KR20200026461A - Metal-clad laminate, adhesive sheet, adhesive polyimide resin composition, and circuit board - Google Patents

Abstract

Provided are a metal-clad laminate and a circuit board, wherein the metal-clad laminate has an adhesive layer having excellent adhesion, a low dielectric constant and dielectric tangent, and capable of reducing transmission loss even in high-frequency transmission. The adhesive layer in the metal-clad laminate comprising an insulating resin layer, the adhesive layer laminated on at least one side of the insulating resin layer, and a metal layer laminated on the insulating resin layer by interposition of the adhesive layer, has a polyimide containing a tetracarboxylic acid residue and a diamine residue, and the polyimide, based on 100 mol parts of the diamine residue, contains 50 mol parts or more of the diamine residue induced by substitution of two terminal carboxylic acid groups of a dimer acid with a primary aminomethyl group or an amino group.

Description

Metal-clad laminates, adhesive sheets, adhesive polyimide resin compositions and circuit boards {METAL-CLAD LAMINATE, ADHESIVE SHEET, ADHESIVE POLYIMIDE RESIN COMPOSITION, AND CIRCUIT BOARD}

The present invention relates to a metal clad laminate, an adhesive sheet, an adhesive polyimide resin composition, and a circuit board.

In recent years, with the progress of miniaturization, weight reduction, and space saving of electronic devices, the demand for flexible printed circuit boards (FPCs) that are thin, light, flexible, and excellent in durability even after repeated bending has increased. have. Since FPCs can be mounted in a limited space in three dimensions and with high density, for example, their use is expanding to wiring of moving parts of electronic devices such as HDDs, DVDs, smartphones, and components such as cables and connectors.

In addition to the above-mentioned densification, since high performance of the device has been advanced, it is also necessary to cope with the high frequency of the transmission signal. If the transmission loss in the transmission path is large when transmitting a high frequency signal, problems such as loss of an electrical signal and a long delay time of the signal occur. Therefore, in future, also in FPC, reduction of transmission loss becomes important. In order to cope with the high frequency, an FPC using a liquid crystal polymer having a low dielectric constant and a low dielectric loss tangent as a dielectric layer is used. However, although the liquid crystal polymer is excellent in dielectric properties, there exists room for improvement in heat resistance or adhesiveness with a metal layer.

In the metal clad laminated board used as a material of circuit boards, such as FPC, the form (three-layer metal clad laminated board) which bonded the metal layer to which wiring process and the insulating resin layer through the adhesive layer by adhesive resin is known (for example, , Patent Document 1). In order to use such a three-layer metal-clad laminated board as a circuit board which transmits a high frequency signal, improvement of the dielectric characteristic of an adhesive layer is considered important.

By the way, as a technique regarding the contact bonding layer which has a polyimide as a main component, it is obtained by making the polyimide which uses diamine compounds derived from aliphatic diamines, such as dimer acid, as a raw material, and the amino compound which has at least two primary amino groups as a functional group reacts. It is proposed to apply crosslinked polyimide resin to the adhesive layer of a coverlay film (for example, patent document 2). The crosslinked polyimide resin of Patent Literature 2 does not generate a volatile component containing a cyclic siloxane compound, has excellent solder heat resistance, and does not lower the adhesive force between the wiring layer and the coverlay film even in a use environment repeatedly exposed to high temperatures. It is to have an advantage. However, in patent document 2, the applicability to high frequency signal transmission and the application to the adhesive layer in a three-layer metal clad laminated board are not examined.

International publication WO2016 / 031960 Japanese Patent No. 5777944

An object of the present invention is to provide a metal-clad laminate and a circuit board having an adhesive layer which is excellent in adhesiveness, small in dielectric constant and dielectric loss tangent, and which can reduce transmission loss even in high frequency transmission.

MEANS TO SOLVE THE PROBLEM As a result of earnest research, while using a polyimide for the adhesive layer which performs the adhesion function of a wiring layer and an insulated resin layer in a circuit board, by controlling the kind and quantity of the monomer used as a raw material of the said polyimide, It was found that low dielectric constant and low dielectric loss tangent were possible while maintaining excellent adhesion, and completed the present invention.

The metal clad laminated board of this invention has an insulating resin layer, the contact bonding layer laminated | stacked on the surface of at least one side of the said insulating resin layer, and the metal layer laminated | stacked on the said insulating resin layer via the said contact bonding layer.

The said contact bonding layer in the metal clad laminated board of this invention has the polyimide containing a tetracarboxylic-acid residue and a diamine residue.

And the polyimide is based on 100 mole parts of the diamine residue,

It is characterized by containing 50 mol part or more of diamine residues derived from the dimer acid type diamine which the 2 or more terminal carboxylic acid group of dimer acid is substituted by the primary aminomethyl group or an amino group.

In the metal-clad laminate of the present invention, the polyimide is derived from tetracarboxylic anhydride represented by the following general formula (1) and / or (2) with respect to 100 mol parts of the tetracarboxylic acid residue. You may contain 90 mol part or more of tetracarboxylic-acid residues in total.

In general formula (1), X represents a bivalent group chosen from a single bond or the following formula, and the cyclic part represented by Y in general formula (2) is a 4-membered ring, a 5-membered ring, a 6-membered ring, a 7-membered ring, or 8 It shows what forms the cyclic saturated hydrocarbon group chosen from a ring.

In the above formula, Z represents -C ₆ H ₄ -,-(CH ₂ ) n- or -CH ₂ -CH (-OC (= 0) -CH ₃ ) -CH _2- , but n represents 1 to The integer of 20 is shown.

In the metal-clad laminate of the present invention, the polyimide is based on 100 mole parts of the diamine residue,

The diamine residue derived from the said dimer acid type diamine may contain 50 mol part or more and 99 mol part or less,

You may contain the diamine residue derived from at least 1 sort (s) of diamine compounds chosen from the diamine compound represented by following General formula (B1)-(B7) within the range of 1 mol part or more and 50 mol part or less.

In formulas (B1) to (B7), R ₁ independently represents a monovalent hydrocarbon or alkoxy group having 1 to 6 carbon atoms, and the linking group A is independently —O—, —S—, —CO—, —SO— , -SO _2- , -COO-, -CH _2- , -C (CH ₃ ) _2- , a divalent group selected from -NH- or -CONH-, n ₁ independently represent an integer of 0 to 4 Indicates. However, it overlaps with Formula (B2) in Formula (B3), and it overlaps with Formula (B4) in Formula (B5).

In the metal-clad laminated board of this invention, the said metal layer contains copper foil, and the surface which contact | connects the said contact bonding layer in this copper foil may be antirust-treated.

The circuit board of this invention is a thing formed by processing the said metal layer of any of the said metal clad laminated boards by wiring.

The adhesive sheet of this invention is a metal-clad laminated board which has an insulating resin layer, the adhesive layer laminated | stacked on the surface of at least one side of the said insulating resin layer, and the metal layer laminated | stacked on the said insulating resin layer via the said adhesive layer, It is an adhesive sheet for forming.

The adhesive sheet of the present invention has a polyimide containing a tetracarboxylic acid residue and a diamine residue.

And the polyimide is based on 100 mole parts of the diamine residue,

It is characterized by containing 50 mol part or more of diamine residues derived from the dimer acid type diamine which the 2 or more terminal carboxylic acid group of dimer acid is substituted by the primary aminomethyl group or an amino group.

In the adhesive sheet of the present invention, the polyimide is tetra-derived from tetracarboxylic anhydride represented by the general formulas (1) and / or (2) above with respect to 100 mol parts of the tetracarboxylic acid residue. You may contain 90 mol part or more of carboxylic acid residues in total.

In the adhesive sheet of this invention, the said polyimide is with respect to 100 mol part of the said diamine residue,

The diamine residue derived from the said dimer acid type diamine may contain 50 mol part or more and 99 mol part or less,

You may contain the diamine residue guide | induced from the at least 1 sort (s) of diamine compound chosen from the diamine compound represented by said general formula (B1)-(B7) within 1 to 50 mol part.

The adhesive polyimide resin composition of this invention is a metal-clad laminated board which has an insulated resin layer, the contact bonding layer laminated | stacked on the surface of at least one side of the said insulated resin layer, and the metal layer laminated | stacked on the said insulating resin layer via the said contact bonding layer. It is a composition for forming the said contact bonding layer.

The adhesive polyimide resin composition of this invention contains the polyimide containing a tetracarboxylic-acid residue and a diamine residue.

And the polyimide is based on 100 mole parts of the diamine residue,

It is characterized by containing 50 mol part or more of diamine residues derived from the dimer acid type diamine which the two terminal carboxylic acid group of dimer acid is substituted by the primary aminomethyl group or an amino group.

In the adhesive polyimide resin composition of this invention, the said polyimide is tetracarboxylic anhydride represented by said general formula (1) and / or (2) with respect to 100 mol part of the said tetracarboxylic-acid residue. You may contain 90 mol part or more of the tetracarboxylic-acid residue guide | induced from a total.

In the adhesive polyimide resin composition of this invention, the said polyimide is with respect to 100 mol part of the said diamine residue,

The diamine residue derived from the said dimer acid type diamine may contain 50 mol part or more and 99 mol part or less,

You may contain the diamine residue guide | induced from the at least 1 sort (s) of diamine compound chosen from the diamine compound represented by said general formula (B1)-(B7) within 1 to 50 mol part.

The metal-clad laminate of the present invention forms an adhesive layer with a polyimide having introduced a specific tetracarboxylic acid residue and a diamine residue, thereby making it possible to secure adhesiveness, lower dielectric constant, and lower dielectric tangent. By using the metal clad laminated board of this invention, application to the circuit board etc. which transmit a high frequency signal of 10 GHz or more, for example is also possible. Therefore, reliability and a yield can be improved in a circuit board.

Embodiments of the present invention will be described in detail.

[Metal Clad Laminate]

The metal-clad laminated board of this embodiment is equipped with the insulated resin layer, the contact bonding layer laminated | stacked on the surface of at least one side of the insulated resin layer, and the metal layer laminated | stacked on the said insulating resin layer via the contact bonding layer, and so-called three-layer metal Coated laminate. In the three-layer metal-clad laminate, the adhesive layer may be provided on one side or both sides of the insulated resin layer, and the metal layer may be provided on one side or both sides of the insulated resin layer via the adhesive layer. In other words, the metal-clad laminate of the present embodiment may be a single-sided metal-clad laminate or a double-sided metal-clad laminate. Single-sided FPC or double-sided FPC can be manufactured by etching the metal layer of the metal-clad laminated board of this embodiment, and wiring circuit processing.

