JP7306449B2 - Laminate for high frequency circuit, flexible printed circuit board, and laminate wound body - Google Patents

Description

TECHNICAL FIELD The present invention relates to a laminate for a high-frequency circuit formed by laminating a resin layer and a film layer, a method for producing the same, a flexible printed circuit board, and a B-stage sheet. The present invention also relates to a laminated body wound body suitable for use as a high-frequency circuit board.

Along with recent advances in performance of information terminal equipment and dramatic progress in network technology, the frequency of electrical signals handled in the field of information communication is increasing toward high-speed, large-capacity transmission. In order to cope with this, the printed wiring board used has a low dielectric constant (low ε _r ) and low dielectric loss tangent (low tan δ) that can reduce transmission loss, which is a problem in transmitting and processing high-frequency signals and high-speed digital signals. ) There is an increasing demand for materials (see, for example, Patent Documents 1 to 4).

As printed wiring boards, flexible printed boards (hereinafter also referred to as "FPC") and flexible flat cables (hereinafter also referred to as "FFC") are used in electronic and electrical equipment. FPC is made by processing a copper-clad laminate (CCL) consisting of an insulator layer and a copper foil layer to form an electric circuit, and then applying a coverlay consisting of an insulation layer and an adhesive layer to protect the circuit. CL) is manufactured through the process of attaching the adhesive part to the circuit part. In addition, FFC is obtained by using a base material consisting of an insulating layer and an adhesive layer and a conductor such as copper foil formed in a wiring shape, and arranging and bonding a plurality of conductors between the adhesive parts of the base material. It is an electrical circuit that

JP 2014-197611 A JP 2015-176921 A JP 2016-087799 A Japanese Unexamined Patent Application Publication No. 2016-032098

However, the higher the frequency of the electrical signal, the more likely it is to attenuate and the greater the transmission loss tends to be. Therefore, in next-generation high-frequency (10 GHz or higher) mounting substrates, low dielectric properties to reduce crosstalk between wires and low dielectric loss properties to suppress transmission loss of electrical signals are essential properties of insulator materials. It's becoming Moreover, in order to suppress the transmission loss of electric signals, it is also important that the mounting board has excellent smoothness. Especially in FPC and FFC, an adhesive is used to laminate the resin layer and the film layer, and the adhesive layer formed by the adhesive is one of the factors that impair the low dielectric loss characteristics and smoothness of the mounting board. it is conceivable that.

Furthermore, when a laminate of a resin layer and a film layer with an adhesive interposed therebetween is stored as a wound body wound around a core, the adhesive layer may deteriorate due to external factors (for example, the storage environment). There was a problem that curling tended to occur when the sheet was pulled out because the sheet was hardened by heating.

SUMMARY OF THE INVENTION It is an object of the present invention to provide a laminate for a high-frequency circuit, which reduces the transmission loss of electric signals in the high-frequency circuit and enables the manufacture of a circuit board with excellent smoothness. . Another object of the present invention is to provide a method for producing a laminate for high-frequency circuits, which can be produced by bonding at a low temperature and has excellent adhesiveness between the resin layer and the film layer.

Further, the present invention provides a laminate roll that can effectively suppress curl even when the laminate for a high-frequency circuit capable of reducing transmission loss of high-frequency signals is wound around a core and stored. is the subject.

The present invention has been made to solve at least part of the above problems, and can be implemented as any of the following aspects.

〔上記一般式（１－１）～（１－３）中、Ｒ^１は、それぞれ独立して、ハロゲン原子、炭素数１～２０の１価の炭化水素基、炭素数１～２０の１価のハロゲン化炭化水素基、ニトロ基、シアノ基、１～３級アミノ基、又は１～３級アミノ基の塩である。ｎは、それぞれ独立して、０～２の整数である。ｎが２の場合、複数のＲ^１は、同一であっても異なっていてもよく、任意の組み合わせで結合して環構造の一部を形成していてもよい。〕One aspect of the laminate for a high-frequency circuit according to the present invention is
A film layer having a glass transition temperature of 150° C. or higher and a resin layer are laminated in contact with each other,
The resin layer contains a polymer having at least one type of repeating unit among repeating units represented by the following general formulas (1-1), (1-2) and (1-3), and the resin layer The elastic modulus of the resin layer is 0.1 to 3.0 GPa, the dielectric loss tangent of the resin layer at a frequency of 10 GHz at 23 ° C. is 0.001 to 0.01, and the relative dielectric constant is 2.0 to 3.0 is.

[In the above general formulas (1-1) to (1-3), R ¹ is each independently a halogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, a monovalent hydrocarbon group having 1 to 20 carbon atoms, is a salt of a halogenated hydrocarbon group, a nitro group, a cyano group, a primary to tertiary amino group, or a primary to tertiary amino group. Each n is independently an integer of 0 to 2. When n is 2, multiple R ^1s may be the same or different, and may be combined in any combination to form a part of the ring structure. ]

In one aspect of the above laminate for high-frequency circuits,
The resin layer may have a thickness of 1 to 30 μm, and the film layer may have a thickness of 10 to 300 μm.

In any one aspect of the above laminate for high-frequency circuits,
A peel strength between the resin layer and the film layer may be 5.0 N/cm or more.

In any one aspect of the above laminate for high-frequency circuits,
A metal layer may be laminated in contact with the surface of the resin layer that is not in contact with the film layer.

In any one aspect of the above laminate for high-frequency circuits,
A peel strength between the resin layer and the metal layer may be 5.0 N/cm or more.

In any one aspect of the above laminate for high-frequency circuits,
The metal layer may have a thickness of 3-50 μm.

In any one aspect of the above laminate for high-frequency circuits,
The film layer is one selected from the group consisting of polyimide, polyetherimide, liquid crystal polymer, polyethylene naphthalate, polystyrene, cycloolefin polymer, polyether ether ketone, polyarylene ether ketone, and polyphenylene ether. can.

One aspect of the flexible printed circuit board according to the present invention is
A laminate for a high-frequency circuit according to any one of the aspects described above is provided.

One aspect of the method for manufacturing a laminate for high-frequency circuits according to the present invention is
A step of bonding a film layer having a glass transition temperature of 150° C. or higher and a B-stage resin layer having a surface roughness Ra of 1 to 100 nm by heating to 50 to 200° C. and applying a linear load of 1 to 19 kN/m. including.

In one aspect of the method for manufacturing the laminate for high-frequency circuits,
Further, a step of bonding a metal layer having a surface roughness Ra of 10 to 300 nm to the back surface of the B-stage resin layer to which the film layer is bonded can be included.

One aspect of the B stage sheet according to the present invention is
A B-stage sheet having a B-stage resin layer and a film layer formed on at least one surface of the B-stage resin layer,
When the B stage resin layer is cured to become a C stage resin layer,
The C-stage resin layer has an elastic modulus of 0.1 to 3.0 GPa,
The C-stage resin layer and the film layer have a dielectric loss tangent of 0.001 to 0.01 at 23° C. and a frequency of 10 GHz, and a relative dielectric constant of 2.0 to 3.0.

One aspect of the laminate roll according to the present invention is
The high-frequency circuit laminate of any one of the aspects described above is wound around a winding core having a radius of 10 to 100 mm.

According to the high-frequency circuit laminate of the present invention, it is possible to reduce the transmission loss of electric signals in the high-frequency circuit and to manufacture a circuit board having excellent smoothness. Further, according to the method for producing a laminate for high frequency circuits according to the present invention, it is possible to produce a laminate for high frequency circuits by lamination at a low temperature and having excellent adhesiveness between the resin layer and the film layer. can. Furthermore, according to the laminated body wound body according to the present invention, even when the high-frequency circuit laminated body capable of reducing the transmission loss of the high-frequency signal is wound around the core and stored, the curl is effective. can be effectively suppressed.

FIG. 1A is a cross-sectional view schematically showing a part of the steps in Production Example A of a laminate for high-frequency circuits. FIG. 1B is a cross-sectional view schematically showing a part of the steps in Production Example A of the laminate for high-frequency circuits. FIG. 1C is a cross-sectional view schematically showing a part of the steps in Production Example A of the laminate for high-frequency circuits. FIG. 1D is a cross-sectional view schematically showing a part of the steps in Production Example A of the laminate for high-frequency circuits. FIG. 1E is a cross-sectional view schematically showing a part of the steps in Production Example A of the laminate for high-frequency circuits. FIG. 2A is a cross-sectional view schematically showing a part of the steps in Production Example B of a laminate for high-frequency circuits. FIG. 2B is a cross-sectional view schematically showing a part of the steps in Production Example B of the laminate for high-frequency circuits. FIG. 2C is a cross-sectional view schematically showing a part of the steps in Production Example B of the laminate for high-frequency circuits. FIG. 3 is a perspective view showing an example of the laminate roll according to this embodiment. FIG. 4 is a perspective view showing an example of a winding core. FIG. 5 is a perspective view showing a state of a push mark generated when a laminate is unwound from a conventional laminate roll.

Preferred embodiments of the present invention will be described in detail below. It should be understood that the present invention is not limited only to the embodiments described below, but includes various modifications implemented without departing from the gist of the present invention.

In the present specification, a numerical range described using "to" means that the numerical values described before and after "to" are included as lower and upper limits.

1. High-Frequency Circuit Laminate The terms used in this specification are defined as follows.
・"High frequency signal" means an electric signal or radio wave with a frequency of 10 GHz or higher.
- "Laminate for high frequency circuit" means a laminate for use in manufacturing a high frequency circuit driven at a frequency of 10 GHz or higher.
- "B stage resin layer" refers to a layer in which the resin is semi-cured.
- "C-stage resin layer" refers to a layer in which the resin is completely cured. In addition, in this invention, a "C stage resin layer" may be called simply a "resin layer."
- "B stage sheet" refers to a sheet including a laminated structure in which a B stage resin layer is formed on at least one surface of a film layer.
- "Wound body" refers to a winding core in which a high-frequency circuit laminate having a uniform width is wound for a predetermined length. Although the winding length and width are not particularly limited, the winding length is usually 0.5 to 100 m and the width is several tens to 1000 mm.

