TW202124529A - Resin composition, resin film, layered body, coverlay film, copper foil with resin, metal-clad layered board and circuit board - Google Patents

Abstract

This resin composition contains: (A) a thermoplastic resin that contains a structural unit derived from a tetracarboxylic anhydride component, and a diamine component containing, with respect to the total diamine component, at least 40 mol% of a dimer diamine composition having, as a main component, a dimer diamine in which two terminal carboxylic acid groups in dimer acid is substituted by a primary aminomethyl group or an amino group; and (B) at least one selected from an aromatic condensed phosphate ester, silica particles, and a liquid-crystalline polymer filler.

Description

Resin composition, resin film, laminate, cover film, copper foil with resin, metal-clad laminate and circuit board

The present invention relates to a resin composition effectively used as an adhesive in a circuit board such as a printed wiring board, a resin film, a laminate, a cover film, a copper foil with resin, a metal-clad laminate, and a circuit board using the resin composition.

In recent years, with the development of miniaturization, weight reduction, and space saving of electronic equipment, flexible printed circuit boards (Flexible Printed Circuits , FPC) increased demand. FPC can achieve three-dimensional and high-density installation even in a limited space, so its use has expanded to electronic devices such as hard disk drives (HDD), digital video disks (DVD), and mobile phones. Wiring, cables, connectors and other parts of the movable part.

In addition to the above-mentioned higher density, the higher performance of equipment has also been continuously developed, so it is also necessary to cope with the higher frequency of transmission signals. In information processing or information communication, in order to transmit and process large-capacity information, efforts have been made to increase the transmission frequency, and printed substrate materials are required to reduce transmission loss through thinning of the insulating layer and improvement of the dielectric properties of the insulating layer. In the future, FPC or adhesives that respond to higher frequencies are required, and reduction of transmission loss becomes important.

For example, in millimeter wave transmission, which is one of 5G transmissions, a direct conversion method in which millimeter waves flow directly through the FPC connecting the antenna and the substrate is being studied. The millimeter wave band becomes a higher frequency than the previous communication frequency, so the dielectric loss in the transmission loss becomes larger, and therefore, the improvement of the dielectric characteristics of the insulating resin layer becomes more important. As a technique for improving the dielectric properties of the insulating resin layer of the circuit board, it has been proposed to blend liquid crystalline polymer particles in a thermoplastic resin or a thermosetting resin (Patent Document 1). Among them, there are no examples other than epoxy resins in Patent Document 1, and no detailed studies have been conducted on thermoplastic resins. In addition, it has been proposed to reduce the thermal expansion coefficient and the relative permittivity by blending silicon dioxide particles in a polyimide-based resin used as an insulating resin layer of a circuit board (Patent Document 2 and Patent Document 3).

Moreover, as a technology related to an adhesive layer mainly composed of polyimide, it is proposed to apply the following cross-linked polyimide resin to the adhesive layer of the cover film. The cross-linked polyimide resin is made of It is obtained by reacting a polyimine compound derived from an aliphatic diamine such as a dimer acid (dimer fatty acid) as a raw material with an amine compound having at least two primary amine groups as functional groups (for example, , Patent Document 4). In addition, it has been proposed to apply a resin composition in which such polyimide and thermosetting resin such as epoxy resin and a crosslinking agent are used in combination to a copper-clad laminate (for example, Patent Document 5). In addition, it has also been proposed to blend a metal salt of organic phosphinic acid in a polyimide using a dimer acid-type diamine to achieve both low dielectric loss tangent and flame retardancy (Patent Document 6). However, in Patent Document 4 to Patent Document 6, no consideration is given to the influence of by-products other than the dimer diamine derived from the dimer acid contained in the raw material.

It is known that dimer acid is used in raw materials such as soybean oil fatty acid, tall oil fatty acid, rapeseed oil fatty acid and other natural fatty acids, as well as oleic acid, linoleic acid, hypolinoleic acid, and mustard produced by refining these acids. The dimerized fatty acid obtained by the Diels-Alder reaction and the polyacid compound derived from the dimer acid can be used as the raw material fatty acid or the fatty acid composition of trimerized or higher Obtained (for example, Patent Document 7). [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent No. 6295013 [Patent Document 2] Japanese Patent Laid-Open No. 2001-185853 [Patent Document 3] Japanese Patent Laid-Open No. 2018-012747 [Patent Document 4] Japanese Patent Laid-Open No. 2013-1730 [Patent Document 5] Japanese Patent Laid-Open No. 2017-119361 [Patent Document 6] Japanese Patent No. 6267509 [Patent Document 7] Japanese Patent Laid-Open No. 2017-137375

[The problem to be solved by the invention] Thermoplastic resins such as polyimine (hereinafter, sometimes referred to as "aliphatic thermoplastic resins") using aliphatic diamine compounds such as dimer diamines as raw materials, although there is room for improvement in flame retardancy, they have With low dielectric loss tangent and flexibility, the cross-linked resin is a material that has both heat resistance and adhesiveness. Therefore, aliphatic thermoplastic resins are expected as materials for high-speed transmission FPCs whose usage has increased due to the spread of 5G communications. On the other hand, the frequency of the signal flowing through the FPC is expected to be higher in the future. Therefore, a material based on an aliphatic thermoplastic resin and further having good dielectric properties is required.

In addition, as a method of controlling the physical properties of a resin containing polyimine as a main component, it is important to control the molecular weight of polyimide or polyimide that is a precursor of polyimide. However, when applying dimer diamine as a raw material, it is used in the state containing the by-product other than dimer diamine derived from a dimer acid. In addition to being difficult to control the molecular weight of polyimide, such by-products affect the dielectric properties in a wide range of frequencies or their humidity dependence.

Therefore, the first object of the present invention is to provide a resin composition and a resin film capable of coping with the increase in high frequency of electronic devices by further improving the dielectric properties of the aliphatic thermoplastic resin. In addition, the second object of the present invention is to provide a resin composition and a resin film that can cope with the high frequency of electronic devices by improving the dielectric properties while using dimer diamine as a raw material. [Means to solve the problem]

The resin composition of the present invention contains the following (A) component and (B) component; (A) A thermoplastic resin containing a structural unit derived from a diamine component, the diamine component containing 40 mol% or more with respect to all diamine components with two terminal carboxylic acid groups of the dimer acid substituted with A dimer diamine composition with a dimer diamine composed of a primary amino methyl group or an amine group as the main component, and (B) One or more selected from aromatic condensed phosphoric acid ester, silica particles, or liquid crystal polymer filler.

In the resin composition of the present invention, the component (A) may be a tetracarboxylic anhydride component, and a diamine containing 40 mol% or more of the dimer diamine composition with respect to all diamine components. The polyimide formed by the reaction of the components, and the (B) component may be the aromatic condensed phosphate. In this case, the weight ratio of the component (B) to the component (A) may be in the range of 0.05 to 0.7, and preferably in the range of 0.2 to 0.5. Moreover, the weight ratio of the phosphorus of the aromatic condensed phosphoric acid ester derived from the said (B) component with respect to the said (A) component may be in the range of 0.01-0.1. Furthermore, the weight ratio of the phosphorus of the aromatic condensed phosphoric acid ester derived from the said (B) component with respect to the dimer diamine composition in the said (A) component can be in the range of 0.01-0.15.

The resin composition of the present invention may further contain an amine compound having at least two primary amine groups as functional groups.

In the resin composition of the present invention, the component (A) may be a tetracarboxylic anhydride component, and a diamine containing 40 mol% or more of the dimer diamine composition with respect to all diamine components. Polyamide acid or polyimide formed by the reaction of components, and the component (B) may be silica particles having a white silica crystal phase or a quartz crystal phase. In this case, the (B) component may It is in the range of 5% by weight to 60% by weight. In addition, among the silicon dioxide particles of the component (B), the peaks originating from the white silica crystal phase and the quartz crystal phase in the range of 2θ=10° to 90° in the X-ray diffraction analysis spectrum of CuKα rays _{The ratio of the total area of SiO 2} to the total area of all peaks derived from SiO 2 may be 20% by weight or more. Furthermore, in the silica particles of the component (B), the cumulative value in the frequency distribution curve obtained by the volume-based particle size distribution measurement by the laser diffraction scattering method becomes 50% of the average particle size D ₅₀ It can be in the range of 6 μm to 20 μm.

In the resin composition of the present invention, the component (A) may be a tetracarboxylic anhydride component, and a diamine containing 40 mol% or more of the dimer diamine composition with respect to all diamine components. The polyimide formed by the reaction of the components, and the (B) component may be the liquid crystal polymer filler. In this case, the (B) component may be in the range of 15% by volume to 50% by volume relative to the total of the (A) component and the (B) component. In addition, the dielectric loss tangent of the component (A) at 10 GHz is Dfa, and the dielectric loss tangent of the liquid crystal polymer filler of the component (B) at 10 GHz is Dfb. At this time, Dfb can be less than 0.0019, and it can be Dfa>Dfb. In addition, with respect to 100% by weight of the non-volatile organic compound component of the resin composition, 15% by weight to 30% by weight of a phosphorus-based flame retardant may be further added.

In the resin composition of the present invention, the component (A) may contain a total of 90 mol parts or more of the following general formula (1) and/or general formula with respect to 100 mol parts of the tetracarboxylic anhydride component (2) Tetracarboxylic anhydride represented.

[化1]

In the general formula (1), X represents a single bond or a divalent group selected from the following formulas, and in the general formula (2), the cyclic moiety represented by Y represents the formation of a four-membered ring, a five-membered ring, and a six-membered ring. A cyclic saturated hydrocarbon group in a ring, a seven-membered ring, or an eight-membered ring.

[化2]

In the formula, Z represents -C ₆ H ₄ -, -(CH ₂ )n- or -CH ₂ -CH(-OC(=O)-CH ₃ )-CH ₂ -, n represents an integer of 1-20 .

The resin film of the present invention is a resin film including a thermoplastic resin layer, and Contains the following components (A) and (B); (A) A thermoplastic resin containing a structural unit derived from a diamine component, the diamine component containing 40 mol% or more with respect to all diamine components with two terminal carboxylic acid groups of the dimer acid substituted with A dimer diamine composition with a dimer diamine composed of a primary amino methyl group or an amine group as the main component, and (B) One or more selected from aromatic condensed phosphoric acid ester, silica particles, or liquid crystal polymer filler.

The thickness of the resin film of the present invention may be in the range of 15 μm to 100 μm.

In the resin film of the present invention, when the (B) component contains silica particles having a white silica crystal phase or a quartz crystal phase, its content is relative to the (A) component and the (B) component The total of can be in the range of 3% by volume to 41% by volume.

In the resin film of the present invention, when the (B) component contains the liquid crystal polymer filler, its content may be 15% by volume based on the total of the (A) component and the (B) component ～40% by volume.

The laminate of the present invention has a substrate and an adhesive layer laminated on at least one surface of the substrate, and the adhesive layer includes the resin film.

The cover film of the present invention has a film material layer for cover and an adhesive layer laminated on the film material layer for cover, and the adhesive layer includes the resin film.

The resin-coated copper foil of the present invention is obtained by laminating an adhesive layer and a copper foil, and the adhesive layer includes the resin film.

The metal-clad laminated board of the present invention has an insulating resin layer and a metal layer laminated on at least one surface of the insulating resin layer, and at least one layer of the insulating resin layer includes the resin film.

The circuit board of the present invention is obtained by performing wiring processing on the metal layer of the metal-clad laminate. [Effects of the invention]

The resin composition of the present invention contains (A) component and (B) component, so the resin film formed using them has excellent dielectric properties and flexibility derived from dimer diamine, and has the advantages of (B) ) The composition of the composition and further improve the dielectric properties. Therefore, the resin composition and resin film of the present invention can be particularly preferably used as a circuit board material such as FPC in electronic equipment that requires high-speed signal transmission.

Hereinafter, an embodiment of the present invention will be described. The resin composition of one embodiment of the present invention contains the following (A) component and (B) component; (A) A thermoplastic resin containing a structural unit derived from a diamine component, the diamine component containing 40 mol% or more with respect to all diamine components with two terminal carboxylic acid groups of the dimer acid substituted with A dimer diamine composition with a dimer diamine composed of a primary amino methyl group or an amine group as the main component, and (B) One or more selected from aromatic condensed phosphoric acid ester, silica particles, or liquid crystal polymer filler.

