TW202102575A - Laminate for high-frequency circuit, method for producing same, flexible printed board, b stage sheet, and wound laminate - Google Patents

Abstract

Provided is a laminate for high-frequency circuit with which it is possible to reduce the transmission loss of an electrical signal in a high-frequency circuit, and to produce a circuit board with outstanding smoothing properties. The laminate for high-frequency circuits according to this invention is obtained by laminating a film layer having a glass transition temperature of at least 150 DEG C, and a resin layer, in contact with one another. The resin layer contains a polymer having at least one type of repeating unit selected from among repeating units represented by general formulas (1-1), (1-2) and (1-3). The modulus of elasticity of the resin layer falls within the range of 0.1-3.0 GPa, and at a temperature of 23 DEG C, the dielectric loss tangent of the resin layer at a frequency of 10 GHz falls within the range of 0.001-0.01 and the relative dielectric constant falls within the range of 2.0-3.0.

Description

Laminated body for high frequency circuit and manufacturing method thereof, flexible printed circuit board, B-stage sheet, and laminated body wound body

The present invention relates to a laminate for high-frequency circuits formed by bonding a resin layer and a film layer, a method for manufacturing the same, a flexible printed circuit board, and a B-stage sheet. In addition, the present invention relates to a laminated body wound body that can be preferably used as a high-frequency circuit board.

With the high performance of information terminal equipment or the rapid progress of network technology in recent years, the high frequency of the telecommunication signals processed in the information communication field for high-speed and large-capacity transmission has been continuously developed. In order to cope with this, the printed wiring board used also transmits high-frequency signals or high-speed digital signals and processes them, and improves the low dielectric constant (low ε _r ) and low dielectric loss that can reduce the problematic transmission loss. Tangent (low tanδ) material requirements (for example, refer to Patent Document 1 to Patent Document 4).

As a printed wiring board, a flexible printed circuit board (hereinafter, also referred to as "FPC (flexible printed circuit)") or a flexible flat cable (hereinafter, also referred to as "FFC (flexible flat cable)") is used in electronic and electrical equipment . FPC is manufactured through the following steps: After processing a copper-clad laminate (CCL) containing an insulator layer and a copper foil layer and forming an electrical circuit, in order to protect the circuit part, it will contain an insulating layer and an adhesive The adhesive part of the coverlay (CL) of the layer is mounted on the circuit part. In addition, FFC is an electric circuit obtained by arranging a plurality of conductors between the adhesive portions of the base material and bonding them using a substrate including an insulator layer and an adhesive layer, and conductors such as copper foil formed in a wiring shape. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2014-197611 [Patent Document 2] Japanese Patent Laid-Open No. 2015-176921 [Patent Document 3] Japanese Patent Laid-Open No. 2016-087799 [Patent Document 4] Japanese Patent Laid-Open No. 2016-032098

[The problem to be solved by the invention] However, the higher the high frequency of the electrical signal, the easier it is to attenuate, and the transmission loss tends to increase. Therefore, in the next generation of high frequency (above 10 GHz) compliant mounting substrates, low dielectric loss characteristics to reduce crosstalk between wiring and low dielectric loss characteristics to suppress transmission loss of electrical signals are necessary for insulator materials. Indispensable features. In addition, in order to suppress the transmission loss of electric signals, it is also important that the smoothness of the mounting substrate is excellent. It is considered that in FPC or FFC, an adhesive is used in order to laminate the resin layer and the film, but the adhesive layer formed of the adhesive is a factor that impairs the low dielectric loss characteristics and smoothness of the mounting substrate.

Furthermore, when the laminate of the resin layer and the film layer with the adhesive interposed therebetween is stored as a wound body wound around the core, the adhesive layer undergoes deterioration due to external factors (such as storage environment). It is hardened, so there is a problem that curls and wrinkles are likely to occur when pulled out.

The present invention was made in view of the above-mentioned actual situation, and its subject is to provide a laminate for high-frequency circuits that can manufacture a circuit board that reduces transmission loss of electric signals in a high-frequency circuit and has excellent smoothness. Moreover, the subject of this invention is providing the manufacturing method of the laminated body for high frequency circuits which can be manufactured by bonding at low temperature, and is excellent in the adhesiveness between a resin layer and a film layer.

Furthermore, the subject of the present invention is to provide a laminate that can effectively suppress curling wrinkles even when a laminate for high-frequency circuits that can reduce transmission loss of high-frequency signals is wound around a core for storage. Rolled body.

[Means to solve the problem] The present invention is made to solve at least a part of the above-mentioned problems, and can be implemented as any of the following aspects.

[所述通式（1-1）～通式（1-3）中，R¹ 分別獨立地為鹵素原子、碳數1～20的一價烴基、碳數1～20的一價鹵化烴基、硝基、氰基、一級胺基～三級胺基、或一級胺基～三級胺基的鹽。n分別獨立地為0～2的整數。於n為2的情況下，多個R¹ 可相同亦可不同，且可以任意的組合鍵結而形成環結構的一部分。]In one aspect of the laminate for high-frequency circuits of the present invention, 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 the resin layer contains the following general formula (1-1), A polymer of at least one of the repeating units represented by the general formula (1-2) and the general formula (1-3), the elastic modulus of the resin layer is 0.1 GPa to 3.0 GPa, at 23°C The dielectric loss tangent of the resin layer at a frequency of 10 GHz is 0.001 to 0.01, and the relative dielectric constant is 2.0 to 3.0. [化1]

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

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

In any aspect of the multilayer body for high-frequency circuits, The peel strength of the resin layer and the film layer may be 5.0 N/cm or more.

In any aspect of the multilayer body for high-frequency circuits, A metal layer may be further laminated on the surface of the resin layer that is not in contact with the film layer.

In any aspect of the multilayer body for high-frequency circuits, The peel strength of the resin layer and the metal layer may be 5.0 N/cm or more.

In any aspect of the multilayer body for high-frequency circuits, The thickness of the metal layer may be 3 μm-50 μm.

In any aspect of the multilayer body for high-frequency circuits, The film layer can be selected from polyimide, polyetherimide, liquid crystal polymer, polyethylene naphthalate, polystyrene, cycloolefin polymer, polyether ether ketone, poly arylene ether One of the group consisting of ketones and polyphenylene ethers.

In one aspect of the flexible printed circuit board of the present invention, A laminate for high-frequency circuits including any of the above-mentioned aspects.

One aspect of the manufacturing method of the laminated body for high-frequency circuits of the present invention includes: The film layer with a glass transition temperature of 150℃ or higher and the B-stage resin layer with a surface roughness Ra of 1 nm-100 nm are heated at 50℃～200℃ and a linear load of 1 kN/m～19 kN/m is applied. To make the steps of fitting.

In one aspect of the manufacturing method of the laminated body for high-frequency circuits, It may further include: a step of attaching a metal layer with a surface roughness Ra of 10 nm to 300 nm on the back surface of the B-stage resin layer on which the film layer is attached.

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

One aspect of the laminated body wound body of the present invention is The laminated body for high-frequency circuits of any of the above-mentioned aspects is formed by winding a core having a radius of 10 mm to 100 mm.

[Effects of the invention] According to the laminate for a high-frequency circuit of the present invention, a circuit board with reduced transmission loss of electric signals in a high-frequency circuit and excellent in smoothness can be manufactured. Moreover, according to the manufacturing method of the laminated body for high frequency circuits of this invention, the laminated body for high frequency circuits which can be manufactured by bonding at low temperature and is excellent in the adhesiveness between a resin layer and a film layer can be manufactured. Furthermore, according to the laminated body wound body of the present invention, even when the laminated body for high-frequency circuits, which can reduce the transmission loss of high-frequency signals, is wound on the winding core and stored, curling wrinkles can be effectively suppressed. .

Hereinafter, preferred embodiments of the present invention will be described in detail. In addition, the present invention is not limited to the embodiments described below, but should be understood to include various modifications implemented in a range that does not change the gist of the present invention.

In this specification, the numerical range described in "～" includes the numerical values described before and after "～" as the meaning of the lower limit and the upper limit.

1. Laminated body for high frequency circuit The terms used in this specification are defined as follows. ·The so-called "high-frequency signal" refers to electrical signals or waves with frequencies above 10 GHz. ·The so-called "layered body for high-frequency circuits" refers to the layered body used in the manufacture of high-frequency circuits that are driven at frequencies above 10 GHz. ·The so-called "B-stage resin layer" refers to a layer in a state where the resin is semi-cured. ·The "C-stage resin layer" refers to a layer in a state where the resin is completely cured. Furthermore, in the invention of this application, the "C-stage resin layer" is sometimes simply referred to as the "resin layer". · The "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. ·The term "wound body" refers to a laminated body for high-frequency circuits of the same width wound around a winding core for a predetermined length. The roll length or width is not particularly limited, but the roll length is usually 0.5 m to 100 m, and the width is about tens of mm to 1000 mm.

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

The laminate for high-frequency circuits of the present embodiment is formed by a film layer and a resin layer in contact with each other and laminated, and an adhesive layer such as a primer resin layer is not interposed between the film layer and the resin layer. In a general laminate for circuits, an adhesive layer is 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 mainly uses an adhesive containing a polymer having a polar functional group, and is formed by a method such as coating. However, this type of adhesive layer has poor electrical properties, and therefore the effective dielectric constant or effective dielectric loss of the resin layer that has an insulating function becomes large, and it is not suitable for high-frequency circuits. On the other hand, even if an adhesive is not used in the laminated body for high frequency circuits of this embodiment, the adhesiveness of a film layer and a resin layer is good. In addition, the film layer and the resin layer are in contact with each other and laminated, so as to successfully obtain a laminated body suitable for high-frequency circuits without deteriorating the effective electrical characteristics of the resin layer.

The peel strength between the resin layer and the film layer of the laminate for high-frequency circuits of this embodiment is preferably 5.0 N/cm or more, more preferably 5.3 N/cm or more, and particularly preferably 6.0 N/cm or more. The laminate for a high-frequency circuit of the present embodiment has a peel strength in the above-mentioned range, and therefore, even if an adhesive is not used, the adhesion between the metal layer and the resin layer is good. In addition, the peel strength can be measured in accordance with the method described in "IPC-TM-650 2.4.9".