The laminate for a high-frequency circuit according to this embodiment may have a structure in which a film layer and a resin layer are laminated in contact with each other, and may have a multilayer structure including the structure. Further, in the high-frequency circuit laminate according to the present embodiment, a metal layer may be further laminated on the surface of the resin layer that is not in contact with the film layer. The combination and order of these layers can be arbitrarily selected for manufacturing a high frequency circuit.

The laminate for a high-frequency circuit according to this embodiment is formed by laminating a film layer and a resin layer in contact with each other, and an adhesive layer such as a primer resin layer is not interposed between the film layer and the resin layer. A general circuit laminate has an adhesive layer interposed between the resin layer and the film layer in order to improve the adhesion between the film layer and the resin layer. The adhesive layer is formed by a method such as coating using an adhesive containing a polymer having a polar functional group. However, since such an adhesive layer has poor electrical properties, it increases the effective dielectric constant and effective dielectric loss of the resin layer that has an insulating function, making it unsuitable for high-frequency circuits. In contrast, the high-frequency circuit laminate according to the present embodiment has good adhesion between the film layer and the resin layer without using an adhesive. In addition, by laminating the film layer and the resin layer in contact with each other, the inventors succeeded in obtaining a laminate suitable for high-frequency circuits without deteriorating the effective electrical properties of the resin layer.

In the high-frequency circuit laminate according to the present embodiment, the peel strength between the resin layer and the film layer is preferably 5.0 N/cm or more, more preferably 5.3 N/cm or more, and 6.0 N/cm or more. /cm or more is particularly preferable. Since the high-frequency circuit laminate according to the present embodiment has a peel strength within the above range, the adhesion between the metal layer and the resin layer is good without using an adhesive. The peel strength can be measured according to the method described in "IPC-TM-650 2.4.9".

The thickness of the high-frequency circuit laminate according to this embodiment is preferably 20 to 200 μm, more preferably 30 to 180 μm, and particularly preferably 50 to 150 μm. When the thickness of the high-frequency circuit laminate is within the above range, not only can a thin high-frequency circuit board be produced, but also curling is less likely to occur when wound around a core.

Further, when a stepped portion is formed on the winding core, the thickness of the high-frequency circuit laminate is particularly preferably the height of the stepped portion (μm)±10 μm. When the thickness of the high-frequency circuit laminate is within the above range, the step at the joint between the stepped portion of the winding core and the high-frequency circuit laminate is eliminated, so that the laminate wound body does not leave impressions. can be more effectively suppressed.

Hereinafter, the structure of each layer constituting the high-frequency circuit laminate according to the present embodiment and the manufacturing method thereof will be described in detail.

1.1. Resin Layer The high-frequency circuit laminate according to the present embodiment includes a resin layer. The elastic modulus of the resin layer is 0.1 to 3.0 GPa, preferably 0.2 to 2.5 GPa. When the elastic modulus of the resin layer is within the above range, the laminate for high-frequency circuits is excellent in flexibility, so that the circuit board can be produced under more flexible conditions. The elastic modulus of the resin layer is a tensile elastic modulus and can be measured according to JIS K7161.

The dielectric constant of the resin layer at 23° C. and a frequency of 10 GHz is 2.0 to 3.0, preferably 2.1 to 2.8. Further, the dielectric loss tangent of the resin layer at 23° C. and a frequency of 10 GHz is 0.001 to 0.01, preferably 0.002 to 0.009. When the dielectric constant and the dielectric loss tangent are within the above ranges, a circuit board having excellent high frequency characteristics can be produced. The dielectric constant and dielectric loss tangent of the resin layer at a frequency of 10 GHz at 23° C. can be measured using a cavity resonator perturbation dielectric constant measuring device.

Also, the lower limit of the thickness of the resin layer is preferably 1 μm, more preferably 3 μm, and particularly preferably 5 μm. The upper limit of the thickness of the resin layer is preferably 30 μm, more preferably 25 μm.

In the invention of the present application, the resin layer also includes an embodiment composed of a plurality of different resin layers. When the resin layer is composed of a plurality of resin layers, the elastic modulus, dielectric constant, and dielectric loss tangent of each resin single layer are not necessarily limited to the preferred ranges described above, and may be within the preferred ranges as a whole. Just do it.

The method for producing such a resin layer is not particularly limited, but it is produced by a method such as applying the resin layer composition to a substrate such as a film layer or metal foil, or extruding to produce a self-supporting film. can do.

The composition of the resin layer composition comprises a polymer having at least one type of repeating unit among repeating units represented by the following general formulas (1-1), (1-2) and (1-3) described later. Although it is not particularly limited as long as it is contained, it may contain a curable compound and, if necessary, another polymer, a curing aid, and a solvent.

1.1.1. Composition for Resin Layer <Polymer>
The resin layer composition includes, as a polymer, a polymer ( Hereinafter, it is also referred to as “specific polymer”.). In addition, the resin layer composition may appropriately contain known materials having low dielectric constant and low dielectric loss tangent properties, such as other polymers such as epoxy resin, polyimide, and polyarylene.

〔式（１－１）～（１－３）中、Ｒ^１は、それぞれ独立して、ハロゲン原子、炭素数１～２０の１価の炭化水素基、炭素数１～２０の１価のハロゲン化炭化水素基、ニトロ基、シアノ基、１～３級アミノ基、又は１～３級アミノ基の塩である。ｎは、それぞれ独立して、０～２の整数である。ｎが２の場合、複数のＲ^１は、同一であっても異なっていてもよく、任意の組み合わせで結合して環構造の一部を形成していてもよい。〕

[In formulas (1-1) to (1-3), R ¹ is each independently a halogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, a monovalent halogen having 1 to 20 carbon atoms, a hydrocarbon group, a nitro group, a cyano group, a primary to tertiary amino group, or a salt of a primary to tertiary amino group. Each n is independently an integer of 0 to 2. When n is 2, multiple R ^1s may be the same or different, and may be combined in any combination to form a part of the ring structure. ]

R ¹ is a halogen atom, a monovalent hydrocarbon group having 1 to 6 carbon atoms, a monovalent halogenated hydrocarbon group having 1 to 6 carbon atoms, a nitro group, a cyano group, a primary to tertiary amino group, or Salts of primary to tertiary amino groups are preferred, and fluorine atom, chlorine atom, methyl group, nitro group, cyano group, tert-butyl group, phenyl group and amino group are more preferred. n is preferably 0 or 1, more preferably 0.

The position of one bond of the repeating unit with respect to the other bond is not particularly limited, but the meta position is preferred in order to improve the polymerization reactivity of the monomer that provides the repeating unit. Moreover, as the repeating unit, a repeating unit represented by the general formula (1-2) having a pyrimidine skeleton is preferable.

Examples of monomers that give such repeating units include 4,6-dichloropyrimidine, 4,6-dibromopyrimidine, 2,4-dichloropyrimidine, 2,5-dichloropyrimidine, 2,5-dibromopyrimidine, 5-bromo-2-chloropyrimidine, 5-bromo-2-fluoropyrimidine, 5-bromo-2-iodopyrimidine, 2-chloro-5-fluoropyrimidine, 2-chloro-5-iodopyrimidine, 2,4-dichloro -5-fluoropyrimidine, 2,4-dichloro-5-iodopyrimidine, 5-chloro-2,4,6-trifluoropyrimidine, 2,4,6-trichloropyrimidine, 4,5,6-trichloropyrimidine, 2 , 4,5-trichloropyrimidine, 2,4,5,6-tetrachloropyrimidine, 2-phenyl-4,6-dichloropyrimidine, 2-methylthio-4,6-dichloropyrimidine, 2-methylsulfonyl-4,6 -dichloropyrimidine, 5-methyl-4,6-dichloropyrimidine, 2-amino-4,6-dichloropyrimidine, 5-amino-4,6-dichloropyrimidine, 2,5-diamino-4,6-dichloropyrimidine, 4-amino-2,6-dichloropyrimidine, 5-methoxy-4,6-dichloropyrimidine, 5-methoxy-2,4-dichloropyrimidine, 5-fluoro-2,4-dichloropyrimidine, 5-bromo-2, 4-dichloropyrimidine, 5-iodo-2,4-dichloropyrimidine, 2-methyl-4,6-dichloropyrimidine, 5-methyl-4,6-dichloropyrimidine, 6-methyl-2,4-dichloropyrimidine, 5 -methyl-2,4-dichloropyrimidine, 5-nitro-2,4-dichloropyrimidine, 4-amino-2-chloro-5-fluoropyrimidine, 2-methyl-5-amino-4,6-dichloropyrimidine, 5 -bromo-4-chloro-2-methylthiopyrimidine; 3,6-dichloropyridazine, 3,5-dichloropyridazine, 4-methyl-3,6-dichloropyridazine; 2,3-dichloropyrazine, 2,6-dichloropyrazine , 2,5-dibromopyrazine, 2,6-dibromopyrazine, 2-amino-3,5-dibromopyrazine, 5,6-dicyano-2,3-dichloropyrazine and the like. In addition, these monomers may be used individually by 1 type, and may use 2 or more types together.

The content of the repeating units represented by the above general formulas (1-1), (1-2) and (1-3) in the specific polymer is 100 mol% of the total of all repeating units in the specific polymer. , the content is preferably 5 to 95 mol%, more preferably 10 to 60 mol%.

A method for synthesizing the specific polymer is not particularly limited, and a known method can be used. For example, the above general formula (1-1), (1-2) and a monomer that provides at least one repeating unit among the repeating units represented by (1-3), and optionally other monomers It can be synthesized by heating the compound with an alkali metal or the like in an organic solvent.

The lower limit of the weight average molecular weight (Mw) of the specific polymer is preferably 500, more preferably 1,000, even more preferably 10,000, especially 30,000 preferable. The upper limit of the weight average molecular weight (Mw) is preferably 600,000, more preferably 400,000, even more preferably 300,000, and particularly preferably 200,000.

The lower limit of the glass transition temperature (Tg) of the specific polymer is preferably 150°C, more preferably 180°C. The upper limit of the glass transition temperature (Tg) is preferably 320°C, more preferably 300°C.

The specific polymer preferably further has a repeating unit represented by the following general formula (2).