[(A) component; thermoplastic resin] The thermoplastic resin of the component (A) refers to the loss tangent (tanδ) that contains the structural unit derived from the diamine component and is measured using a dynamic viscoelasticity measuring device (dynamic mechanical analyzer (DMA)) A resin with a maximum value of less than 200°C, the diamine component contains 40 mol% or more relative to all diamine components with the two terminal carboxylic acid groups of the dimer acid substituted with primary amino methyl groups or amines A dimer diamine composition composed of a base dimer diamine as the main component. Therefore, as the thermoplastic resin, there can be mentioned: thermoplastic polyimide containing 40 mol% or more of the diamine component of the dimer diamine composition as a raw material, polyimide as its precursor, and thermoplastic bimar Leximine resin, thermoplastic epoxy resin, thermoplastic polyamide resin, hardened products of these, etc. These thermoplastic resins can be formulated in combination of two or more kinds. Among these thermoplastic resins, more preferred is a thermoplastic polyimide (hereinafter, sometimes referred to as " DDA-based thermoplastic polyimide") and its cross-linked hardened product, the diamine component contains 40 mol% or more with respect to all the diamine components with the two terminal carboxylic acid groups of the dimer acid substituted with A dimer diamine composition in which a dimer diamine composed of a primary amino methyl group or an amine group is the main component.

Hereinafter, DDA-based thermoplastic polyimide will be cited as a representative example of the thermoplastic resin, and the details will be described. In addition, the so-called "thermoplastic polyimide" generally refers to the polyimide whose glass transition temperature (Tg) can be clearly confirmed, but in the present invention means: 30 Polyimide with a storage elasticity coefficient of 1.0×10 ⁸ Pa or more at ℃ and a storage elasticity coefficient of less than 3.0×10 ⁷ Pa at 300 ℃. In addition, the so-called "non-thermoplastic polyimide" generally refers to a polyimide that does not soften and exhibits adhesiveness even if heated, but in the present invention means: 30°C measured using a dynamic viscoelasticity measuring device (DMA) A polyimide with a storage elastic coefficient of 1.0×10 ⁹ Pa or more and a storage elastic coefficient of 3.0×10 ⁸ Pa or more at 300°C.

＜DDA series thermoplastic polyimide＞ DDA-based thermoplastic polyimide is an aliphatic thermoplastic polyimide, which is rich in flexibility. Even when a large amount of liquid crystal polymer filler is added, it has sufficient toughness and maintains its toughness when forming a resin film. The shape ability is high. Therefore, the content of the DDA-based thermoplastic polyimide in the component (A) is preferably 60% by weight or more, more preferably 70% by weight or more, and most preferably 80% by weight or more. If the content of the DDA-based thermoplastic polyimide in the component (A) is less than 60% by weight, the toughness of the thermoplastic resin decreases, and the film retention when forming a resin film decreases.

The DDA-based thermoplastic polyimide contains a tetracarboxylic acid residue derived from a tetracarboxylic anhydride as a raw material and a diamine residue derived from a diamine compound as a raw material. By reacting the tetracarboxylic acid anhydride and diamine compound as the raw material with approximately equal molar reaction, the type and amount of the tetracarboxylic acid residue and the diamine residue contained in the DDA-based thermoplastic polyimide and the type of the raw material can be made It roughly corresponds to the amount.

(Tetracarboxylic anhydride component) The DDA-based thermoplastic polyimide can be used as a raw material with tetracarboxylic anhydride generally used in thermoplastic polyimine without particular limitation, and it is preferable to contain 90 mol% or more of the following in total with respect to all tetracarboxylic anhydride components. Tetracarboxylic anhydride represented by general formula (1) and/or general formula (2). In other words, it is preferable that the DDA-based thermoplastic polyimide contains a total of 90 mol parts or more with respect to 100 mol parts of all tetracarboxylic acid residues, which are selected from the following general formula (1) and/or general formula (2). Represents a tetracarboxylic acid residue derived from tetracarboxylic anhydride. By containing a total of 90 mol parts or more of the tetracarboxylic acid residue derived from the tetracarboxylic anhydride represented by the following general formula (1) and/or general formula (2) with respect to 100 mol parts of the tetracarboxylic acid residue Base, it is easy to achieve the compatibility of the flexibility and heat resistance of the DDA-based thermoplastic polyimide, which is preferable. When the total amount of tetracarboxylic acid residues derived from the tetracarboxylic acid anhydride represented by the following general formula (1) and/or general formula (2) is less than 90 moles, the solvent dissolves in the presence of DDA-based thermoplastic polyimide Tendency to decrease sex.

[化3]

In the general formula (1), X represents a single bond or a divalent group selected from the following formulas, and in the general formula (2), the cyclic moiety represented by Y represents the formation of a four-membered ring, a five-membered ring, and a six-membered ring. A cyclic saturated hydrocarbon group in a ring, a seven-membered ring, or an eight-membered ring.

[化4]

In the formula, Z represents -C ₆ H ₄ -, -(CH ₂ )n- or -CH ₂ -CH(-OC(=O)-CH ₃ )-CH ₂ -, n represents an integer of 1-20 .

As the tetracarboxylic anhydride represented by the general formula (1), for example, 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA), 3,3',4,4'- Benzophenone tetracarboxylic dianhydride (BTDA), 3,3',4,4'-diphenyl tetracarboxylic dianhydride (DSDA), 4,4'-oxydiphthalic anhydride ( ODPA), 4,4'-(hexafluoroisopropylidene) diphthalic anhydride (6FDA), 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane Anhydride (BPADA), p-phenylene bis (trimellitic acid monoester anhydride) (TAHQ), ethylene glycol bis trimellitic anhydride (TMEG), etc. Among these, 3,3',4,4'-benzophenone tetracarboxylic dianhydride (BTDA) is particularly preferred. In the case of using BTDA, the carbonyl group (ketone group) contributes to the adhesiveness, so the reduction in peel strength when the liquid crystal polymer filler is added as the component (B) can be suppressed, and the adhesiveness of the DDA-based thermoplastic polyimide can be improved . In addition, in BTDA, the ketone group present in the molecular skeleton reacts with the amine group of the amino compound formed by crosslinking described later to form a C=N bond, and it is easy to exhibit the effect of improving heat resistance. From this viewpoint, it is preferable to contain a tetracarboxylic acid residue derived from BTDA in an amount of preferably 50 mol parts or more, more preferably 60 mol parts or more with respect to 100 mol parts of tetracarboxylic acid residues.

In addition, as the tetracarboxylic anhydride represented by the general formula (2), for example, 1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2,3,4-cyclopentane tetracarboxylic acid can be cited Dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 1,2,4,5-cycloheptanetetracarboxylic dianhydride, 1,2,5,6-cyclooctane tetracarboxylic acid Acid dianhydride and so on.

The DDA-based thermoplastic polyimide may contain a tetracarboxylic acid residue derived from an acid anhydride other than the tetracarboxylic anhydride represented by the general formula (1) and the general formula (2) within a range that does not impair the effect of the invention. The tetracarboxylic acid residue is not particularly limited, and examples include pyromellitic dianhydride, 2,3',3,4'-biphenyltetracarboxylic dianhydride, 2,2',3, 3'-benzophenone tetracarboxylic dianhydride or 2,3,3',4'-benzophenone tetracarboxylic dianhydride, 2,3',3,4'-diphenyl ether tetracarboxylic acid Dianhydride, bis(2,3-dicarboxyphenyl) ether dianhydride, 3,3``,4,4''-terrestrial tetracarboxylic dianhydride, 2,3,3``,4'' -Perphenyltetracarboxylic dianhydride or 2,2``,3,3''-Perphenyltetracarboxylic dianhydride, 2,2-bis(2,3-dicarboxyphenyl)-propane dianhydride Or 2,2-bis(3,4-dicarboxyphenyl)-propane dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride or bis(3,4-dicarboxyphenyl)methane dianhydride , Bis(2,3-dicarboxyphenyl) dianhydride or bis(3,4-dicarboxyphenyl) dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride Or 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,2,7,8-phenanthrene-tetracarboxylic dianhydride, 1,2,6,7-phenanthrene-tetracarboxylic acid Dianhydride or 1,2,9,10-phenanthrene-tetracarboxylic dianhydride, 2,3,6,7-anthracene tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)tetra Fluoropropane dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 4,8-Dimethyl-1,2,3,5,6,7-hexahydronaphthalene-1,2,5,6-tetracarboxylic dianhydride, 2,6-dichloronaphthalene-1,4, 5,8-tetracarboxylic dianhydride or 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,3,6,7-(or 1,4,5,8- ) Tetrachloronaphthalene-1,4,5,8-(or 2,3,6,7-)tetracarboxylic dianhydride, 2,3,8,9-perylene-tetracarboxylic dianhydride, 3,4, 9,10-perylene-tetracarboxylic dianhydride, 4,5,10,11-perylene-tetracarboxylic dianhydride or 5,6,11,12-perylene-tetracarboxylic dianhydride, pyrazine-2,3 ,5,6-tetracarboxylic dianhydride, pyrrolidine-2,3,4,5-tetracarboxylic dianhydride, thiophene-2,3,4,5-tetracarboxylic dianhydride, 4,4'-bis (2,3-Dicarboxyphenoxy) tetracarboxylic acid residue derived from aromatic tetracarboxylic dianhydride such as diphenylmethane dianhydride.

(Diamine component) The DDA-based thermoplastic polyimide uses as a raw material a diamine component containing a dimer diamine composition of 40 mol% or more, and more preferably 60 mol% or more with respect to all diamine components. By containing the dimer diamine composition in the above amount, the dielectric properties of polyimide can be improved, and the thermocompression bonding properties can be improved by lowering the glass transition temperature of polyimide (lower Tg) And the internal stress is alleviated by lowering the coefficient of elasticity.

(Dimer diamine composition) The dimer diamine composition contains the following component (a) as a main component, and the amounts of the component (b) and the component (c) are controlled.

(A) Dimer diamine; The dimer diamine as component (a) means that the two terminal carboxylic acid groups (-COOH) of the dimer acid are substituted with a primary aminomethyl group (-CH _2- NH ₂ ) or amine group (-NH ₂ ) formed diamine. Dimer acid is a known dibasic acid obtained by the intermolecular polymerization of unsaturated fatty acids. Its industrial manufacturing process has been roughly standardized in the industry, and the use of clay catalysts to reduce the carbon number of unsaturated fatty acids 11-22 Fatty acid is obtained by dimerization. Regarding the industrially obtained dimer acid, the main component is the 36 carbon dibasic acid obtained by dimerizing oleic acid, linoleic acid, hypolinoleic acid, and other unsaturated fatty acids with 18 carbon atoms. The degree of purification contains arbitrary amounts of monomeric acid (18 carbon atoms), trimer acid (54 carbon atoms), and other polymerized fatty acids having 20 to 54 carbon atoms. In addition, the double bond remains after the dimerization reaction, but in the present invention, the dimer acid also includes those that further undergo a hydrogenation reaction to reduce the degree of unsaturation. The dimer diamine as the component (a) can be defined by substituting the terminal carboxylic acid group of a dibasic acid compound in the range of carbon number 18 to 54, preferably in the range of 22 to 44, with a primary amino group Group or amine group to obtain a diamine compound.

As a feature of dimer diamine, it can impart characteristics derived from the dimer acid skeleton. That is, the dimer diamine is an aliphatic with a huge molecule with a molecular weight of about 560 to 620, so the molar volume of the molecule can be increased, and the polar group of the DDA-based thermoplastic polyimide can be relatively reduced. It is believed that the characteristics of such dimer acid-type diamine help to suppress the decrease in the heat resistance of the DDA-based thermoplastic polyimide, while reducing the relative permittivity and the dielectric loss tangent, and improving the dielectric properties. In addition, since it has two freely movable hydrophobic chains with 7-9 carbons and two chain aliphatic amine groups with a length close to 18 carbons, it can not only impart flexibility to the DDA-based thermoplastic polyimide Moreover, the DDA-based thermoplastic polyimide has an asymmetric chemical structure or a non-planar chemical structure, so it is considered that a low dielectric constant can be achieved.

The dimer diamine composition preferably uses a purification method such as molecular distillation to increase the content of the dimer diamine as component (a) to 96% by weight or more, preferably 97% by weight or more, more preferably 98% by weight The above. By setting the content of the dimer diamine as the component (a) to be 96% by weight or more, it is possible to suppress the spread of the molecular weight distribution of the DDA-based thermoplastic polyimide. Furthermore, if it is technically feasible, it is most preferable that the entire dimer diamine composition (100% by weight) includes the dimer diamine as the component (a).

(B) A monoamine compound obtained by substituting a terminal carboxylic acid group of a monobasic acid compound having a carbon number of 10-40 with a primary aminomethyl group or an amino group; Monobasic acid compounds in the range of carbon number 10 to 40 are monobasic unsaturated fatty acids in the range of carbon number 10 to 20 derived from the raw material of dimer acid, and by-products in the production of dimer acid. A mixture of monobasic acid compounds having a carbon number of 21-40. The monoamine compound is obtained by substituting the terminal carboxylic acid group of these monobasic acid compounds with a primary aminomethyl group or an amino group.

