Example 8)
The insulating resin layer prepreg and low profile copper foil of Preparation Example 3 described above are arranged in this order on the surface on the conductor circuit side of the single-sided circuit board with an adhesive layer of Comparative Production Example 3 (the M surface of the low profile copper foil is arranged in this order). Then, the multilayer printed wiring board (three-layer board) of Comparative Example 8 was obtained by heat-press molding under press conditions of 2.9 MPa at 20 ° C. for 70 minutes.

(Comparative Example 9)
Without forming an adhesive layer on the single-sided circuit board obtained in Production Example 1, the prepreg for insulating resin layer and low profile copper foil of Production Example 1 described above are arranged in this order on the surface on the side of the conductor circuit. (The M surface of the low-profile copper foil is the prepreg side), and these are heated and pressed under pressure of 2.9 MPa at 20 ° C. for 70 minutes, whereby the multilayer printed wiring board of Comparative Example 9 ( A three-layer plate) was obtained.

(Comparative Example 10)
The single-sided circuit board obtained in Production Example 1 was subjected to the same roughening treatment as in Production Example 5, so that the surface roughness of the conductor circuit was 3.0 μm.

  Then, without forming an adhesive layer on the roughened single-sided circuit board, the insulating resin layer prepreg and low profile copper foil of Production Example 1 described above were formed in this order on the surface on the conductor circuit side. (The M surface of the low-profile copper foil is the prepreg side), and these are heated and pressed under pressure conditions of 2.9 MPa at 20 ° C. for 70 minutes, whereby the multilayer printed wiring of Comparative Example 10 A plate (three-layer plate) was obtained.

  Table 3 shows the resin varnish (curable resin composition) used in Examples 1 to 7 and Comparative Examples 1 to 5 and the surface roughness of the conductor circuit at the time of production. Table 4 summarizes the surface roughness of the resin varnish (curable resin composition) used in Examples 8 to 14 and Comparative Examples 6 to 10 and the conductor circuit during production.

[Measurement of peel strength of copper foil in multilayer printed wiring boards]
In the multilayer printed wiring boards (four-layer board) of Examples 1 to 7 and Comparative Examples 1 to 5, the insulating layer (laminated board) of the core substrate was split into two in the laminating direction and peeled off, and the insulating layer exposed after peeling Either surface was rubbed with sandpaper, and a 1 cm long conductor circuit was exposed in the width direction of the wiring to produce a sample for evaluation. The copper foil peel strength (unit: kN / m) after being held in the normal state and pressure cooker test (PCT) apparatus (conditions: 121 ° C., 2.2 atm) for 5 hours is JIS-C- Measured in accordance with “Test method for copper-clad laminate for printed wiring board” of 6481-1996. The results are shown in Table 3. In addition, about this copper foil peeling strength, about what was less than 0.01 kN / m, peeling was already confirmed before peeling.

[Evaluation of solder heat resistance of multilayer printed wiring boards]
In the multilayer printed wiring boards (four-layer boards) of Examples 1 to 7 and Comparative Examples 1 to 5, the copper foils on both sides of the multilayer printed wiring board cut into 50 mm squares were etched on the entire surface to prepare evaluation samples. . The normal and pressure cooker test (PCT) apparatus (conditions: 121 ° C., 2.2 atm) after being held for a predetermined time (1 to 3 hours) is immersed in molten solder at 260 ° C. for 20 seconds, The appearance of the obtained sample for evaluation was examined visually. The results are shown in Table 3. The numbers in the table indicate the occurrence of swelling between the insulating resin layer and the conductor circuit or the etched surface (laminated board) in the multilayer printed wiring board after solder immersion, and the occurrence of measling in the insulating resin layer. It means the number of items that were not.