（式（２）中、Ｒ^３及びＲ^４はそれぞれ独立して、ハロゲン原子、ニトロ基、シアノ基又は炭素数１～２０の１価の有機基、ｃ及びｄはそれぞれ独立して０～８の整数、ｅ、ｆ、ｙはそれぞれ独立して０～２の整数、Ｌは、単結合、－Ｏ－、－Ｓ－、－ＣＯ－、－ＳＯ－、－ＳＯ_２－又は炭素数１～２０の２価の有機基である。）

(wherein R ³ and R ⁴ are each independently a halogen atom, a nitro group, a cyano group, or a monovalent organic group having 1 to 20 carbon atoms; c and d are each independently 0 to 8; , e, f, and y are each independently an integer of 0 to 2, L is a single bond, —O—, —S—, —CO—, —SO—, —SO ₂ —, or 1 to 1 carbon atoms 20 divalent organic groups.)

Halogen atoms represented by R ³ and R ⁴ include, for example, fluorine, chlorine, bromine and iodine atoms.

Examples of monovalent organic groups having 1 to 20 carbon atoms represented by R ³ and R ⁴ include monovalent chain hydrocarbon groups, monovalent alicyclic hydrocarbon groups, and monovalent aromatic hydrocarbon groups. A hydrogen group, a monovalent halogenated hydrocarbon group, and the like can be mentioned.

Examples of the monovalent chain hydrocarbon group include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, tert-butyl group, Alkyl groups such as n-pentyl group; alkenyl groups such as ethenyl group, propenyl group, butenyl group and pentenyl group; alkynyl groups such as ethynyl group, propynyl group, butynyl group and pentynyl group;

Examples of the monovalent alicyclic hydrocarbon group include monocyclic cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group and cyclohexyl group; polycyclic cycloalkyl groups such as norbornyl group and adamantyl group; monocyclic cycloalkenyl groups such as cyclopropenyl group, cyclobutenyl group, cyclopentenyl group and cyclohexenyl group; and polycyclic cycloalkenyl groups such as norbornenyl group.

Examples of the monovalent aromatic hydrocarbon group include aryl groups such as phenyl group, tolyl group, xylyl group, naphthyl group and anthryl group; aralkyl groups such as benzyl group, phenethyl group, phenylpropyl group and naphthylmethyl group; etc.

As the monovalent halogenated hydrocarbon group, for example, some or all of the hydrogen atoms of the monovalent hydrocarbon groups having 1 to 20 carbon atoms exemplified as the groups represented by R ³ and R ⁴ are fluorine and groups substituted with halogen atoms such as atoms, chlorine atoms, bromine atoms and iodine atoms.

Examples of the divalent organic group having 1 to 20 carbon atoms represented by L include a divalent chain hydrocarbon group having 1 to 20 carbon atoms and a divalent alicyclic hydrocarbon group having 1 to 20 carbon atoms. group, a divalent fluorinated chain hydrocarbon group having 1 to 20 carbon atoms, a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, or a divalent fluorinated aromatic hydrocarbon group having 6 to 20 carbon atoms etc.

Examples of the divalent chain hydrocarbon group include methylene group, ethylene group, n-propylene group, isopropylene group, n-butylene group, sec-butylene group, t-butylene group, neopentylene group, 4-methyl -pentane-2,2-diyl group, nonane-1,9-diyl group and the like.

Examples of the divalent alicyclic hydrocarbon group include monocyclic cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group and cyclohexyl group; polycyclic cycloalkyl groups such as norbornyl group and adamantyl group; monocyclic cycloalkenyl groups such as cyclopropenyl group, cyclobutenyl group, cyclopentenyl group and cyclohexenyl group; and polycyclic cycloalkenyl groups such as norbornenyl group.

As the divalent fluorinated chain hydrocarbon group, for example, some or all of the hydrogen atoms of the divalent chain hydrocarbon group having 1 to 20 carbon atoms exemplified as the group represented by L are fluorine Atom-substituted groups and the like are included.

Examples of the divalent aromatic hydrocarbon group include aryl groups such as phenyl group, tolyl group, xylyl group, naphthyl group and anthryl group; aralkyl groups such as benzyl group, phenethyl group, phenylpropyl group and naphthylmethyl group; etc.

The content of the repeating unit represented by the general formula (2) in the specific polymer is 5 to 95 mol% when the total of all repeating units in the specific polymer is 100 mol%. It is preferably 10 to 60 mol %, and more preferably 10 to 60 mol %.

Examples of these polymers include the polymers described in JP-A-2015-209511, WO 2016/143447, JP-A-2017-197725, JP-A-2018-024827, and the like.

The content of the polymer in the resin layer composition is preferably 10 parts by mass or more and 90 parts by mass or less with respect to a total of 100 parts by mass of the curable compound and the polymer, which will be described later.

<Curable compound>
The curable compound is a compound that is cured by irradiation with heat or light (e.g., visible light, ultraviolet rays, near-infrared rays, far-infrared rays, electron beams, etc.), and may require a curing aid, which will be described later. . Examples of such curable compounds include epoxy compounds, cyanate ester compounds, vinyl compounds, silicone compounds, oxazine compounds, maleimide compounds, allyl compounds, acrylic compounds, methacrylic compounds, urethane compounds, oxetane compounds, methylol compounds, and propargyl. compound. These may be used individually by 1 type, and 2 or more types may be used together. Among these, at least one of epoxy compounds, cyanate ester compounds, vinyl compounds, silicone compounds, oxazine compounds, maleimide compounds, and allyl compounds is used in order to improve compatibility with the specific polymer and heat resistance. and more preferably at least one of an epoxy compound, a cyanate ester compound, a vinyl compound, an allyl compound, and a silicone compound.

Examples of the epoxy compound include compounds represented by the following formulas (c1-1) to (c1-6). The compound represented by the following formula (c1-6) is epoxy group-containing NBR particles "XER-81" manufactured by JSR Corporation. Further examples of the epoxy compound include polyglycidyl ether of dicyclopentadiene-phenol polymer, phenol novolac type liquid epoxy compound, epoxidized styrene-butadiene block copolymer, and 3′,4′-epoxycyclohexylmethyl-3,4. -epoxycyclohexane carboxylate and the like.

［式（ｃ１－５）中、ｎは０～５０００であり、ｍは独立して、０～５０００である。］

[In the formula (c1-5), n is 0 to 5000, and m is independently 0 to 5000. ]

Examples of the cyanate ester compounds include compounds represented by the following formulas (c2-1) to (c2-7).

［式（ｃ２－６）及び（ｃ２－７）中、ｎは独立して、０～３０である。］

[In formulas (c2-6) and (c2-7), n is independently 0 to 30. ]

Examples of the vinyl compound include compounds represented by the following formulas (c3-1) to (c3-5).

［式（ｃ３－４）中、ｎは１～５０００である。］

[In the formula (c3-4), n is 1 to 5000. ]

Examples of the silicone compound include compounds represented by the following formulas (c4-1) to (c4-16). As R in formula (c4-1), one of the following is selected, and when one having a vinyl group is selected, it can be treated as the vinyl compound, and one having an oxetane group is selected. can be treated as the oxetane compound. In formulas (c4-2) to (c4-16), each R is independently an organic group selected from an alkyl group, an alicyclic hydrocarbon group, an aryl group, and an alkenyl group, and n is 0. It is an integer of up to 1000 (preferably an integer of 0-100).

The alkyl group includes methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, tert-butyl group, n-pentyl group and the like. The alicyclic hydrocarbon group includes monocyclic cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl; polycyclic cycloalkyl groups such as norbornyl and adamantyl; cyclopropenyl and cyclobutenyl. monocyclic cycloalkenyl groups such as , cyclopentenyl group and cyclohexenyl group; and polycyclic cycloalkenyl groups such as norbornenyl group. Aryl groups include phenyl, tolyl, xylyl, naphthyl, and anthryl groups. The alkenyl group includes ethenyl group, 1-propenyl group, 2-propenyl group and the like.

Examples of the oxazine compound include compounds represented by the following formulas (c5-1) to (c5-5).

Examples of the maleimide compound include compounds represented by the following formulas (c6-1) to (c6-5).

［式（ｃ６－２）中、Ｅｔはエチル基であり、式（ｃ６－３）中、ｎは０～３０である。］

[In the formula (c6-2), Et is an ethyl group, and in the formula (c6-3), n is 0 to 30. ]

Examples of the allyl compound include compounds represented by the following formulas (c7-1) to (c7-6). In particular, the allyl compound is preferably a compound having two or more (especially 2 to 6, further 2 to 3) allyl groups.

Examples of the oxetane compound include compounds represented by the following formulas (c8-1) to (c8-3).

［式（ｃ８－１）及び（ｃ８－２）中、括弧で括った繰り返し単位の繰り返し単位数はそれぞれ独立に、０～３０である。］

[In the formulas (c8-1) and (c8-2), the number of repeating units in parenthesized repeating units is independently 0 to 30. ]

Examples of the methylol compound include those described in JP-A-2006-178059 and JP-A-2012-226297. Specifically, for example, melamine-based methylol compounds such as polymethylolated melamine, hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, hexabutoxymethylmelamine; polymethylolated glycoluril, tetramethoxymethylglycoluril, glycoluril-based methylol compounds such as tetrabutoxymethylglycoluril; 3,9-bis[2-(3,5-diamino-2,4,6-triazaphenyl)ethyl]-2,4,8,10-tetra Oxospiro[5.5]undecane, 3,9-bis[2-(3,5-diamino-2,4,6-triazaphenyl)propyl]-2,4,8,10-tetraoxospiro[5 5] Compounds obtained by methylolating guanamine such as undecane, and guanamine-based methylol compounds such as compounds obtained by alkyl-etherifying all or part of the active methylol groups in the compound.

Examples of the propargyl compound include compounds represented by the following formulas (c9-1) to (c9-2).