The thickness of the laminate for high-frequency circuits of this embodiment is preferably 20 μm to 200 μm, more preferably 30 μm to 180 μm, and particularly preferably 50 μm to 150 μm. If the thickness of the high-frequency circuit laminate is in the above-mentioned range, not only can a thinned high-frequency circuit board be produced, but also curling wrinkles are less likely to occur when wound on a core.

In addition, when the step portion is formed in the winding core, the thickness of the high-frequency circuit laminate is particularly preferably the height (μm) of the step portion ±10 μm. If the thickness of the high-frequency circuit laminate is within the above-mentioned range, the step difference between the step portion of the winding core and the junction portion of the high-frequency circuit laminate can be eliminated, and therefore it is possible to more effectively suppress the winding of the laminate. The formation of indentation.

Hereinafter, the structure and manufacturing method of each layer which comprises the laminated body for high frequency circuits of this embodiment is demonstrated in detail.

1.1. Resin layer The laminate for high-frequency circuits of this embodiment includes a resin layer. The elastic coefficient of the resin layer is 0.1 GPa to 3.0 GPa, preferably 0.2 GPa to 2.5 GPa. If the coefficient of elasticity of the resin layer is in the above range, it becomes a laminate for high-frequency circuits having excellent flexibility, and therefore, a circuit board can be manufactured under more free conditions. The so-called coefficient of elasticity of the resin layer is the coefficient of tensile elasticity, which can be measured in accordance with Japanese Industrial Standards (JIS) K 7161.

The relative dielectric constant of the resin layer at a frequency of 10 GHz at 23° C. is 2.0 to 3.0, preferably 2.1 to 2.8. In addition, the dielectric loss tangent of the resin layer at a frequency of 10 GHz at 23° C. is 0.001 to 0.01, preferably 0.002 to 0.009. If the relative dielectric constant and the dielectric loss tangent fall within the above ranges, a circuit board excellent in high-frequency characteristics can be manufactured. The relative 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 method dielectric constant measuring device.

In addition, 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 this application, the resin layer also includes the aspect including a plurality of different resin layers. In the case where the resin layer includes a plurality of resin layers, the elastic modulus, relative permittivity, and dielectric loss tangent of each resin single layer need not be limited to the preferred ranges described above, as long as the whole becomes a preferred range. can.

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

The composition of the resin layer composition should contain at least one of the repeating units represented by the following general formula (1-1), general formula (1-2) and general formula (1-3) as described later The polymer is not particularly limited, and may contain a curable compound, other polymers, curing aids, and solvents if necessary.

1.1.1. Composition for resin layer ＜Polymer＞ The composition for the resin layer contains at least one of the repeating units represented by the following general formula (1-1), general formula (1-2) and general formula (1-3) as a polymer The polymer (hereinafter, also referred to as "specific polymer"). In addition, the composition for the resin layer may contain other polymers, such as epoxy resin, polyimide, polyarylenes, and other known materials having low dielectric constant and low dielectric loss tangent characteristics.

[式（1-1）～式（1-3）中，R¹ 分別獨立地為鹵素原子、碳數1～20的一價烴基、碳數1～20的一價鹵化烴基、硝基、氰基、一級胺基～三級胺基、或一級胺基～三級胺基的鹽。n分別獨立地為0～2的整數。於n為2的情況下，多個R¹ 可相同亦可不同，且可以任意的組合鍵結而形成環結構的一部分。][化2]

[In formulas (1-1) to (1-3), R ^{1 is} each independently a halogen atom, a monovalent hydrocarbon group with 1 to 20 carbons, a monovalent halogenated hydrocarbon group with 1 to 20 carbons, a nitro group, a cyano group A salt of an amino group, a primary amino group to a tertiary amino group, or a primary amino group to a tertiary amino group. n is an integer of 0-2 each independently. When n is 2, a plurality of R ¹ may be the same or different, and may be bonded in any combination to form a part of the ring structure. ]

R ^{1 is} preferably a halogen atom, a monovalent hydrocarbon group with 1 to 6 carbons, a monovalent halogenated hydrocarbon group with 1 to 6 carbons, a nitro group, a cyano group, a primary amino group to a tertiary amino group, or a primary amino group to a tertiary amino group. The salt of the grade amino group is more preferably a fluorine atom, a chlorine atom, a methyl group, a nitro group, a cyano group, a tertiary butyl group, a phenyl group, or an amino group. n is preferably 0 or 1, more preferably 0.

The position of the other bonding bond relative to one of the bonding bonds of the repeating unit is not particularly limited. In order to improve the polymerization reactivity of the monomer providing the repeating unit, the meta position is preferred. In addition, the repeating unit is preferably a repeating unit represented by the general formula (1-2) having a pyrimidine skeleton.

As a monomer providing such a repeating unit, for example, 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.

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

The synthesis method of the specific polymer is not particularly limited, and a known method can be used. For example, a monomer that provides at least one of the repeating units represented by the general formula (1-1), the general formula (1-2) and the general formula (1-3) and optionally Other monomers are synthesized by heating together with alkali metals and 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, still more preferably 10,000, and particularly preferably 30,000. The upper limit of the weight average molecular weight (Mw) is preferably 600,000, more preferably 400,000, still more preferably 300,000, 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，R³ 及R⁴ 分別獨立地為鹵素原子、硝基、氰基或碳數1～20的一價有機基，c及d分別獨立地為0～8的整數，e、f、y分別獨立地為0～2的整數，L為單鍵、-O-、-S-、-CO-、-SO-、-SO₂ -或碳數1～20的二價有機基。）[化3]

(In formula (2), 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 carbons, c and d are each independently an integer of 0 to 8, e , F, y are each independently an integer of 0-2, and L is a single bond, -O-, -S-, -CO-, -SO-, -SO ₂ -or a divalent organic group with 1 to 20 carbons .)

Examples of the halogen atom represented by R ³ and R ⁴ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Examples of the monovalent organic group having 1 to 20 carbons represented by R ³ and R ⁴ include a monovalent chain hydrocarbon group, a monovalent alicyclic hydrocarbon group, a monovalent aromatic hydrocarbon group, and a monovalent halogenated hydrocarbon group.

Examples of the monovalent chain hydrocarbon group include alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second butyl, tertiary butyl, and n-pentyl. Group; alkenyl groups such as vinyl, propenyl, butenyl, and pentenyl; alkynyl groups such as ethynyl, propynyl, butynyl, and pentynyl.

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

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

As the monovalent halogenated hydrocarbon group, for example, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom will be ^{exemplified as the group represented by R 3} and R ⁴ with 1 to 20 carbon atoms. A group in which part or all of the hydrogen atoms of the monovalent hydrocarbon group are substituted, and the like.

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

Examples of the divalent chain hydrocarbon group include: methylene, ethylene, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, and neopentyl. , 4-Methyl-pentane-2,2-diyl, nonane-1,9-diyl, etc.

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

As the divalent fluorinated chain hydrocarbon group, for example, a part or all of the hydrogen atoms of the divalent chain hydrocarbon group having 1 to 20 carbons exemplified as the group represented by L may be substituted by a fluorine atom The base and so on.

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

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

Examples of these polymers include those described in Japanese Patent Laid-Open No. 2015-209511, International Publication No. 2016/143447, Japanese Patent Laid-Open No. 2017-197725, Japanese Patent Laid-Open No. 2018-024827, etc. polymer.

The content ratio 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 100 parts by mass in total of the curable compound and polymer described later.

＜Curable compound＞ The curable compound is a compound that is cured by irradiating heat or light (for example, visible light, ultraviolet rays, near infrared rays, far infrared rays, electron beams, etc.), and may also be those that require a hardening auxiliary agent 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, and methacrylic acid compounds. Compounds, urethane compounds, oxetane compounds, methylol compounds, and propargyl compounds. These may be used individually by 1 type, and may use 2 or more types together. Among these, in order to improve compatibility with the specific polymer, heat resistance, etc., epoxy compounds, cyanate ester compounds, vinyl compounds, silicone compounds, oxazine compounds, and maleimides are preferred. At least one of the compound and the allyl compound is more preferably at least one of an epoxy compound, a cyanate ester compound, a vinyl compound, an allyl compound, and a silicone compound.

As said epoxy compound, the compound represented by following formula (c1-1)-a formula (c1-6) is mentioned, for example. In addition, the compound represented by the following formula (c1-6) is an epoxy group-containing nitrile-butadiene rubber (NBR) particle "XER-81" manufactured by JSR (Stocks). Examples of the epoxy compound include: polyglycidyl ether of dicyclopentadiene-phenol polymer, phenol novolak type liquid epoxy compound, epoxy of styrene-butadiene block copolymer Products, 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate, etc.

[式（c1-5）中，n為0～5000，m獨立地為0～5000。][化4]

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

As said cyanate ester compound, the compound represented by following formula (c2-1)-a formula (c2-7) is mentioned, for example.

[式（c2-6）及（c2-7）中，n獨立地為0～30。][化5]

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

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

[式（c3-4）中，n為1～5000。][化6]

[In 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). Furthermore, as R in the formula (c4-1), any one of the following can be selected. In the case of selecting a compound including a vinyl group, it can also be treated as the vinyl compound, and when selecting a compound including oxetane In the case of the compound of the group, it can also be treated as the oxetane compound. In addition, in formulas (c4-2) to (c4-16), R is each independently an organic group selected from an alkyl group, an alicyclic hydrocarbon group, an aryl group, and an alkenyl group, and n is an integer of 0 to 1000 (Preferably an integer of 0-100).

Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second butyl, tertiary butyl, n-pentyl, and the like. Examples of alicyclic hydrocarbon groups include: monocyclic cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl; polycyclic cycloalkyl groups such as norbornyl and adamantyl; cyclopropenyl, Cyclobutenyl, cyclopentenyl, cyclohexenyl and other monocyclic cycloalkenyl groups; norbornenyl and other polycyclic cycloalkenyl groups. As an aryl group, a phenyl group, a tolyl group, a xylyl group, a naphthyl group, an anthryl group, etc. are mentioned. As an alkenyl group, a vinyl group, 1-propenyl group, 2-propenyl group, etc. are mentioned.

[化7]

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

[化8]

As said maleimide compound, the compound represented by following formula (c6-1)-a formula (c6-5) is mentioned, for example.

[式（c6-2）中，Et為乙基，式（c6-3）中，n為0～30。][化9]

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

As said allyl compound, the compound represented by following formula (c7-1)-a formula (c7-6) is mentioned, for example. In particular, the allyl compound is preferably a compound having two or more (especially 2 to 6, and further 2 to 3) allyl groups.

[化10]

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

[式（c8-1）及（c8-2）中，由括號括起的重複單元的重複單元數分別獨立地為0～30。][化11]

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

As said hydroxymethyl compound, the hydroxymethyl compound described in Unexamined-Japanese-Patent No. 2006-178059 and Unexamined-Japanese-Patent No. 2012-226297 can be mentioned, for example. Specifically, for example, melamine-based methylol groups such as polymethylolated melamine, hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, hexabutoxymethylmelamine, etc. Base compound; polymethylolated glycol urea, tetramethoxymethyl glycol urea, tetrabutoxymethyl glycol urea and other glycol urea methylol compounds; 3,9-bis[2-( 3,5-Diamino-2,4,6-triazaphenyl)ethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane, 3,9-bis[2 -(3,5-diamino-2,4,6-triazaphenyl) propyl]-2,4,8,10-tetraoxa[5.5]undecane, etc. Add guanamine to hydroxymethyl A guanamine-based methylol compound such as a compound obtained by radicalization, and a compound obtained by alkyl-etherifying all or part of the active methylol group in the compound.

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

[化12]

The content ratio of the curable compound in the resin layer composition is preferably 10 parts by mass or more and 90 parts by mass or less, and more 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.

＜Hardening aids＞ Examples of the curing aid include polymerization initiators such as photoreaction initiators (photoradical generators, photoacid generators, and photobase generators). Specific examples of the curing aid include: onium salt compounds, sulfonium compounds, sulfonate compounds, sulfonylimide compounds, disulfonylimide compounds, disulfonylmethane compounds, and oxime sulfonate compounds , Hydrazine sulfonate compounds, triazine compounds, nitrobenzyl compounds, benzyl imidazole compounds, organic halides, octanoic acid metal salts, dioxins, etc. Regardless of the type of these hardening aids, one kind may be used alone, or two or more kinds may be used in combination.

The content ratio of the curing aid in the resin layer composition is preferably 5 parts by mass or more and 20 parts by mass or less, and 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.

＜Solvent＞ The composition for a resin layer may contain a solvent as needed. Examples of solvents include not only N,N-dimethylacetamide, N,N-dimethylformamide, N-methyl-2-pyrrolidone, and N-ethyl-2-pyrrolidone. , 1,3-Dimethyl-2-imidazolidinone and other amide solvents; γ-butyrolactone, butyl acetate and other ester solvents; cyclopentanone, cyclohexanone, methyl ethyl ketone, diphenyl Ketone solvents such as ketone; ether solvents such as 1,2-methoxyethane and diphenyl ether; polyfunctional solvents such as 1-methoxy-2-propanol and propylene glycol methyl ether acetate; ring Butylene, dimethyl sulfide, diethyl sulfide, dimethyl sulfide, diethyl sulfide, diisopropyl sulfide, diphenyl sulfide, and other solid waste solvents, including dichloromethane, benzene, toluene, etc. , Xylene, dialkoxybenzene (carbon number of alkoxy group: 1 to 4), trialkoxybenzene (carbon number of alkoxy group: 1 to 4), etc. These solvents may be used singly, or two or more of them may be used in combination.

When the resin layer composition contains a solvent, it is preferably 2000 parts by mass or less, and more preferably 200 parts by mass or less with respect to 100 parts by mass of the resin layer composition other than the solvent.

＜Other ingredients＞ The composition for a resin layer may contain other components as needed. Examples of other components include antioxidants, reinforcing agents, lubricants, flame retardants, antibacterial agents, colorants, mold release agents, foaming agents, polymers other than the above-mentioned polymers, and the like.

<Preparation method of composition for resin layer> The preparation method of the composition for the resin layer is not particularly limited. For example, it can be obtained by uniformly mixing a polymer, a curable compound, and other additives (such as a curing aid, a solvent, an antioxidant, etc.) as necessary. preparation. In addition, the form of the composition may be a liquid form, a paste form, or the like.

1.2. Membrane The laminate for high-frequency circuits of this embodiment includes a film layer having a glass transition temperature (Tg) of 150°C or higher. As the film layer, it is preferably selected from polyimide (PI), polyether imide (PEI), liquid crystal polymer (LCP), polyethylene naphthalate ( polyethylene naphthalate (PEN), polystyrene (PS), cycloolefin polymer (COP), polyether-ether-ketone (PEEK), polyarylene ether ketones (polyarylene ether ketones) , PAEK) and polyphenylene ether (polyphenylene ether, PPE) is a kind of membrane in the group. Among these, polyimide (PI), liquid crystal polymer (LCP), polyethylene naphthalate (PEN), polyether ether ketone (PEEK) are more preferred, and polyimide (PI) is particularly preferred. ), Liquid Crystal Polymer (LCP). In addition, when the laminated body for a high-frequency circuit of this embodiment has a plurality of film layers, the same type of film may be used for the film layer, or different types of films may be used.

As a specific example of polyimide (PI), a brand name "Kapton (registered trademark)" (manufactured by Toray Dupont) and the like can be cited. As a specific example of polyetherimide (PEI), a brand name "Superio" (manufactured by Mitsubishi Chemical Corporation) and the like can be cited. As a specific example of the liquid crystal polymer (LCP), the trade name "Vecstar" (manufactured by Kuraray) and the like can be cited. As a specific example of polyethylene naphthalate (PEN), a brand name "Teonex" (manufactured by Teijin Corporation), etc. can be cited. As a specific example of the cycloolefin polymer (COP), the trade name "Zeonor" (manufactured by Zeon Corporation) and the like can be cited. As a specific example of polyether ether ketone (PEEK), a brand name "APTIV" (manufactured by Victex Corporation) and the like can be cited. As a specific example of polyarylene ether ketone (PAEK), a brand name "AvaSpire" (manufactured by Solvay) and the like can be cited. As a specific example of polyphenylene ether (PPE), the trade name "modified polyphenylene ether (NORYL)" (manufactured by Saudi Basic Industries (SABIC)) and the like can be cited.

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, particularly preferably 180 μm.

1.3. Metal layer The laminate for high-frequency circuits of this embodiment may include not only a film layer but also a metal layer. The metal layer is preferably a metal foil or a sputtering film. The metal foil is preferably copper foil. There are electrolytic foils and rolled foils in the types of copper foils, and any of them can be used.

The surface roughness Ra of the metal layer is preferably 10 nm to 300 nm, more preferably 30 nm to 200 nm, and particularly preferably 30 nm to 100 nm. If the surface roughness Ra of the metal layer is in the above-mentioned range, the adhesiveness between the resin layer and the metal layer can be further improved when it is used as a laminate for high-frequency circuits. Furthermore, the in-plane thickness of the high-frequency circuit laminate can be made more uniform, and the peeling of the resin layer and the metal layer can be suppressed when the high-frequency circuit laminate is wound into a roll shape. In addition, the surface roughness Ra of the metal layer refers to the "arithmetic mean roughness" measured in accordance with JIS B0601-2001.

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

In the case of using metal foil as the metal layer, if the surface roughness Ra of the metal foil is in the above range, it can be used as it is thinned, but the surface can also be treated physically or chemically. On the other hand, the surface roughness Ra is controlled within the above-mentioned range. As a method of controlling the surface roughness of the metal foil, there are methods such as etching treatment (acid treatment, etc.), laser treatment, electrolytic plating, electroless plating, sputtering treatment, sandblasting, etc., but are not limited For that.

1.4. Manufacturing method of laminated body for high frequency circuit The method of manufacturing the laminate for high-frequency circuits of 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 so-called "resin layer and film layer in contact" is not limited to the case where one surface of the resin layer is in contact with the film layer on the entire surface, and includes the case where at least a part of one surface of the resin layer is in contact with the film layer.

Hereinafter, a preferable manufacturing example of the laminated body for high-frequency circuits of the present embodiment will be described. In addition, even if it is a halfway stage of each manufacturing example, as long as it is a necessary laminated body, it can use suitably.

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

(Step A1) As shown in FIG. 1A, the composition for a resin layer is coated on the film layer 10, and the B-stage resin layer 12 is formed, and the "B-stage resin layer/film laminated body" is produced. The film layer 10 can use a film containing PI, PEI, LCP, PEN, PS, COP, PEEK, PAEK, PPE and other materials. The coating method of the composition for a resin layer can use a well-known coating method, For example, it is preferable to use a bar coater and adjust a film thickness for coating.

After applying the resin layer composition to the film layer 10 in this way, it is preferable to use a known heating mechanism such as an oven to form the B-stage resin layer 12 in a semi-cured state. The heating temperature is preferably 50°C to 150°C, more preferably 70°C to 130°C. At the time of heating, heating may be performed in multiple stages, such as 50°C to 100°C and 100°C to 150°C, for example. In addition, the total heating time is preferably less than 30 minutes, and more preferably less than 20 minutes. By heating under the conditions of the temperature and time in the above-mentioned range, the B-stage resin layer 12 with high film thickness uniformity can be produced.