<Insulation resin layer>

The insulating resin layer is not particularly limited as long as it is made of a resin having electrical insulation properties, and examples thereof include polyimide, epoxy resin, phenol resin, polyethylene, polypropylene, polytetrafluoroethylene, silicone, and ETFE. However, it is preferable that it is comprised by polyimide. Although the polyimide layer which comprises the insulated resin layer may be a single layer, or multiple layers may be sufficient, It is preferable that a non-thermoplastic polyimide layer is included. Here, "non-thermoplastic polyimide" is a polyimide which generally does not show softening and adhesiveness even when heated. In the present invention, the storage modulus at 30 ° C measured using a dynamic viscoelasticity measuring device (DMA) is 1.0. × 10 ⁹ Pa or more, and refers to the storage modulus of the polyimide at 300 ℃ less than 3.0 × 10 ⁸ Pa.

Since a polyimide is manufactured by imidating the polyamic acid of the precursor obtained by making a specific acid anhydride and a diamine compound react, the specific example of a non-thermoplastic polyimide is understood by explaining an acid anhydride and a diamine compound (forming the adhesive layer mentioned later) The same applies to the thermoplastic polyimide. In addition to the so-called polyimide, the polyimide in the present invention includes those having an imide group in structures such as polyamideimide, polybenzimidazole, polyimide ester, polyetherimide and polysiloxaneimide.

(Acid anhydride)

As an acid anhydride used for the non-thermoplastic polyimide which comprises a non-thermoplastic polyimide layer, it is 3,3 ', 4,4'-biphenyl tetracarboxylic dianhydride, a pyromellitic dianhydride, 1,4, for example. -Phenylenebis (trimelitic acid monoester) dianhydride, 3,3 ', 4,4'-diphenylsulfontetracarboxylic dianhydride, 4,4'-oxydiphthalic anhydride, 2,3', 3 , 4'-biphenyltetracarboxylic dianhydride, 2,2 ', 3,3'-, 2,3,3', 4'- or 3,3 ', 4,4'-benzophenonetetracarboxylic Acid dianhydride, 2,3 ', 3,4'-diphenylethertetracarboxylic dianhydride, bis (2,3-dicarboxyphenyl) ether dianhydride, 3,3 ", 4,4"-, 2 , 3,3 ", 4"-or 2,2 ", 3,3" -p-terphenyltetracarboxylic dianhydride, 2,2-bis (2,3- or 3,4-dicarboxyphenyl) Propane dianhydride, bis (2,3- or 3,4-dicarboxyphenyl) methane dianhydride, bis (2,3- or 3,4-dicarboxyphenyl) sulfon dianhydride, 1,1-bis (2 , 3- or 3,4- Carboxyphenyl) ethane dianhydride, 1,2,7,8-, 1,2,6,7- or 1,2,9,10-phenanthrene-tetracarboxylic dianhydride, 2,3,6,7 Anthracenetetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) tetrafluoropropane dianhydride, 2,3,5,6-cyclohexane dianhydride, 1,2,5,6 -Naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 4,8-dimethyl-1,2 , 3,5,6,7-hexahydronaphthalene-1,2,5,6-tetracarboxylic dianhydride, 2,6- or 2,7-dichloronaphthalene-1,4,5,8-tetracar Acid dianhydrides, 2,3,6,7- (or 1,4,5,8-) tetrachloronaphthalene-1,4,5,8- (or 2,3,6,7-) tetracarboxyl Acid dianhydrides, 2,3,8,9-, 3,4,9,10-, 4,5,10,11- or 5,6,11,12-perylene-tetracarboxylic dianhydride, cyclo Pentane-1,2,3,4-tetracarboxylic dianhydride, pyrazine-2,3,5,6-tetracarboxylic dianhydride Anhydride, pyrrolidine-2,3,4,5-tetracarboxylic dianhydride, thiophene-2,3,4,5-tetracarboxylic dianhydride, 4,4'-bis (2,3- Dicarboxyphenoxy) diphenylmethane dianhydride, 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride, 4,4 '-(hexafluoroisopropylidene) diphthalic acid Acid dianhydrides, such as anhydride, p-phenylene bis (trimelitic acid monoester acid anhydride), and ethylene glycol bis-anhydro trimellitate, are mentioned.

(Diamine compound)

As a diamine compound used for the non-thermoplastic polyimide which comprises a non-thermoplastic polyimide layer, an aromatic diamine compound or an aliphatic diamine compound is mentioned. Specific examples thereof include 1,4-diaminobenzene (p-PDA; paraphenylenediamine), 2,2'-dimethyl-4,4'-diaminobiphenyl (m-TB), and 2,2'- n-propyl-4,4'-diaminobiphenyl (m-NPB), 4-aminophenyl-4'-aminobenzoate (APAB), 2,2-bis- [4- (3-aminophenoxy) Phenyl] propane, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) biphenyl, bis [1- (3-aminophenoxy)] biphenyl, bis [ 4- (3-aminophenoxy) phenyl] methane, bis [4- (3-aminophenoxy) phenyl] ether, bis [4- (3-aminophenoxy)] benzophenone, 9,9-bis [4 -(3-aminophenoxy) phenyl] fluorene, 2,2-bis- [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis- [4- (3-aminophenoxy Phenyl] hexafluoropropane, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-methylenedi-o-toluidine, 4,4'-methylenedi-2,6- Xyldine, 4,4'-methylene-2,6-diethylaniline, 3,3'-diaminodiphenylethane, 3,3'-diaminobiphenyl, 3,3'-dimethock Benzidine, 3,3 "-diamino-p-terphenyl, 4,4 '-[1,4-phenylenebis (1-methylethylidene)] bisaniline, 4,4'-[1,3- Phenylenebis (1-methylethylidene)] bisaniline, bis (p-aminocyclohexyl) methane, bis (p-β-amino-t-butylphenyl) ether, bis (p-β-methyl-δ- Aminopentyl) benzene, p-bis (2-methyl-4-aminopentyl) benzene, p-bis (1,1-dimethyl-5-aminopentyl) benzene, 1,5-diaminonaphthalene, 2,6-dia Minonaphthalene, 2,4-bis (β-amino-t-butyl) toluene, 2,4-diaminotoluene, m-xylene-2,5-diamine, p-xylene-2,5-diamine, m-ch Silylenediamine, p-xylylenediamine, 2,6-diamino pyridine, 2,5-diamino pyridine, 2,5-diamino-1,3,4-oxadiazole, piperazine, 2'- Methoxy-4,4'-diaminobenzanilide, 4,4'-diaminobenzanilide, 1,3-bis [2- (4-aminophenyl) -2-propyl] benzene, 6-amino-2- (4-aminophenoxy) benzoxazole, 1,3-bis (3-aminophenoxy) benzene, dimer acid 2 And diamine compounds such as dimer acid type diamine in which the terminal carboxylic acid groups are substituted with a primary aminomethyl group or an amino group.

In the non-thermoplastic polyimide, the thermal expansion coefficient, storage modulus, tensile modulus, and the like can be controlled by selecting the types of the acid anhydride and the diamine compound, and the molar ratios in the case of applying two or more acid anhydrides and the diamine compound. have. Moreover, in the non-thermoplastic polyimide, when it has two or more structural units of a polyimide, although it exists as a block or may exist at random, it is preferable to exist at random from a viewpoint of suppressing in-plane fluctuations.

It is preferable to exist in the range of 1-125 micrometers, for example, and, as for the thickness of an insulated resin layer, the inside of the range which is 5-50 micrometers is more preferable. When the thickness of an insulated resin layer does not satisfy | fill the said lower limit, the problem of not being able to ensure sufficient electrical insulation may arise. On the other hand, when the thickness of an insulated resin layer exceeds the said upper limit, the problem that a warpage of a metal-clad laminated board becomes easy to generate | occur | produce arises. In addition, the ratio (thickness of the thickness of the insulating resin layer / adhesive layer) of the thickness of the insulating resin layer and the thickness of the adhesive layer is preferably in the range of 0.5 to 2.0. By setting it as such a ratio, the curvature of a metal clad laminated board can be suppressed.

The non-thermoplastic polyimide layer constituting the insulating resin layer is low thermally expandable, and the coefficient of thermal expansion (CTE) is preferably in the range of 10 ppm / K or more and 30 ppm / K or less, more preferably 10 ppm / K or more and 25 ppm / K or less. In range If the CTE is less than 10 ppm / K or more than 30 ppm / K, warpage occurs or dimensional stability is degraded. It can be set as the polyimide layer which has a desired CTE by changing suitably the combination of the raw material to be used, thickness, and drying and hardening conditions.

In the case where the insulating resin layer is applied to, for example, a circuit board, in order to suppress deterioration of the dielectric loss, the dielectric tangent (Tanδ) at 10 GHz is 0.02 or less, more preferably in the range of 0.0005 or more and 0.01 or less. More preferably, it is good in the range of 0.001 or more and 0.008 or less. When the dielectric loss tangent at 10 GHz of the insulated resin layer exceeds 0.02, problems such as loss of an electrical signal are likely to occur on a transmission path of a high frequency signal when used for a circuit board such as an FPC. On the other hand, the lower limit of the dielectric loss tangent at 10 GHz of the insulated resin layer is not particularly limited, but physical property control as the insulated resin layer of the circuit board is considered.

In the case where the insulating resin layer is applied as an insulating layer of a circuit board, for example, in order to ensure impedance matching, the dielectric constant at 10 GHz is preferably 4.0 or less as the whole insulating layer. When the dielectric constant at 10 GHz of the insulated resin layer exceeds 4.0, when used in a circuit board such as an FPC, the dielectric loss of the insulated resin layer is deteriorated, and problems such as loss of an electrical signal on a transmission path of a high frequency signal are caused. It is easy to occur.

The insulated resin layer may contain a filler as needed. Examples of the filler include silicon dioxide, aluminum oxide, magnesium oxide, beryllium oxide, boron nitride, aluminum nitride, silicon nitride, aluminum fluoride, calcium fluoride, metal salts of organic phosphinic acid, and the like. These can be used 1 type or in mixture of 2 or more types.