The content of the curable compound in the composition for the resin layer is preferably 10 parts by mass or more and 90 parts by mass or less, and is preferably 20 parts by mass or more and 80 parts by mass or less with respect to 100 parts by mass of the composition for the resin layer. It is more preferable to have

<Curing aid>
Examples of curing aids include polymerization initiators such as photoreaction initiators (photoradical generators, photoacid generators, photobase generators). Specific examples of curing aids include onium salt compounds, sulfone compounds, sulfonic acid ester compounds, sulfonimide compounds, disulfonyldiazomethane compounds, disulfonylmethane compounds, oximesulfonate compounds, hydrazinesulfonate compounds, triazine compounds, nitrobenzyl compounds, Examples include benzylimidazole compounds, organic halides, metal octylate, disulfones, and the like. These curing aids may be used singly or in combination of two or more regardless of the type.

The content of the curing aid in the composition for the resin layer is preferably 5 parts by mass or more and 20 parts by mass or less, more preferably 5 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the composition for the resin layer. It is more preferable to have

<Solvent>
The resin layer composition may contain a solvent, if necessary. Examples of solvents include amides such as N,N-dimethylacetamide, N,N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, etc. Ester solvents such as γ-butyrolactone and butyl acetate; Ketone solvents such as cyclopentanone, cyclohexanone, methyl ethyl ketone and benzophenone; Ether solvents such as 1,2-methoxyethane and diphenyl ether; 1-methoxy-2- Polyfunctional solvents such as propanol and propylene glycol methyl ether acetate; Examples thereof include dialkoxybenzene (the number of carbon atoms in the alkoxy group; 1 to 4) and trialkoxybenzene (the number of carbon atoms in the alkoxy group; 1 to 4). These solvents may be used singly or in combination of two or more.

When the resin layer composition contains a solvent, it is preferably 2000 parts by mass or less, more preferably 200 parts by mass or less, relative to 100 parts by mass of the resin layer composition excluding the solvent.

<Other ingredients>
The resin layer composition may contain other components as necessary. Other components include, for example, antioxidants, reinforcing agents, lubricants, flame retardants, antibacterial agents, colorants, release agents, foaming agents, and polymers other than the above polymers.

<Method for Preparing Resin Layer Composition>
The method for preparing the resin layer composition is not particularly limited, but for example, a polymer, a curable compound, and optionally other additives (e.g., other components such as a curing aid, a solvent, and an antioxidant). can be prepared by uniformly mixing Moreover, the form of the composition can be liquid, paste, or the like.

1.2. Film Layer The high-frequency circuit laminate according to the present embodiment includes a film layer having a glass transition temperature (Tg) of 150° C. or higher. Film layers include polyimide (PI), polyetherimide (PEI), liquid crystal polymer (LCP), polyethylene naphthalate (PEN), polystyrene (PS), cycloolefin polymer (COP), polyetheretherketone (PEEK), It is preferably one film selected from the group consisting of polyarylene ether ketone (PAEK) and polyphenylene ether (PPE). Among these, polyimide (PI), liquid crystal polymer (LCP), polyethylene naphthalate (PEN), and polyetheretherketone (PEEK) are more preferable, and polyimide (PI) and liquid crystal polymer (LCP) are particularly preferable. Moreover, when the laminate for high-frequency circuits according to the present embodiment has a plurality of film layers, the film layers may be made of the same type of film or different types of films.

Specific examples of polyimide (PI) include trade name "Kapton (registered trademark)" (manufactured by DuPont-Toray Co., Ltd.). Specific examples of polyetherimide (PEI) include trade name "Superio" (manufactured by Mitsubishi Chemical Corporation). Specific examples of the liquid crystal polymer (LCP) include trade name "Vecstar" (manufactured by Kuraray Co., Ltd.). Specific examples of polyethylene naphthalate (PEN) include trade name "Teonex" (manufactured by Teijin Limited). Specific examples of the cycloolefin polymer (COP) include trade name "Zeonor" (manufactured by Nippon Zeon Co., Ltd.). Specific examples of polyetheretherketone (PEEK) include trade name "APTIV" (manufactured by Victex). Specific examples of polyarylene ether ketone (PAEK) include trade name "AvaSpire" (manufactured by Solvay). Specific examples of polyphenylene ether (PPE) include trade name "NORYL" (manufactured by SABIC).

The lower limit of the thickness of the film layer is preferably 10 µm, more preferably 15 µm, and particularly preferably 20 µm. The upper limit of the thickness of the film layer is preferably 300 μm, more preferably 250 μm, still more preferably 200 μm, and particularly preferably 180 μm.

1.3. Metal Layer The laminate for a high-frequency circuit according to this embodiment may include a metal layer in addition to the film layer. As the metal layer, it is preferable to use a metal foil or a sputtered film. A copper foil is preferable as the metal foil. There are electrolytic foil and rolled foil as types of copper foil, and either of them may be used.

The surface roughness Ra of the metal layer is preferably 10 to 300 nm, more preferably 30 to 200 nm, particularly preferably 30 to 100 nm. When the surface roughness Ra of the metal layer is within the above range, the adhesion between the resin layer and the metal layer can be further improved when the laminate for high frequency circuits is produced. Furthermore, the in-plane thickness of the high-frequency circuit laminate can be made more uniform, and peeling of the resin layer and the metal layer can be suppressed when the high-frequency circuit laminate is wound into a roll. can. The surface roughness Ra of the metal layer means "arithmetic mean roughness" measured according to JIS B0601-2001.

The lower limit of the thickness of the metal layer is preferably 3 μm, more preferably 5 μm, particularly preferably 7 μm. The upper limit of the thickness of the metal layer is preferably 50 μm, more preferably 40 μm, particularly preferably 35 μm.

When a metal foil is used as the metal layer, if the surface roughness Ra of the metal foil is within the above range, the thinned metal foil may be used as it is. is controlled within the above range. Methods for controlling the surface roughness of the metal foil include, but are not limited to, etching treatment (acid treatment, etc.), laser treatment, electrolytic plating, electroless plating, sputtering treatment, sandblasting, and the like. not something.

1.4. Method for Manufacturing Laminate for High-Frequency Circuits The method for manufacturing the laminate for high-frequency circuits according to the present embodiment is not particularly limited as long as the resin layer and the film layer can be laminated in contact with each other. "The resin layer and the film layer are in contact" is not limited to the case where one surface of the resin layer is in contact with the entire surface of the film layer, and at least a portion of one surface of the resin layer is in contact with the film layer. Including cases.

A preferable manufacturing example of the high-frequency circuit laminate according to the present embodiment will be described below. It should be noted that even in the middle stages of each production example, any necessary laminate can be used as appropriate.

<Production example A>
1A to 1E are diagrams schematically showing cross sections in each step of Production Example A. FIG. Manufacturing Example A will be described with reference to FIGS. 1A to 1E.

(Step A1)
As shown in FIG. 1A, a resin layer composition is applied onto a film layer 10 to form a B-stage resin layer 12 to produce a "B-stage resin layer/film layer laminate". As the film layer 10, films made of materials such as PI, PEI, LCP, PEN, PS, COP, PEEK, PAEK, and PPE can be used. As for the coating method of the resin layer composition, a known coating method can be used, but it is preferable to adjust the film thickness using a bar coater, for example.

After the resin layer composition is applied to the film layer 10 in this way, it is preferable to form a semi-cured B-stage resin layer 12 using a known heating means such as an oven. The heating temperature is preferably 50 to 150°C, more preferably 70 to 130°C. When heating, the heating may be performed in multiple stages such as 50 to 100.degree. C. and 100 to 150.degree. Also, the total heating time is preferably less than 30 minutes, more preferably less than 20 minutes. A B-stage resin layer 12 with high film thickness uniformity can be produced by heating under conditions of temperature and time within the above ranges.

The surface roughness Ra of the B-stage resin layer 12 exposed on the surface is preferably 1 to 100 nm, more preferably 10 to 50 nm. When the surface roughness Ra of the B-stage resin layer 12 is within the above range, the adhesion between the resin layer and the film layer or between the resin layer and the metal layer can be further improved when manufacturing a laminate for high frequency circuits. The surface roughness Ra of the B-stage resin layer in the present invention means "arithmetic mean roughness" measured according to JIS B0601-2001.

The elastic modulus of the B-stage resin layer 12 preferably has a maximum elastic modulus (MPa) of 1 MPa or higher, more preferably 3 MPa or higher, at 50° C. or higher and lower than 80° C. under the measurement condition of 1 Hz. Also, the minimum value of the elastic modulus (MPa) within the temperature range of 80° C. to 200° C. is preferably 20 MPa or less, more preferably 15 MPa or less. When the elastic modulus of the B-stage resin layer is within each temperature range, when the laminated body for high-frequency circuits is produced by hot pressing, unevenness between the wiring portion and the non-wiring portion can be suppressed, and transmission loss can be suppressed. be able to.

(Step A2)
As shown in FIG. 1B, the exposed resin layer surface 13 and the metal layer 14 of the "B stage resin layer/film layer laminate" produced in step A1 are bonded together to form a "metal layer/B stage resin layer/film layer laminate. Create a "body". The surface roughness Ra of the metal layer 14 bonded to the resin layer surface 13 is preferably 10 to 300 nm, more preferably 30 to 200 nm, and particularly preferably 30 to 100 nm.

When laminating together, the resin layer surface 13 and the metal layer 14 of the "B-stage resin layer/film layer laminate" are superimposed, and then a heated roll (also referred to as a "heat roll" in this specification) is applied. It is preferable to carry out thermocompression bonding using, for example. A line load during thermocompression bonding is preferably 1 to 19 kN/m, more preferably 5 to 18 kN/m. The temperature for thermocompression bonding is preferably 50 to 200.degree. C., more preferably 50 to 150.degree. C., and particularly preferably 70 to 130.degree.

Further, in step A2, the "metal layer/B stage resin layer/film layer laminate" immediately after bonding is subsequently annealed by bringing it into contact with a heated roll or passing it through a heating furnace. may Such annealing treatment may be performed at a temperature equal to or higher than the melting point of the resin, preferably 100 to 250.degree. C., more preferably 110 to 230.degree. The heating time is not particularly limited, but is preferably 5 to 600 seconds, more preferably 10 to 300 seconds. A B-stage resin layer with high film thickness uniformity can be produced by annealing in a short period of time, for example, about 5 to 600 seconds using a hot roll. It should be noted that the above-mentioned "continuously treating the 'metal layer/B stage resin layer/film layer laminate' immediately after bonding" means that the laminated body that has been bonded in the production line for bonding the laminate. It is a step of in-line processing subsequent to the bonding process without removing from the production line.