The surface roughness Ra of the B-stage resin layer 12 exposed on the surface is preferably 1 nm to 100 nm, more preferably 10 nm to 50 nm. If the surface roughness Ra of the B-stage resin layer 12 is in the above-mentioned range, in the case of manufacturing a laminate for a high-frequency circuit, the adhesion between the resin layer and the film layer or the resin layer and the metal layer can be further improved. In addition, the surface roughness Ra of the B-stage resin layer in the invention of this application refers to the "arithmetic mean roughness" measured in accordance with JIS B0601-2001.

Regarding the coefficient of elasticity of the B-stage resin layer 12, under the measurement conditions of 1 Hz, the maximum value of the coefficient of elasticity (MPa) at 50° C. or more and less than 80° C. is preferably 1 MPa or more, more preferably 3 MPa or more. In addition, the minimum value of the coefficient of elasticity (MPa) in the temperature range of 80° C. or higher and 200° C. or lower is preferably 20 MPa or lower, and more preferably 15 MPa or lower. If the coefficient of elasticity of the B-stage resin layer is in each temperature range, when the laminate for high-frequency circuits is manufactured by hot pressing, the unevenness of the wiring portion and the non-wiring portion can be suppressed, and the transmission loss can be suppressed.

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

It is preferable to superimpose the resin layer 13 and the metal layer 14 of the "B-stage resin layer/film laminate" at the time of lamination, and then use a heated roller (also referred to as a "hot roller" in this specification), etc. Heating and crimping. The wire load during heating and crimping is preferably 1 kN/m to 19 kN/m, more preferably 5 kN/m to 18 kN/m. The temperature of the heating and compression bonding is preferably 50°C to 200°C, more preferably 50°C to 150°C, particularly preferably 70°C to 130°C.

In addition, in step A2, the "metal layer/B-stage resin layer/film laminate" shortly after bonding may be continuously contacted with a heated roll or passed through a heating furnace for annealing treatment. Such annealing treatment may be at a temperature equal to or higher than the melting point of the resin. For example, it is preferably 100°C to 250°C, and more preferably 110°C to 230°C. The heating time is not particularly limited, but is preferably 5 seconds to 600 seconds, more preferably 10 seconds to 300 seconds. By using a hot roll and performing annealing treatment in a short time of, for example, about 5 seconds to 600 seconds, a B-stage resin layer with high film thickness uniformity can be produced. In addition, the so-called "continue processing the "metal layer/B-stage resin layer/film laminate" immediately after bonding" means that in the production line where the laminate is bonded, the bonding is not performed. The layered body is taken out from the production line and continues to be processed online after the lamination process.

(Step A3) As shown in FIG. 1C, the B-stage resin layer 16 is formed on the film layer 10 of the "metal layer/B-stage resin layer/film 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 the material of the B-stage resin layer 12.

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

(Step A5) As shown in FIG. 1E, by curing the B-stage resin layer 12 and the B-stage resin layer 16 to form a C-stage resin layer 20 and a C-stage resin layer 22, respectively, a laminate 100 for high-frequency circuits can be obtained. In order to harden the B-stage resin layer 12 and the B-stage resin layer 16, it is preferable to use a known heating mechanism such as an oven to heat the laminate obtained in step A4 at 50°C to 200°C, more preferably Heat at 100°C to 200°C. During heating, heating may be performed in multiple stages, such as 50°C to 100°C and 100°C to 200°C. In addition, the heating time is preferably less than 5 hours, more preferably less than 3 hours. By heating under the conditions of temperature and time in the above-mentioned range, a C-stage resin layer with high film thickness uniformity can be produced by hardening the B-stage resin layer.

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

(Step B1) As shown in FIG. 2A, a composition for a resin layer is applied to the metal layer 30 to form a B-stage resin layer 32, thereby producing a "metal layer/B-stage resin laminated body". The coating method of the composition for a resin layer can use a well-known coating method, For example, it is preferable to use a bar coater and adjust a film thickness for coating.

It is preferable to apply the resin layer composition to the metal layer 30 in this way, and then use a known heating mechanism such as an oven to form the B-stage resin layer 32 in a semi-cured state. The heating temperature is preferably 50°C to 150°C, more preferably 70°C to 130°C. At the time of heating, heating may be performed in multiple stages, such as 50°C to 100°C and 100°C to 150°C, for example. In addition, the total heating time is preferably less than 30 minutes, and more preferably less than 20 minutes. By heating under the conditions of the temperature and time in the above-mentioned range, the B-stage resin layer 32 with high film thickness uniformity can be produced.

(Step B2) As shown in FIG. 2B, prepare the "metal layer/B-stage resin laminate" produced in two steps B1, and attach the exposed resin layer 33 of the "metal layer/B-stage resin laminate" to the film layer. 34 on both sides to produce "metal layer/B-stage resin layer/film layer/B-stage resin layer/metal laminate". When bonding the film layer 34 to the exposed resin layer layer 33, it is preferable to overlap the exposed resin layer layer 33 and the film layer 34, and then heat and pressure-bond it using a heat roller or the like. In addition, the thermal compression bonding is preferably under the same conditions as in the step A2.

In addition, in step B2, the "metal layer/B-stage resin layer/film layer/B-stage resin layer/metal laminated body" can also be kept in contact with a heated roller or in a heating furnace shortly after lamination. The annealing treatment is carried out in the middle pass. The annealing treatment is preferably the same conditions as the step A2.

The surface roughness Ra of the exposed resin layer 33 is preferably 1 nm to 100 nm, more preferably 10 nm to 50 nm. If the surface roughness Ra of the B-stage resin layer is in the above range, when manufacturing a laminate for high-frequency circuits, the adhesiveness between the resin layer and the film layer can be further improved. In addition, the glass transition temperature (Tg) of the film layer 34 bonded to the resin layer layer 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. 2(C), by hardening the B-stage resin layer 32 to form the C-stage resin layer 36, a laminate 200 for high-frequency circuits can be obtained. In step B3, it is preferable that the "metal layer/B-stage resin layer/film layer/B-stage resin layer/metal laminate" produced in step B2 is heated at 50°C to 200°C using a known heating mechanism such as an oven. Heating is performed, more preferably at 100°C to 200°C. At the time of heating, it is also possible to perform heating in two stages, such as 50°C to 100°C and 100°C to 200°C. In addition, the heating time is preferably less than 5 hours, more preferably less than 3 hours. By heating under the conditions of the temperature and time in the above-mentioned range, the C-stage resin layer 36 with high film thickness uniformity can be produced by curing the B-stage resin layer 32.

2. Laminated body wound body The laminated body of this embodiment is characterized in that it is formed by winding a high-frequency circuit laminated body on a core with a radius of 10 mm to 100 mm, and the high-frequency circuit laminated body contains a glass transition temperature (Tg ) It is a structure in which a film layer above 150°C and a resin layer containing a specific polymer are in contact and laminated.

Hereinafter, the laminated body wound body of the present embodiment will be described with reference to the drawings.

Fig. 3 is a perspective view showing an example of the laminated body wound body of the present 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 wound laminated body 300 of the present embodiment includes a winding core 40 and a high-frequency circuit laminated body 50 wound around the winding core 40. Such a laminate for high-frequency circuits is generally in the form of a long sheet with a certain width in order to be processed efficiently, and it is wound in the state of a laminate wound body formed by winding it on a core. Use or keep.

The laminated body wound body of this embodiment preferably uses a substantially cylindrical core. In this case, by reducing the radius of the cylindrical winding core and reducing the radius of curvature as much as possible, even a roll formed by winding a laminated body for a high-frequency circuit of the same length can be more compact, and Can improve productivity. In addition, in the laminated body wound body with a small radius of curvature, curling wrinkles tend to remain in the laminated body for high-frequency circuits, and it tends to be difficult to process the laminated body for high-frequency circuits. Therefore, it is difficult to reduce the radius of curvature of the laminated body wound body in order to suppress the curl wrinkles remaining in the laminated body for high-frequency circuits.

In addition, in the conventional laminate for high-frequency circuits, an adhesive layer is interposed in order to improve the adhesion between the resin layer and the film layer. Therefore, in the case of storing the laminated body wound body formed by winding the conventional laminated body for high-frequency circuits on the core, the adhesive layer is altered and hardened due to external factors, so it is likely to be produced when pulled out. Curly wrinkles.

However, in the laminated body wound body of this embodiment, by using the following laminated body for high-frequency circuits, it is possible to produce a compact laminated body for high-frequency circuits wound on a core with a radius of 10 mm to 100 mm A jelly-rolled body including 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 winding core 40 and the laminated body 50 for a high-frequency circuit may be joined using a joining member, and may not be joined. For example, as shown in FIG. 4, when the winding core 40 has a stepped portion 42, the end 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 rotates and winds up the laminated body 50 for high frequency circuits, so that the laminated body wound body 300 can be manufactured. In addition, as the winding core in which the stepped portion is formed, for example, the winding core described in Utility Model Registration No. 3147706, etc. can be used.

In addition, the type of the joining member is not particularly limited, and various joining members can be used. For example, an adhesive, an adhesive, and a double-sided tape can be used. Only one kind of these may be used, or two or more kinds may be used in combination. In addition, this joining member may join the whole length of the width direction of the laminated body 50 for high frequency circuits to the winding core 40, and may join only a part.

The radius of the core 40 is 10 mm to 100 mm, but is preferably 10 mm to 50 mm, and more preferably 15 mm to 40 mm. If 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 winding body 300 and processed, the formation of the high-frequency circuit laminate 50 and the winding core can be effectively suppressed. The indentation 51 shown in FIG. 5 is caused by the step difference of the junction part (winding start part) of 40. Furthermore, this type of indentation 51 becomes a main cause of a decrease in yield during processing of a laminate for high-frequency circuits, and therefore is one of curling wrinkles that should be suppressed as much as possible in order to improve productivity.

The height of the step portion 42 is preferably 50 μm to 300 μm, more preferably 60 μm to 180 μm, particularly preferably 70 μm to 150 μm. In addition, the height of the step portion 42 is particularly preferably the thickness (μm) of the laminate 50 for high-frequency circuits ±10 μm. If the height of the step portion 42 is within the above range, the step difference between the step portion 42 of the winding core 40 and the junction portion of the laminated body 50 for high-frequency circuits can be eliminated, so the formation of the laminated body can be more effectively suppressed. Indentation around body 300.