<Adhesive layer>

The adhesive layer contains a polyimide containing a tetracarboxylic acid residue derived from tetracarboxylic anhydride and a diamine residue derived from a diamine compound, and preferably contains a thermoplastic polyimide. Here, "thermoplastic polyimide" is generally a polyimide which can clearly confirm the glass transition temperature (Tg), but in the present invention, the storage modulus at 30 ° C. measured using DMA is 1.0 × 10 ⁸ Pa It is the above and says the polyimide whose storage elastic modulus in 300 degreeC is less than 3.0 * 10 <^7> Pa. In addition, in this invention, a tetracarboxylic acid residue means the tetravalent group derived from tetracarboxylic dianhydride, and a diamine residue means the divalent group derived from a diamine compound.

(Tetracarboxylic acid residue)

The thermoplastic polyimide which forms an adhesive layer is a tetracarboxylic acid residue derived from tetracarboxylic anhydride represented by following General formula (1) and / or (2) with respect to 100 mol part of tetracarboxylic acid residue ( Hereinafter, it is preferable to contain "tetracarboxylic acid residue (1) and the" tetracarboxylic acid residue (2) "may be 90 mol part or more in total. In the present invention, the solvent solubility is imparted to the thermoplastic polyimide forming the adhesive layer by containing tetracarboxylic acid residues (1) and / or (2) in total of 90 mol parts or more with respect to 100 mol parts of the tetracarboxylic acid residues. In addition, both the flexibility and the heat resistance of the thermoplastic polyimide are easy to achieve, and are preferable. When the sum total of tetracarboxylic-acid residue (1) and / or (2) is less than 90 mol part, the solvent solubility of a thermoplastic polyimide will fall.

In general formula (1), X represents a bivalent group chosen from a single bond or the following formula, and the cyclic part represented by Y in general formula (2) is a 4-membered ring, a 5-membered ring, a 6-membered ring, a 7-membered ring, or 8 It shows what forms the cyclic saturated hydrocarbon group chosen from a ring.

In the above formula, Z represents -C ₆ H ₄ -,-(CH ₂ ) n- or -CH ₂ -CH (-OC (= 0) -CH ₃ ) -CH _2- , but n represents 1 to The integer of 20 is shown.

Examples of the tetracarboxylic dianhydride for deriving the tetracarboxylic acid residue (1) include 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (BPDA), 3,3', 4,4'-benzophenonetetracarboxylic dianhydride (BTDA), 3,3 ', 4,4'-diphenylsulfontetracarboxylic dianhydride, 4,4'-oxydiphthalic anhydride (ODPA), 4,4 '-(hexafluoroisopropylidene) diphthalic anhydride (6FDA), 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride (BPADA), p-phenyl Lenbis (trimelitic acid monoester acid anhydride) and the like.

Moreover, as tetracarboxylic dianhydride for inducing the tetracarboxylic acid residue (2), for example, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4- Cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 1,2,4,5-cycloheptane tetracarboxylic dianhydride, 1,2,5,6 -Cyclooctane tetracarboxylic dianhydride, etc. are mentioned.

The thermoplastic polyimide which forms an adhesive layer is a tetracarboxylic-acid residue derived from acid anhydrides other than tetracarboxylic anhydride represented by said General formula (1) or (2) in the range which does not impair the effect of this invention. It may contain. As acid anhydride residues other than tetracarboxylic-acid residue (1) or (2), the residue of what was illustrated as an acid anhydride used for the non-thermoplastic polyimide which comprises the non-thermoplastic polyimide layer in the insulating resin layer mentioned above is mentioned. Can be mentioned.

(Diamine residues)

The thermoplastic polyimide forming the adhesive layer contains 50 mol parts or more, preferably 50 mol parts or more of dimer acid type diamine residues derived from dimer acid type diamine with respect to 100 mol parts of diamine residues. By containing the dimer acid type diamine residue in the said quantity, the dielectric property of an adhesive layer can be improved and the flexibility required for an adhesive layer can be ensured. When the dimer acid type diamine residue is less than 50 mol part with respect to 100 mol part of a diamine residue, sufficient adhesiveness may not be obtained as an adhesive layer interposed between an insulated resin layer and a metal layer, and the curvature of a metal clad laminated board arises. There is.

Here, the dimer acid type is a diamine, the two terminal carboxylic acid groups (-COOH) of the dimer acid is substituted with amino group (-CH ₂ -NH ₂₎ or amino group (-NH ₂₎ of the first class means comprising diamine. Dimer acid is a known dibasic acid obtained by intermolecular polymerization of unsaturated fatty acids, and its industrial production process is almost standardized in the industry, and is obtained by dimerizing unsaturated fatty acids having 11 to 22 carbon atoms with a clay catalyst or the like. . The industrially obtained dimer acid is a dibasic acid having 36 carbon atoms obtained by dimerizing an unsaturated fatty acid having 18 carbon atoms such as oleic acid or linoleic acid, and according to the degree of purification, an arbitrary amount of monomeric acid (18 carbon atoms) and trimer acid (54 carbon atoms) and other polymerized fatty acids having 20 to 54 carbon atoms are contained. In this invention, it is preferable to use what dimer acid raised the dimer acid content to 90 weight% or more by molecular distillation. In addition, although a double bond remains after a dimerization reaction, in this invention, what was further hydrogenated and the degree of unsaturation is also included in dimer acid.

As a characteristic of the dimer acid type diamine, the characteristic derived from the skeleton of a dimer acid can be provided to a polyimide. That is, since the dimer acid type diamine is aliphatic of the macromolecule of the molecular weight about 560-620, it can enlarge the molar volume of a molecule | numerator and can reduce the polar group of polyimide relatively. It is thought that such a characteristic of the dimer-type diamine contributes to improving the dielectric properties by reducing the dielectric constant and dielectric loss tangent while suppressing the decrease in heat resistance of the polyimide. In addition, it has two freely moving hydrophobic chains having 7 to 9 carbon atoms and two chain aliphatic amino groups having a length close to 18 carbon atoms, which not only gives flexibility to the polyimide but also has a non-target chemical structure. Since it is possible to have a non-planar chemical structure, it is thought that low dielectric constant and low dielectric loss tangent can be achieved.

A commercial item is available for the dimer-type diamine, for example, PRIAMINE1073 (brand name), copper PRIAMINE1074 (brand name), copper PRIAMINE1075 (brand name), copper BASamine 551 (brand name) made by Cogness Japan company, the copper bar Samine 552 (brand name) etc. are mentioned.

In addition, the thermoplastic polyimide which forms an adhesive layer has a diamine residue derived from at least 1 sort (s) of diamine compounds chosen from the diamine compounds represented by the following general formula (B1)-(B7) with respect to 100 mol part of all diamine components. In total, it is preferable to contain in 1 mol part or more and 50 mol part or less, and it is more preferable to contain in 1 mol part or more and 20 mol part or less. Since the diamine compounds represented by the general formulas (B1) to (B7) have a molecular structure having flexibility, the flexibility of the polyimide molecular chain by using at least one diamine compound selected from these in an amount within the above range Can be improved and thermoplasticity can be provided. When the total amount of diamines (B1) to diamine (B7) exceeds 50 mol parts with respect to 100 mol parts of all the diamine components, the solvent solubility of polyimide may become low, and if it is less than 1 mol part, the flexibility of polyimide will be insufficient, Workability at high temperature may decrease.

In formulas (B1) to (B7), R ₁ independently represents a monovalent hydrocarbon or alkoxy group having 1 to 6 carbon atoms, and the linking group A is independently —O—, —S—, —CO—, —SO— , -SO _2- , -COO-, -CH _2- , -C (CH ₃ ) _2- , a divalent group selected from -NH- or -CONH-, n ₁ independently represent an integer of 0 to 4 Indicates. However, it overlaps with Formula (B2) in Formula (B3), and it overlaps with Formula (B4) in Formula (B5).

In the formulas (B1) to (B7), the hydrogen atom in the terminal two amino groups may be substituted, for example, -NR ₂ R ₃ (wherein R ₂ and R ₃ are independently an alkyl group). Arbitrary substituents, such as these) may be sufficient.

The diamine represented by Formula (B1) (hereinafter may be described as "diamine (B1)") is an aromatic diamine which has two benzene rings. This diamine (B1) has an amino group and a divalent linking group A directly connected to at least one benzene ring in the meta position, thereby increasing the degree of freedom of the polyimide molecular chain and having high bendability. It seems to contribute to improvement. Therefore, the thermoplasticity of a polyimide becomes high by using diamine (B1). As the linking group A, -O-, -CH _2- , -C (CH ₃ ) _2- , -CO-, -SO _2- , -S-, and -COO- are preferable.

As diamine (B1), it is 3,3'- diamino diphenylmethane, 3,3'- diamino diphenyl propane, 3,3'- diamino diphenyl sulfide, 3,3'- diamino, for example. Diphenylsulfone, 3,3-diaminodiphenylether, 3,4'-diaminodiphenylether, 3,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylpropane, 3,4 '-Diaminodiphenyl sulfide, 3,3'-diaminobenzophenone, (3,3'-bisamino) diphenylamine, etc. are mentioned.

The diamine represented by Formula (B2) (hereinafter may be described as "diamine (B2)") is an aromatic diamine which has three benzene rings. The diamine (B2) has a high degree of flexibility due to an increase in the degree of freedom of the polyimide molecular chain by having an amino group and a divalent linking group A directly connected to at least one benzene ring in a meta position, and the flexibility of the polyimide molecular chain. It seems to contribute to improvement. Therefore, the thermoplasticity of a polyimide becomes high by using diamine (B2). Here, as the linking group A, -O- is preferable.

Examples of the diamine (B2) include 1,4-bis (3-aminophenoxy) benzene, 3- [4- (4-aminophenoxy) phenoxy] benzeneamine, and 3- [3- (4-amino Phenoxy) phenoxy] benzeneamine etc. are mentioned.

The diamine represented by Formula (B3) (hereinafter may be described as "diamine (B3)") is an aromatic diamine which has three benzene rings. The diamine (B3) has a high degree of flexibility due to an increase in the degree of freedom of the polyimide molecular chain due to the presence of two divalent linking groups A directly connected to one benzene ring in a meta position, and thus the polyimide molecular chain It seems to contribute to the improvement of flexibility. Therefore, the thermoplasticity of a polyimide becomes high by using diamine (B3). Here, as the linking group A, -O- is preferable.

As diamine (B3), it is 1, 3-bis (4-amino phenoxy) benzene (TPE-R), 1, 3-bis (3-amino phenoxy) benzene (APB), 4,4'-, for example. [2-methyl- (1,3-phenylene) bisoxy] bisaniline, 4,4 '-[4-methyl- (1,3-phenylene) bisoxy] bisaniline, 4,4'-[5 -Methyl- (1,3-phenylene) bisoxy] bisaniline and the like.