The monoamine compound as the component (b) is a component that suppresses the increase in the molecular weight of polyimine. During the polymerization of polyamide acid or polyimide, the monofunctional amine group of the monoamine compound reacts with the terminal acid anhydride group of polyamide acid or polyimide, whereby the terminal acid anhydride group is sealed, thereby Suppresses the increase of the molecular weight of polyamide acid or polyimide.

(C) An amine compound obtained by substituting a terminal carboxylic acid group of a polybasic acid compound having a hydrocarbon group in the range of 41 to 80 carbon atoms with a primary aminomethyl group or an amine group (wherein, the dimer diamine except); The polybasic acid compound having a hydrocarbon group in the range of carbon number 41 to 80 is a polybasic acid compound having a tribasic acid compound in the range of carbon number 41 to 80, which is a by-product during the production of dimer acid, as a main component. In addition, polymerized fatty acids other than the dimer acid having 41 to 80 carbon atoms may be included. The amine compound is obtained by substituting the terminal carboxylic acid group of these polybasic acid compounds with a primary aminomethyl group or an amine group.

The amine compound as the component (c) is a component that promotes an increase in the molecular weight of polyimine. A trifunctional or higher amine group containing a triamine body derived from a trimer acid as a main component reacts with the terminal anhydride group of a polyamide acid or polyimine, and the molecular weight of the polyimide is rapidly increased. In addition, amine compounds derived from polymerized fatty acids other than dimer acids having 41 to 80 carbon atoms also increase the molecular weight of polyimine and cause the gelation of polyimide or polyimine.

When the dimer diamine composition is quantified by measurement using gel permeation chromatography (gel permeation chromatography, GPC), in order to easily confirm each component of the dimer diamine composition For the peak start, peak top, and peak end of the components, a sample processed with a dimer diamine composition with acetic anhydride and pyridine was used, and cyclohexanone was used as the internal standard material. Using the sample prepared in the manner described above, each component was quantified using the area percentage of the chromatogram of GPC. The peak start and peak end of each component can be used as the minimum value of each peak curve, and the area percentage of the chromatogram can be calculated based on it.

In addition, in the dimer diamine composition used in the present invention, based on the area percentage of the chromatogram obtained by GPC measurement, the total of component (b) and component (c) is preferably 4% or less, which is more The best is less than 4%. By setting the total of the component (b) and the component (c) to 4% or less, the expansion of the molecular weight distribution of the polyimide can be suppressed.

In addition, the area percentage of the chromatogram of the component (b) is preferably 3% or less, more preferably 2% or less, and still more preferably 1% or less. By setting it as such a range, the reduction of the molecular weight of polyimide can be suppressed, and further, the range of the molar ratio of the input of a tetracarboxylic anhydride component and a diamine component can be expanded. In addition, the component (b) may not be included in the dimer diamine composition.

In addition, the area percentage of the chromatogram of the component (c) is preferably 2% or less, more preferably 1.8% or less, and more preferably 1.5% or less. By setting it in such a range, it is possible to suppress a rapid increase in the molecular weight of the polyimide, and it is possible to suppress the increase in the dielectric loss tangent of the resin film over a wide range of frequencies. In addition, the component (c) may not be included in the dimer diamine composition.

In addition, when the area percentage ratio (b/c) of the chromatogram of the component (b) and the component (c) is 1 or more, the molar ratio of the tetracarboxylic anhydride component and the diamine component (tetracarboxylic anhydride component /Diamine component) is preferably set to 0.97 or more and less than 1.0. By setting it to such a molar ratio, it is easier to control the molecular weight of the polyimide.

In addition, when the ratio (b/c) of the area percentage of the chromatogram of the component (b) and the component (c) is less than 1, the molar ratio of the tetracarboxylic anhydride component and the diamine component (tetracarboxylic acid The acid anhydride component/diamine component) is preferably 0.97 or more and 1.1 or less. By setting it as such a molar ratio, it is easier to control the molecular weight of the polyimide.

The dimer diamine composition used in the present invention is preferably purified for the purpose of reducing components other than the dimer diamine as the component (a). The purification method is not particularly limited, but a known method such as distillation or precipitation purification is preferred. The dimer diamine composition before refining can be obtained from commercially available products, for example, PRIAMINE 1073 (trade name) manufactured by Croda Japan, and Croda Japan PRIAMINE 1074 (trade name) manufactured by Croda Japan, PRIAMINE 1075 (trade name) manufactured by Croda Japan, etc.

Examples of diamine compounds other than the dimer diamine used in the DDA-based thermoplastic polyimide include aromatic diamine compounds and aliphatic diamine compounds. Specific examples of these include: 1,4-diaminobenzene (p-PDA; p-phenylenediamine), 2,2'-dimethyl-4,4'-diaminobiphenyl (m -TB), 2,2'-n-propyl-4,4'-diaminobiphenyl (m-NPB), 4-aminophenyl-4'-aminobenzoate (APAB), 2 ,2-Bis-[4-(3-aminophenoxy)phenyl]propane, bis[4-(3-aminophenoxy)phenyl]sulfonate, bis[4-(3-aminophenoxy)phenyl]propane Oxy)]biphenyl, bis[1-(3-aminophenoxy)]biphenyl, bis[4-(3-aminophenoxy)phenyl]methane, bis[4-(3-amine Phenyloxy)phenyl]ether, bis[4-(3-aminophenoxy)]benzophenone, 9,9-bis[4-(3-aminophenoxy)phenyl]fluorene , 2,2-bis-[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis-[4-(3-aminophenoxy)phenyl]hexafluoropropane , 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-methylene bis-o-toluidine, 4,4'-methylene bis-2,6-di Toluidine, 4,4'-methylene-2,6-diethylaniline, 3,3'-diaminodiphenylethane, 3,3'-diaminobiphenyl, 3,3' -Dimethoxybenzidine, 3,3''-diamino-p-terphenyl, 4,4'-[1,4-phenylenebis(1-methylethylene)]bisaniline, 4 ,4'-[1,3-Phenylenebis(1-methylethylene)]bisaniline, bis(p-aminocyclohexyl)methane, bis(p-β-amino-tertiary butylbenzene) Base) ether, bis(p-β-methyl-δ-aminopentyl)benzene, p-bis(2-methyl-4-aminopentyl)benzene, p-bis(1,1-dimethyl- 5-aminopentyl)benzene, 1,5-diaminonaphthalene, 2,6-diaminonaphthalene, 2,4-bis(β-amino-tertiary butyl)toluene, 2,4-di Aminotoluene, m-xylene-2,5-diamine, p-xylene-2,5-diamine, m-xylylenediamine, p-xylylenediamine, 2,6-diaminopyridine, 2,5 -Diaminopyridine, 2,5-diamino-1,3,4-oxadiazole, piperazine, 2'-methoxy-4,4'-diaminobenzaniline, 4,4 '-Diaminobenzaniline, 1,3-bis[2-(4-aminophenyl)-2-propyl]benzene, 6-amino-2-(4-aminophenoxy) Diamine compounds such as benzoxazole and 1,3-bis(3-aminophenoxy)benzene.

The DDA-based thermoplastic polyimide can be produced by reacting the tetracarboxylic anhydride component and the diamine component in a solvent to generate polyamide acid and then heating the ring. For example, the tetracarboxylic anhydride component and the diamine component are dissolved in an organic solvent at approximately equal moles and stirred at a temperature in the range of 0°C to 100°C for 30 minutes to 24 hours to carry out the polymerization reaction, thereby obtaining the polymer Polyamide acid which is the precursor of imine. During the reaction, the reaction components are dissolved so that the generated precursor is in the range of 5% by weight to 50% by weight, preferably in the range of 10% by weight to 40% by weight, in the organic solvent. Examples of the organic solvent used in the polymerization reaction include: N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), and N,N-diethylacetamide Amine, N-methyl-2-pyrrolidone (NMP), 2-butanone, dimethyl sulfide (DMSO), hexamethylphosphamide, N-methylcaprolactone, dimethyl sulfate , Cyclohexanone, methylcyclohexane, dioxane, tetrahydrofuran, diglyme, triglyme, methanol, ethanol, benzyl alcohol, cresol, etc. These solvents may be used in combination of two or more, and aromatic hydrocarbons such as xylene and toluene may also be used in combination. In addition, the amount of the organic solvent used is not particularly limited, but it is preferably adjusted so that the concentration of the polyamide acid solution obtained by the polymerization reaction becomes about 5% to 50% by weight. .

The synthesized polyamide acid is generally advantageously used as a reaction solvent solution, and can be concentrated, diluted, or replaced with other organic solvents if necessary. In addition, polyamide acid is generally used advantageously because it is excellent in solvent solubility. The viscosity of the polyamide acid solution is preferably in the range of 500 cps to 100,000 cps. If it deviates from this range, defects such as thickness unevenness and streaks are likely to occur in the film during coating work using a coater or the like.

There is no particular limitation on the method of imidizing polyamide acid to form polyimide. For example, it can be preferably used in the solvent at a temperature in the range of 80°C to 400°C for 1 hour. Heat treatment such as heating is performed for 24 hours. In addition, the temperature can be heated under a fixed temperature condition, or the temperature can be changed in the middle of the step.

In the DDA-based thermoplastic polyimide, by selecting the types of the tetracarboxylic anhydride component and the diamine component, or the respective molar ratio when two or more tetracarboxylic anhydride components or diamine components are applied, it is possible to control Dielectric properties, coefficient of thermal expansion, coefficient of tensile elasticity, glass transition temperature, etc. In addition, when DDA-based thermoplastic polyimine has a plurality of polyimine structural units, it may exist in the form of a block or may exist randomly, and it is preferable to exist randomly.

The weight average molecular weight of the DDA-based thermoplastic polyimide is, for example, preferably in the range of 10,000 to 200,000, and if it is within such a range, it is easy to control the weight average molecular weight of the polyimide. In addition, for example, when suitable as an adhesive for FPC, the weight average molecular weight of the DDA-based thermoplastic polyimide is more preferably in the range of 20,000 to 150,000, and still more preferably in the range of 40,000 to 150,000. When used as an adhesive for FPC, when the weight average molecular weight of the DDA-based thermoplastic polyimide is less than 20,000, the flow resistance tends to deteriorate. On the other hand, if the weight average molecular weight of the DDA-based thermoplastic polyimide exceeds 150,000, the viscosity increases excessively and does not dissolve in the solvent, which tends to cause defects such as uneven thickness of the adhesive layer and streaks during the coating operation. .

The concentration of the imine group of the DDA-based thermoplastic polyimide is preferably 22% by weight or less, and more preferably 20% by weight or less. Here, the "imine group concentration" refers to _{the value obtained by dividing the molecular weight of the polyimine group (-(CO) 2} -N-) by the molecular weight of the entire structure of the polyimide . If the concentration of the imine group exceeds 22% by weight, the molecular weight of the resin itself becomes small, and the low hygroscopicity is also deteriorated due to the increase of the polar group, and the Tg and elastic coefficient increase.

The best DDA-based thermoplastic polyimide has a completely imidized structure. Among them, a part of polyimide may become amide acid. The rate of imidization can be determined by using a Fourier transform infrared spectrophotometer (commercial product: FT/IR620 manufactured by JASCO Corporation), and using the attenuated total reflection (ATR) method to determine the polyimide The infrared absorption spectrum of the film was measured, and the benzene ring absorber in the vicinity of ^{1015 cm -1 was used as a reference, and it was calculated from the absorbance of 1780 cm -1} derived from the C=O stretch of the imino group.

＜Crosslink formation＞ When the DDA-based thermoplastic polyimide in component (A) has a ketone group, the ketone group is combined with an amino compound having at least two primary amino groups as functional groups (hereinafter, sometimes referred to as "cross The amine group of the amine compound for link formation ") reacts to form a C=N bond, thereby forming a crosslinked structure. By forming a cross-linked structure, the heat resistance of DDA-based thermoplastic polyimide can be improved. As a tetracarboxylic acid anhydride that is preferable for forming a DDA-based thermoplastic polyimide having a ketone group, for example, 3,3',4,4'-benzophenone tetracarboxylic dianhydride (BTDA), as the two Examples of amine compounds include 4,4'-bis(3-aminophenoxy)benzophenone (BABP) and 1,3-bis[4-(3-aminophenoxy)benzyl ] Benzene (BABB) and other aromatic diamines.

For the purpose of forming a cross-linked structure, the resin composition of the present embodiment particularly preferably includes: a resin composition containing at least 50 mol%, and more preferably at least 60 mol% relative to all tetracarboxylic acid residues. The DDA-based thermoplastic polyimide in the component (A) of the BTDA residue derived from BTDA and the amine compound for crosslinking. Furthermore, the "BTDA residue" in the present invention refers to a tetravalent group derived from BTDA.