The material of the core 40 is not particularly limited, and examples include paper, metal, and thermoplastic resin. When the material of the core 40 is paper, the surface can be coated with resin or the like. Examples of metals include SUS, iron, aluminum, and the like. Examples of thermoplastic resins include olefin resins (polyethylene, polypropylene, etc.), styrene resins (ABS resin, AES resin, AS resin, MBS resin, polystyrene, etc.), polyvinyl chloride, vinylidene chloride Resin, methacrylic resin, polyvinyl alcohol, styrene block copolymer resin, polyamide, polyacetal, polycarbonate, modified polyphenylene ether, polyester (polybutylene terephthalate) , Polyethylene terephthalate, etc.), fluororesin, polyphenylene sulfide, polyether, amorphous polyarylate, polyether imine, polyether ketone, polyether ketone, liquid crystal polymer, polyether Amine imines, thermoplastic polyimines, syndiotactic polystyrene, etc. Only one kind of these may be used, or two or more kinds may be used in combination. In the case where the material of the winding core 40 is a thermoplastic resin, the winding core 40 and the stepped portion 42 thereof can be manufactured by extrusion molding or cutting molding.

The method of winding the laminated body for high frequency circuits into a roll shape is not specifically limited, It can follow the method used for manufacture of the laminated body for high frequency circuits, or a film.

3. Circuit board (flexible printed circuit board) The laminate for high-frequency circuits of the invention of the present application can be used to manufacture circuit boards such as FPC. In such a circuit board, the laminate for a high-frequency circuit of the invention of the present application is used as at least a part of the laminate structure, and even if it is driven at a high frequency, the transmission loss can be reduced. Such a circuit board only needs to include the laminate for high-frequency circuits of the present application as a part of the laminate structure, and it can be manufactured by a known method. For example, International Publication No. 2012/014339 and Japanese Patent Laid-Open 2009 can be applied. -231770 Bulletin, etc. described in the manufacturing process.

Laminating the laminate for high-frequency circuits of the invention of this application, or patterning, perforating, or cutting the metal layer of the laminate for high-frequency circuits of the invention of this application by etching, to a desired size Etc., thereby making it possible to manufacture a circuit board.

Such a circuit board does not have an adhesive layer interposed therebetween. Therefore, the resin layer of the metal wiring layer that is the convex portion does not have a large step difference, and the surface of the resin layer becomes smooth. Therefore, even with multilayer circuits, high positioning accuracy can be satisfied, and more layers of circuits can be accumulated.

Such a circuit board can be manufactured through the following steps, for example: ·Step (a): A step of laminating a resin film on a circuit board and forming a resin layer, ·Step (b): A step of heating and pressurizing the resin layer to planarize it, Step (c): A step of forming a circuit layer on the resin layer.

The method of laminating the resin film on the circuit board in step (a) is not particularly limited. Examples include the use of a multi-stage press, a vacuum press, an atmospheric pressure laminator, and a laminator that heats and presses under vacuum. The method of lamination etc. is preferably a method using a laminator that is heated and pressurized under vacuum. Thereby, even if the circuit board has a fine wiring circuit on the surface, it is possible to fill the space between the circuits with resin without voids. The lamination conditions are not particularly limited, and the lamination is preferably performed at a crimping temperature of 70°C to 130°C, a crimping pressure of 1 kgf/cm ² to 11 kgf/cm ² , and reduced pressure or vacuum. The lamination may be a batch type or a continuous type using rollers.

The circuit substrate is not particularly limited, and glass epoxy substrates, metal substrates, polyester substrates, polyimide substrates, BT resin substrates, thermosetting polyphenylene ether substrates, fluororesin substrates, etc. can be used. The circuit surface of the resin film-laminated surface of the circuit board may be roughened in advance. In addition, the number of circuit layers of the circuit board is not limited. For example, in the case of manufacturing a printed wiring board for millimeter wave radar, 2 to 20 layers can be freely selected according to the design.

In the step (b), the resin film and the circuit board laminated in the step (a) are heated and pressurized to planarize. The conditions are not particularly limited, but the temperature ranges from 100°C to 250°C, pressure from 0.2 MPa to 10 MPa, and time ranges from 30 minutes to 120 minutes, and more preferably from 150°C to 220°C.

In step (c), a circuit layer is further formed on the resin layer produced by heating and pressing the resin film and the circuit board. The formation method of the circuit layer produced on the resin layer in this way is not specifically limited, For example, it can form by an etching method, such as a substractive method, a semi-additive method, etc.

The subtractive method is the following method: an etching resist layer of a shape corresponding to the desired pattern shape is formed on the metal layer, and the metal layer of the removed part of the resist is dissolved by a chemical solution through the subsequent development process And removed, thereby forming the desired circuit.

The semi-additive method is a method in which a metal film is formed on the surface of the 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 an electrolytic plating method is used After the metal layer is formed, the unnecessary electroless plating layer is removed with a chemical solution or the like to form a desired circuit layer.

In addition, if necessary, holes such as through holes may be formed in the resin layer. The hole formation method is not limited. Numerical control (NC) drilling, carbon dioxide laser, ultraviolet (UV) laser, yttrium aluminum garnet (YAG) laser, plasma can be used Wait.

4. Example Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited to these examples. The "parts" and "%" in the examples and comparative examples are quality standards unless otherwise specified.

4.1. Synthesis of polymers ＜Synthesis example 1＞ Measure 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (BisTMC) (18.6 g, 60.0 mmol) into a four-neck separable flask equipped with a stirring device, 4,6-Dichloropyrimidine (Pym) (8.9 g, 60.0 mmol), and potassium carbonate (11.1 g, 81.0 mmol), add N-methyl-2-pyrrolidone (64 g), React at 130°C for 6 hours. After the reaction was completed, N-methyl-2-pyrrolidone (368 g) was added, and after removing the salt by filtration, the solution was poured into methanol (9.1 kg). The precipitated solid was separated by filtration, washed with a small amount of methanol, separated by filtration again and recovered, and then dried with a vacuum dryer at 120°C under reduced pressure for 12 hours to obtain the following formula (P-1) The polymer P-1 of the structural unit represented (yield: 20.5 g, yield: 90%, weight average molecular weight (Mw): 32,000, glass transition temperature (Tg): 206° C.).

[化13]

In addition, the glass transition temperature (Tg) was measured using a dynamic viscoelasticity measuring device (manufactured by Seiko Instruments, "DMS7100") at a frequency of 1 Hz and a heating rate of 10°C/min, and the loss tangent became Great temperature. The loss tangent is set to a value obtained by dividing the storage elastic coefficient by the loss elastic coefficient.

In addition, the weight average molecular weight (Mw) was measured under the following conditions using a gel permeation chromatograph (GPC) device (“HLC-8320 type” of Tosoh Corporation). Column: A column connecting Tosoh's "TSK gel (TSKgel) α-M" and Tosoh's "TSK gel guard column (TSKgel guardcolumn) α" Developing solvent: N-methyl-2-pyrrolidone Column temperature: 40℃ Flow rate: 1.0 mL/min Sample concentration: 0.75% by mass Sample injection volume: 50 μL Detector: Differential refractometer Standard material: monodisperse polystyrene

＜Synthesis example 2＞ Measure 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (BisTMC) (10.7 g, 34.5 mmol) into a four-neck separable flask equipped with a stirring device, 3,6-Dichloropyridazine (Pyd) (5.1 g, 34.2 mmol), and potassium carbonate (6.5 g, 47.0 mmol), add N-methyl-2-pyrrolidone (36 g), under nitrogen React at 145°C for 9 hours. After the completion of the reaction, N-methyl-2-pyrrolidone (150 g) was added for dilution, and after the salt was removed by filtration, the solution was poured into methanol (3 kg). The precipitated solid was separated by filtration, washed with a small amount of methanol, separated again by filtration and recovered, and then dried under the same conditions as in Synthesis Example 1, thereby obtaining a structural unit represented by the following formula (P-2) The polymer P-2 (yield 7.6 g, yield 48%, weight average molecular weight (Mw): 30,000, glass transition temperature (Tg): 232°C). In addition, the weight average molecular weight and the glass transition temperature were measured in the same manner as in Synthesis Example 1.

[化14]

＜Synthesis example 3＞ Measure 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (BisTMC) (18.6 g, 60.0 mmol) into a four-neck separable flask equipped with a stirring device, 4,6-Dichloro-2-phenylpyrimidine (PhPym) (13.7 g, 61.1 mmol) and potassium carbonate (11.4 g, 82.5 mmol), add N-methyl-2-pyrrolidone (75 g), The reaction was carried out at 130°C for 6 hours under a nitrogen atmosphere. After the reaction was completed, N-methyl-2-pyrrolidone (368 g) was added for dilution, and the salt was removed by filtration, and the solution was poured into methanol (9.1 kg). The precipitated solid was separated by filtration, washed with a small amount of methanol, separated again by filtration and recovered, and then dried under the same conditions as in Synthesis Example 1, thereby obtaining a structural unit represented by the following formula (P-3) Polymer P-3 (yield 20.5 g, yield 90%, weight average molecular weight (Mw): 187,000, glass transition temperature (Tg): 223°C). In addition, the weight average molecular weight and the glass transition temperature were measured in the same manner as in Synthesis Example 1.

[化15]

＜Synthesis example 4＞ Measure 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (BisTMC) (12.4 g, 40.0 mmol) into a four-neck separable flask equipped with a stirring device, 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), add N-methyl-2-pyrrolidone (75 g), react at 130°C for 6 hours in a nitrogen environment. After the reaction was completed, N-methyl-2-pyrrolidone (368 g) was added for dilution, and the salt was removed by filtration, and the solution was poured into methanol (9.1 kg). The precipitated solid was separated by filtration, washed with a small amount of methanol, separated again by filtration and recovered, and then dried under the same conditions as in Synthesis Example 1, thereby obtaining a structural unit represented by the following formula (P-4) The polymer P-4 (yield 23.5 g, yield 87%, weight average molecular weight (Mw): 165,000, glass transition temperature (Tg): 196°C). In addition, the weight average molecular weight and the glass transition temperature were measured in the same manner as in Synthesis Example 1.