(Step A3)
As shown in FIG. 1C, a B-stage resin layer 16 is formed on the film layer 10 of the "metal layer/B-stage resin layer/film layer laminate" produced in step A2 in the same manner as in step A1. The material of the B-stage resin layer 16 may be the same as or different from that of the B-stage resin layer 12 .

(Step A4)
As shown in FIG. 1D, a metal layer 18 is laminated on the B-stage resin layer 16 of "metal layer/B-stage resin layer/film layer/B-stage resin layer" produced in step A3 in the same manner as in step A2. A "metal layer/B stage resin layer/film layer/B stage resin layer/metal layer laminate" is produced. In step A4, it is preferable to perform the same crimping step as in step A2.

(Step A5)
As shown in FIG. 1E, the high-frequency circuit laminate 100 is obtained by curing the B-stage resin layers 12 and 16 to form the C-stage resin layers 20 and 22, respectively. In order to cure the B-stage resin layers 12 and 16, the laminate obtained in step A4 is preferably heated to 50 to 200°C using a known heating means such as an oven, and heated to 100 to 200°C. is more preferable. When heating, the heating may be performed in multiple stages such as 50 to 100.degree. C. and 100 to 200.degree. Also, the heating time is preferably less than 5 hours, more preferably less than 3 hours. By heating under conditions of temperature and time within the above ranges, a C-stage resin layer having high film thickness uniformity can be produced by curing the B-stage resin layer.

<Manufacturing example B>
2A to 2C are diagrams schematically showing cross sections in each step of Production Example B. FIG. Manufacturing Example B will be described with reference to FIGS. 2A to 2C.

(Step B1)
As shown in FIG. 2A, a resin layer composition is applied to a metal layer 30 to form a B-stage resin layer 32 to produce a "metal layer/B-stage resin layer laminate". As for the coating method of the resin layer composition, a known coating method can be used, but it is preferable to adjust the film thickness using a bar coater, for example.

After the resin layer composition is applied to the metal layer 30 in this way, it is preferable to form a semi-cured B-stage resin layer 32 using a known heating means such as an oven. The heating temperature is preferably 50 to 150°C, more preferably 70 to 130°C. When heating, the heating may be performed in multiple stages such as 50 to 100.degree. C. and 100 to 150.degree. Also, the total heating time is preferably less than 30 minutes, more preferably less than 20 minutes. A B-stage resin layer 32 with high film thickness uniformity can be produced by heating under conditions of temperature and time within the above ranges.

(Step B2)
As shown in FIG. 2B, two “metal layer/B stage resin layer laminates” prepared in step B1 were prepared, and the “metal layer/B stage resin layer laminate” was exposed on both sides of the film layer 34. The resin layer surfaces 33 are bonded together to produce a "metal layer/B stage resin layer/film layer/B stage resin layer/metal layer laminate". When the film layer 34 is attached to the exposed resin layer surface 33, it is preferable that the exposed resin layer surface 33 and the film layer 34 are superimposed and then heat-pressed using a hot roll or the like. Moreover, the conditions similar to said process A2 are preferable for thermocompression-bonding.

Further, in step B2, the "metal layer/B stage resin layer/film layer/B stage resin layer/metal layer laminate" immediately after bonding is subsequently brought into contact with a heated roll or passed through a heating furnace. By doing so, annealing may be performed. The annealing treatment is preferably performed under the same conditions as in step A2 above.

The surface roughness Ra of the exposed resin layer surface 33 is preferably 1 to 100 nm, more preferably 10 to 50 nm. When the surface roughness Ra of the B-stage resin layer is within the above range, it is possible to further improve the adhesion between the resin layer and the film layer when producing a laminate for high frequency circuits. Also, the glass transition temperature (Tg) of the film layer 34 bonded to the resin layer surface 33 is preferably 150° C. or higher, more preferably 160° C. or higher, and particularly preferably 170° C. or higher.

(Step B3)
As shown in FIG. 2C, the high-frequency circuit laminate 200 is obtained by curing the B-stage resin layer 32 to form the C-stage resin layer 36 . In step B3, the "metal layer/B stage resin layer/film layer/B stage resin layer/metal layer laminate" prepared in step B2 can be heated to 50 to 200°C using a known heating means such as an oven. Heating at 100 to 200° C. is more preferable. When heating, for example, the heating may be performed in two steps such as 50 to 100°C and 100 to 200°C. Also, the heating time is preferably less than 5 hours, more preferably less than 3 hours. By heating under the temperature and time conditions within the above ranges, the C-stage resin layer 36 having high film thickness uniformity can be produced by curing the B-stage resin layer 32 .

2. Laminate roll The laminate roll according to the present embodiment includes a structure in which a film layer having a glass transition temperature (Tg) of 150°C or higher and a resin layer containing a specific polymer are laminated in contact with each other. The high-frequency circuit laminate is wound around a core having a radius of 10 to 100 mm.

Hereinafter, a laminate wound body according to the present embodiment will be described with reference to the drawings.

FIG. 3 is a perspective view showing an example of the laminate roll according to this embodiment. FIG. 4 is a perspective view showing an example of a winding core that can be used in this embodiment. As shown in FIG. 3 , the laminate wound body 300 according to the present embodiment includes a core 40 and a high frequency circuit laminate 50 wound around the core 40 . Such a high-frequency circuit laminate is used or stored in the form of a long sheet having a constant width and wound around a core for efficient processing. It is common to

It is preferable to use a substantially cylindrical winding core for the laminated body wound body according to the present embodiment. In this case, by reducing the radius of the cylindrical winding core and making the radius of curvature as small as possible, it is possible to further reduce the size of the roll wound with the high-frequency circuit laminate of the same length, thereby improving productivity. can be improved. However, in the case of a laminated body wound with a small radius of curvature, curling tends to remain in the high-frequency circuit laminated body, which tends to make it difficult to process the high-frequency circuit laminated body. For this reason, it has been difficult to reduce the curvature radius of the laminated body for suppressing the curl remaining in the laminated body for high-frequency circuits.

Further, conventional laminates for high-frequency circuits have an adhesive layer interposed therebetween in order to improve the adhesion between the resin layer and the film layer. For this reason, when a laminate roll obtained by winding a conventional laminate for high-frequency circuits around a core is stored, the adhesive layer is deteriorated and hardened due to an external factor, so that when the laminate is pulled out, there is a tendency to curl. was likely to occur.

However, the laminate roll according to the present embodiment includes a structure in which a film layer having a glass transition temperature (Tg) of 150 ° C. or higher and a resin layer containing a specific polymer are laminated in contact with each other. By using the laminate, it has become possible to produce a compact wound laminate for high-frequency circuits, which is wound around a core with a radius of 10 to 100 mm.

The winding core 40 and the high-frequency circuit laminate 50 may or may not be joined using a joining member. For example, as shown in FIG. 4, when the winding core 40 has a stepped portion 42, the end portion of the high-frequency circuit laminate 50 is joined to the stepped portion 42 of the winding core 40 via a joining member, and then the winding core 40 is attached. By rotating the high-frequency circuit laminate 50 , the laminate roll 300 can be produced. As for the winding core having the stepped portion, for example, the winding core described in Japanese Utility Model Registration No. 3147706 can be used.

The type of joining member is not particularly limited, and various joining members can be used. For example, adhesives, adhesives, double-sided tapes, and the like can be used. These may use only 1 type and may use 2 or more types together. Moreover, this joining member may join the entire length of the high-frequency circuit laminate 50 in the width direction to the winding core 40, or may join only a part thereof.

The radius of the winding core 40 is 10 to 100 mm, preferably 10 to 50 mm, more preferably 15 to 40 mm. When the radius of the winding core 40 is within the above range, when the high-frequency circuit laminate 50 is pulled out from the laminate wound body 300 and processed, the joint portion (wound portion) between the high-frequency circuit laminate 50 and the winding core 40 It is possible to effectively suppress the formation of the impression 51 as shown in FIG. Such impressions 51 are one of the curls that should be suppressed as much as possible in order to improve productivity, since such impressions 51 are a major factor in lowering the yield during processing of the laminate for high-frequency circuits.

The height of the step portion 42 is preferably 50-300 μm, more preferably 60-180 μm, and particularly preferably 70-150 μm. Moreover, it is particularly preferable that the height of the step portion 42 is within the thickness (μm) of the high-frequency circuit laminate 50±10 μm. When the height of the stepped portion 42 is within the above range, the stepped portion at the junction between the stepped portion 42 of the core 40 and the high-frequency circuit laminate 50 is eliminated. Formation can be suppressed more effectively.

The material of the winding core 40 is not particularly limited, but examples thereof include paper, metal, thermoplastic resin, and the like. When the material of the core 40 is paper, the surface may be coated with resin or the like. Examples of metals include SUS, iron, and aluminum. Thermoplastic resins include olefin resins (polyethylene, polypropylene, etc.), styrene resins (ABS resin, AES resin, AS resin, MBS resin, polystyrene, etc.), polyvinyl chloride, vinylidene chloride resins, methacrylic resins, polyvinyl alcohol. , styrene block copolymer resin, polyamide, polyacetal, polycarbonate, modified polyphenylene ether, polyester (polybutylene terephthalate, polyethylene terephthalate, etc.), fluororesin, polyphenylene sulfide, polysulfone, amorphous polyarylate, polyetherimide, polyethersulfone, poly Ether ketones, liquid crystal polymers, polyamideimides, thermoplastic polyimides, syndio-type polystyrene, and the like. These may use only 1 type and may use 2 or more types together. When the material of the winding core 40 is a thermoplastic resin, the winding core 40 and its stepped portion 42 can be produced by extrusion molding or cutting molding.

The method of winding the laminated body for high-frequency circuits into a roll is not particularly limited, and may be in accordance with the method used in the production of the laminated body for high-frequency circuits or the film.