[Evaluation of transmission loss of multilayer printed wiring boards]
In the multilayer printed wiring boards (three-layer boards) of Examples 8 to 14 and Comparative Examples 6 to 10, the transmission loss (unit: dB / m) was measured. The multilayer printed wiring board (three-layer board) has a line structure (triplate line structure) in which an in-plane conductor (conductor circuit) is disposed between two out-of-plane conductors (low profile copper foil). These transmission losses were measured by the triplate line resonator method as an evaluation sample. A vector type network analyzer was used for the triplate line resonator method. Measurement conditions were as follows: line width: 0.6 mm, insulating layer distance between upper and lower ground conductors: about 1.04 mm, line length: 200 mm, characteristic impedance: about 50Ω, frequency: 3 GHz, measurement temperature: 25 ° C. The results are shown in Table 4.

It is a fragmentary sectional view of the circuit board with an adhesion layer concerning a 1st embodiment of the present invention. It is a fragmentary sectional view of the multilayer printed wiring board concerning a 3rd embodiment of the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10, 50 ... Circuit board | substrate, 12, 52 ... Laminate board (insulation board), 14, 54 ... Conductor circuit, 14a, 54a ... Surface of conductor circuit, 12a, 52a ... Surface of laminate board (insulation board), 20 ... Adhesion Layer, 60 ... hardened layer, 70 ... insulating resin layer, 80 ... metal foil, 100 ... circuit board with adhesive layer, 200 ... multilayer printed wiring board.

Claims (27)

A circuit board with an adhesive layer comprising: a circuit board on which a conductor circuit is formed on one or both main surfaces of an insulating plate; and an adhesive layer provided on at least the surface of the conductor circuit,
The adhesive layer is
(A) component; polyamideimide,
(B) component; a compound having a functional group capable of reacting with the amide group of the polyamideimide and having an ethylenically unsaturated bond;
(E) component; radical polymerization initiator;
A circuit board with an adhesive layer, comprising a curable resin composition containing   The circuit board with an adhesive layer according to claim 1, wherein the component (A) has a structural unit composed of a saturated hydrocarbon.   The circuit board with an adhesive layer according to claim 1, wherein the component (B) has an oxirane ring or an oxetane ring.   Any one of Claims 1-3 which has 1 or more types of groups chosen from the group which consists of a vinyl group, an allyl group, an acryl group, and a methacryl group as a functional group which has the said ethylenically unsaturated bond in the said (B) component. A circuit board with an adhesive layer according to claim 1.   The circuit board with an adhesive layer according to claim 1, wherein the component (B) is an epoxy compound having a polybutadiene structure and an oxirane ring. A modified polybutadiene in which the epoxy compound has one or more groups selected from the group consisting of phenolic hydroxyl groups, alcoholic hydroxyl groups, carboxyl groups, amide groups, amino groups, imino groups, and groups represented by the following formula (III) The circuit board with an adhesive layer according to claim 5, which is a compound obtained by reacting a compound having two or more oxirane rings.

  The circuit board with an adhesive layer according to claim 5 or 6, wherein the epoxy compound has a vinyl group at a side chain or a terminal thereof. The adhesion according to claim 5, wherein the epoxy compound is one represented by the following general formula (1), (2) or (3) or a structural unit represented by the following general formula (5). Circuit board with layers.

(In formula, n shows the integer of 2-8, and the sum total of n and m shows the integer of 10-10000.)

(In the formula, R ¹ and R ² each independently represent a hydrogen atom or a hydroxyl group, and R ³ represents an acrylic group or an oxiranyl group.)

(Wherein, ^{R 4} represents a group represented by the following formula (4), i is an integer of 0 to 100, the sum of i and j is an integer of 10 to 10,000.)