[化16]

＜Synthesis example 5＞ Measure 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (BisTMC) (12.4 g, 40.0 mmol) into a four-neck separable flask equipped with a stirring device, 4,4'-(1,3-dimethylbutylene) 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), add N-methyl-2 -Pyrrolidone (75 g), reacted at 130°C for 6 hours in a nitrogen atmosphere. After the reaction was completed, N-methyl-2-pyrrolidone (368 g) was added for dilution, and the salt was removed by filtration, and the solution was poured into methanol (9.1 kg). The precipitated solid was separated by filtration, washed with a small amount of methanol, separated again by filtration and recovered, and then dried under the same conditions as in Synthesis Example 1, thereby obtaining a structural unit represented by the following formula (P-5) The polymer P-5 (yield 23.8 g, yield 88%, weight average molecular weight (Mw): 157,000, glass transition temperature (Tg): 190°C). In addition, the weight average molecular weight and the glass transition temperature were measured in the same manner as in Synthesis Example 1.

[化17]

4.2. Example 1 4.2.1. Production of B-stage resin layer/peel-laminated laminate 50 parts of polymer P-1, 50 parts of 2,2'-bis(4-cyanooxyphenyl)propane (manufactured by Tokyo Chemical Industry Co., Ltd.) as a curable compound, and 5 parts of 1 as a curing aid -Benzyl-2-methylimidazole (manufactured by Mitsubishi Chemical Corporation, product name "BMI 12") and 160 parts of cyclopentanone were mixed to prepare a resin layer composition.

The resin layer composition prepared as described above was applied to a PET film (manufactured by Teijin Membrane Solution Co., Ltd., Teijin Tetoron) as a peeling layer using a bar coater so that the thickness of the cured film became 25 μm. The film (Teijin Tetoron Film) G2) was heated at 70°C for 10 minutes in an oven, and then heated at 130°C for 10 minutes to obtain a "B-stage resin layer/peeling" with a B-stage resin layer laminated on the PET film. Layered layered body".

＜Surface roughness Ra＞ Using a white interference microscope (New View 5032 manufactured by ZYGO) to measure the surface of the resin layer of the "B-stage resin layer/release laminate" obtained as described above, it will be based on JIS B0601- The "arithmetic mean roughness" calculated in 2001 for the range of 10 μm×10 μm is defined as the surface roughness Ra. The results are shown in Table 1.

＜Measuring the coefficient of elasticity of resin layer at 50℃～200℃＞ The peeling layer (PET film) was peeled from the "B-stage resin layer/peeling laminate" obtained as described above, a test piece (width 3 mm × length 2 cm) was cut out, and a DMS tester (Seiko Instruments) was used. Manufactured by the company), the maximum value of the coefficient of elasticity (MPa) in the temperature range of 50°C or more and less than 80°C and the maximum value of the elastic coefficient (MPa) in the temperature range of 80°C or more and 200°C or less under the measurement conditions of 1 Hz and 10°C/min The minimum value of the coefficient of elasticity (MPa). The results are shown in Table 1.

4.2.2. Fabrication of B-stage resin layer/film layer laminate On a PI film with a thickness of 25 μm (manufactured by Toray Dupont, Kapton EN) as a film, apply the above-mentioned medium with a bar coater so that the cured film thickness becomes 5 μm. The prepared resin layer composition is heated at 70°C for 10 minutes in an oven, and then heated at 130°C for 10 minutes to obtain a "B-stage resin layer/film layer" formed by laminating a B-stage resin layer on the PI film Laminated body".

4.2.3. Production of metal layer/B-stage resin layer/film laminate A copper foil with a thickness of 18 μm (manufactured by Mitsui Metals Corporation, model "TQ-M4-VSP", surface roughness 110 nm) is superimposed on the exposed resin of the "B-stage resin layer/film laminate" obtained above On the layer, it was pressed with a heat roller at 150°C under a line load of 10 kN/m to produce a "metal layer/B-stage resin layer/film layer" with a laminate structure of copper foil/B-stage resin layer/film layer Laminated body". Furthermore, the surface roughness Ra of the copper foil is measured using a white interference microscopy device (New View 5032 manufactured by ZYGO), and the measurement of 10 μm×10 μm is based on JIS B0601-2001. The "arithmetic mean roughness" calculated by the range is defined as the surface roughness Ra. The results are shown in Table 1.

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

4.2.4. Production of metal layer/B-stage resin layer/film layer/B-stage resin laminate On the film surface of the "metal layer/B-stage resin layer/film laminate" obtained above, apply the resin layer composition prepared above with a bar coater so that the film thickness after curing becomes 5 μm After heating at 70°C for 10 minutes in an oven, and then heating at 130°C for 10 minutes, a B-stage resin layer is laminated on the film layer to produce "metal layer/B-stage resin layer/film layer/B-stage resin layer Laminated body".

4.2.5. Production of metal layer/B-stage resin layer/film layer/B-stage resin layer/metal laminate A copper foil with a thickness of 18 μm (manufactured by Mitsui Metals, model "TQ-M4-VSP", surface roughness 110 nm) is superimposed on the above-mentioned "metal layer/B-stage resin layer/film layer/B-stage resin" On the B-stage resin layer on the outer side of the laminated body, it is pressed with a heat roller at 150°C under a linear load of 10 kN/m to produce a "metal layer/B-stage resin layer/film layer/B-stage resin layer" /Metal laminate".

4.2.6. Production and evaluation of laminates for high-frequency circuits The "metal layer/B-stage resin layer/film layer/B-stage resin layer/metal laminate" obtained above was pressed with a heat roller at 150°C under a linear load of 10 kN/m, and then an oven was used to press Heating at 250°C for 3 hours to produce a "copper foil (film thickness: 18 μm)/C-stage resin layer (film thickness: 5 μm)/film layer (25 μm)/ A laminate for high-frequency circuits with a "C-stage resin layer (film thickness: 5 μm)/copper foil (film thickness: 18 μm)" laminated structure. In addition, the surface roughness Ra of the copper foil (metal layer) is measured using a white interference microscopy device (New View 5032 manufactured by ZYGO), which will be measured in accordance with JIS B0601-2001. The "arithmetic mean roughness" calculated in the range of ×10 μm is defined as the surface roughness Ra. The results are shown in Table 1.

＜Peel strength＞ A test piece (width 1 cm x length 10 cm) was cut out from the fabricated laminate for high-frequency circuits, and "Instron 5567" manufactured by Instron was used. The test piece was measured at 500 mm/ Under the condition of min, the metal layer is stretched in the direction of 90 degrees, and the peel strength is measured according to "IPC-TM-650 2.4.9". Next, after further peeling the C-stage resin layer from the laminated body for high-frequency circuits from which the metal layer was peeled off, the film layer was stretched in the direction of 90 degrees under the same conditions as when the metal layer was peeled off. According to "IPC-TM-650 2.4 .9" to measure the peel strength. The results are shown in Table 1.

4.2.7. Evaluation of C-stage resin characteristics ＜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 became 20 μm, heated at 70°C for 10 minutes in an oven, and then heated at 130°C In 10 minutes, a "metal layer/B-stage resin laminate" is produced. Furthermore, the laminate for high-frequency circuits heated at 250° C. for 3 hours in an oven was subjected to etching treatment to remove the copper foil, thereby taking out the C-stage resin layer and using it as a resin film for evaluation. The JIS K 7161 No. 7 dumbbell-shaped test piece was cut from the prepared resin film, and the "Ez-LX" manufactured by Shimadzu Corporation was used to stretch at 5 mm/min. The stress at break was measured as the tensile strength. And measure the elongation as the tensile elongation. The results are shown in Table 1.

＜Glass transition temperature (Tg)＞ A test piece (width 3 mm x length 1 cm) was cut out from the resin film prepared above, and the glass transition temperature (Tg) was measured using a DMS tester (Seiko Instruments, model "EXSTAR4000") . The results are shown in Table 1.

＜Elasticity coefficient＞ JIS K 7161 No. 7 dumbbells were cut out from the resin film prepared above, and using "Ez-LX" manufactured by Shimadzu Corporation, a tensile test was performed at 5 mm/min in accordance with JIS K 7161, and the tensile elasticity coefficient was measured. The results are shown in Table 1.

<Electrical characteristics (relative permittivity, dielectric loss tangent)> A test piece (width 2.6 mm×length 80 mm) was cut out from the resin film made above, and a cavity resonator perturbation method dielectric constant measurement device (manufactured by Agilent Technologies, model "PNA- L network analyzer N5230A, manufactured by Kanto Electronics Application Development Co., Ltd., model "CP531 for Cavity Resonator 10 GHz") measures the relative permittivity and dielectric loss tangent at 23°C and 10 GHz. The results are shown in Table 1.

4.2.8. Production and evaluation of laminated body wound body For the high-frequency circuit laminate produced above, a double-sided tape with a thickness of 10 μm was applied to a thick paper core with a width of 250 mm and a core radius of 40 mm at the center in the width direction over a length of 100 mm. After that, the produced laminate for high-frequency circuits was joined to a double-sided tape, and the laminate for high-frequency circuits was wound with a winding tension of 150 N/m into 1,000 layers to produce a wound laminate.

After storing the laminated body for high-frequency circuits wound around the laminated body wound body produced above at 25° C. for one month, the entire laminated body was rewinded from the winding core. After that, the curl wrinkles of the rewinded laminate were evaluated visually. It is judged as "good" when no curl wrinkles are confirmed, and it is judged as "bad" when curl wrinkles are severe and cannot be used for practical use. The results are shown in Table 1.