As the amine-based compound for crosslinking formation, (I) a dihydrazine compound, (II) an aromatic diamine, (III) an aliphatic amine, and the like can be exemplified. Among these, dihydrazine compounds are preferred. Aliphatic amines other than the dihydrazine compound easily form a crosslinked structure even at room temperature, and there is a concern about the storage stability of the varnish. On the other hand, the aromatic diamine needs to be set to a high temperature in order to form a crosslinked structure. In the case of using a dihydrazine compound in this way, both the storage stability of the varnish and the shortening of the curing time can be achieved. As the dihydrazine compound, for example, dihydrazine oxalate, dihydrazine malonate, dihydrazine succinate, dihydrazine glutarate, dihydrazine adipate, and dihydrazine pimelate are preferred. , Dihydrazine suberate, Dihydrazine azelate, Dihydrazine sebacate, Dihydrazine dodecanedioate, Dihydrazine maleate, Dihydrazine fumarate, Diglycolic acid dihydrazide Dihydrazine, dihydrazine tartrate, dihydrazine malate, dihydrazine phthalate, dihydrazine isophthalate, dihydrazine terephthalate, dihydrazine 2,6-naphthoate, 4, Dihydrazine compounds such as 4-bisphenyldihydrazine, 1,4-naphthoic acid dihydrazine, 2,6-pyridine diacid dihydrazide, and itaconic acid dihydrazine. The above dihydrazine compounds may be used alone, or two or more of them may be mixed and used.

In addition, the (I) dihydrazine compound, (II) aromatic diamine, (III) aliphatic amine and other amine-based compounds may be, for example, a combination of (I) and (II), (I) and (III) Like the combination of (I), (II) and (III), the super category uses two or more combinations.

In addition, from the viewpoint of making the network structure formed by the crosslinking of the crosslinking amine-based compound denser, the molecular weight of the crosslinking amine-based compound used in the present invention (in the crosslinking forming When the amino compound is an oligomer, the weight average molecular weight) is preferably 5,000 or less, more preferably 90 to 2,000, and still more preferably 100 to 1,500. Among these, particularly preferred is an amine-based compound for crosslinking formation having a molecular weight of 100 to 1,000. If the molecular weight of the amine-based compound for cross-linking is less than 90, one amine group of the amine-based compound for cross-linking is limited to forming a C=N bond with the ketone group of the DDA-based thermoplastic polyimide, and the remaining amine groups are around It is three-dimensionally bulky, so there is a tendency that the remaining amine groups are not easy to form a C=N bond.

When the ketone group in the DDA-based thermoplastic polyimide in the component (A) is cross-linked with the amine-based compound for cross-linking formation, the cross-linking is added to the resin solution containing the component (A) The amine-based compound for formation is a condensation reaction between the ketone group in the DDA-based thermoplastic polyimide and the primary amine group of the amine-based compound for crosslinking. Due to this condensation reaction, the resin solution is cured to become a cured product. In this case, the amount of the amine compound for crosslinking formation can be 0.004 mol to 1.5 mol in total, and preferably 0.005 mol to 1.2 mol in total with respect to 1 mol of the ketone group. The ears are more preferably 0.03 mol to 0.9 mol, most preferably 0.04 mol to 0.6 mol. Regarding the addition amount of the crosslinking amine compound such as the total primary amine group being less than 0.004 mol relative to 1 mol of the ketone group, the crosslinking by the crosslinking amine compound is not sufficient. It shows the tendency of heat resistance after curing. If the addition amount of the amine-based compound for cross-link formation exceeds 1.5 mol, the unreacted amine-based compound for cross-link formation functions as a thermoplastic The heat resistance tends to decrease.

If the conditions for the condensation reaction for crosslinking formation are that the ketone group in the DDA-based thermoplastic polyimine in component (A) reacts with the primary amine group of the crosslinking amine-based compound to form an imine The condition of the key (C=N key) is not particularly limited. Regarding the temperature of the heating condensation, the water produced by the condensation is released to the outside of the system, or when the heating condensation reaction is performed after the synthesis of the DDA-based thermoplastic polyimide in the component (A) For reasons such as simplification of the condensation step, for example, it is preferably in the range of 120°C to 220°C, and more preferably in the range of 140°C to 200°C. The reaction time is preferably about 30 minutes to 24 hours. The end point of the reaction can be measured, for example, by using a Fourier transform infrared spectrophotometer (commercial product: FT/IR620 manufactured by JASCO Corporation) to measure the infrared absorption spectrum, and using a polyimide-derived resin near ^{1670 cm -1} It was confirmed that the absorption peak of the ketone group decreased or disappeared, and the absorption peak derived from the imine group near ^{1635 cm -1 appeared.}

(A) The heating condensation of the ketone group of the DDA-based thermoplastic polyimide in the component and the primary amine group of the amine compound for crosslinking can be carried out by, for example, the following method: (1) Immediately after the synthesis (imination) of the DDA-based thermoplastic polyimide in the component (A), an amine-based compound for crosslinking formation is added and the method is heated; (2) Preliminarily put an excessive amount of amine-based compound as the diamine component, followed by the synthesis of the DDA-based thermoplastic polyimide in component (A) (imination), and will not participate in the imidization or amide A method in which the remaining amine-based compound after conversion is used as an amine-based compound for cross-linking and is heated together with DDA-based thermoplastic polyimide; or (3) After processing the composition of the DDA-based thermoplastic polyimide in the component (A) to which the amine-based compound for crosslinking is added into a predetermined shape (for example, coating on any substrate Or after forming into a film) heating method.

In order to impart heat resistance to the DDA-based thermoplastic polyimide in the component (A), the formation of the imine bond was explained in the formation of the crosslinked structure, but it is not limited to this, as the polyimide in the component (A) The hardening method of imidine, for example, can also prepare and harden the compound which has an unsaturated bond, such as an epoxy resin, an epoxy resin hardener, a maleimide, an activated ester resin, or resin which has a styrene skeleton.

[(B) Ingredient] The resin composition of this embodiment contains one or more selected from the group consisting of aromatic condensed phosphoric acid esters, silica particles, and liquid crystal polymer fillers as the (B) component. In addition, as (B) component, you may use 2 or more types together. Hereinafter, the aromatic condensed phosphoric acid ester will be described as the "(B1) component", the silicon dioxide particles as the "(B2) component", and the liquid crystal polymer filler as the "(B3) component".

[(B1) Ingredient; Aromatic Condensed Phosphate] The so-called "aromatic condensed phosphoric acid ester" as the component (B1) refers to a phosphoric acid ester compound or phosphorus oxychloride having a chemical structure in which two or more phosphoric acid ester units are linked by a divalent organic group having an aromatic ring , Reaction products with divalent phenolic compounds and phenol or alkylphenol. By combining an aromatic condensed phosphate and a polyimide obtained by using a fixed amount or more of a dimer diamine composition, the dielectric properties can be improved. The reason for this is not clear, but it is speculated that based on the unique chemical structure of the aromatic condensed phosphate, although the dielectric properties of the aromatic condensed phosphate itself are compatible with the polyimide obtained using the dimer diamine composition, However, since it does not excessively increase the mobility of the molecular chain, it contributes to low dielectric constant and low dielectric loss tangent. In addition, the resin film obtained by using the component (B1) has low humidity dependence of dielectric properties and excellent stability.

As a preferable example of aromatic condensed phosphoric acid ester, the compound of the structure of the following general formula (3) is mentioned.

[化5]

In the general formula (3), a plurality of Rs are each independently an optionally substituted aromatic hydrocarbon group, Ar is a divalent organic group having an aromatic ring, and n is an integer of 1 or more. The aromatic condensed phosphate represented by the general formula (3) may be a polymer in which n is 2 or more in addition to a dimer in which n is 1. In addition, it is not limited to a single compound, and may be a mixture.

Examples of the optionally substituted aromatic hydrocarbon group represented by R in the general formula (3) include aryl groups having 6 to 15 carbon atoms, and more specifically, phenyl groups, methyl phenyl groups, and dimethyl phenyl groups. Phenyl group, trimethyl phenyl group, ethyl phenyl group, butyl phenyl group, nonyl phenyl group and the like. In addition, in the general formula (3), preferred examples of the divalent organic group represented by Ar include, for example, an alkylene group, an arylene group, and the like, and these groups may have a substituent. More preferably, for example, a phenylene group or a group represented by the following formula (4) and the like can be mentioned.

[化6]

In formula (4), Y ₁ refers to a single bond, -CH ₂ -, -C(CH ₃ ) ₂ -, -SO ₂ -, -C ₅ H ₁₀ -, -C ₆ H ₁₂ -, -C ₇ H ₁₄ -, -C ₈ H ₁₆ -etc. Among the groups represented by the formula (4), _{a biphenyldiyl group in which Y 1} is a single bond is more preferable.

Examples of aromatic condensed phosphate esters include resorcinol bis-diphenyl phosphate, resorcinol bis-xylyl phosphate, bisphenol A bis-diphenyl phosphate, and the like. As these aromatic condensed phosphate esters, commercially available products are available, for example, CR-733S (trade name), CR-741 (trade name), CR-747 (trade name), PX-200 (trade name), PX-200B (trade name) [above, manufactured by Daha Chemical Industry Co., Ltd.] etc. These aromatic condensed phosphoric acid esters can be used in combination of two or more kinds.

＜(B1) Blending amount of ingredients＞ The weight ratio of the component (B1) to the component (A) in the resin composition of the present embodiment is in the range of 0.05 to 0.7, and the film properties such as the coefficient of tensile elasticity when forming the resin film are considered. It is in the range of 0.2 to 0.5 (the same applies to the resin film described later). When the weight ratio of the component (B1) to the component (A) is less than 0.05, the improvement of the dielectric properties may be insufficient. If it exceeds 0.7, it may be difficult to form polyimide, and there may be The embrittlement of the obtained polyimide film. By setting the blending amount of the component (B1) within the above range, the dielectric properties can be improved. In addition, in the case of polyamide acid, the component (A) shall be converted into polyimide to calculate the weight ratio (hereinafter, the same).

In addition, in the resin composition of the present embodiment, the component (B1) is preferably formulated so that the weight ratio of the phosphorus derived from the component (B1) to the thermoplastic resin of the component (A) is in the range of 0.01 to 0.1 . If the weight ratio of phosphorus derived from the component (B1) is less than 0.01, the improvement of the dielectric properties is insufficient, and if it exceeds 0.1, embrittlement of the polyimide film (or polyimide layer) may occur.

The weight ratio of the phosphorus derived from the component (B1) in the component (B1) of the resin composition of this embodiment to the dimer diamine composition contained in the component (A) {phosphorus derived from the component (B1)/ (A) The dimer diamine composition in the component} is preferably in the range of 0.01 to 0.15. If the lower limit is less than, the improvement of the dielectric properties may be insufficient. If the upper limit is exceeded, it may be difficult to form polyimide, and the resulting polyimide film may become brittle. condition.

[(B2) Ingredient: Silica particles] As the silicon dioxide particles of the component (B2), any of crystalline silicon dioxide particles and amorphous silicon dioxide particles can be used, but it is preferable to include crystalline silicon dioxide having a white silica crystal phase or a quartz crystal phase. Silicon particles. By blending silicon dioxide particles as the component (B2), the dielectric loss tangent when forming the resin film can be reduced. From the viewpoint of achieving a low dielectric loss tangent when forming a resin film, it is particularly preferable to use silica particles having a white silica crystal phase as the crystalline silica particles. Compared with ordinary silica particles, silica particles with a schauxite crystal phase have excellent dielectric properties (for example, silica particles containing more than 90% by weight of the schauxite crystal phase are based on the monomer The dielectric loss tangent at 20 GHz is about 0.0001), which can greatly contribute to the low dielectric loss tangent of the resin film.

In addition, as the silica particles of the component (B2), it is preferable to use spherical silica particles. Spherical silica particles refer to silica particles whose shape is close to a spherical shape and the ratio of the average long diameter to the average short diameter is 1 or close to 1.

In addition, since silicon dioxide does not undergo thermal decomposition at normal combustion temperatures, the flame retardancy can be improved by adding silicon dioxide particles as the component (B2).

In addition, from the viewpoint of achieving a low dielectric loss tangent when forming a resin film, as the entire silicon dioxide particles used, the X-ray diffraction analysis spectrum of CuKα rays is 2θ=10°～90° The ratio of the total area of the peaks derived from the white silica crystal phase and the quartz crystal phase to the total area _{of all the peaks derived from SiO 2} in the range is preferably 20% by weight or more, more preferably 40% by weight or more, ideally Is more than 80% by weight. By increasing the proportion of the silica crystal phase and/or quartz crystal phase in the entire silica particles, the polyimide can be further reduced in dielectric loss tangent. If the area ratio of the peaks derived from the white silica crystal phase and the quartz crystal phase in the entire silica particles is less than 20% by weight, the effect of improving the dielectric properties is unclear. Furthermore, when the target peak in the X-ray diffraction analysis spectrum is difficult to separate from the amorphous broad peak or when it overlaps with other crystalline phase peaks, various known analysis methods, such as internal standard method or PONKCS method and so on.