3. Circuit board (flexible printed circuit board)
A circuit board such as an FPC can be manufactured using the above-described high-frequency circuit laminate of the present invention. Such a circuit board can reduce transmission loss even when driven at a high frequency by using the high-frequency circuit laminate of the present invention as at least a part of the laminate structure. Such a circuit board may be provided with the high-frequency circuit laminate of the present invention as part of the laminate structure, and can be produced by a known method. It can be manufactured by applying the manufacturing process described in JP-A-231770 or the like.

Manufacture a circuit board by laminating the high-frequency circuit laminate of the present invention, patterning the metal layer of the high-frequency circuit laminate of the present invention by etching, drilling holes, cutting to a required size, etc. can do.

Since such a circuit board does not have an adhesive layer interposed therebetween, the resin layer covering the metal wiring layer, which is a convex portion, does not form a large step, and the surface of the resin layer becomes smooth. Therefore, even if the circuits are stacked, high positioning accuracy can be satisfied, and circuits with more layers can be integrated.

Such a circuit board may, for example,
- Step (a): a step of laminating a resin film on a circuit substrate to form a resin layer;
- Step (b): a step of flattening the resin layer by heating and pressurizing it;
- Step (c): a step of further forming a circuit layer on the resin layer;
etc. can be manufactured.

The method of laminating the resin film on the circuit board in the step (a) is not particularly limited, but examples thereof include a method of laminating using a multistage press, a vacuum press, a normal pressure laminator, and a laminator that heats and presses under vacuum. A method using a laminator that heats and presses under vacuum is preferred. As a result, even if the circuit substrate has fine wiring circuits on its surface, the gaps between the circuits can be filled with resin without voids. Although the lamination conditions are not particularly limited, it is preferable to laminate at a compression temperature of 70 to 130° C. and a compression pressure of 1 to 11 kgf/cm ² under reduced pressure or vacuum. Lamination may be batchwise or continuous on rolls.

The circuit substrate is not particularly limited, and glass epoxy substrates, metal substrates, polyester substrates, polyimide substrates, BT resin substrates, thermosetting polyphenylene ether substrates, fluorine resin substrates, etc. can be used. The surface of the circuit board on which the resin film is laminated may be roughened in advance. Moreover, the number of circuit layers of the circuit board is not limited. For example, when manufacturing a printed wiring board for millimeter wave radar, it is possible to freely select from 2 to 20 layers according to the design.

In step (b), the resin film laminated in step (a) and the circuit board are heated and pressurized to flatten them. Although the conditions are not particularly limited, a temperature of 100°C to 250°C, a pressure of 0.2 to 10 MPa, and a time of 30 to 120 minutes are preferable, and 150°C to 220°C are more preferable.

In the step (c), a circuit layer is further formed on the resin layer produced by heating and pressurizing the resin film and circuit board. The method of forming the circuit layer formed on the resin layer in this manner is not particularly limited, and may be formed, for example, by an etching method such as a subtractive method, a semi-additive method, or the like.

In the subtractive method, an etching resist layer having a shape corresponding to the desired pattern shape is formed on the metal layer, and the metal layer where the resist has been removed is dissolved and removed with a chemical solution by subsequent development processing. is a method of forming a desired circuit.

In the semi-additive method, a metal film is formed on the surface of a resin layer by electroless plating, a plating resist layer having a shape corresponding to a desired pattern is formed on the metal film, and then a metal layer is formed by electrolytic plating. After that, the unnecessary electroless plating layer is removed with a chemical solution or the like to form a desired circuit layer.

Moreover, holes such as via holes may be formed in the resin layer as necessary. A hole forming method is not limited, but NC drill, carbon dioxide laser, UV laser, YAG laser, plasma, etc. can be applied.

4. Examples Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited to these examples. "Parts" and "%" in Examples and Comparative Examples are based on mass unless otherwise specified.

4.1. Synthesis of Polymer <Synthesis Example 1>
1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (BisTMC) (18.6 g, 60.0 mmol), 4,6- Dichloropyrimidine (Pym) (8.9 g, 60.0 mmol) and potassium carbonate (11.1 g, 81.0 mmol) were weighed, N-methyl-2-pyrrolidone (64 g) was added, and the temperature was maintained at 130°C under a nitrogen atmosphere. was reacted for 6 hours. After completion of the reaction, N-methyl-2-pyrrolidone (368 g) was added, the salt was removed by filtration, and this solution was poured into methanol (9.1 kg). The precipitated solid was filtered off, washed with a small amount of methanol, filtered again and collected, dried under reduced pressure at 120 ° C. for 12 hours using a vacuum dryer, and the structure represented by the following formula (P-1) A polymer P-1 having units was obtained (yield: 20.5 g, yield: 90%, weight average molecular weight (Mw): 32,000, glass transition temperature (Tg): 206°C).

The glass transition temperature (Tg) is measured using a dynamic viscoelasticity measuring device (manufactured by Seiko Instruments Inc., "DMS7100") at a frequency of 1 Hz and a heating rate of 10 ° C./min. temperature. The loss tangent was obtained by dividing the storage modulus by the loss modulus.

Further, the weight average molecular weight (Mw) was measured using a GPC apparatus (“HLC-8320 type” manufactured by Tosoh Corporation) under the following conditions.
Column: Tosoh's "TSKgel α-M" and Tosoh's "TSKgel guard column α" Developing solvent: N-methyl-2-pyrrolidone Column temperature: 40°C
Flow rate: 1.0 mL/min Sample concentration: 0.75% by mass
Sample injection volume: 50 μL
Detector: Differential refractometer Standard substance: Monodisperse polystyrene

<Synthesis Example 2>
1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (BisTMC) (10.7 g, 34.5 mmol), 3,6- Dichloropyridazine (Pyd) (5.1 g, 34.2 mmol) and potassium carbonate (6.5 g, 47.0 mmol) were weighed, N-methyl-2-pyrrolidone (36 g) was added, and the temperature was maintained at 145°C under a nitrogen atmosphere. was reacted for 9 hours. After completion of the reaction, N-methyl-2-pyrrolidone (150 g) was added for dilution, and after removing salts by filtration, this solution was poured into methanol (3 kg). The precipitated solid was filtered, washed with a small amount of methanol, filtered again and collected, dried under the same conditions as in Synthesis Example 1, and polymer P having a structural unit represented by the following formula (P-2): -2 was obtained (yield 7.6 g, yield 48%, weight average molecular weight (Mw); 30,000, glass transition temperature (Tg); 232°C). The weight average molecular weight and glass transition temperature were measured in the same manner as in Synthesis Example 1.

<Synthesis Example 3>
1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (BisTMC) (18.6 g, 60.0 mmol), 4,6- Dichloro-2-phenylpyrimidine (PhPym) (13.7 g, 61.1 mmol) and potassium carbonate (11.4 g, 82.5 mmol) were weighed, N-methyl-2-pyrrolidone (75 g) was added, and a nitrogen atmosphere was added. The mixture was reacted at 130° C. for 6 hours. After completion of the reaction, N-methyl-2-pyrrolidone (368 g) was added for dilution, and after removing salts by filtration, this solution was poured into methanol (9.1 kg). The precipitated solid was filtered off, washed with a small amount of methanol, filtered again and collected, dried under the same conditions as in Synthesis Example 1, and polymer P having a structural unit represented by the following formula (P-3): -3 was obtained (yield 20.5 g, yield 90%, weight average molecular weight (Mw); 187,000, glass transition temperature (Tg); 223°C). The weight average molecular weight and glass transition temperature were measured in the same manner as in Synthesis Example 1.

<Synthesis Example 4>
1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (BisTMC) (12.4 g, 40.0 mmol), 2,2- bis(4-hydroxyphenyl)-propane (BisA) (2.3 g, 10.0 mmol), 1,1-bis(4-hydroxyphenyl)-nonane (BisP-DED) (3.3 g, 10.0 mmol), 4,6-dichloro-2-phenylpyrimidine (PhPym) (13.7 g, 61.1 mmol) and potassium carbonate (11.4 g, 82.5 mmol) were weighed in and N-methyl-2-pyrrolidone (75 g) was added. In addition, they were reacted at 130° C. for 6 hours under a nitrogen atmosphere. After completion of the reaction, N-methyl-2-pyrrolidone (368 g) was added for dilution, and after removing salts by filtration, this solution was poured into methanol (9.1 kg). The precipitated solid was filtered, washed with a small amount of methanol, filtered again and collected, dried under the same conditions as in Synthesis Example 1, and the polymer P having a structural unit represented by the following formula (P-4): -4 was obtained (yield 23.5 g, yield 87%, weight average molecular weight (Mw); 165,000, glass transition temperature (Tg); 196°C). The weight average molecular weight and glass transition temperature were measured in the same manner as in Synthesis Example 1.

<Synthesis Example 5>
1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (BisTMC) (12.4 g, 40.0 mmol), 4,4′ was added to a four-necked separable flask equipped with a stirrer. -(1,3-dimethylbutylidene)bisphenol (BisP-MIBK) (2.7 g, 10.0 mmol), 1,1-bis(4-hydroxyphenyl)-nonane (BisP-DED) (3.3 g, 10 .0 mmol), 4,6-dichloro-2-phenylpyrimidine (PhPym) (13.7 g, 61.1 mmol), and potassium carbonate (11.4 g, 82.5 mmol) were weighed into N-methyl-2-pyrrolidone. (75 g) was added and reacted at 130° C. for 6 hours under nitrogen atmosphere. After completion of the reaction, N-methyl-2-pyrrolidone (368 g) was added for dilution, and after removing salts by filtration, this solution was poured into methanol (9.1 kg). The precipitated solid was filtered, washed with a small amount of methanol, filtered again and collected, dried under the same conditions as in Synthesis Example 1, and polymer P having a structural unit represented by the following formula (P-5). -5 was obtained (yield 23.8 g, yield 88%, weight average molecular weight (Mw); 157,000, glass transition temperature (Tg); 190°C). The weight average molecular weight and glass transition temperature were measured in the same manner as in Synthesis Example 1.

4.2. Example 1
4.2.1. Preparation of B-stage resin layer / release layer laminate 50 parts of polymer P-1, 50 parts of 2,2'-bis (4-cyanatophenyl) propane (manufactured by Tokyo Chemical Industry Co., Ltd.) as a curable compound, and cured 5 parts of 1-benzyl-2-methylimidazole (manufactured by Mitsubishi Chemical Corporation, product name “BMI 12”) as an auxiliary agent and 160 parts of cyclopentanone were mixed to prepare a resin layer composition.