4.2.9. Production and evaluation of circuit boards For the single side of the laminate for high-frequency circuits produced in the above, the copper foil was patterned with a photosensitive dry film, and the production pitch was 150 μm and the line width was 40 μm, 45 μm, 50 μm, 55 μm, and 60 μm. μm and copper wiring patterns with a pitch of 750 μm and a line width of 200 μm, 220 μm, 240 μm, 260 μm, and 280 μm, respectively. Then, the "B-stage resin layer/peel-off laminate" produced as described above was placed on the produced copper wiring so that the B-stage resin layer side was in contact with the copper wiring of the patterned laminate for high-frequency circuits Place a mirror plate on the surface of the pattern, heat and press at a pressing condition of 120°C/3.0 MPa/5 minutes, and then peel off the peeling layer (PET film) and heat it at 250°C for 3 hours to produce a circuit board .

＜Evaluation of transmission loss＞ Regarding the circuit board produced in the above, the measurement probe (made by Cascade Microtech, single (ACP40GSG250)) and a vector network analyzer (Keysight technology E8363B) were used to measure at 25°C The transmission loss of the frequency 20 GHz. When the transmission loss is -5 dB/100 mm or more, it is judged to be good.

＜Evaluation of substrate level difference＞ For both sides of the laminate for high-frequency circuits produced above, the copper foil was etched on both sides so that the thickness of the copper foil was 9 μm, and then the copper foil was patterned with a photosensitive dry film to produce a pitch of 100 μm and a line width It is a 50 μm copper wiring pattern. Next, the peeling layer (PET film) is peeled from the "metal layer/B-stage resin layer/peeling laminate" made above, and the resin layer exposed by the peeling is placed in contact with the copper wiring pattern produced. It was sandwiched on both sides with mirror plates, heated and pressurized under the pressing conditions of 120°C/1.1 MPa/2 minutes, and then heated at 250°C for 3 hours. After that, the copper foil was patterned using a photosensitive dry film, and a copper wiring pattern with a pitch of 100 μm and a line width of 50 μm was produced on both sides. Finally, the peeling layer (PET film) is peeled from the "B-stage resin layer/peeling laminate" produced above, and the resin layer on the peeling surface is placed on both sides so that the copper wiring pattern is in contact with the copper wiring pattern. It was sandwiched by a mirror plate, heated and press-formed under a pressing condition of 120°C/1.1 MPa/2 minutes, and then heated at 250°C for 3 hours to produce an evaluation substrate with four layers of copper wiring.

The cross-sectional shape of the prepared evaluation substrate was observed with a scanning electron microscope. When the difference between the concave portion and the convex portion is less than 5%, it is judged to be practical and good, and when it exceeds 5%, it is judged to be impractical. And bad. The results are shown in Table 1.

4.3. Example 2 to Example 6, Example 9 and Comparative Example 1 to Comparative Example 3 The composition for the resin layer was changed to the composition in Table 1, and the type of metal layer and film layer or various film thicknesses, lamination conditions, and production conditions of the laminated body wound body were changed as shown in Table 1. Other than that, use and examples 1 In the same way, a laminate for high-frequency circuits was produced and evaluated. The results are shown in Table 1.

4.4. Example 7 Coat a copper foil with a thickness of 18 μm (manufactured by Mitsui Metals Co., Ltd., model "TQ-M4-VSP", surface roughness 110 nm) so that the cured film thickness becomes 15 μm. Table 1 The composition for the resin layer described in is heated at 70°C for 10 minutes in an oven, and then heated at 130°C for 10 minutes to produce a "metal layer/B-stage resin layer" with a copper foil/B-stage resin layer laminate structure Layered layered body".

On the other hand, on the PAEK film (manufactured by Solvay, AvaSpire) with a thickness of 75 μm as a film, the film thickness after curing was 15 μm, and it was coated with a bar coater as described in Table 1. The composition for the resin layer is heated at 70°C for 10 minutes in an oven, and then heated at 130°C for 10 minutes to obtain a "B-stage resin layer/film laminated body" formed by laminating a B-stage resin layer on a PAEK film ". A copper foil with a thickness of 18 μm (manufactured by Mitsui Metals, model "TQ-M4-VSP", surface roughness 110 nm) was superimposed on the exposed resin layer of the obtained "B-stage resin layer/film laminate" Then, it was pressed with a heat roller at 150°C under a line load of 10 kN/m to produce a "metal layer/B-stage resin layer/film laminate" with a laminate structure of copper foil/B-stage resin layer/film layer ".

Laminate the "metal layer/B-stage resin layer/film laminate" made above on the exposed resin layer of the "metal layer/B-stage resin laminate", and use a 150°C hot roller to load it linearly. Pressed under the condition of 10 kN/m, and then heated in an oven at 250°C for 3 hours to produce a copper foil (film thickness of 18 μm)/C-stage resin layer (film thickness of 15 μm)/film layer (film thickness) 75 μm)/C-stage resin layer (15 μm)/Copper foil (film thickness 18 μm)" laminated structure for high-frequency circuits. The laminated body for high frequency circuits produced in this way was evaluated in the same manner as in Example 1. The results are shown in Table 1.

4.5. Example 8, Comparative Example 4 The resin layer composition was prepared in the same manner as in Example 1 so as to have the composition of Table 1, and the resin layer composition was used to produce a high-frequency circuit laminate in the same manner as in Example 7. The laminated body for high frequency circuits produced in this way was evaluated in the same manner as in Example 1. The results are shown in Table 1.

4.6. Comparative Example 5 As the film layer, a polyimide film having a thickness of 25 μm (manufactured by Toray Dupont, trade name "Kapton 100H") was used. In addition, maleic acid modified styrene-ethylene butene-styrene block copolymer (manufactured by Asahi Kasei Chemical Co., Ltd., trade name "Tuftec M1913") used to make the adhesive layer is used instead of the resin layer. Except for the composition, in the same manner as in Example 1, a laminate for high-frequency circuits was produced. The laminated body for high frequency circuits produced in this way was evaluated in the same manner as in Example 1. The results are shown in Table 1.

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

[Table 1] Example Comparative example 1 2 3 4 5 6 7 8 9 1 2 3 4 5 Composition for resin layer polymer species P-1 P-1 P-1 P-2 P-3 P-4 P-5 P-5 P-4 P-1 P-1 P-4 P-1 SEBS Mass parts 50 35 80 50 50 50 50 50 100 10 5 10 80 100 Hardening compound species Compound A Compound B Compound C Compound A Compound A Compound A Compound A Compound A - Compound B Compound B Compound B Compound C - Mass parts 50 65 20 50 50 50 50 50 - 90 10 90 20 - species - - - - - - - - - - Compound D - - - Mass parts - - - - - - - - - - 85 - - - Hardening additives species Hardening aid A Hardening aid A Hardening aid A Hardening aid A Hardening aid B Hardening aid A Hardening aid A Hardening aid A - Hardening aid A Hardening aid A Hardening aid A Hardening aid A - Mass parts 5 2.5 5 5 0.2 5 5 5 - 5 5 5 5 - Solvent species Solvent A Solvent B Solvent A Solvent A Solvent A Solvent A Solvent A Solvent A Solvent A Solvent A Solvent A Solvent A Solvent A - Mass parts 160 200 160 160 160 160 160 160 160 160 160 160 160 - B-stage film Constitution Metal / resin / film / resin / metal Metal / resin / film / resin / metal Metal / resin / film / resin / metal Metal / Resin / Film / Resin / Film / Resin / Metal Metal / resin / film / resin / metal Metal / resin / film / resin / metal Metal / resin / film / resin / metal Metal / resin / film / resin / metal Metal / resin / film / resin / metal Metal / resin / film / resin / metal Metal / resin / film / resin / metal Metal / resin / film / resin / metal Metal / resin / film / resin / metal Metal / resin / film / resin / metal Metal layer species Electrolytic copper foil A Electrolytic copper foil B Electrolytic copper foil A Rolled copper foil A Electrolytic copper foil A Electrolytic copper foil A Electrolytic copper foil A Electrolytic copper foil A Electrolytic copper foil A Electrolytic copper foil A Electrolytic copper foil B Electrolytic copper foil B Electrolytic copper foil A - Surface roughness Ra (nm) 110 150 110 35 110 110 110 110 110 110 350 350 110 - Thickness (μm) 18 18 18 35 12 18 18 18 18 18 18 18 18 - B-stage resin layer Surface roughness Ra (nm) 35 29 42 32 34 34 34 34 34 29 15 0.01 42 - Thickness (μm) 5 5 5 5 10 25 5 15 15 25 25 25 5 5 The surface roughness of the peeling layer after peeling Ra (nm) 20 18 twenty one 19 20 twenty two twenty one twenty one twenty one 18 14 37 twenty one - The maximum value of the coefficient of elasticity under 50℃ and below 80℃ (MPa) 6 4 10 6 6 5 6 6 9 4 0.007 3 10 - The minimum value of the coefficient of elasticity above 80°C and below 200°C (MPa) 0.5 0.08 15 0.5 0.5 0.3 0.5 0.5 60 0.08 0.0004 3 15 - Membrane species PI LCP PEEK Special polystyrene PEI PEN PAEK PPE PI PI PI PI PET PI Tg (℃) >200 >200 150 >200 >200 165 158 172 >200 >200 >200 >200 69 >200 Thickness (μm) 25 25 25 25 50 188 75 25 25 25 25 25 25 25 Laminated body for high frequency circuit C-stage resin characteristics Thickness (μm) 5 5 5 5 10 25 15 15 15 25 25 25 5 5 Tensile strength (MPa) 100 70 89 75 56 78 84 84 86 70 12 44 89 330 Tensile elongation (%) 4 11 3 3 10 38 28 28 95 11 250 6 3 80 Tg (℃) 230 168 220 173 162 164 173 173 196 168 30 150 220 >200 Elasticity coefficient (GPa) 1.8 0.3 2.4 1.8 1.8 1.4 1.7 1.7 2.5 0.3 0.05 0.2 2.4 3.4 Relative permittivity 2.6 3 2.9 2.6 2.6 2.8 2.8 2.8 2.5 3.2 2.9 3.2 2.9 3.3 Dielectric loss tangent 0.005 0.009 0.008 0.005 0.005 0.004 0.004 0.004 0.003 0.02 0.012 0.02 0.008 0.018 Metal layer species Electrolytic copper foil A Electrolytic copper foil B Electrolytic copper foil A Rolled copper foil A Electrolytic copper foil A Electrolytic copper foil A Electrolytic copper foil A Electrolytic copper foil A Electrolytic copper foil A Electrolytic copper foil B Electrolytic copper foil B Sputtered copper film Electrolytic copper foil A Electrolytic copper foil A Surface roughness Ra (nm) 110 150 110 35 110 110 110 110 110 350 350 3 110 110 Thickness (μm) 18 18 18 35 12 18 18 18 18 18 18 1 18 18 Build-up conditions Heating temperature (℃) 150 150 190 160 110 180 170 170 190 150 40 220 210 120 Load (kN/m) 10 17 10 14 15 16 15 15 17 20 10 0.5 10 10 Laminated body characteristics Layer thickness (μm) 71 71 71 135 94 274 141 91 91 111 111 77 71 71 Metal peeling strength (N/cm) 7 7.8 6 5.3 6.2 7.5 8.3 8.3 5.9 7.8 4.9 3.3 6 5 Film peeling strength (N/cm) 6.6 8 6.5 6 7 11 7.6 6.5 5.4 6.5 6.8 6.1 5.5 7.4 Circuit board evaluation Transmission loss (dB/100 mm) -4.6 -4.9 -4.9 -4.2 -4.5 -4.2 -4 -3.8 -3.6 -5.5 -6.2 -6.8 Deformation during processing -7.1 Substrate step good good good good good good good good good bad bad bad - good Laminated body wound body Core Material paper paper paper ABS SUS SUS SUS SUS SUS SUS paper SUS SUS SUS Radius (mm) 40 100 30 40 80 100 100 100 100 30 10 30 30 100 Evaluation of laminated body wound body good good good good good good good good good good bad good good bad