The average particle diameter D _{50 of the} silicon dioxide particles is preferably in the range of 6 μm to 20 μm, more preferably in the range of 8 μm to 15 μm. Here, the average particle diameter D ₅₀ is a value at which the cumulative value in the frequency distribution curve obtained by the volume-based particle size distribution measurement using the laser diffraction scattering method becomes 50%. If the average particle size D ₅₀ is within this range, the dielectric properties can be effectively improved, and a low-dielectric film with good appearance can be obtained without deteriorating the surface smoothness when the resin film is formed from the resin composition. If the average particle diameter D _{50 is} less than the above range, the specific surface area of the silica particles increases, and the adsorbed water or polar groups on the surface of the silica particles may affect the dielectric properties. If the average particle diameter D ₅₀ exceeds the above range, it may appear as irregularities on the surface of the resin film, and the smoothness of the film surface may be deteriorated.

In addition, 90% by weight or more of silicon dioxide particles having a particle size of 3 μm or more preferably have a circularity of 0.7 or more, and more preferably 0.9 or more. The circularity of the silicon dioxide particles can be determined by the image analysis method, assuming a circle having the same projected area as the imaged particle, and calculating the ratio of the circumference of the circle to the circumference of the particle. If the circularity is less than 0.7, the surface area increases, which may adversely affect the dielectric properties, and further increase the viscosity when blended into the resin solution, making it difficult to handle. In addition, it is preferable that the sphericity obtained three-dimensionally also substantially corresponds to the value of the circularity.

In addition, the silica particles preferably have a true specific gravity of 2.3 or more. If the true specific gravity is less than 2.3, it implies that the crystallinity of the silicon dioxide particles is small, and the effect of improving the dielectric properties is small.

The silicon dioxide particles can be suitably selected from commercially available products and used. For example, spherical white silica powder (manufactured by Nippon Steel Chemical & Materials Co., Ltd., trade name: CR10-20), spherical amorphous silica powder (manufactured by Nippon Steel Chemical & Materials Co., Ltd., Trade name: SC70-2) etc. Furthermore, two or more different silica particles may be used in combination as the silica particles.

<The compounding amount of the component (B2)> The weight ratio of the component (B2) of the resin composition of the present embodiment to the total of the component (A) and the component (B2) is in the range of 5% by weight to 60% by weight (described later The same in the resin film). When the weight ratio of (B2) component to the total of (A) component and (B2) component is less than 5% by weight, the effect of improving dielectric properties and flame retardancy may be insufficient. If it exceeds 60% by weight, It may be difficult to form polyimide, and there may be embrittlement of the obtained polyimide film. By setting the blending amount of the component (B2) within the above range, the dielectric properties and flame retardancy can be improved. In addition, when the content of the (B2) component is within the range of 5% by weight to 20% by weight relative to the total of the (A) component and (B2) component, it is preferable to use X-ray diffraction by CuKα rays. It is prepared so that the total area of the peaks derived from the white silica crystal phase and the quartz crystal phase in the range of 2θ=10°～90° of the analysis spectrum is 40% by weight or more _{relative to the total area of all peaks derived from SiO 2} Crystalline silica particles. On the other hand, when the content of the (B2) component exceeds 20% by weight relative to the total of the (A) component and (B2) component, it is preferable to use the peak value derived from the white silica crystal phase and the quartz crystal phase. The crystalline silica particles are prepared so that the area becomes 30% by weight or more.

In addition, from the viewpoint of improving the adhesion to metal layers such as copper foil when forming a resin film, the volume ratio of the (B2) component to the total of the (A) component and (B2) component is preferably 3% to 41 It is within the range of %, and more preferably within the range of 10% to 35% (the same in the resin film described later). In addition, the volume ratio can be calculated from the density and weight ratio of the (A) component and the (B2) component to be blended, or can be determined by cross-sectional observation with a scanning electron microscope.

[(B3) Ingredient: Liquid crystal polymer filler] The liquid crystal polymer filler is a particle containing a liquid crystal polymer forming an optically anisotropic melt phase. The liquid crystal polymer that forms the optically anisotropic melt phase is also called thermotropic liquid crystal polymer. The polymer that forms an optically anisotropic molten phase is a polymer that transmits polarized light when a sample in a molten state is observed under crossed Nicols with a polarizing microscope including a heating device. Liquid crystal polymers have almost no frequency dependence, have very excellent dielectric properties, and also contribute to the improvement of flame retardancy. Therefore, by blending liquid crystal polymers, the dielectric properties and flame retardancy of the resin film can be improved.

The liquid crystal polymer is not particularly limited, and examples thereof include known thermotropic liquid crystal polyesters and polyesteramides derived from compounds classified into the following (1) to (4) and their derivatives. (1) Aromatic or aliphatic dihydroxy compound (2) Aromatic or aliphatic dicarboxylic acid (3) Aromatic hydroxy carboxylic acid (4) Aromatic diamine, aromatic hydroxylamine or aromatic amino carboxylic acid The more aromatic rings in the liquid crystal polymer, the more the effect of improving the dielectric properties or flame retardancy can be expected. Therefore, it is preferable to include an aromatic dihydroxy compound (aromatic diol) as the above (1), including an aromatic Dicarboxylic acid is referred to as (2).

As a representative example of a liquid crystal polymer obtained from these raw material compounds, a copolymer having a combination of two or more structural units selected from the following formulas (a) to (g), preferably containing A copolymer of any one of the structural unit represented by the formula (a) or the structural unit represented by the formula (b), more preferably comprising the structural unit represented by the formula (a) and the structural unit represented by the formula (b) Copolymer. Formulas (a) and (b) are representative examples of structural units derived from aromatic hydroxycarboxylic acids, and formulas (c), (d), and (e) are structural units derived from aromatic dicarboxylic acids As a representative example, Formula (f) and Formula (g) are representative examples of structural units derived from aromatic dihydroxy compounds (aromatic diols). In addition, in the structural unit represented by formula (a) to formula (g), the aromatic ring may have any substituent.

Especially as a liquid crystal polymer with a low dielectric loss tangent, examples include: · A liquid crystal polymer containing structural units represented by formulas (a) and (b), structural units selected from formula (c), formula (d), or formula (e), and selected from formulas at a specific ratio (F) or the structural unit in formula (g); · A liquid crystal polymer containing the structural unit represented by formula (b), the structural unit selected from formula (c), formula (d) or formula (e), and the structural unit selected from formula (f) or formula at a specific ratio (G) The structural unit, etc.

[化7]

In order to improve the dielectric properties of the resin film obtained from the resin composition, the liquid crystalline polymer filler is preferably used as follows: As a monomer, the relative dielectric constant at 10 GHz is preferably in the range of 2.8 to 3.6, more preferably In the range of 3.0 to 3.4, the dielectric loss tangent at 10 GHz is preferably less than 0.0019, and more preferably less than 0.0015. In addition, the liquid crystal polymer filler is more preferably when the dielectric loss tangent of the component (A) at 10 GHz is Dfa and the dielectric loss tangent of the component (B3) at 10 GHz is Dfb. Dfb is less than 0.0019, and Dfa>Dfb.

In addition, as a liquid crystal polymer, from the viewpoint of achieving improvement in flame retardancy, it is preferable to contain aromatic rings in abundance. The weight ratio of the aromatic ring in the liquid crystalline polymer filler is preferably 60% by weight or more, and more preferably 70% by weight or more.

In addition, as the liquid crystal polymer particles, it is preferable to use spherical liquid crystal polymer particles. Spherical liquid crystal polymer particles refer to liquid crystal polymer particles having a shape close to a spherical shape and a ratio of an average long diameter to an average short diameter of 1 or close to 1.

The average particle diameter D _{50 of the} liquid crystal polymer particles is preferably in the range of 6 μm to 20 μm, more preferably in the range of 8 μm to 15 μm. Here, the average particle diameter D ₅₀ is a value at which the cumulative value in the frequency distribution curve obtained by the volume-based particle size distribution measurement using the laser diffraction scattering method becomes 50%. When the average particle diameter D ₅₀ is within this range, a low-dielectric film with a good appearance can be obtained without deteriorating the surface smoothness when the resin film is formed from the resin composition. If the average particle diameter D _{50 is} less than the above-mentioned range, the liquid crystal polymer particles aggregate during the preparation as a resin composition, and there is a possibility that a uniform resin composition cannot be obtained. If the average particle diameter D ₅₀ exceeds the above range, it may appear as irregularities on the surface of the resin film, and the smoothness of the film surface may be deteriorated.

The melting point of the liquid crystal polymer is preferably higher than the curing temperature of the resin composition, for example, preferably 250°C or higher.

The liquid crystal polymer particles can be appropriately selected and used. For example, a low-dielectric liquid crystal polymer (manufactured by JXTG Energy Corporation) or the like can be preferably used. Furthermore, two or more different liquid crystal polymer particles may be used in combination as the liquid crystal polymer particles.

＜(B3) Blending amount of ingredients＞ The ratio of the (B3) component of the resin composition of this embodiment to the total of the (A) component and (B3) component is in the range of 15% by volume to 50% by volume, preferably 15% by volume to 40% by volume Within the range (the same in the resin film described later). When the volume ratio of (B3) component to the total of (A) component and (B3) component is less than 15% by volume, the effect of improving dielectric properties and flame retardancy may be insufficient. If it exceeds 50% by volume, There are cases where it is difficult to form polyimide, and there are cases where embrittlement of the obtained resin film occurs. By setting the blending amount of the component (B3) within the above range, the dielectric properties and flame retardancy can be improved. Furthermore, the volume ratio of (B3) component to the total of (A) component and (B3) component can be calculated by observing the cross-section of the cured film with a scanning electron microscope or the like to calculate the liquid crystallinity in the resin composition The ratio of the polymer filler can be determined.

[Arbitrary Ingredients] The resin composition of this embodiment may contain an organic solvent. For example, it may be a polyimide solution containing a solvent-soluble DDA-based thermoplastic polyimide and a solvent. Examples of the organic solvent include: N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), N,N-diethylacetamide, N-methyl 2-pyrrolidone (NMP), 2-butanone, dimethyl sulfide (DMSO), hexamethylphosphamide, N-methylcaprolactam, dimethyl sulfate, cyclohexanone, Dioxane, tetrahydrofuran, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, cresol, etc. Two or more of these solvents may be used in combination, and aromatic hydrocarbons such as xylene and toluene may also be used in combination. The content of the organic solvent is not particularly limited, but it is preferably adjusted to a usage amount such that the concentration of the thermoplastic resin becomes about 5 to 30% by weight.

In addition, the resin composition of this embodiment may contain a flame retardant when a liquid crystalline polymer filler is used as the (B) component. The flame retardant is not particularly limited, but it is preferably a phosphorus flame retardant. Aliphatic thermoplastic resins such as DDA-based thermoplastic polyimide have a low aromatic ring concentration. Therefore, even if a phosphorus-based flame retardant is added, the flame-retardant properties cannot be fully exhibited. In the resin composition, since the concentration of the aromatic ring derived from the liquid crystal polymer becomes higher, the formation of carbon (carbonized film) during combustion is promoted, and a high flame retardant effect is exhibited. From the above viewpoint, in the case of using the liquid crystalline polymer filler as the component (B3), it is preferable to further add 15% to 30% by weight relative to 100% by weight of the nonvolatile organic compound component of the resin composition. Phosphorus flame retardant in wt%. Here, the "non-volatile organic compound component" refers to the remaining solid component after removing the solvent and the inorganic solid component from the resin composition. That is, the non-volatile organic compound component contains the thermoplastic resin as the component (A) and the liquid crystalline polymer filler as the component (B3), and as an optional component, it may contain resins other than the thermoplastic resin, and organic materials other than the liquid crystalline polymer filler. Fillers, plasticizers, hardening accelerators, coupling agents, organic pigments, organic flame retardants other than phosphorus flame retardants, etc.

Examples of phosphorus-based flame retardants include aromatic condensed phosphoric acid esters having the same structure as the component (B1), metal salts of organic phosphinic acid, alkyl phosphines (except for red phosphorus), and the like. These flame retardants can use two or more kinds of different compounds in combination.

The metal salt of organic phosphinic acid is a metal salt of phosphoric acid in which two organic groups are bonded to phosphorus, as represented by the following general formula (5), for example.