As a release layer, the resin layer composition prepared above so that the film thickness after curing is 25 μm on a 100 μm thick PET film (manufactured by Teijin Film Solution Co., Ltd., Teijin Tetoron Film G2) is coated with a bar coater. and heated at 70 ° C. for 10 minutes using an oven, then heated at 130 ° C. for 10 minutes, and the B stage resin layer was laminated on the PET film "B stage resin layer / release layer lamination got a body

<Surface roughness Ra>
The surface of the resin layer of the "B stage resin layer / peeling layer laminate" obtained above was measured using a white interference microscope (New View 5032 manufactured by ZYGO), and 10 μm in accordance with JIS B0601-2001. The "arithmetic mean roughness" calculated for the range of ×10 μm was defined as the surface roughness Ra. Table 1 shows the results.

<Measurement of elastic modulus of resin layer at 50°C to 200°C>
Peel off the release layer (PET film) from the "B stage resin layer / release layer laminate" obtained above, cut out a test piece (width 3 mm × length 2 cm), DMS tester (manufactured by Seiko Instruments Inc.) At 1 Hz, 10 ° C./min, the maximum value of the elastic modulus (MPa) in the temperature range of 50 ° C. or higher and lower than 80 ° C. and the elastic modulus (MPa) in the temperature range of 80 ° C. or higher and 200 ° C. or lower was measured. Table 1 shows the results.

4.2.2. Preparation of B-stage resin layer/film layer laminate As a film, on a 25 μm thick PI film (manufactured by Toray DuPont, Kapton EN), the resin layer prepared above so that the film thickness after curing is 5 μm The composition was coated using a bar coater, heated at 70 ° C. for 10 minutes using an oven, and then heated at 130 ° C. for 10 minutes to form a B-stage resin layer laminated on the PI film. A "stage resin layer/film layer laminate" was obtained.

4.2.3. Preparation of metal layer / B stage resin layer / film layer laminate On the exposed resin layer of the "B stage resin layer / film layer laminate" obtained above, a copper foil with a thickness of 18 µm (manufactured by Mitsui Kinzoku Co., Ltd., Model number "TQ-M4-VSP", surface roughness 110 nm) are superimposed and further pressed with a hot roll at 150 ° C under the condition of a line load of 10 kN / m to form a laminated structure of copper foil / B stage resin layer / film layer. A "metal layer/B stage resin layer/film layer laminate" having The surface roughness Ra of the copper foil was measured using a white interference microscope (New View 5032 manufactured by ZYGO), and was calculated for a range of 10 μm × 10 μm according to JIS B0601-2001. ” was taken as the surface roughness Ra. Table 1 shows the results.

<Surface roughness Ra after film layer peeling>
The film layer was peeled off from the "metal layer/B stage resin layer/film layer laminate" obtained above, and the surface of the exposed resin layer was measured using a white interference microscope (New View 5032 manufactured by ZYGO). The "arithmetic mean roughness" calculated for a range of 10 μm×10 μm in accordance with JIS B0601-2001 was defined as the surface roughness Ra. Table 1 shows the results.

4.2.4. Production of metal layer/B stage resin layer/film layer/B stage resin layer laminate The resin layer prepared above on the film surface of the "metal layer/B stage resin layer/film layer laminate" obtained above was applied using a bar coater so that the film thickness after curing was 5 μm, heated in an oven at 70° C. for 10 minutes, and further heated at 130° C. for 10 minutes to form a film layer. A B-stage resin layer was laminated thereon to prepare a "metal layer/B-stage resin layer/film layer/B-stage resin layer laminate".

4.2.5. Production of metal layer/B stage resin layer/film layer/B stage resin layer/metal layer laminate Outside B of "metal layer/B stage resin layer/film layer/B stage resin layer laminate" obtained above A copper foil with a thickness of 18 μm (manufactured by Mitsui Kinzoku Co., Ltd., model number “TQ-M4-VSP”, surface roughness: 110 nm) is superimposed on the stage resin layer, and further heated with a hot roll at 150° C. under the condition of a line load of 10 kN/m. It was pressed to produce a "metal layer/B stage resin layer/film layer/B stage resin layer/metal layer laminate".

4.2.6. Preparation and Evaluation of High-Frequency Circuit Laminate The "metal layer/B stage resin layer/film layer/B stage resin layer/metal layer laminate" obtained above was heated with a hot roll at 150° C. under the condition of a line load of 10 kN/m. and then heated at 250 ° C. for 3 hours using an oven to laminate the C stage resin layer on both sides of the film layer "copper foil (thickness 18 μm) / C stage resin layer (thickness 5 μm) / A high-frequency circuit laminate having a laminated structure of film layer (25 μm)/C-stage resin layer (5 μm thick)/copper foil (18 μm thick) was produced. The surface roughness Ra of the copper foil (metal layer) was measured using a white interference microscope (New View 5032 manufactured by ZYGO), and was calculated for a range of 10 μm × 10 μm in accordance with JIS B0601-2001. Arithmetic mean roughness" was taken as the surface roughness Ra. Table 1 shows the results.

<Peel strength>
A test piece (width 1 cm x length 10 cm) was cut out from the produced high-frequency circuit laminate, and using "Instron 5567" manufactured by Instron, the metal layer was pulled in the direction of 90 degrees at 500 mm / min, and "IPC-TM -650 2.4.9" to measure the peel strength. Next, after further peeling off the C-stage resin layer from the high-frequency circuit laminate from which the metal layer was peeled off, the film layer was pulled in a 90-degree direction under the same conditions as when the metal layer was peeled off. The peel strength was measured according to TM-650 2.4.9. Table 1 shows the results.

4.2.7. Evaluation of C stage resin properties <Tensile strength and tensile elongation>
The resin layer composition prepared above was coated on the metal layer using a bar coater so that the film thickness after curing was 20 μm, heated at 70° C. for 10 minutes using an oven, and then heated at 70° C. for 10 minutes. C. for 10 minutes to prepare a "metal layer/B stage resin layer laminate". Further, the high-frequency circuit laminate heated at 250° C. for 3 hours in an oven was etched to remove the copper foil, thereby taking out the C-stage resin layer, which was used as a resin film for evaluation. A JIS K 7161 No. 7 dumbbell-shaped test piece is cut out from the prepared resin film, and is pulled at 5 mm/min using "Ez-LX" manufactured by Shimadzu Corporation. bottom. Table 1 shows the results.

<Glass transition temperature (Tg)>
A test piece (3 mm wide x 1 cm long) was cut out from the resin film prepared above, and the glass transition temperature (Tg) was measured with a DMS tester (manufactured by Seiko Instruments Inc., model number "EXSTAR4000"). Table 1 shows the results.

<Elastic modulus>
A JIS K 7161 No. 7 dumbbell was cut out from the resin film prepared above, and a tensile test was performed at 5 mm/min according to JIS K 7161 using "Ez-LX" manufactured by Shimadzu Corporation to measure the tensile modulus. . Table 1 shows the results.

<Electrical properties (relative permittivity, dielectric loss tangent)>
A test piece (width 2.6 mm × length 80 mm) is cut out from the resin film prepared above, and a cavity resonator perturbation method dielectric constant measurement device (manufactured by Agilent Technologies, model number “PNA-L network analyzer N5230A”, Kanto Denshi application The relative permittivity and dielectric loss tangent were measured at 23° C. and 10 GHz using model number “CP531 for cavity resonator 10 GHz” manufactured by Kaihatsu Co., Ltd. The results are shown in Table 1.

4.2.8. Preparation and Evaluation of Laminate Winding Body The high-frequency circuit laminate prepared above was attached to a cardboard core having a width of 250 mm and a core radius of 40 mm, and a double-sided tape having a thickness of 10 μm was attached to the center in the width direction over a length of 100 mm. attached. Then, after bonding the produced high-frequency circuit laminate to a double-sided tape, 1,000 layers of the high-frequency circuit laminate were wound around a winding core at a winding tension of 150 N/m to produce a laminate roll.

After the high-frequency circuit laminate wound around the laminate wound body thus produced was stored at 25° C. for one month, the laminate was completely unwound from the winding core. After that, the curl of the unwound laminate was visually evaluated. When no curl was observed, it was judged as "good", and when the curl was severe and practical use was not possible, it was judged as "poor". Table 1 shows the results.

4.2.9. Production and Evaluation of Circuit Board On one side of the high-frequency circuit laminate produced above, a copper foil was patterned using a photosensitive dry film, and the pitch was 150 μm and the line widths were 40, 45, 50, 55, and 60 μm, respectively. and copper wiring patterns with a pitch of 750 μm and line widths of 200, 220, 240, 260 and 280 μm, respectively. Then, the "B stage resin layer/release layer laminate" prepared above is placed on the surface of the prepared copper wiring pattern so that the B stage resin layer side is in contact with the copper wiring of the patterned high frequency circuit laminate. , Place a panel on top of it, heat and pressure mold under press conditions of 120°C/3.0 MPa/5 minutes, peel off the release layer (PET film) and heat at 250°C for 3 hours to produce a circuit board. bottom.

<Transmission loss evaluation>
For the circuit board produced above, the transmission loss at a frequency of 20 GHz at 25° C. was measured using a measurement probe (manufactured by Cascade Microtech, single (ACP40GSG250), vector type network analyzer (Keysight technology E8363B). Transmission loss is − A value of 5 dB/100 mm or more was judged to be good.