Diamine (Hereinafter, it may describe as "diamine (B4)") represented by Formula (B4) is aromatic diamine which has four benzene rings. This diamine (B4) has high flexibility by having the amino group and the divalent linking group A directly connected to at least one benzene ring in the meta position, and is thought to contribute to the improvement of the flexibility of the polyimide molecular chain. Therefore, thermoplasticity of a polyimide becomes high by using diamine (B4). As the linking group A, -O-, -CH _2- , -C (CH ₃ ) _2- , -SO _2- , -CO-, and -CONH- are preferable.

Examples of the diamine (B4) include bis [4- (3-aminophenoxy) phenyl] methane, bis [4- (3-aminophenoxy) phenyl] propane and bis [4- (3-aminophenoxy) phenyl] ether , Bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy)] benzophenone, bis [4,4 '-(3-aminophenoxy)] benzanilide, etc. Can be mentioned.

The diamine represented by Formula (B5) (hereinafter may be described as "diamine (B5)") is an aromatic diamine which has four benzene rings. The diamine (B5) has a high degree of flexibility and a high degree of flexibility because the two divalent linking groups A directly connected to at least one benzene ring are in a meta position with each other and thus have a high flexibility. It is thought to contribute to the improvement of flexibility. Therefore, thermoplasticity of a polyimide becomes high by using diamine (B5). Here, as the linking group A, -O- is preferable.

Examples of the diamine (B5) include 4- [3- [4- (4-aminophenoxy) phenoxy] phenoxy] aniline, 4,4 '-[oxybis (3,1-phenylene oxy)] bisaniline, and the like. Can be mentioned.

The diamine represented by Formula (B6) (hereinafter may be described as "diamine (B6)") is an aromatic diamine which has four benzene rings. This diamine (B6) has high flexibility by having at least two ether bonds, and is considered to contribute to the improvement of the flexibility of a polyimide molecular chain. Therefore, thermoplasticity of a polyimide becomes high by using diamine (B6). As the linking group A, -C (CH ₃ ) _2- , -O-, -SO _2- , and -CO- are preferable.

As the diamine (B6), for example, 2,2-bis [4- (4-aminophenoxy) phenyl] propane (BAPP), bis [4- (4-aminophenoxy) phenyl] ether (BAPE), bis [4- (4-aminophenoxy) phenyl] sulfone (BAPS), bis [4- (4-aminophenoxy) phenyl] ketone (BAPK), etc. are mentioned.

The diamine represented by Formula (B7) (hereinafter may be described as "diamine (B7)") is an aromatic diamine which has four benzene rings. Since this diamine (B7) has the bivalent coupling group A which is highly flexible in each side of a diphenyl skeleton, it is thought that it contributes to the improvement of the flexibility of a polyimide molecular chain. Therefore, the thermoplasticity of a polyimide becomes high by using diamine (B7). Here, as the linking group A, -O- is preferable.

As diamine (B7), bis [4- (3-amino phenoxy)] biphenyl, bis [4- (4-amino phenoxy)] biphenyl, etc. are mentioned, for example.

The thermoplastic polyimide forming the adhesive layer may contain diamine residues derived from diamine compounds other than the dimer acid diamines and diamines (B1) to (B7) within a range that does not impair the effects of the invention. As a diamine residue derived from the said dimer acid type diamine and diamine compounds other than diamine (B1)-(B7), it is a diamine compound used for the non-thermoplastic polyimide which comprises the non-thermoplastic polyimide layer in the insulating resin layer mentioned above. The residue of what was illustrated is mentioned.

In the thermoplastic polyimide forming the adhesive layer, the thermal expansion coefficient and the tensile strength are selected by selecting the kind of the tetracarboxylic acid residue and the diamine residue or the molar ratios when two or more tetracarboxylic acid residues or diamine residues are applied. Modulus of elasticity, glass transition temperature and the like can be controlled. In addition, in the thermoplastic polyimide, in the case of having a plurality of structural units of the polyimide, although present as a block or may exist randomly, it is preferable to exist randomly.

It is preferable that the imide group concentration of a thermoplastic polyimide is 33 weight% or less. Here, "imide group concentration" means the value which divided the molecular weight of the imide group part (-(CO) _2- N-) in a polyimide by the molecular weight of the whole structure of a polyimide. When an imide group concentration exceeds 33 weight%, while the molecular weight of resin itself becomes small, low hygroscopicity also worsens by increase of a polar group. In this embodiment, by selecting the combination of the said diamine compound, by controlling the orientation of the molecule | numerator in a thermoplastic polyimide, the increase of CTE accompanying the fall of imide group concentration is suppressed, and low hygroscopicity is ensured. In addition, when the hygroscopicity of the polyimide is increased, it becomes a deterioration factor of the dielectric properties of the polyimide film. Therefore, the low hygroscopic collateral can be prevented from increasing the dielectric constant and dielectric loss tangent.

The inside of the range of 10,000-400,000 is preferable, for example, and the inside of the range of 20,000-350,000 of the weight average molecular weight of a thermoplastic polyimide is more preferable. When the weight average molecular weight is less than 10,000, the strength of the adhesive layer is lowered and tends to be brittle. On the other hand, when the weight average molecular weight exceeds 400,000, the viscosity increases excessively, and there is a tendency that defects such as thickness unevenness and streaks of the adhesive layer tend to occur during coating work.

Since the thermoplastic polyimide which forms an adhesive layer is interposed between the insulating resin layer and wiring layer of a circuit board, for example, the structure fully imidated in order to suppress the spread | diffusion of copper is the most preferable. However, a part of polyimide may be amic acid. The imidation ratio measured the infrared absorption spectrum of a polyimide thin film by a one-time reflection ATR method using a Fourier transform infrared spectrophotometer (commercial product: FT / IR620 made from Nippon Bunko Corporation), and the benzene ring absorber of 1015 cm <^-1> vicinity. Based on the above, it can be calculated from the absorbance of C═O stretching derived from an imide group of 1780 cm ⁻¹ .

(Bridge formation)

When the thermoplastic polyimide forming the adhesive layer has a ketone group, a crosslinked structure can be formed by reacting the ketone group with an amino group of an amino compound having at least two primary amino groups as a functional group to form a C = N bond. have. By forming a crosslinked structure, the heat resistance of the thermoplastic polyimide which forms an adhesive layer can be improved. As a preferable tetracarboxylic anhydride in order to form the thermoplastic polyimide which has a ketone group, 3,3 ', 4,4'- benzophenone tetracarboxylic dianhydride (BTDA) is mentioned as a diamine compound, for example. For example, aromatic diamine, such as 4,4'-bis (3-amino phenoxy) benzophenone (BABP) and 1, 3-bis [4- (3-amino phenoxy) benzoyl] benzene (BABB), is mentioned.

As said amino compound which can be used for crosslinking of the thermoplastic polyimide which forms an adhesive layer, a dihydrazide compound, an aromatic diamine, an aliphatic amine, etc. can be illustrated. Among these, a dihydrazide compound is preferable. When using a dihydrazide compound, the hardening time after crosslinking can be shortened compared with the case where another amino compound is used. As a dihydrazide compound, for example, oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, fimel acid dihydrazide, subersandihydrazide, azela dihydrazide Gide, sebacic acid hydrazide, dodecane diacid hydrazide, maleic acid hydrazide, fumaric acid hydrazide, diglycolic acid hydrazide, tartaric acid hydrazide, malsan hydrazide, phthalic acid hydrazide, isophthalic hydrazide Gide, terephthalic acid dihydrazide, 2,6-naphthoic acid dihydrazide, 4,4-bisbenzene dihydrazide, 1,4-naphthosan dihydrazide, 2,6-pyridine diacid dihydrazide, itaconic acid Dihydrazide compounds, such as hydrazide, are preferable. The above dihydrazide compounds may be used alone or in combination of two or more thereof.

<Production of Adhesive Layer>

The thermoplastic polyimide which forms an adhesive layer can be manufactured by making said tetracarboxylic dianhydride and a diamine compound react in a solvent, generating a polyamic acid, and heat-closing. For example, the polyamic acid which is a precursor of a polyimide is dissolved by dissolving the tetracarboxylic dianhydride and the diamine compound in an organic solvent at about equimolar in about 30 minutes to 24 hours at a temperature within the range of 0 to 100 ° C. Obtained. In reaction, the reaction component is melt | dissolved so that the produced precursor may exist in the range of 5-50 weight% in an organic solvent, Preferably it exists in the range of 10-40 weight%. As an organic solvent used for a polymerization reaction, for example, N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAc), N, N-diethylacetamide, N-methyl-2-pi Ralidone (NMP), 2-butanone, dimethyl sulfoxide (DMSO), hexamethylphosphoramide, N-methylcaprolactam, dimethyl sulfate, cyclohexanone, dioxane, tetrahydrofuran, diglyme, triglyme And cresols. Two or more types of these solvents may be used in combination, and in addition, combinations of aromatic hydrocarbons such as xylene and toluene may be used in combination. The amount of the organic solvent used is not particularly limited, but it is preferable to adjust the amount of the organic solvent to an amount such that the concentration of the polyamic acid solution obtained by the polymerization reaction is about 5 to 50% by weight.

The synthesized polyamic acid is usually advantageously used as a reaction solvent solution, but may be concentrated, diluted or substituted with other organic solvents as necessary. In addition, polyamic acids are advantageously used because they are generally excellent in solvent solubility. The solution viscosity of the polyamic acid is preferably in the range of 500 cps to 100,000 cps. If it is out of this range, defects, such as thickness nonuniformity and a stripe, will arise easily in a film at the time of coating work by a coater etc.

The method of imidating a polyamic acid and forming a thermoplastic polyimide is not specifically limited, For example, the heat processing of heating over 1 to 24 hours at the temperature conditions within the range of 80-400 degreeC in the said solvent suitably is suitable. Are employed.

When crosslinking forming the thermoplastic polyimide obtained as mentioned above, the said amino compound is added to the resin solution containing the thermoplastic polyimide which has a ketone group, and the ketone group in a thermoplastic polyimide condenses the primary amino group of an amino compound. React. By this condensation reaction, a resin solution hardens and becomes a hardened | cured material. In this case, the amount of the amino compound added is 0.004 mol to 1.5 mol, preferably 0.005 mol to 1.2 mol, more preferably 0.03 mol to 0.9 mol, most preferably 1 mol of the primary amino group with respect to 1 mol of the ketone group. For example, the amino compound may be added to be 0.04 mol to 0.5 mol. Since the crosslinking of the thermoplastic polyimide by an amino compound is not enough in the addition amount of the amino compound in which the primary amino group becomes less than 0.004 mol in total with respect to 1 mol of ketone groups, heat resistance is expressed in the adhesive layer after hardening When the amount of the amino compound added exceeds 1.5 mol, the unreacted amino compound acts as a plasticizer, which tends to lower the heat resistance of the adhesive layer.