[化8]

In the general formula (5), the two organic groups R ₁₁ and R _{12 are} preferably linear or branched alkyl groups having 1 to 6 carbon atoms or phenyl groups or tolyl groups that are the same or different from each other. In addition, in the general formula (5), the metal type M is preferably selected from Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na and K. In the group. Furthermore, when the metal type M is an n-valent metal having a valence of two or more, M in the general formula (5) is deformed to M1/n. In addition, in order to increase the flame retardant effect, it is preferable to increase the phosphorus content. Specifically, the two organic groups R ₁₁ and R _{12 are} preferably alkyl groups having 1 to 3 carbon atoms. For flexibility and suppression of solubility in water as a metal salt, the metal species M is preferably aluminum (Al).

As the metal salt of organic phosphinic acid, commercially available products can be obtained, for example, the aluminum phosphinate salt manufactured by Clariant Japan Co., Ltd., Exolit OP930 (trade name), Exolit OP935 (trade name), Exolit OP940 (trade name), etc.

In the resin composition of this embodiment, if necessary, other resin components other than the thermoplastic resin of component (A), crosslinking agents, inorganic fillers other than silica particles, and organic fillers other than liquid crystal polymer fillers can be appropriately blended. , Plasticizers, hardening accelerators, coupling agents, pigments, etc. as optional ingredients. Examples of the crosslinking agent include amine compounds having at least two primary amine groups as functional groups (amino compounds for crosslinking formation), epoxy compounds, bismaleimide compounds, and acrylic (methacrylic)-based compounds. Compound etc. As an inorganic filler, aluminum oxide, magnesium oxide, beryllium oxide, boron nitride, aluminum nitride, silicon nitride, aluminum fluoride, calcium fluoride, etc. are mentioned, for example. These can be used singly or in combination of two or more.

[Viscosity] As the viscosity range for improving the handleability when coating the resin composition and facilitating the formation of a uniform thickness of the coating film, the viscosity of the resin composition is preferably, for example, in the range of 3000 cps to 100,000 cps, more preferably 5000 cps Within the range of ~50,000 cps. If it deviates from the viscosity range, defects such as thickness unevenness and streaks are likely to occur in the film when the coating operation is performed using a coater or the like.

[Preparation of resin composition] The resin composition of this embodiment can be prepared, for example, by making a solution of the component (A) using an arbitrary solvent, adding the component (B) to it, and mixing uniformly. For example, the component (B) may be directly blended in the resin solution of DDA-based thermoplastic polyimide. In addition, a part of (A) component can be prepared simultaneously with (B) component or after adding (B) component. In either method, the component (B) can be added all at once, or added little by little in fractions. In addition, the raw materials can also be put in together, and can also be mixed little by little.

When the resin composition of the present embodiment is used to form an adhesive layer, in addition to excellent flexibility and thermoplasticity, it also has excellent dielectric properties and flame retardancy. Therefore, the resin composition of this embodiment has preferable characteristics as an adhesive agent for a cover film which protects wiring parts, such as FPC, a rigid/flexible circuit board, etc., for example.

[Resin Film] The resin film of this embodiment is a resin film including a thermoplastic resin layer (preferably a DDA-based thermoplastic polyimide layer), which is the solid content of the resin composition (the remaining part after removing the solvent) It is made by filming the main components. That is, the resin film of this embodiment contains (A) component and (B) component, and the weight ratio of (B) component to (A) component is adjusted to the predetermined range similarly to the said resin composition. In addition to flexibility and adhesiveness, the resin film of this embodiment also has excellent high frequency characteristics and flame retardancy, so it can be preferably used to protect the cover film of wiring parts such as FPC, rigid/flexible circuit boards, etc. For applications such as adhesive layer or bonding sheet of multilayer FPC.

The resin film of this embodiment is not particularly limited as long as it is a film of an insulating resin containing a thermoplastic resin layer formed of the resin composition, and it may be a film (sheet) containing an insulating resin, or may be laminated on copper foil. A film of insulating resin in the state on a substrate such as a resin sheet such as a glass plate, a polyimide-based film, a polyimide-based film, and a polyester-based film.

＜Glass transition temperature＞ The glass transition temperature (Tg) of the resin film of this embodiment is preferably 250°C or lower, and more preferably in the range of 40°C or higher and 200°C or lower. Since the Tg of the resin film is 250°C or less, thermocompression bonding can be performed at low temperatures, so internal stress generated during lamination can be alleviated, and dimensional changes after circuit processing can be suppressed. If the Tg of the resin film exceeds 250°C, the subsequent temperature will increase, which may impair the dimensional stability after circuit processing.

When using the component (B1) as the component (B), the resin film preferably has the following physical properties. <Dielectric properties> In the case of using component (B1) as component (B), the resin film is based on the following formula (i) E ₁ =√ε ₁ ×Tanδ ₁ ···(i) [here, ε ₁ represents the relative permittivity at 10 GHz measured by a separation dielectric resonator (SPDR) after 24 hours of humidity adjustment under constant temperature and humidity conditions (normal) at 23°C and 50% RH. Tanδ ₁ represents The dielectric loss tangent at 10 GHz was measured by SPDR after adjusting the humidity for 24 hours under constant temperature and humidity conditions of 23°C and 50% RH. Furthermore, "√ε ₁ "refers to _{the square root of ε 1 ] and is calculated to indicate the E 1} value, which is an index of the dielectric properties at 10 GHz after 24 hours of humidity control under constant temperature and humidity conditions of 23°C and 50% RH. It is 0.010 or less, preferably 0.009 or less, and more preferably 0.008 or less. If the E ₁ value exceeds the upper limit, for example, when it is used in a circuit board such as an FPC, defects such as electrical signal loss are likely to occur on the transmission path of high-frequency signals.

<Relative permittivity> In the case of using component (B1) as component (B), for the resin film, in order to ensure impedance matching when used in circuit boards such as FPC, and to reduce electrical signal loss, _{The relative permittivity (ε 1} ) at 10 GHz after humidity adjustment for 24 hours under constant temperature and humidity conditions of 23° C. and 50% RH is preferably 3.2 or less, and more preferably 3.0 or less. If the relative dielectric constant exceeds 3.2, for example, when it is used in a circuit board such as an FPC, defects such as electrical signal loss are likely to occur on the transmission path of high-frequency signals.

<Dielectric loss tangent> In addition, when the component (B1) is used as the component (B), for the resin film, in order to reduce the loss of electrical signals when used in a circuit board such as FPC, the temperature is at 23°C and 50°C. _{The dielectric loss tangent (Tanδ 1} ) at 10 GHz after the humidity is adjusted for 24 hours under a constant temperature and humidity condition of %RH is preferably less than 0.005, and more preferably less than 0.004. If the dielectric loss tangent is 0.005 or more, for example, when it is used in a circuit board such as an FPC, defects such as electrical signal loss are likely to occur on the transmission path of high-frequency signals.

<Moisture absorption dependence> In the case of using component (B1) as component (B), the resin film is used to reduce the loss of electrical signals during dry and wet conditions or to ensure impedance when used in circuit boards such as FPC. The matching is based on the following formula (ii) E ₂ =√ε ₂ ×Tanδ ₂ ···(ii) [Here, ε ₂ represents the relative value at 10 GHz measured by SPDR after absorbing water at 23°C for 24 hours The dielectric constant, Tanδ ₂ represents the dielectric loss tangent at 10 GHz measured by SPDR after absorbing water at 23°C for 24 hours. In addition, "√ε ₂ "refers to _{the square root of ε 2 ] In the E 2} value, which is an index calculated to indicate the dielectric characteristics at 10 GHz after absorbing water at 23°C for 24 hours, the _{value of E 2} is relative to the value based on _{The ratio of E 1} values (E ₂ /E ₁ ) calculated from the formula (i) is in the range of 3.0 to 1.0, preferably in the range of 2.5 to 1.0, more preferably 2.2 to 1.0 Within range. If E ₂ /E ₁ exceeds the upper limit, for example, when it is used in a circuit board such as FPC, the relative permittivity and dielectric loss tangent when wet will increase, which is likely to cause electrical generation in the transmission path of high-frequency signals. Defects such as signal loss.

＜Moisture absorption rate＞ In the case of using component (B1) as component (B), as for the resin film, in order to reduce the influence of humidity when used in circuit boards such as FPC, the moisture absorption rate of the resin film is preferably 0.5 weight % Or less, more preferably less than 0.3% by weight. Here, the "moisture absorption rate" refers to the rate of moisture absorption after 24 hours or more under constant temperature and humidity conditions of 23° C. and 50% RH (the same meaning in this specification). If the moisture absorption rate of the resin film exceeds 0.5% by weight, for example, when it is used in a circuit board such as an FPC, it is easily affected by humidity, and problems such as fluctuations in the transmission speed of high-frequency signals are likely to occur. That is, if the moisture absorption rate of the resin film exceeds the above range, it is easy to absorb water with a high relative permittivity, which results in an increase in the relative permittivity and dielectric loss tangent, which is likely to occur in the transmission path of high-frequency signals. Defects such as electrical signal loss.

<Storage elastic coefficient> In the case of using component (B1) as component (B), the resin film may have a temperature range in which the storage elastic coefficient decreases at a steep slope in the range of 40°C to 250°C as the temperature rises. . The characteristics of such a resin film are considered to be a factor that relaxes internal stress during thermocompression bonding and maintains dimensional stability after circuit processing. The storage elastic coefficient of the resin film at the upper limit temperature of the temperature range is preferably 5×10 ⁷ [Pa] or less. By setting such a storage elasticity coefficient, even if it is set as the upper limit of the temperature range, thermocompression bonding can be performed below 250° C., which can ensure adhesion and suppress dimensional changes after circuit processing. Furthermore, although the resin film of this embodiment has high thermal expansion properties, it has low elasticity. Therefore, even if the coefficient of thermal expansion (CTE) exceeds 30 ppm/K, the internal stress generated during lamination can be alleviated.

When using the component (B2) as the component (B), the resin film preferably has the following physical properties. ＜Relative dielectric constant＞ In the case of using component (B2) as component (B), for the resin film, in order to ensure impedance matching when used in circuit boards such as FPC, and to reduce the loss of electrical signals, the temperature is at 23°C, 50%RH The relative permittivity at 20 GHz after the humidity is adjusted for 24 hours under the constant temperature and humidity conditions is preferably 3.2 or less, and more preferably 3.0 or less. If the relative dielectric constant exceeds 3.2, for example, when it is used in a circuit board such as an FPC, defects such as electrical signal loss are likely to occur on the transmission path of high-frequency signals.

＜Dielectric loss tangent＞ In addition, in the case of using component (B2) as component (B), for the resin film, in order to reduce the loss of electrical signals when used in circuit boards such as FPC, the constant temperature and humidity conditions at 23°C and 50%RH The dielectric loss tangent at 20 GHz after 24 hours of down conditioning is preferably less than 0.005, more preferably less than 0.004, and most preferably less than 0.002. If the dielectric loss tangent is 0.005 or more, for example, when it is used in a circuit board such as an FPC, defects such as electrical signal loss are likely to occur on the transmission path of high-frequency signals.

When using the component (B3) as the component (B), the resin film preferably has the following physical properties. ＜Relative dielectric constant＞ In the case of using component (B3) as component (B), for the resin film, in order to ensure impedance matching when used in circuit boards such as FPC, and to reduce the loss of electrical signals, the temperature is at 23°C, 50%RH The relative permittivity at 20 GHz after the humidity is adjusted for 24 hours under the constant temperature and humidity conditions is preferably 3.2 or less, and more preferably 3.0 or less. If the relative dielectric constant exceeds 3.2, for example, when it is used in a circuit board such as an FPC, defects such as electrical signal loss are likely to occur on the transmission path of high-frequency signals.

＜Dielectric loss tangent＞ In addition, in the case of using component (B3) as component (B), for the resin film, in order to reduce the loss of electrical signals when used in circuit boards such as FPC, the constant temperature and humidity conditions at 23°C and 50%RH The dielectric loss tangent at 20 GHz after 24 hours of down conditioning is preferably less than 0.005, more preferably less than 0.004, and most preferably less than 0.002. If the dielectric loss tangent is 0.005 or more, for example, when it is used in a circuit board such as an FPC, defects such as electrical signal loss are likely to occur in the transmission path of high-frequency signals.

＜Thickness＞ When using the component (B1) as the component (B), the thickness of the resin film is preferably in the range of 5 μm or more and 125 μm or less, and more preferably in the range of 8 μm or more and 100 μm or less, for example. If the thickness of the resin film is less than 5 μm, defects such as wrinkles may occur during transportation such as the manufacture of the resin film. On the other hand, if the thickness of the resin film exceeds 125 μm, the productivity of the resin film may occur. Reduce the risk.