(In the formula, p and u each independently represent an integer of 1 to 10,000, q represents an integer of 1 to 100, r and s each independently represents an integer of 0 to 100, and t represents 1 to 10,000. Represents an integer, where either r or s represents an integer of 1 or more.)   The circuit board with an adhesive layer according to any one of claims 1 to 8, wherein a blending ratio of the component (B) is 5 to 200 parts by mass with respect to 100 parts by mass of the component (A).   The said circuit board is provided with the layer formed by hardening | curing the curable resin composition containing the said (A) component and the said (B) component between the said insulating board and the said conductor circuit. The circuit board with an adhesive layer according to any one of 1 to 9. A circuit board with an adhesive layer comprising: a circuit board on which a conductor circuit is formed on one or both main surfaces of an insulating plate; and an adhesive layer provided on at least the surface of the conductor circuit,
The adhesive layer is
(A) component; polyamideimide,
(C) component; a compound having two or more functional groups capable of reacting with the amide group of the polyamideimide;
(D) component; a compound having a functional group capable of reacting with the component (C) and having an ethylenically unsaturated bond;
(E) component; radical polymerization initiator;
A circuit board with an adhesive layer, comprising a curable resin composition containing   The circuit board with an adhesive layer according to claim 11, wherein the component (A) has a structural unit composed of a saturated hydrocarbon.   The circuit board with an adhesive layer according to claim 11 or 12, wherein the component (C) has two or more oxirane rings or oxetane rings. The component (D) has a vinyl group at its side chain or terminal, and is represented by a phenolic hydroxyl group, an alcoholic hydroxyl group, a carboxyl group, an amide group, an amino group, an imino group, and the following formula (III): The circuit board with an adhesive layer according to any one of claims 11 to 13, which is a modified polybutadiene having one or more groups selected from the group consisting of groups.

  The total blending ratio of the component (C) and the component (D) is 5 to 200 parts by mass with respect to 100 parts by mass of the component (A), and the blending ratio of the component (D) is the component (C). The circuit board with an adhesive layer according to claim 11, which is 5 to 1000 parts by mass with respect to 100 parts by mass of the component.   The circuit board is provided with a layer formed by curing the curable resin composition containing the component (A), the component (C), and the component (D) between the insulating plate and the conductor circuit. The circuit board with an adhesive layer according to any one of claims 11 to 15. The adhesive layer is obtained by volatilizing the solvent a resin varnish containing the curable resin composition and a solvent after coating on the surface of the conductor circuit, one of the claim 1-16 A circuit board with an adhesive layer according to claim 1. The thickness of the adhesive layer is 0.1 to 10 [mu] m, the adhesive layer with the circuit board according to any one of claims 1 to 17. The circuit board with an adhesive layer according to any one of claims 1 to 18 , wherein a ten-point average roughness (Rz) of the surface of the conductor circuit is 2 µm or less. The circuit board with an adhesive layer according to any one of claims 1 to 19 , wherein the adhesive layer is provided on the main surface of the insulating plate and on a surface of the conductor circuit. The circuit board with an adhesive layer according to any one of claims 1 to 20 , wherein the circuit board is a core board. An insulating resin sheet containing an insulating resin and a metal foil are laminated in this order on at least the surface of the adhesive layer of the circuit board with an adhesive layer according to any one of claims 1 to 21. The manufacturing method of a multilayer printed wiring board which has the process of obtaining a multilayer body, and the process of heating and pressurizing this multilayer body. The insulating resin sheet contains one or more materials selected from the group consisting of E glass, S glass, NE glass, D glass, Q glass, paper material, aramid, fluororesin, polyester, and liquid crystalline polymer. The manufacturing method of the multilayer printed wiring board of Claim 22 which is a prepreg formed by impregnating the resin which has the said insulating property in a fiber base material. The method for producing a multilayer printed wiring board according to claim 22 or 23 , wherein the insulating resin contains a resin having an ethylenically unsaturated bond. The multilayer printed wiring board according to claim 24 , wherein the resin having an ethylenically unsaturated bond is at least one resin selected from the group consisting of polybutadiene, polytriallyl cyanurate, polytriallyl isocyanurate, and polyphenylene ether. Manufacturing method. The method for producing a multilayer printed wiring board according to any one of claims 22 to 25 , wherein the insulating resin contains polyphenylene ether. Multilayer printed wiring board obtained by the method for manufacturing a multilayer printed wiring board according to any one of claims 22-26.

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