The conditions of the condensation reaction for crosslinking are not particularly limited as long as the ketone group and the primary amino group of the amino compound in the thermoplastic polyimide react to form an imine bond (C = N bond). The temperature of the heat condensation is, for example, 120 to simplify the condensation step in order to release the water produced by condensation out of the system or to carry out the heat condensation reaction after the synthesis of the thermoplastic polyimide. The inside of the range of -220 degreeC is preferable, and the inside of the range which is 140-200 degreeC is more preferable. The reaction time is preferably about 30 minutes to 24 hours, and the end point of the reaction is 1670 cm ⁻ by measuring an infrared absorption spectrum using a Fourier transform infrared spectrophotometer (commercially available product: FT / IR620 manufactured by Nihon Bunko Co., Ltd.). ^It can confirm by the reduction or disappearance of the absorption peak derived from the ketone group in polyimide resin of ¹ vicinity, and the appearance of the absorption peak derived from the imine group of 1635 cm <^-1> vicinity.

The heat condensation of the ketone group of the thermoplastic polyimide with the primary amino group of the amino compound is, for example, followed by (a) synthesis (imidization) of the thermoplastic polyimide, followed by addition of an amino compound and heating (b) A method in which an excess amount of an amino compound is added as a diamine component in advance, followed by synthesis (imidation) of the thermoplastic polyimide, followed by heating the thermoplastic polyimide together with the remaining amino compound not involved in imidization or amidation; Or (c) after processing the composition (adhesive polyimide resin composition mentioned later) of the thermoplastic polyimide which added the amino compound to predetermined shape (for example, after apply | coating to arbitrary base materials or forming into a film shape), Can be performed by a heating method).

(Thickness of the adhesive layer)

It is preferable to exist in the range of 0.1-100 micrometers, for example, and, as for the thickness of an adhesive layer, the inside of the range which is 0.3-50 micrometers is more preferable. In the three-layer metal-clad laminate of the present embodiment, if the thickness of the adhesive layer does not satisfy the lower limit, there may be a problem that sufficient adhesiveness cannot be secured. On the other hand, when the thickness of an adhesive layer exceeds the said upper limit, problems, such as a dimensional stability fall, arise. Moreover, it is preferable that the thickness of an adhesive layer shall be 3 micrometers or more from a viewpoint of the low dielectric constant of the whole insulating layer which is a laminated body of an insulated resin layer and an adhesive layer, and low dielectric loss tangent.

(CTE of adhesive layer)

The thermoplastic polyimide forming the adhesive layer is highly thermally expandable, and CTE is preferably in the range of 35 ppm / K or more, more preferably in the range of 35 ppm / K or more and 80 ppm / K or less, still more preferably 35 ppm / K or more and 70 ppm / K It is in the following ranges. It can be set as the polyimide layer which has a desired CTE by changing suitably the combination of the raw material to be used, thickness, and drying and hardening conditions.

(Dielectric Junction of Adhesive Layer)

In the case where the adhesive layer is applied to, for example, a circuit board, in order to suppress the deterioration of the dielectric loss, the dielectric tangent (Tanδ) at 10 GHz is 0.004 or less, more preferably in the range of 0.001 or more and 0.004 or less. Preferably it is good in the range of 0.002 or more and 0.003 or less. When the dielectric loss tangent at 10 GHz of the adhesive layer exceeds 0.004, problems such as loss of an electrical signal are likely to occur on a transmission path of a high frequency signal when used for a circuit board such as an FPC. On the other hand, the lower limit of the dielectric loss tangent at 10 GHz of the adhesive layer is not particularly limited.

(Dielectric constant of adhesive layer)

In the case where the adhesive layer is applied, for example, as an insulating layer of a circuit board, in order to ensure impedance matching, the dielectric constant at 10 GHz is preferably 4.0 or less. When the dielectric constant at 10 GHz of the adhesive layer exceeds 4.0, when used for a circuit board such as an FPC, the dielectric loss of the adhesive layer is deteriorated, and problems such as loss of an electrical signal on a transmission path of a high frequency signal are likely to occur. .

(filler)

The adhesive layer may contain a filler as necessary. Examples of the filler include silicon dioxide, aluminum oxide, magnesium oxide, beryllium oxide, boron nitride, aluminum nitride, silicon nitride, aluminum fluoride, calcium fluoride, metal salts of organic phosphinic acid, and the like. These can be used 1 type or in mixture of 2 or more types.

<Metal layer>

There is no restriction | limiting in particular as a material of the metal layer in the metal clad laminated board of this embodiment, For example, copper, stainless steel, iron, nickel, beryllium, aluminum, zinc, indium, silver, gold, tin, zirconium, tantalum, titanium , Lead, magnesium, manganese and alloys thereof. Among these, copper or a copper alloy is particularly preferable. In addition, the material of the wiring layer in the circuit board of this embodiment mentioned later is the same as that of a metal layer.

Although the thickness of a metal layer is not specifically limited, For example, when using copper foil as a metal layer, Preferably it is 35 micrometers or less, More preferably, it is good in the range of 5-25 micrometers. It is preferable that the lower limit of the thickness of copper foil shall be 5 micrometers from a viewpoint of production stability and handling property. In addition, when using copper foil, it may be rolled copper foil or electrolytic copper foil. Moreover, as copper foil, commercially available copper foil can be used.

(Rust prevention processing)

When using copper foil as a metal layer in this embodiment, this copper foil is equipped with a base material copper foil and the rust-preventing layer formed on the surface of the adhesion layer (or insulating resin layer) formation surface side in the said base material copper foil. It is desirable to do it. By antirust process, suppression of the fall of the adhesive strength of copper foil and an adhesive layer at the time of wiring process of a metal clad laminated board, and suppression of the fall of the tolerance with respect to the chemical liquid by etching can be aimed at. The base metal copper foil may be either an electrolytic copper foil or a rolled copper foil. Although the thickness of such a base material copper foil will not be restrict | limited especially if it is the thickness range of the copper foil used for a general copper clad laminated board, From a flexible viewpoint of a copper clad laminated board, it is preferable that it is 70 micrometers or less. When thickness exceeds 70 micrometers, since the use of the copper clad laminated board obtained is limited, it is not preferable. Moreover, when using a copper clad laminated board as a flexible copper clad laminated board, it is preferable that the thickness of the said base material copper foil is 5-35 micrometers. When the thickness of the said base material copper foil is less than 5 micrometers, wrinkles etc. are easy to enter at the time of manufacture, and there exists a tendency for cost of manufacture of a thin copper foil, and when the thickness exceeds 35 micrometers, the copper clad laminated board obtained is used. In some cases, there is a tendency that thickness reduction and miniaturization of an IC mounting substrate for driving a liquid crystal display which is a display unit of a personal computer, a cellular phone or a portable information terminal (PDA) become insufficient.

It is preferable to use the thing which performed the roughening process to the surface from a viewpoint of improving the adhesive strength (fill strength) and chemical-resistance between the said base material copper foil, copper foil, and an adhesive layer. And 10 point average roughness (Rz) of the said base material copper foil is 1.5 micrometers or less from a viewpoint of the said viewpoint and the flexibility and conductor loss reduction of the obtained copper clad laminated board, for example, It is preferable that it is the range of 0.1-1.0 micrometer. More preferred.

The antirust process layer which concerns on this invention is a layer which has antirust property formed on the surface of the formation surface side of the said contact bonding layer in the said base material copper foil. In the present invention, by providing such a rust preventive treatment layer on the base material copper foil, it is possible to provide sufficient rust prevention property to the base material copper foil and to improve the adhesive strength between the adhesive layer and the copper foil. It is preferable that the thickness of such an antirust process layer is a range of 10-50 nm, for example. If the thickness is less than the lower limit, the surface of the base material copper foil is not uniformly covered, and a sufficient rust preventing effect tends to be difficult to be obtained. On the other hand, if the upper limit is exceeded, solubility in the copper etching solution of the rust-prevented layer (etchability) This tends to be insufficient.

It is preferable that the said antirust process layer is equipped with the plating process layer and chromate treatment layer containing zinc. Such a treatment layer forms a zinc plating treatment layer by plating the surface of the base material copper foil using a plating solution containing a zinc compound, and further comprises a chromate treatment layer, thereby providing an antirust effect and adhesion with an adhesive layer. You can improve the sex further. The chromate treatment layer can be formed by performing immersion or electrolytic chromate treatment using a chromate treatment agent containing chromium oxide or the like on the surface of the rustproof treatment layer.

Moreover, it is preferable that zinc content in the said antirust process layer is 0.01 mg / dm <^2> or more. If zinc content is less than the said minimum, the solubility (etching property) with respect to the copper etching liquid of an antirust process layer will become inadequate, and the adhesive strength between an adhesive layer and copper foil by the thermal deterioration at the time of manufacture of the copper clad laminated board of an antirust process layer. Tends to be insufficient. Moreover, it is more preferable that zinc content is the range of 0.01-1.5 mg / dm <^2> from a viewpoint of further improving the etching property of an antirust process layer, and the adhesive strength between an adhesive layer and copper foil.

Moreover, you may contain metal other than zinc in the said antirust process layer. As metals other than zinc, nickel, cobalt, molybdenum, etc. are mentioned, for example. For example, the nickel content in the rustproof treatment layer is 0.1 mg / dm ² It is preferable that it is above. When nickel content is less than the said minimum, the rust prevention effect of the copper foil surface is not enough, and there exists a tendency for the discoloration of the copper foil surface to occur easily after heating or in an environment of high temperature and high humidity. Moreover, it is more preferable that nickel content is the range of 0.1-3 mg / dm <^2> from a viewpoint of fully preventing the copper from a base material copper foil spread | diffused to an rustproof process layer or an contact bonding layer.

Nickel is a total solid solution solid with respect to copper, and can produce an alloy state, or nickel is easy to diffuse with respect to copper, and it is easy to make an alloy state. In such a state, electrical resistance is large compared with copper single body, in other words, electrical conductivity becomes small. In this regard, when a large amount of nickel is contained in the rust-preventing layer, an increase in resistance of copper alloyed with nickel occurs. As a result, the loss in signal transmission due to an increase in the resistance of the signal wiring due to the skin effect is increased. From such a viewpoint, in the copper clad laminated board of this embodiment, when using for a process, such as a circuit board which performs a high frequency transmission of 10 GHz, for example, it is preferable to suppress the amount of nickel to 0.01 mg / dm <^2> or less.