In addition, in the case of using component (B2) or component (B3) as component (B), the thickness of the resin film is, for example, preferably in the range of 15 μm to 100 μm, more preferably in the range of 20 μm to 50 μm . If the thickness of the resin film is less than 15 μm, defects such as wrinkles may occur during transportation such as the manufacture of the resin film. On the other hand, if the thickness of the resin film exceeds 100 μm, the productivity of the resin film may occur. Reduce the risk. In addition, when the thickness of the resin film is in the range of 15 μm to 20 μm, in order to suppress irregularities on the surface of the resin film and maintain the smoothness of the film surface, silicon dioxide particles as component (B2) or component (B3) The liquid crystalline polymer filler of is preferably one having an average particle diameter D ₅₀ in the range of 9 μm to 12 μm.

[Layered body] The laminate of one embodiment of the present invention has a substrate and an adhesive layer laminated on at least one surface of the substrate, and the adhesive layer includes the resin film. In addition, the layered body may include any layers other than those described above. Examples of the base material in the laminate include base materials made of inorganic materials such as copper foils and glass plates, or base materials made of resin materials such as polyimide-based films, polyamide-based films, and polyester-based films. As a preferable aspect of a laminated body, a cover film, copper foil with resin, etc. are mentioned.

[Cover film] A cover film as one aspect of a laminate has a cover film material layer as a base material and an adhesive layer laminated on one side of the cover film material layer, and the adhesive layer includes the resin film. In addition, the cover film may include any layer other than the above.

The material of the covering film material layer is not particularly limited. For example, polyimide-based films such as polyimide, polyetherimide, and polyimide-based films, or polyimide-based films, polyester-based films, etc. can be used. Film and so on. Among these, it is preferable to use a polyimide-based film having excellent heat resistance. In addition, in order to effectively express light-shielding, concealment, design, etc., the covering film material may also contain black pigments. In addition, matting pigments that inhibit surface gloss may be included within a range that does not impair the improvement effect of dielectric properties. And other optional ingredients.

The thickness of the film material layer for coating is not particularly limited, but for example, it is preferably in the range of 5 μm or more and 100 μm or less. In addition, the thickness of the adhesive layer is not particularly limited. For example, it is preferably within a range of 10 μm or more and 75 μm or less.

The cover film of this embodiment can be manufactured by the method exemplified below. First, as the first method, a varnish-like resin composition containing a solvent is applied to one side of the covering film material layer, and then dried at a temperature of 80°C to 180°C to form an adhesive layer. Covering film of film material layer and adhesive layer.

In addition, as a second method, a varnish-like resin composition containing a solvent is applied to an arbitrary substrate, for example, dried at a temperature of 80°C to 180°C and then peeled off, thereby forming an adhesive film for the adhesive layer The adhesive film and the covering film material layer are thermocompression-bonded, for example, at a temperature of 60°C to 220°C, thereby forming a covering film.

[Copper foil with resin] The copper foil with resin which is another aspect of a laminate is formed by laminating an adhesive layer on at least one side of a copper foil as a base material, and the adhesive layer includes the resin film. In addition, the copper foil with resin of this embodiment may contain arbitrary layers other than the above.

The thickness of the adhesive layer in the resin-coated copper foil is, for example, preferably in the range of 2 μm to 125 μm, and more preferably in the range of 2 μm to 100 μm. If the thickness of the adhesive layer is less than the lower limit, problems such as insufficient adhesion may not be ensured. On the other hand, if the thickness of the adhesive layer exceeds the upper limit, disadvantages such as reduced dimensional stability may occur. In addition, from the viewpoint of low dielectric constant and low dielectric loss tangent, the thickness of the adhesive layer is preferably 3 μm or more.

The material of the copper foil in the resin-coated copper foil is preferably one containing copper or a copper alloy as a main component. The thickness of the copper foil is preferably 35 μm or less, more preferably in the range of 5 μm to 25 μm. From the viewpoint of production stability and handleability, the lower limit of the thickness of the copper foil is preferably 5 μm. Furthermore, the copper foil may be a rolled copper foil or an electrolytic copper foil. In addition, as the copper foil, a commercially available copper foil can be used.

Copper foil with resin can be prepared, for example, by sputtering metal on the resin film to form a seed layer, for example, copper plating is used to form a copper layer, or it can also be prepared by laminating the resin film and the copper foil by a method such as thermocompression bonding. To prepare. Furthermore, in order to form an adhesive layer on the copper foil with resin, the coating liquid of a resin composition may be cast, and after drying to form a coating film, it may be prepared by performing required heat treatment.

[Metal Clad Laminate] (The first aspect) A metal-clad laminated board according to an embodiment of the present invention includes an insulating resin layer and a metal layer laminated on at least one surface of the insulating resin layer, and at least one layer of the insulating resin layer includes the resin film. In addition, the metal-clad laminated sheet of this embodiment may include any layer other than the above.

(Second aspect) The metal-clad laminate of another embodiment of the present invention includes, for example, an insulating resin layer, an adhesive layer laminated on at least one side of the insulating resin layer, and an adhesive layer laminated on the insulating resin layer via the adhesive layer The so-called three-layer metal-clad laminate of the metal layer, the adhesive layer contains the resin film. In addition, the three-layer metal-clad laminate may include any layers other than those described above. The adhesive layer of the three-layer metal-clad laminated board may be provided on one side or both sides of the insulating resin layer, and the metal layer may be provided on one side or both sides of the insulating resin layer via the adhesive layer. That is, the three-layer metal-clad laminated board may be a single-sided metal-clad laminated board or a double-sided metal-clad laminated board. Single-sided FPC or double-sided FPC can be manufactured by etching the metal layer of a three-layer metal-clad laminate and performing wiring circuit processing.

The insulating resin layer in the three-layer metal-clad laminate is not particularly limited as long as it includes a resin having electrical insulating properties. Examples include polyimide, epoxy resin, phenol resin, polyethylene, and polypropylene. , Polytetrafluoroethylene, silicone, ETFE, etc., preferably including polyimide. The polyimide layer constituting the insulating resin layer may be a single layer or multiple layers, and preferably includes a non-thermoplastic polyimide layer.

The thickness of the insulating resin layer in the three-layer metal-clad laminate is, for example, preferably in the range of 1 μm to 125 μm, and more preferably in the range of 5 μm to 100 μm. If the thickness of the insulating resin layer is less than the lower limit, problems such as insufficient electrical insulation may not be ensured. On the other hand, if the thickness of the insulating resin layer exceeds the upper limit, problems such as warpage of the three-layer metal-clad laminate may occur.

The thickness of the adhesive layer in the three-layer metal-clad laminate is, for example, preferably in the range of 0.1 μm to 125 μm, and more preferably in the range of 0.3 μm to 100 μm. In the three-layer metal-clad laminate of the present embodiment, if the thickness of the adhesive layer is less than the lower limit, problems such as insufficient adhesion may not be ensured. On the other hand, if the thickness of the adhesive layer exceeds the upper limit, disadvantages such as reduced dimensional stability may occur. In addition, from the viewpoint of low dielectric constant and low dielectric loss tangent of the entire insulating layer as a laminate of the insulating resin layer and the adhesive layer, the thickness of the adhesive layer is preferably 3 μm or more .

In addition, the ratio of the thickness of the insulating resin layer to the thickness of the adhesive layer (thickness of the insulating resin layer/thickness of the adhesive layer) is, for example, preferably in the range of 0.1 to 3.0, and more preferably in the range of 0.15 to 2.0. By setting this ratio, the warpage of the three-layer metal-clad laminate can be suppressed. In addition, the insulating resin layer may contain fillers as necessary. Examples of the filler include silicon dioxide, aluminum oxide, magnesium oxide, beryllium oxide, boron nitride, aluminum nitride, silicon nitride, aluminum fluoride, calcium fluoride, metal salts of organic phosphinic acid, and the like. These can be used singly or in combination of two or more.

[Circuit Board] The circuit board of one embodiment of the present invention is obtained by performing wiring processing on the metal layer of the metal-clad laminate of any one of the above-mentioned embodiments. One or more metal layers of the metal-clad laminate are processed into a pattern by a conventional method to form a wiring layer (conductor circuit layer), thereby making it possible to manufacture circuit boards such as FPC. Furthermore, the circuit board may also include a cover film covering the wiring layer. [Example]

Examples are shown below to describe the features of the present invention in more detail. However, the scope of the present invention is not limited to the examples. In addition, in the following examples, unless otherwise specified, various measurements and evaluations were performed as follows.

[Method for measuring amine value] Weigh about 2 g of the dimer diamine composition into a 200-250 mL Erlenmeyer flask, use phenolphthalein as an indicator, and add 0.1 mol/L ethanolic potassium hydroxide solution dropwise Until the solution is light pink, it is dissolved in about 100 mL of neutralized butanol. Add 3 to 7 drops of phenolphthalein solution, and titrate while stirring with a 0.1 mol/L ethanolic potassium hydroxide solution until the sample solution turns light pink. Add 5 drops of bromophenol blue solution to it, and titrate while stirring with a 0.2 mol/L hydrochloric acid/isopropanol solution until the sample solution turns yellow. The amine value is calculated by the following formula (1). Amine value={(V ₂ ×C ₂ )-(V ₁ ×C ₁ )}×M _KOH /m･･･(1) Here, the amine value is the value represented by mgKOH/g, and M _KOH is hydrogen The molecular weight of potassium oxide is 56.1. In addition, V and C are the volume and concentration of the solution used in the titration, and the subscripts 1 and 2 respectively represent 0.1 mol/L ethanolic potassium hydroxide solution and 0.2 mol/L hydrochloric acid/isopropanol solution. Furthermore, m is the weight of the sample expressed in gram.

[Determination of the weight average molecular weight (Mw) of polyimide] The weight average molecular weight is measured by a gel permeation chromatography (TOSOH Co., Ltd. product, using HLC-8220GPC). Polystyrene was used as a standard substance, and tetrahydrofuran (THF) was used for the developing solvent.

[Calculation of area percentage of GPC and chromatogram] Regarding GPC, a 100 mg solution obtained by pre-treating 20 mg of dimer diamine composition with 200 μL of acetic anhydride, 200 μL of pyridine and 2 mL of THF, using 10 mL of THF (containing 1000 ppm of cyclohexanone) was diluted to prepare a sample. For the prepared sample, use the trade name of TOSOH Co., Ltd.: HLC-8220GPC, column: TSK-gel G2000HXL, G1000HXL, flow rate: 1 mL/min, column (oven) temperature: Measure under the conditions of 40°C and injection volume: 50 μL. In addition, cyclohexanone is treated as a standard substance in order to correct the outflow time.

At this time, adjust so that the peak top of the main peak of cyclohexanone changes from 27 minutes to 31 minutes in retention time, and adjust so that the peak to the end of the main peak of cyclohexanone is 2 minutes. , So that the peak top of the main peak except the peak of cyclohexanone was changed from 18 minutes to 19 minutes, and the peak of the main peak except the peak of cyclohexanone was changed to 4 from 2 minutes to the end of the peak. Under the condition of minutes and 30 seconds, detect each component (a) ~ component (c); (A) The components represented by the main peak; (B) The component represented by the GPC peak detected at the later time based on the minimum value on the time side of the main peak with the later retention time; (C) The component represented by the GPC peak detected at an earlier time based on the minimum value on the time side where the retention time of the main peak is earlier.

[Evaluation of dielectric properties] Using a vector network analyzer (manufactured by Agilent, trade name: vector network analyzer E8363C) and an SPDR resonator, the polyimide film (hardened polyimide) The film) is placed for 24 hours under the conditions of temperature: 23°C and humidity: 50%, and then the relative dielectric constant (ε ₁ ) and dielectric loss tangent (Tanδ ₁ ) at a frequency of 10 GHz are measured. In addition, after absorbing water at 23°C for 24 hours, the relative dielectric constant (ε ₂ ) and dielectric loss tangent (Tanδ _{2) of the polyimide film (cured polyimide film) at a frequency of 10 GHz were measured.} ).

[Determination of Moisture Absorption Rate] Prepare two polyimide film test pieces (width 4 cm x length 25 cm), and dry them at 80°C for 1 hour. Immediately after drying, it was placed in a constant temperature and humidity room at 23° C./50% RH and left to stand for 24 hours or more, and the weight change before and after that was obtained by the following formula. Moisture absorption rate (weight%)=[(weight after moisture absorption-weight after drying)/weight after drying]×100

[Determination of Water Absorption] Prepare two polyimide film test pieces (width 4 cm x length 25 cm), and dry them at 80°C for 1 hour. Immediately after drying, it was placed in pure water at 23° C. and left to stand for 24 hours or longer, and the weight change before and after that was obtained by the following formula. Water absorption (weight%)=[(weight after absorbing water-weight after drying)/weight after drying]×100

[Glass transition temperature (Tg) and storage elasticity coefficient] The glass transition temperature (Tg) and storage elasticity coefficient are for a polyimide film with a size of 5 mm×20 mm, using a dynamic viscoelasticity measuring device (DMA: manufactured by DBM Corporation, trade name: E4000F), from 30°C to 400°C The measurement was performed at a temperature increase rate of 4°C/min and a frequency of 11 Hz. The temperature at which the change in the coefficient of elasticity (tanδ) is the largest is the glass transition temperature.