In Table 1 above, the following abbreviations, etc. are supplemented. ＜Polymer＞ ·SEBC: Maleic acid modified styrene-ethylene butene-styrene block copolymer (manufactured by Asahi Kasei Chemical Co., Ltd., trade name "Tuftec M1913") ＜Curable compound＞ ·Compound A: 2,2'-bis(4-cyanooxyphenyl)propane (manufactured by Tokyo Chemical Industry Co., Ltd.) ·Compound B: SR-16H (manufactured by Sakamoto Pharmaceutical 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 Pharmaceutical Co., Ltd., epoxy equivalent: 305 g/eq) ＜Hardening aids＞ · Hardening aid A: 1-benzyl-2-methylimidazole (manufactured by Mitsubishi Chemical Corporation, product name "BMI 12") · Hardening aid B: Zinc 2-ethyloctanoate (manufactured by Wako Pure Chemical Industries, Ltd.) ＜Solvent＞ ·Solvent A: Cyclopentanone (manufactured by Tokyo Chemical Industry Co., Ltd.) ·Solvent B: Dichloromethane (manufactured by Tokyo Chemical Industry Co., Ltd.) ＜Type of metal layer＞ ·Electrolytic copper foil A: manufactured by Mitsui Metals Co., Ltd., product code "TQ-M4-VSP" ·Electrolytic copper foil B: manufactured by Mitsui Metals Co., Ltd., product number "3EC-M3S-HTE" ·Rolled copper foil A: manufactured by JX Metal Co., Ltd., product code "GHY5-HA" ＜Type of film＞ ·PI: manufactured by Toray Dupont, trade name "Kapton", polyimide · LCP: Kuraray (Kuraray) company, trade name "Vecstar", liquid crystal polymer ·PEEK: manufactured by Solvay, trade name "KT-820", polyether ether ketone ·Special polystyrene: manufactured by Kurashiki Textile Co., Ltd., trade name "Oidys" ·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", poly(aryl ether ketone) ·PPE: manufactured by Sabic, trade name "modified polyphenylene ether (Noryl) EFR-735", polyphenylene oxide ·PET: manufactured by Teijin Film Solutions, trade name "Teijin Tetoron Film", polyethylene terephthalate

According to the results of Table 1, it can be seen that if the laminates for high-frequency circuits obtained in Examples 1 to 8 are used to make a circuit board, it is possible to produce a circuit board that reduces the transmission loss of electric signals in the high-frequency circuit and is excellent in smoothness. Circuit board.

In addition, from the results of Table 1, it can be seen that the laminated body wound body obtained in Examples 1 to 8 is even suitable for winding the laminated body for high-frequency circuits, which reduces the transmission loss of electric signals in the high-frequency circuit, on the winding core. In the case of storage, curling wrinkles can also be effectively suppressed.

10: Membrane 11: Resin layer (exposed surface) 12, 16: B-stage resin layer 13: Resin layer (exposed surface) 14, 18: metal layer 20, 22: C-stage resin layer 30: Metal layer 32: B-stage resin layer 33: Resin layer (exposed surface) 34: Membrane 36: C-stage resin layer 40: roll core 42: step part 50: Laminated body for high frequency circuit 51: Indentation (curl wrinkles) 100: Laminated body for high frequency circuit 200: Laminated body for high frequency circuit 300: Laminated body wound body

FIG. 1A is a cross-sectional view schematically showing a part of the steps in the manufacturing example A of the laminated body for high-frequency circuits. FIG. 1B is a cross-sectional view schematically showing a part of the steps in the manufacturing example A of the laminated body for high-frequency circuits. FIG. 1C is a cross-sectional view schematically showing a part of the steps in the manufacturing example A of the laminated body for high-frequency circuits. FIG. 1D is a cross-sectional view schematically showing a part of the steps in the manufacturing example A of the laminated body for high-frequency circuits. FIG. 1E is a cross-sectional view schematically showing a part of the steps in the manufacturing example A of the laminated body for high-frequency circuits. 2A is a cross-sectional view schematically showing a part of the steps in the manufacturing example B of the laminated body for high-frequency circuits. 2B is a cross-sectional view schematically showing a part of the steps in the manufacturing example B of the laminated body for high-frequency circuits. 2C is a cross-sectional view schematically showing a part of the steps in the manufacturing example B of the laminated body for high-frequency circuits. Fig. 3 is a perspective view showing an example of the laminated body wound body of the present embodiment. Fig. 4 is a perspective view showing an example of a winding core. Fig. 5 is a perspective view showing a state of indentation generated when the laminated body is inverted from the conventional laminated body wound body.

10: Membrane

11: Resin layer (exposed surface)

12, 16: B-stage resin layer

13: Resin layer (exposed surface)

14, 18: metal layer

20, 22: C-stage resin layer

100: Laminated body for high frequency circuit

Claims (12)

A laminate for high-frequency circuits, in which a film layer with a glass transition temperature of 150°C or higher is in contact with a resin layer and laminated, and the resin layer contains the following general formula (1-1) and general formula (1-2). ) And a polymer of at least one of the repeating units represented by the general formula (1-3), the elastic modulus of the resin layer is 0.1 GPa to 3.0 GPa, and the frequency of the resin layer is 10 GHz at 23°C The dielectric loss tangent is 0.001～0.01, and the relative dielectric constant is 2.0～3.0,

In the general formulas (1-1) to (1-3), R ^{1 is} each independently a halogen atom, a monovalent hydrocarbon group having 1 to 20 carbons, a monovalent halogenated hydrocarbon group having 1 to 20 carbons, nitro A group, a cyano group, a primary amino group to a tertiary amino group, or a salt of a primary amino group to a tertiary amino group; n is each independently an integer of 0-2; when n is 2, multiple R ¹ may be The same may be different, and they may be bonded in any combination to form a part of the ring structure. The laminate for high-frequency circuits according to claim 1, wherein the resin layer has a thickness of 1 μm to 30 μm, and the film layer has a thickness of 10 μm to 300 μm. The laminate for high-frequency circuits according to claim 1 or 2, wherein the peel strength between the resin layer and the film layer is 5.0 N/cm or more. The laminate for high-frequency circuits according to any one of claims 1 to 3, wherein a metal layer is further laminated on the surface of the resin layer that is not in contact with the film layer. The laminate for high-frequency circuits according to claim 4, wherein the peel strength of the resin layer and the metal layer is 5.0 N/cm or more. The laminate for high-frequency circuits according to claim 4 or claim 5, wherein the thickness of the metal layer is 3 μm to 50 μm. The laminate for high-frequency circuits according to any one of claim 1 to claim 6, wherein the film layer is selected from the group consisting of polyimide, polyetherimide, liquid crystal polymer, polyethylene naphthalate One of the group consisting of diester, polystyrene, cyclic olefin polymer, polyether ether ketone, polyarylene ether ketone, and polyphenylene ether. A flexible printed circuit board comprising the laminate for high-frequency circuits according to any one of claims 1 to 7. A method for manufacturing a laminate for high-frequency circuits includes: heating and heating a film layer with a glass transition temperature of 150°C or higher and a B-stage resin layer with a surface roughness Ra of 1 nm to 100 nm at 50°C to 200°C. The step of bonding by applying a linear load of 1 kN/m to 19 kN/m. The method for manufacturing a laminate for a high-frequency circuit according to claim 9, further comprising: on the back of the B-stage resin layer on which the film layer is bonded, the bonding surface roughness Ra is 10 nm to 300 nm metal layer steps. A B-stage sheet having a B-stage resin layer and a film layer formed on at least one side of the B-stage resin layer. In the B-stage sheet, When the B-stage resin layer is cured to become a C-stage resin layer, The elastic coefficient of the C-stage resin layer is 0.1 GPa～3.0 GPa, The C-stage resin layer and the film layer have a dielectric loss tangent of 0.001-0.01 at a frequency of 10 GHz at 23° C., and a relative dielectric constant of 2.0-3.0. A laminated body wound body, which is formed by winding the laminated body for high-frequency circuits according to any one of claims 1 to 7 on a core having a radius of 10 mm to 100 mm.

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