0.01 mg / dm ² of nickel in the antirust layer When suppressing below, it is preferable to contain at least cobalt and molybdenum in the said antirust process layer. The rust-prevented layer has a nickel content of 0.01 mg / dm ² or less, a cobalt content of 0.01 to 0.5 mg / dm ² , a molybdenum content of 0.01 to 0.5 mg / dm ² , and a cobalt element and a molybdenum element. It is preferable to control so that total amount (Co + Mo) may be in the range of 0.1-0.7 mg / dm <^2> . By setting it in such a range, the etching residue of the resin part between wirings at the time of the wiring process of a copper clad laminated board is suppressed, suppression of the fall of the tolerance with respect to the chemical liquid by etching, and the fall of the adhesive strength between copper foil and resin, and its long-term reliability. It can be suppressed.

Moreover, the copper foil used for the copper clad laminated board of this embodiment is the surface of a copper foil with a siding, aluminum alcoholate, aluminum chelate, a silane coupling agent, etc. for the purpose of improving adhesive force other than the said antirust process. You may perform a process.

<Method for producing metal clad laminate>

Even if a metal-clad laminated board prepares the resin film which laminated | stacked the contact bonding layer and the insulated resin layer, for example, sputter | spatters a metal and forms a seed layer in the contact bonding layer side, for example, even if it manufactures by forming a metal layer by plating, do.

In addition, you may manufacture a metal clad laminated board by preparing the resin film which laminated | stacked the contact bonding layer and the insulated resin layer, and laminating metal foils, such as copper foil, by the method of thermocompression bonding on the contact bonding layer side.

Moreover, a metal-clad laminated board casts the coating liquid for forming an adhesive layer on metal foil, such as copper foil, and makes it into a coating film, and casts the coating liquid for forming an insulating resin layer on this coating film. You may manufacture by drying and heat-processing collectively after making it into a coating film. In this case, as a coating liquid for forming an adhesive layer, the adhesive polyimide resin composition (after-mentioned) and the polyamic-acid solution which is a precursor of the thermoplastic polyimide which forms an adhesive layer can be used. In addition, about the thermoplastic polyimide which forms an adhesive layer, you may make bridge formation in the said method.

[Circuit board]

The metal clad laminated board of this embodiment is useful mainly as circuit board materials, such as an FPC and a rigid flex circuit board. That is, the FPC which is one Embodiment of this invention can be manufactured by processing the metal layer of the metal clad laminated board of this embodiment on a pattern by a conventional method, and forming a wiring layer.

[Adhesive sheet]

The adhesive sheet of this embodiment is the said adhesive layer in the metal-clad laminated board which has an insulated resin layer, the adhesive layer laminated | stacked on the surface of at least one side of the said insulated resin layer, and the metal layer laminated | stacked on the said insulated resin layer via the said adhesive layer. It is an adhesive sheet for forming. This adhesive sheet is formed by forming the thermoplastic polyimide which forms the adhesive layer mentioned above in a sheet form. That is, the thermoplastic polyimide which forms an adhesive sheet contains a predetermined amount of tetracarboxylic-acid residue and diamine residue similarly to the said adhesive layer.

The adhesive sheet may be laminated | stacked on arbitrary base materials, such as a copper foil, a glass plate, a polyimide film, a polyamide film, and a polyester film. The thickness of the adhesive sheet, the coefficient of thermal expansion, the dielectric tangent, the dielectric constant and the like correspond to the adhesive layer. In addition, an adhesive sheet can contain arbitrary components, such as a filler.

As a manufacturing method form of the adhesive sheet of this embodiment, for example, [1] the support base material is apply | coated and dried, the solution of polyamic acid, heat-processes, and imidizes, and peels from a support base material, and manufactures an adhesive sheet, for example. [2] a method for producing an adhesive sheet by applying a method of drying a polyamic acid to a supporting substrate and drying the polyamic acid from the supporting substrate, followed by heat treatment to imidize the method. After apply | coating and drying the solution of adhesive polyimide resin composition (after-mentioned), the method of peeling from a support base material and manufacturing an adhesive sheet is mentioned. Moreover, you may make crosslinking formation with respect to the thermoplastic polyimide which comprises an adhesive sheet by the said method.

The method of applying the polyimide solution (or polyamic acid solution) on the support substrate is not particularly limited, and for example, it is possible to apply a coater such as a comma, a die, a knife, or a lip. It is preferable to form the adhesive sheet manufactured by apply | coating and drying the polyimide solution which completed imidation in a polyamic-acid solution on a support base material. Since the polyimide of this embodiment is solvent soluble, it is advantageous because the polyamic acid can be imidated in the state of a solution and can be used as it is as a coating liquid of polyimide.

The adhesive sheet obtained as described above has excellent flexibility and dielectric properties (low dielectric constant and low dielectric loss tangent) when the adhesive layer of the circuit board is formed using this, for example, FPC, rigid flex circuit board It becomes what has a characteristic characteristic as adhesive layers, such as these.

Adhesive Polyimide Resin Composition

The adhesive polyimide resin composition of this embodiment is a metal-clad laminated board which has an insulated resin layer, the contact bonding layer laminated | stacked on the surface of at least one side of the said insulated resin layer, and the metal layer laminated | stacked on the said insulating resin layer via the said contact bonding layer. In to form the adhesive layer. Adhesive polyimide resin composition contains the polyimide containing a tetracarboxylic-acid residue and a diamine residue, and two terminal carboxylic acid groups of a dimer acid are the primary aminomethyl group with respect to 100 mol part of the said diamine residue. Or 50 mol parts or more, preferably 80 mol parts or more of the diamine residue derived from the dimer acid type diamine substituted by the amino group, and with respect to 100 mol parts of the said tetracarboxylic-acid residue, the said General formula (1) and / or ( 90 mol part or more of tetracarboxylic-acid residues derived from the tetracarboxylic anhydride represented by 2) are contained.

In addition, the adhesive polyimide resin composition has a diamine moiety derived from at least one diamine compound selected from the diamine compounds represented by the general formulas (B1) to (B7) within a range of 1 mole part to 50 mole parts or less. It is preferable to contain.

The adhesive polyimide resin composition of this embodiment is solvent soluble and can contain an organic solvent as an arbitrary component. As a preferable organic solvent, for example, N, N-dimethylformamide, N, N-dimethylacetamide (DMAC), N-methyl-2-pyrrolidone, 2-butanone, dimethyl sulfoxide, dimethyl sulfate, cyclo Hexanone, dioxane, tetrahydrofuran, diglyme, triglyme, etc. are mentioned. These solvent can also be used in combination of 2 or more types, and can also use together the aromatic hydrocarbons, such as xylene and toluene.

The adhesive polyimide resin composition of this embodiment is another arbitrary component, such as an amino compound, an inorganic filler, a plasticizer, an epoxy resin, etc. which have at least two primary amino groups used for the crosslinking formation described above as functional groups. Another resin component, a hardening accelerator, a coupling agent, a filler, a pigment, a solvent, a flame retardant, etc. can be mix | blended suitably.

The adhesive polyimide resin composition obtained as described above has excellent flexibility and dielectric properties (low dielectric constant and low dielectric loss tangent) when the adhesive layer or the adhesive sheet is formed using this, for example, FPC, rigid Applicable suitably as adhesive layer forming materials, such as a flex circuit board.

EXAMPLE

EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited at all by these Examples. In addition, in the following Examples, unless otherwise indicated, various measurements and evaluation are based on the following.

[Measurement of coefficient of thermal expansion (CTE)]

The polyimide film of the size of 3mm x 20mm was heated up from 30 degreeC to 300 degreeC at a constant temperature increase rate, applying the load of 5.0g using a thermomechanical analyzer (Bruker company make, brand name; 4000SA), and also the temperature After hold | maintaining at 10 minutes, it cooled at the speed | rate of 5 degree-C / min, and calculated | required the average thermal expansion coefficient (thermal expansion coefficient) from 250 degreeC to 100 degreeC.

[Measurement of Surface Roughness of Copper Foil]

The surface roughness of copper foil is AFM (Bruker-A-X-S Corporation, brand name: Dimension Icon type SPM), probe (Bruker-A-X-S Corporation, brand name: TESPA (NCHV), tip curvature radius 10nm, a spring constant 42N / m), in the tapping mode, it measured about the range of 80 micrometers x 80 micrometers of the copper foil surface, and calculated | required 10-point average roughness (Rzjis).

[Measurement of Surface Metal Elements of Copper Foils Treated with Metals]

After masking the analytical surface of the copper foil, the analytical surface was dissolved with 1N-nitric acid, and fixed to 100 mL, and then measured using Perkin Elmer's Inductively Coupled Plasma Emission Spectroscopy (ICP-AES) Optima4300. It was.

[Evaluation method of warpage]

Evaluation of curvature was performed by the following method. A 10 cm × 10 cm film was placed, and the average of the heights of warping of the four corners of the film was measured, and 10 mm or less was defined as “good” and the case of exceeding 10 mm as “not possible”.

[Measurement of dielectric constant (Dk) and dielectric loss tangent (Df)]

The dielectric constant and dielectric loss tangent are formed on a resin sheet (or insulating resin layer) at a frequency of 10 GHz by using a cavity resonator perturbation dielectric constant evaluation device (manufactured by Agilent, trade name; vector network analyzer E8363C) and a split post dielectric resonator (SPDR resonator). The dielectric constant and dielectric loss tangent of the insulating layer laminated | stacked by the resin sheet were measured. In addition, the resin sheet (or the insulating layer which the resin sheet laminated | stacked on the insulated resin layer) used for the measurement is temperature; 24 to 26 ° C., humidity; It is left to stand for 24 hours on 45-55% of conditions.

[Evaluation Method of Laser Workability]

Evaluation of laser workability was performed with the following method. UV-YAG, the third harmonic 355nm laser light is irradiated at a frequency of 60 kHz and 1.0 W, and the bottom via is processed, and it is possible that recess or undercut does not occur in the adhesive layer. This occurrence was evaluated as "impossible."

[Measurement of Peel Strength]

Peel strength was performed by the following method. The peeling strength at the time of pulling the insulated resin layer of the test piece width 5mm in the 90 degree direction of an adhesive bond layer at the speed | rate 50mm / min using the tensile tester (made by Toyo Seiki Seisakusho, strograph VE) was measured. Moreover, the peeling strength evaluated 0.9 kN / m or more as "good", the peeling strength was 0.4 kN / m or more and less than 0.9 kN / m as "possible", and the peeling strength was less than 0.4 kN / m as "not possible".