<Substrate level difference evaluation>
Both sides of the laminate for high-frequency circuits prepared above are subjected to double-sided etching so that the copper foil has a thickness of 9 μm, and the copper foil is patterned using a photosensitive dry film, so that the pitch is 100 μm and the line width is 50 μm. A copper wiring pattern was produced.
Next, the release layer (PET film) is peeled off from the "metal layer/B stage resin layer/release layer laminate" prepared above, and the resin layer exposed by peeling is in contact with the prepared copper wiring pattern. , sandwiched between end plates, heated and pressurized under press conditions of 120° C./1.1 MPa/2 minutes, and further heated at 250° C. for 3 hours.
Thereafter, the copper foil was patterned using a photosensitive dry film to form copper wiring patterns with a pitch of 100 μm and a line width of 50 μm on both sides.
Finally, the release layer (PET film) was peeled off from the "B stage resin layer/release layer laminate" prepared above, and the resin layer on the release surface and the prepared copper wiring pattern were placed on both sides so that they were in contact with each other. Then, it was further sandwiched between end plates, heat-pressed under press conditions of 120° C./1.1 MPa/2 min, and further heated at 250° C. for 3 hours to prepare an evaluation board having four layers of copper wiring.

The cross-sectional shape of the prepared evaluation substrate is observed using a scanning electron microscope. If the difference between the concave and convex portions is 5% or less, it is judged to be practical and good, and if it exceeds 5%, it is not practical. It was judged to be bad. Table 1 shows the results.

4.3. Examples 2-6, 9 and Comparative Examples 1-3
Example 1 except that the resin layer composition was changed to the composition shown in Table 1, and the types of metal layers and film layers, various film thicknesses, lamination conditions, and conditions for producing the laminated body roll were changed as shown in Table 1. A laminate for high-frequency circuits was produced and evaluated in the same manner as in the above. Table 1 shows the results.

4.4. Example 7
On a 18 μm thick copper foil (manufactured by Mitsui Kinzoku Co., Ltd., model number “TQ-M4-VSP”, surface roughness 110 nm), so that the film thickness after curing is 15 μm, the resin layer composition described in Table 1 The object is coated using a bar coater, heated at 70 ° C. for 10 minutes using an oven, and then heated at 130 ° C. for 10 minutes to form a "metal layer" having a laminated structure of copper foil / B stage resin layer. /B stage resin layer laminate” was produced.

On the other hand, as a film, a 75 μm thick PAEK film (manufactured by Solvay, AvaSpire) is coated with the resin layer composition described in Table 1 using a bar coater so that the film thickness after curing is 15 μm. After heating at 70 ° C. for 10 minutes using an oven, it is further heated at 130 ° C. for 10 minutes to obtain a "B stage resin layer / film layer laminate" in which the B stage resin layer is laminated on the PAEK film. Obtained. A 18 μm thick copper foil (manufactured by Mitsui Kinzoku Co., Ltd., model number “TQ-M4-VSP”, surface roughness 110 nm) is overlaid on the exposed resin layer of the obtained “B-stage resin layer/film layer laminate”. Combined and further pressed with a hot roll at 150° C. under the condition of a line load of 10 kN/m to obtain a “metal layer/B stage resin layer/film layer laminate” having a laminated structure of copper foil/B stage resin layer/film layer. made.

The "metal layer/B stage resin layer/film layer laminate" prepared above is superimposed on the exposed resin layer surface of the prepared "metal layer/B stage resin layer laminate", and a hot roll is applied at 150°C. Press under the condition of a line load of 10 kN / m, then heat at 250 ° C. for 3 hours using an oven, "copper foil (film thickness 18 μm) / C stage resin layer (film thickness 15 μm) / film layer (film thickness 75 μm )/C-stage resin layer (15 μm)/copper foil (thickness 18 μm)”. The high-frequency circuit laminate thus produced was evaluated in the same manner as in Example 1. Table 1 shows the results.

4.5. Example 8, Comparative Example 4
A resin layer composition was prepared in the same manner as in Example 1 so as to have the composition shown in Table 1, and a high-frequency circuit laminate was produced in the same manner as in Example 7 using the resin layer composition. The high-frequency circuit laminate thus produced was evaluated in the same manner as in Example 1. Table 1 shows the results.

4.6. Comparative example 5
A 25 μm thick polyimide film (trade name “Kapton 100H” manufactured by Toray DuPont Co., Ltd.) was used as the film layer. In addition, instead of the resin layer composition, maleic acid-modified styrene - ethylene butylene - styrene block copolymer (manufactured by Asahi Kasei Chemicals, trade name "Tuftec M1913") for preparing the adhesive layer was used. A high-frequency circuit laminate was produced in the same manner as in Example 1. The high-frequency circuit laminate thus produced was evaluated in the same manner as in Example 1. Table 1 shows the results.

4.7. Evaluation Results Table 1 shows the composition of the resin layer composition used in each example and each comparative example, the evaluation results of each layer, the high-frequency circuit laminate, and the laminate roll.

In Table 1 above, the following abbreviations, etc. are supplemented.
<Polymer>
・ SEBC: maleic acid-modified styrene-ethylene butylene-styrene block copolymer (manufactured by Asahi Kasei Chemicals, trade name “Tuftec M1913”)
<Curable compound>
- Compound A: 2,2'-bis (4-cyanatophenyl) propane (manufactured by Tokyo Chemical Industry Co., Ltd.)
- Compound B: SR-16H (manufactured by Sakamoto Yakuhin Kogyo Co., Ltd., epoxy equivalent: 160 g / eq)
- Compound C: HP-4032D (manufactured by DIC, epoxy equivalent; 141 meq / g)
- Compound D: SR-4PG (manufactured by Sakamoto Yakuhin Kogyo Co., Ltd., epoxy equivalent: 305 g / eq)
<Curing aid>
- Curing aid A: 1-benzyl-2-methylimidazole (manufactured by Mitsubishi Chemical Corporation, product name "BMI 12")
・ Curing aid B: Zinc 2-ethyloctylate (manufactured by Wako Pure Chemical Industries, Ltd.)
<Solvent>
- Solvent A: cyclopentanone (manufactured by Tokyo Chemical Industry Co., Ltd.)
・ Solvent B: methylene chloride (manufactured by Tokyo Chemical Industry Co., Ltd.)
<Type of metal layer>
・Electrolytic copper foil A: manufactured by Mitsui Kinzoku Co., Ltd., product number “TQ-M4-VSP”
・Electrolytic copper foil B: manufactured by Mitsui Kinzoku Co., Ltd., product number “3EC-M3S-HTE”
・ Rolled copper foil A: JX Metals Co., Ltd., product number “GHY5-HA”
<Film layer type>
・PI: manufactured by DuPont Toray Co., Ltd., trade name “Kapton 100H”, polyimide ・LCP: manufactured by Kuraray Co., Ltd., trade name “Vecstar”, liquid crystal polymer ・PEEK: manufactured by Solvay Co., Ltd., trade name “KT-820”, polyether ether ketone・Special polystyrene: Made by Kurabo Industries, trade name “Oidis”
・PEI: manufactured by Solvay, trade name “Ajedium”, polyetherimide ・PEN: manufactured by Teijin, trade name “Teonex”, polyethylene naphthalate ・PAEK: manufactured by Solvay, trade name “AV-630”, polyarylene ether Ketone/PPE: manufactured by Sabic, trade name “Nory EFR-735” Polyphenylene oxide/PET: manufactured by Teijin Film Solutions, trade name “Teijin Tetron”, polyethylene terephthalate

From the results in Table 1, when a circuit board is produced using the high-frequency circuit laminates obtained in Examples 1 to 8, the transmission loss of electrical signals in the high-frequency circuit is reduced, and a circuit board with excellent smoothness is produced. It turns out you can.

Further, from the results of Table 1, the laminated body wound bodies obtained in Examples 1 to 8 are stored by winding the laminated body for high frequency circuits, which reduces the transmission loss of electric signals in the high frequency circuit, around the winding core. It was found that curling can be effectively suppressed even in the case of

10 Film layer 11 Resin layer surface (exposed surface) 12 16 B stage resin layer 13 Resin layer surface (exposed surface) 14 18 Metal layer 20 22 C stage resin layer 30 Metal layer 32... B stage resin layer 33... Resin layer surface (exposed surface) 34... Film layer 36... C stage resin layer 40... Winding core 42... Stepped portion 50... High frequency circuit laminate 51 100 Laminated body for high frequency circuit 200 Laminated body for high frequency circuit 300 Laminated body wound body

Claims (8)

A laminate for a high-frequency circuit, wherein a film layer having a glass transition temperature of 150° C. or higher and a resin layer are laminated in contact with each other, and a metal layer is further laminated in contact with the surface of the resin layer that is not in contact with the film layer. and
The resin layer contains a polymer having at least one repeating unit selected from repeating units represented by the following general formulas (1-1), (1-2) and (1-3),
The tensile elastic modulus of the resin layer measured according to JIS K 7161 is 0.1 to 3.0 GPa,
A laminate for a high-frequency circuit, wherein the resin layer has a dielectric loss tangent of 0.001 to 0.01 at a frequency of 10 GHz at 23° C. and a dielectric constant of 2.0 to 3.0.

[In the above general formulas (1-1) to (1-3), R ¹ is each independently a halogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, a monovalent hydrocarbon group having 1 to 20 carbon atoms, is a salt of a halogenated hydrocarbon group, a nitro group, a cyano group, a primary to tertiary amino group, or a primary to tertiary amino group. Each n is independently an integer of 0 to 2. When n is 2, multiple R ^1s may be the same or different, and may be combined in any combination to form a part of the ring structure. ] 2. The high-frequency circuit laminate according to claim 1, wherein the resin layer has a thickness of 1 to 30 μm, and the film layer has a thickness of 10 to 300 μm. 3. The laminate for high-frequency circuits according to claim 1, wherein a peel strength between said resin layer and said film layer is 5.0 N/cm or more. 4. The high-frequency circuit laminate according to claim 1 , wherein a peel strength between said resin layer and said metal layer is 5.0 N/cm or more. 5. The high-frequency circuit laminate according to claim 1, wherein the metal layer has a thickness of 3 to 50 μm. The film layer is one selected from the group consisting of polyimide, polyetherimide, liquid crystal polymer, polyethylene naphthalate, cycloolefin polymer, polyether ether ketone, polyarylene ether ketone, and polyphenylene ether. The laminate for high-frequency circuits according to any one of claims 1 to 5 . A flexible printed circuit board comprising the high-frequency circuit laminate according to any one of claims 1 to 6 . 7. A wound laminate, in which the laminate for a high-frequency circuit according to claim 1 is wound around a core having a radius of 10 to 100 mm.

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