The symbol used in the present Example shows the following compounds.

BTDA: 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride

BPDA: 3,3 ', 4,4'-diphenyltetracarboxylic dianhydride

6FDA: 4,4 '-(hexafluoroisopropylidene) diphthalic anhydride

BPADA: 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride

PMDA: pyromellitic dianhydride

APB: 1,3-bis (3-aminophenoxy) benzene

BAPP: 2,2-bis [4- (4-aminophenoxy) phenyl] propane

DDA: C 36 aliphatic diamine (manufactured by Croda Japan Co., Ltd., trade name; PRIAMINE1074, amine number; 210 mgKOH / g, mixture of dimer diamine of cyclic and chain structure, content of dimer component; 95 wt% or more)

m-TB: 2,2'-dimethyl-4,4'-diaminobiphenyl

ODPA: 4,4'-oxydiphthalic anhydride (alias; 5,5'-oxybis-1,3-isobenzofurandone)

N-12: Dodecane Isandihydrazide

NMP: N-methyl-2-pyrrolidone

DMAc: N, N-dimethylacetamide

Synthesis Example 1

<Production of Resin Solution for Adhesive Layer>

Into a 1000 ml separable flask, 56.18 g of BTDA (0.174 mole), 93.82 g of DDA (0.176 mole), 210 g of NMP and 140 g of xylene were charged and mixed well at 40 ° C. for 1 hour to prepare a polyamic acid solution. Prepared. The polyamic acid solution was heated to 190 ° C., heated and stirred for 4 hours to add 140 g of xylene and completed imidization. Polyimide solution 1 (solid content; 30 wt%, viscosity; 5,100 cps, weight average molecular weight; 66,100).

Synthesis Examples 2 to 10

<Production of Resin Solution for Adhesive Layer>

Except having set it as the raw material composition shown in Table 1, it carried out similarly to the synthesis example 1, and manufactured the polyimide solution 2-10.

Synthesis Example 11

<Production of Resin Solution for Adhesive Layer>

1.1 g of N-12 (0.004 mol) was added to 100 g (30 g as a solid) of the polyimide solution 1 prepared in Synthesis Example 1, diluted with addition of 0.1 g of NMP and 10 g of xylene, and further 1 hour. The polyimide solution 11 was prepared by stirring.

Synthesis Examples 12 to 17

<Production of Resin Solution for Adhesive Layer>

Except having used the polyimide solution 5-10 shown in Table 2, it carried out similarly to the synthesis example 11, and manufactured the polyimide solution 12-17.

Synthesis Example 18

<Production of Polyimide Film for Insulation Resin Layer>

Under a stream of nitrogen, 2.196 g of DDA (0.0041 mol), 16.367 g of m-TB (0.0771 mol) and 212.5 g of DMAc were added to a 300 ml separable flask, followed by stirring at room temperature to dissolve. Subsequently, 4.776 g of BPDA (0.0162 mol) and 14.161 g of PMDA (0.0649 mol) were added, followed by stirring for 3 hours at room temperature to carry out the polymerization reaction to prepare a polyamic acid solution P (viscosity; 26,000 cps). It was.

The polyamic acid solution P was uniformly coated on the copper foil (surface roughness Rz; 2.1 µm) so that the thickness after curing was about 25 µm, followed by heating to dryness at 120 ° C. to remove the solvent. Furthermore, step heat treatment was performed from 120 degreeC to 360 degreeC, the imidation was completed, and the metal coating laminated body P was manufactured. About the metal-clad laminate P, copper foil was etched away using the ferric chloride aqueous solution, and polyimide film P (CTE; 20 ppm / K, Dk; 2.95, Df; 0.0041) was produced.

(Production Example 1)

<Production of Resin Sheet for Adhesive Layer>

The resin sheet 1a (thickness; 25 micrometers) was produced by apply | coating the polyimide solution 1 to the single side | surface of the mold-released PET film, and drying at 80 degreeC for 15 minutes, and peeling. The dielectric constant (Dk) and dielectric loss tangent (Df) of the resin sheet 1a are shown in Table 3.

(Production Examples 2 to 7)

<Production of Resin Sheet for Adhesive Layer>

Using the polyimide solution 1, it carried out similarly to manufacture example 1, and manufactured resin sheet 1b-1g which changed the thickness of the resin sheet. The dielectric constant (Dk) and dielectric loss tangent (Df) of the resin sheets 1b to 1g are shown in Table 3.

(Production Examples 8 to 16)

<Production of Resin Sheet for Adhesive Layer>

Except having used the polyimide solution shown in Table 4, it carried out similarly to Production Example 1, and manufactured resin sheet 2a-10a of 25 micrometers in thickness. The dielectric constants (Dk) and dielectric tangent (Df) of the resin sheets 2a to 10a are shown in Table 4.

(Production Example 17)

<Production of Copper Foil Having Antirust Treatment>

Electrolytic copper foil (thickness; 12 micrometers) and surface roughness Rz (0.3 micrometer) of MD direction (Machine Direction (flow direction of long copper foil)) by the resin layer side were prepared. After the roughening treatment was performed on the surface of the copper foil, plating treatment containing a predetermined amount of cobalt and molybdenum (metal precipitation treatment) was performed, followed by zinc plating and chromate treatment, and copper foil 1 (Ni; 0.01 mg / dm ² or less). ^{, Co; 0.23mg / dm 2,} Mo; 0.36mg / dm 2, Zn; 0.11mg / dm 2, Cr; to 0.14mg / dm ²⁾ was prepared.

Example 1

Resin sheet 1a (thickness; 25 micrometers, Dk; 2.4, Df; 0.0020) was put on copper foil 1 (surface roughness Rz; 0.3 micrometer), and polyimide film 1 (made by Toray Dupont, brand name; Kapton EN) was placed on it. -S, thickness; 25 μm, CTE; 16 ppm / K, Dk; 3.79, Df; 0.0126), vacuum laminated at conditions of temperature 170 ° C., pressure 0.85 MPa, hour 1 minute, then temperature in oven It heated on the conditions of 160 degreeC and time 1 hour, and manufactured the copper clad laminated board 1. Table 5 shows the evaluation results of the copper clad laminate 1.

Example 2

A copper clad laminate 2 was produced in the same manner as in Example 1 except that 1 g (thickness; 50 μm, Dk; 2.4, Df; 0.0020) of the resin sheet was used instead of the resin sheet 1a. The evaluation results of the copper clad laminate 2 are shown in Table 5.

Example 3

The resin sheet 1g was used instead of the resin sheet 1a, and the liquid crystal polymer film 3 (made by Kuraray Corporation, brand name; CT-Z, thickness; 50 micrometers, CTE; 18 ppm / K, Dk; 3.40, Df instead of the polyimide film 1) Copper clad laminate 3 was produced in the same manner as in Example 1, except that 0.0022) was used. Table 5 shows the evaluation results of the copper clad laminate 3.

Table 5 summarizes the results of Examples 1-3.

Example 4

The polyimide solution 1 was apply | coated to the single side | surface of the polyimide film P manufactured by the synthesis example 18, and it dried for 15 minutes at 80 degreeC, and produced the insulation film 4 (thickness of an adhesive layer; 3 micrometers). In the state which laminated | stacked the contact bonding layer surface of the insulation film 4 on the rust-preventing surface side of copper foil 1, it vacuum- laminates on conditions of temperature 170 degreeC, pressure 0.85 MPa, and 1 minute, and after that temperature in an oven of 160 degreeC and time for 1 hour It heated on conditions, and produced the copper clad laminated board 4. Table 6 shows the results of the evaluation of the copper clad laminate 4.

Example 5

A copper clad laminate 5 was produced in the same manner as in Example 4 except that the thickness of the adhesive layer was 1 μm. Table 6 shows the results of the evaluation of the copper clad laminate 5.

Example 6

A copper clad laminate 6 was produced in the same manner as in Example 4 except that the thickness of the adhesive layer was 0.3 μm. The evaluation results of the copper clad laminate 6 are shown in Table 6.

Table 6 summarizes the results of Examples 4-6.

Example 7

The polyimide solution 1 was apply | coated to the polyimide film surface of the copper clad laminated board 4 manufactured in Example 4, and it dried for 15 minutes at 80 degreeC, after making the thickness of an adhesive layer 3 micrometers, the antirust process surface of copper foil 1 Was laminated on the surface of the adhesive layer at a temperature of 170 ° C., a pressure of 0.85 MPa and a time of 1 minute, and then vacuum laminated, and then heated in an oven at a temperature of 160 ° C. and a time of 1 hour to prepare a copper clad laminate 7. . The evaluation results of the copper clad laminate 7 are shown in Table 7.

Example 8

A copper clad laminate 8 was produced in the same manner as in Example 7 except that the thickness of the adhesive layer was 1 μm. Table 7 shows the evaluation results of the copper clad laminate 8.

Example 9

A copper clad laminate 9 was produced in the same manner as in Example 7 except that the thickness of the adhesive layer was 0.3 μm. Table 7 shows the evaluation results of the copper clad laminate 9.

Table 7 summarizes the results of Examples 7-9.

Example 10

The polyimide solution 1 was apply | coated to the single side | surface of the polyimide film 1, and it dried for 15 minutes at 80 degreeC, and produced the insulation film 5 (thickness of an adhesive layer; 12 micrometers). In the state which laminated | stacked the contact bonding layer surface of the insulating film 5 on the rust-preventing surface side of copper foil 1, it vacuum- laminates on conditions of temperature 170 degreeC, pressure 0.85 MPa, and time for 1 minute, and after that in an oven of temperature 160 degreeC, time 1 hour It heated on conditions, and produced the copper clad laminated board 10. Table 8 shows the evaluation results of the copper clad laminate 10.

Example 11

The polyimide solution 1 was apply | coated to the rust-prevention surface side of copper foil 1, and it dried at 80 degreeC for 15 minutes, and manufactured the film 6 (thickness of an adhesive layer; 5 micrometers) with copper foil. In the state where the adhesive layer surface of the film 6 provided with copper foil and polyimide film 2 (made by Toray Dupont, brand name; Kapton EN, thickness; 5 micrometers, CTE; 16 ppm / K, Dk; 3.70, Df; 0.0076) were overlapped It vacuum-laminated on the conditions of 170 degreeC, the pressure of 0.85 Mpa, and 1 minute of time, and after that, it heated in the oven on the conditions of the temperature of 160 degreeC, and 1 hour, and manufactured the copper clad laminated board 11. The evaluation result of the copper clad laminated board 11 is shown in Table 8.

Example 12

The polyimide solution 13 was apply | coated to the polyimide film surface of the copper clad laminated board 4 manufactured in Example 4, and it dried for 15 minutes at 80 degreeC, and made the thickness of an adhesive layer 25 micrometers, Then, the antirust process surface of copper foil 1 Was laminated on the surface of the adhesive layer, vacuum laminated at a temperature of 170 ° C, a pressure of 0.85 MPa and a time of 1 minute, and then heated in a oven at a temperature of 160 ° C and a time of 1 hour to prepare a copper clad laminate 12. . Table 8 shows the evaluation results of the copper clad laminate 12.

Example 13

The polyimide solution 16 was apply | coated to the polyimide film surface of the copper clad laminated board 4 manufactured in Example 4, and it dried for 15 minutes at 80 degreeC, and made the thickness of an adhesive layer 25 micrometers, and then the rust-treated surface of copper foil 1 Was laminated on the surface of the adhesive layer, vacuum laminated at a temperature of 170 ° C., a pressure of 0.85 MPa and a time of 1 minute, and then heated in a oven at a temperature of 160 ° C. and a time of 1 hour to prepare a copper clad laminate 13. . Table 8 shows the evaluation results of the copper clad laminate 13.

Synthesis Examples 19 to 21

<Production of Resin Solution for Adhesive Layer>

Except having set it as the raw material composition shown in Table 9, it carried out similarly to the synthesis example 1, and manufactured the polyimide solution 19-21.

(Production Examples 18 to 20)

<Production of Resin Sheet for Adhesive Layer>

Except having used the polyimide solution shown in Table 10, it carried out similarly to Production Example 1, and manufactured the resin sheets 18a-20a of 25 micrometers in thickness. Dielectric constants (Dk) and dielectric tangent (Df) of the resin sheets 18a to 20a are shown in Table 10.

(Comparative Example 1)

The polyimide solution 19 was apply | coated to the single side | surface of the polyimide film 1, and it dried at 80 degreeC for 15 minutes, and produced the insulation film 7 (thickness of an adhesive layer; 12 micrometers). In the state which laminated | stacked the contact bonding layer surface of the insulating film 7 on the rust-preventing surface side of copper foil 1, it vacuum- laminates on conditions of temperature 170 degreeC, pressure 0.85 MPa, and 1 minute, and after that temperature in an oven of 160 degreeC and time for 1 hour It heated on conditions, and produced the copper clad laminated board 18. Table 11 shows the evaluation results of the copper clad laminate 18.

(Comparative Example 2)

A copper clad laminate 19 was produced in the same manner as in Comparative Example 1 except that Polyimide Solution 20 was used. Table 11 shows the evaluation results of the copper clad laminate 19.

(Comparative Example 3)

A copper clad laminate 20 was produced in the same manner as in Comparative Example 1 except that Polyimide Solution 21 was used. The evaluation results of the copper clad laminate 20 are shown in Table 11.

As mentioned above, although embodiment of this invention was described in detail for the purpose of illustration, this invention is not restrict | limited to the said embodiment, A various deformation | transformation is possible.

Claims (11)

It is a metal clad laminated board which has an insulated resin layer, the contact bonding layer laminated | stacked on the surface of at least one side of the said insulated resin layer, and the metal layer laminated | stacked on the said insulating resin layer via the said contact bonding layer,
The adhesive layer has a polyimide containing a tetracarboxylic acid residue and a diamine residue,
The polyimide is based on 100 mole parts of the diamine residue,
A metal-coated laminate comprising at least 50 mole parts of a diamine residue derived from a dimer acid type diamine in which two terminal carboxylic acid groups of dimer acid are substituted with a primary aminomethyl group or an amino group. The polyimide of claim 1, wherein the polyimide is based on 100 moles of the tetracarboxylic acid residue.
A metal-coated laminate comprising at least 90 mol parts in total of tetracarboxylic acid residues derived from tetracarboxylic anhydrides represented by the following General Formulas (1) and / or (2).

[In general formula (1), X represents a bivalent group chosen from a single bond or a following formula, and the cyclic part represented by Y in general formula (2) represents a 4-membered ring, a 5-membered ring, a 6-membered ring, a 7-membered ring, or Forms cyclic saturated hydrocarbon groups selected from eight-membered rings]

[Wherein Z represents —C ₆ H ₄ —, — (CH ₂ ) n — or —CH ₂ —CH (—OC (═O) —CH ₃ ) —CH ₂ —, but n represents 1 An integer of from 20 to 20] The polyimide of claim 1 or 2, wherein the polyimide is based on 100 mole parts of the diamine moiety.
It contains a diamine residue derived from the said dimer-type diamine within 50 mol part or more and 99 mol part or less,
A metal-coated laminate comprising a diamine residue derived from at least one diamine compound selected from diamine compounds represented by the following general formulas (B1) to (B7) within a range of 1 mole part to 50 mole parts.

[In formula (B1)-(B7), R <_1> represents a C1-C6 monovalent hydrocarbon group or an alkoxy group independently, and linking group A is independently -O-, -S-, -CO-, -SO -, -SO _2- , -COO-, -CH _2- , -C (CH ₃ ) _2- , a divalent group selected from -NH- or -CONH-, n ₁ independently represent an integer of 0 to 4 Wherein, except for overlapping with formula (B2) in formula (B3), overlapping with formula (B4) in formula (B5) is excluded. The metal-clad laminate as described in any one of Claims 1-3 in which the said metal layer contains copper foil and the surface which contact | connects the said contact bonding layer in this copper foil is rust-proofed. The circuit board which processes the said metal layer of the metal clad laminated board as described in any one of Claims 1-4 by wiring. An adhesive sheet for forming the said adhesive layer in the metal clad laminated board which has an insulated resin layer, the contact bonding layer laminated | stacked on the surface of at least one side of the said insulated resin layer, and the metal layer laminated | stacked on the said insulating resin layer via the said contact bonding layer,
The adhesive sheet has a polyimide containing a tetracarboxylic acid residue and a diamine residue,
The polyimide is based on 100 mole parts of the diamine residue,
An adhesive sheet comprising at least 50 mole parts of a diamine residue derived from a dimer acid type diamine in which two terminal carboxylic acid groups of a dimer acid are substituted with a primary aminomethyl group or an amino group. The polyimide of claim 6, wherein the polyimide is based on 100 mole parts of the tetracarboxylic acid residue,
The adhesive sheet containing 90 mol part or more of total tetracarboxylic-acid residues derived from tetracarboxylic anhydride represented by following General formula (1) and / or (2) below.

[In general formula (1), X represents a bivalent group chosen from a single bond or a following formula, and the cyclic part represented by Y in general formula (2) represents a 4-membered ring, a 5-membered ring, a 6-membered ring, a 7-membered ring, or Forms cyclic saturated hydrocarbon groups selected from eight-membered rings]

[Wherein Z represents —C ₆ H ₄ —, — (CH ₂ ) n — or —CH ₂ —CH (—OC (═O) —CH ₃ ) —CH ₂ —, but n represents 1 An integer of from 20 to 20] The polyimide of claim 6 or 7, wherein the polyimide is based on 100 mole parts of the diamine residue,
It contains a diamine residue derived from the said dimer-type diamine within 50 mol part or more and 99 mol part or less,
Containing diamine residues derived from at least one diamine compound selected from the diamine compounds represented by the following general formulas (B1) to (B7) within a range of 1 to 50 mol parts.
Adhesive sheet characterized in that.

[In formula (B1)-(B7), R <_1> represents a C1-C6 monovalent hydrocarbon group or an alkoxy group independently, and linking group A is independently -O-, -S-, -CO-, -SO -, -SO _2- , -COO-, -CH _2- , -C (CH ₃ ) _2- , a divalent group selected from -NH- or -CONH-, n ₁ independently represent an integer of 0 to 4 Wherein, except for overlapping with formula (B2) in formula (B3), overlapping with formula (B4) in formula (B5) is excluded. Adhesive polyimide for forming the said contact bonding layer in the metal clad laminated board which has an insulated resin layer, the contact bonding layer laminated | stacked on the surface of at least one side of the said insulating resin layer, and the metal layer laminated | stacked on the said insulating resin layer via the said contact bonding layer. Resin composition,
The said adhesive polyimide resin composition contains the polyimide containing a tetracarboxylic-acid residue and a diamine residue,
The polyimide is based on 100 mole parts of the diamine residue,
Adhesive polyimide resin composition characterized by containing 50 mol part or more of diamine residues derived from the dimer acid type diamine which the two terminal carboxylic acid groups of dimer acid are substituted by the primary aminomethyl group or an amino group. The said polyimide is tetracarboxyl derived from the tetracarboxylic anhydride represented by following General formula (1) and / or (2) with respect to 100 mol part of the said tetracarboxylic-acid residue. The adhesive polyimide resin composition containing 90 mol part or more of acid residues in total.

[In general formula (1), X represents a bivalent group chosen from a single bond or a following formula, and the cyclic part represented by Y in general formula (2) represents a 4-membered ring, a 5-membered ring, a 6-membered ring, a 7-membered ring, or Forms cyclic saturated hydrocarbon groups selected from eight-membered rings]

[Wherein Z represents —C ₆ H ₄ —, — (CH ₂ ) n — or —CH ₂ —CH (—OC (═O) —CH ₃ ) —CH ₂ —, but n represents 1 An integer of from 20 to 20] The polyimide of claim 9 or 10, wherein the polyimide is based on 100 mole parts of the diamine moiety.
It contains a diamine residue derived from the said dimer-type diamine within 50 mol part or more and 99 mol part or less,
Adhesive polyimide resin composition containing diamine residue derived from at least 1 sort (s) of diamine compound chosen from diamine compound represented by following General formula (B1)-(B7) within 1 mol part-50 mol part.

[In formula (B1)-(B7), R <_1> represents a C1-C6 monovalent hydrocarbon group or an alkoxy group independently, and linking group A is independently -O-, -S-, -CO-, -SO -, -SO _2- , -COO-, -CH _2- , -C (CH ₃ ) _2- , a divalent group selected from -NH- or -CONH-, n ₁ independently represent an integer of 0 to 4 Wherein, except for overlapping with formula (B2) in formula (B3), overlapping with formula (B4) in formula (B5) is excluded.