[Tensile elasticity coefficient] The coefficient of tensile elasticity is measured by using a tension tester (manufactured by Orientec, trade name Tensilon), using a test piece with a width of 12.7 mm × a length of 127 mm at 50 mm/min In a tensile test, the coefficient of tensile elasticity at 25°C was determined.

[Solder heat resistance test (dry)] Prepare the following printed circuit board: Conduct circuit processing on polyimide copper clad laminate (manufactured by Nippon Steel Chemical & Materials Co., Ltd., trade name: Espanex MB12-25-12UEG) to form wiring width/wiring Interval (L/S) = 1 mm/1 mm circuit. The adhesive side of the test piece was placed on the wiring of the printed circuit board, and pressed under the conditions of a temperature of 160°C, a pressure of 3.5 MPa, and a time of 60 minutes. After the copper foil-attached test piece was dried at 105°C, it was immersed in a solder bath set to each evaluation temperature for 10 seconds, and the bonding state was observed to confirm whether there were defects such as foaming, swelling, and peeling. The heat resistance is expressed by the upper limit temperature that does not cause defects. For example, "320°C" means that the evaluation was performed in a 320°C solder bath, and no defects were confirmed.

[Solder heat resistance test (moisture absorption)] Prepare the following printed circuit board: Conduct circuit processing on polyimide copper clad laminate (manufactured by Nippon Steel Chemical & Materials Co., Ltd., trade name: Espanex MB12-25-12UEG) to form wiring width/wiring Interval (L/S) = 1 mm/1 mm circuit. The adhesive side of the test piece was placed on the wiring of the printed circuit board, and pressed under the conditions of a temperature of 160°C, a pressure of 3.5 MPa, and a time of 60 minutes. After leaving the test piece with copper foil at 40°C and a relative humidity of 80% for 72 hours, it was immersed in a solder bath set to each evaluation temperature for 10 seconds, and the bonding state was observed to confirm whether there was foaming, swelling, or peeling. And other bad conditions. The heat resistance is expressed by the upper limit temperature that does not cause defects. For example, "260°C" means that the evaluation was performed in a 260°C solder bath, and no defects were confirmed.

[Measurement of peel strength] The peel strength is using a Tensilon testing machine (manufactured by Toyo Seiki Seisakusho Co., Ltd., trade name: Strograph VE-10), and the resin layer side of a sample with a width of 1 mm (including a substrate/resin layer laminate) is fixed with a double-sided tape For an aluminum plate, determine the force when peeling the resin layer from the base material at a speed of 50 mm/min in the 180° direction for the base material.

[Evaluation of warpage] Coat the polyimide film material (manufactured by Toray DuPont Co., Ltd., trade name: Kapton 100EN) or 12 On the copper foil of μm, a test piece was produced. In this state, place the polyimide film material or copper foil on the bottom surface, measure the average value of the height of the four corners of the test piece, and set 5 mm or less as "good", and set it to exceed In the case of 5 mm, set it to "Not possible".

The abbreviations used in the examples indicate the following compounds. DDA1: The product name: PRIAMINE 1075 manufactured by Croda Japan Co., Ltd. is distilled and refined (component a: 98.2% by weight, component b: 0%, component c: 1.9% , Amine value: 206 mgKOH/g) DDA2: Distilled and refined from the trade name of Croda Japan Co., Ltd.: PRIAMINE 1075 (component a: 99.2% by weight, component b ：0%, component c: 0.8%, amine value: 210 mgKOH/g) APB: 1,3-bis(3-aminophenoxy)benzene BTDA: 3,3',4,4'-benzyl Ketotetracarboxylic dianhydride N-12: Dodecanedioic acid dihydrazine NMP: N-methyl-2-pyrrolidone PX-200: Phosphate (manufactured by Daha Chemical Industry Co., Ltd., trade name: PX -200, non-halogen aromatic condensed phosphate ester, phosphorus content: 9.0%) PX-202: phosphate ester (manufactured by Daha Chemical Industry Co., Ltd., trade name: PX-202, non-halogen aromatic condensed phosphate ester, phosphorus content ：8.1%) SR-3000: Phosphate (manufactured by Daha Chemical Industry Co., Ltd., trade name: SR-3000, non-halogen aromatic condensed phosphate, phosphorus content: 7.0%) DA-850: Phosphate (Daba Chemical Industry Co., Ltd.) Manufactured by Chemical Industry Co., Ltd., trade name: DAIGUARD-850, non-halogen aromatic condensed phosphate, phosphorus content: 16.0% or more) TPP (manufactured by Daha Chemical Industry Co., Ltd., trade name: TPP, non-halogen phosphate, Phosphorus content: 9.5%) TCP (manufactured by Daha Chemical Industry Co., Ltd., trade name: TCP, non-halogen phosphate, phosphorus content: 8.4%) TXP (manufactured by Daha Chemical Industry Co., Ltd., trade name: TXP, non Halogen phosphate ester, phosphorus content: 7.6%) CR-733 (manufactured by Daha Chemical Industry Co., Ltd., trade name: CR-733S, non-halogen aromatic condensed phosphate ester, phosphorus content: 10.9%) CR-741 (Daba Chemical Industry Co., Ltd.) Manufactured by Chemical Industry Co., Ltd., trade name: CR-741, non-halogen aromatic condensed phosphate, phosphorus content: 8.9%) CM-6R: Phosphorus-nitrogen compound (manufactured by Daiwa Chemical Industry Co., Ltd., trade name: Fran (Fran) CM-6R, average particle size 5 μm) MC-6000: (manufactured by Nissan Chemical Co., Ltd., trade name: MC-6000, non-halogen melamine isocyanurate) Filler 1: Nissan Chemical & Materials Manufactured by the company, trade name: CR10-20 (spherical white silica powder, spherical shape, silica content: 99.4% by weight, white silica crystal phase: 93% by weight, true specific gravity: 2.33, D ₅₀ : 10.8 μm, D ₉₀ : 16.4 μm, D ₁₀₀ : 24 .1 μm, relative dielectric constant at 10 GHz: 3.16, dielectric loss tangent at 10 GHz: 0.0008) Filler 2: manufactured by Nippon Steel Chemical & Materials Co., Ltd., trade name: SC70-2 (spherical amorphous two Silicon oxide powder, spherical shape, silicon dioxide content: 99.9% by weight, true specific gravity: 2.21, D ₅₀ : 11.7 μm, D ₉₀ : 16.4 μm, D ₁₀₀ : 24.1 μm, relative permittivity at 10 GHz: 3.08, 10 GHz dielectric loss tangent: 0.0015) Flame retardant 1: manufactured by Clariant Japan, trade name: Exolit OP935 (Aluminum Alkyl Phosphate) Flame Retardant 2 : Manufactured by Dahachi Chemical Company, trade name: SR-3000 (condensed phosphate ester) LCP filler: manufactured by JXTG Energy Company (low dielectric liquid crystal polymer, particle size (D ₅₀ ): 9.6 μm, relative dielectric under 10 GHz Electrical constant: 3.27, dielectric loss tangent at 10 GHz: 0.0009) Furthermore, in the DDA1 and DDA2, the "%" of the b component and the c component refer to the area percentage of the chromatogram in the GPC measurement. In addition, the molecular weights of DDA1 and DDA2 are calculated by the following formula (1). Molecular weight=56.1×2×1000/amine price···(1)

(Synthesis Example 1-1) Put 55.51 g of BTDA (0.1721 mol), 94.49 g of DDA1 (0.1735 mol), 210 g of NMP and 140 g of xylene into a 1000 ml separable flask, and mix thoroughly for 1 hour at 40°C , Preparation of polyamide acid solution. The polyimide solution was heated to 190°C, heated and stirred for 10 hours, and 125 g of xylene was added to prepare an imidized polyimide solution 1-a (solid content concentration: 30% by weight, Weight average molecular weight: 82,900, amine value: 206 mgKOH/g).

(Synthesis example 1-2~Synthesis example 1-3) Except having set it as the raw material composition shown in Table 1-1, it carried out similarly to Synthesis Example 1-1, and prepared polyimide solution 1-b-polyimide solution 1-c.

[Table 1-1] Synthesis example Polyimide solution type Diamine (p) [mole%] Acid anhydride (q) [mole%] q/p mol ratio Weight average molecular weight Amine value [mgKOH/g] Solid content concentration [wt%] 1-1 1-a DDA1 (100) BTDA (100) 0.992 82,900 206 30 1-2 1-b DDA2 (100) BTDA (100) 1.002 70,100 210 30 1-3 1-c DDA1 (60) APB (40) BTDA (100) 0.996 89,200 206 30

(Production example 1-1) To 169.49 g (50 g as a solid content) of the polyimide solution 1-a obtained in Synthesis Example 1-1, 2.7 g of N-12 (0.0105 mol; Ear, the primary amine group is equivalent to 0.35 mol), add 6.0 g of NMP to dilute, and then stir for 1 hour to obtain a polyimide solution 1-1a.

Coat the obtained polyimide solution 1-1a on one side of a release PET film (manufactured by Dongshan Film Co., Ltd., trade name: HY-S05, length×width×thickness=200 mm×300 mm×25 μm) It was dried at 80°C for 15 minutes and peeled off from the release PET film, thereby preparing a polyimide film 1-1a' with a thickness of 25 μm. The polyimide film 1-1a' was pressed under the conditions of a temperature of 160°C, a pressure of 3.5 MPa, and a time of 60 minutes to obtain a polyimide film 1-1a. The various evaluation results of the polyimide film 1-1a are as follows. Relative permittivity (ε ₁ ): 2.7, Dielectric loss tangent (Tanδ ₁ ): 0.0024, Relative permittivity (ε ₂ ): 2.7, Dielectric loss tangent (Tanδ ₂ ): 0.0034, Moisture absorption rate: 0.07%, water absorption: 0.6%, Tg: 54℃, 200℃ storage elasticity coefficient: 5.0×10 ⁶ Pa, tensile elasticity coefficient: 0.7 GPa, solder heat resistance (drying): 280℃, solder heat resistance (moisture absorption): 260°C, peel strength: 1.0 kN/m or more

(Production Example 1-2, Production Example 1-3) Instead of polyimide solution 1-a, polyimide solution 1-b and polyimide solution 1-c were used, and other than that, production example 1- 1 In the same manner, a polyimide solution 1-1b, a polyimide solution 1-1c, a polyimide film 1-1b, and a polyimide film 1-1c were obtained. The various evaluation results of the polyimide film 1-1b and the polyimide film 1-1c are as follows. <Polyimide film 1-1b> Relative permittivity (ε ₁ ): 2.7, Dielectric loss tangent (Tanδ ₁ ): 0.0024, Relative permittivity (ε ₂ ): 2.7, Dielectric loss tangent ( Tanδ ₂ ): 0.0034, moisture absorption rate: 0.07%, water absorption rate: 0.2%, Tg: 54°C, 200°C storage elastic coefficient: not determined, tensile elastic coefficient: 0.7 GPa <Polyimide film 1-1c> Relative permittivity (ε ₁ ): 2.9, dielectric loss tangent (Tanδ ₁ ): 0.0028, relative permittivity (ε ₂ ): 2.9, dielectric loss tangent (Tanδ ₂ ): 0.0052, moisture absorption rate: 0.17%, water absorption rate: 0.7%, Tg: 106℃, 200℃ storage elasticity coefficient: less than 1.0×10 ⁶ Pa, tensile elasticity coefficient: 1.4 GPa

[Example 1-1] With respect to the polyimide solution 1-1a (100 parts by weight as a solid content) obtained in Preparation Example 1-1, 10 parts by weight of SR-3000 was blended to obtain polyimide Composition 1-1. The obtained polyimide composition 1-1 was coated on one side of a release PET film, dried at 80°C for 15 minutes, and peeled from the release PET film, thereby preparing a 25 μm thick poly The imine film 1-1'. The polyimide film 1-1' was heated in an oven at a temperature of 160°C for 2 hours to obtain a polyimide film 1-1. The various evaluation results of the polyimide film 1-1 are as follows. Relative permittivity (ε ₁ ): 2.6, dielectric loss tangent (Tanδ ₁ ): 0.0022

[Example 1-2 to Example 1-16] The respective components were blended in the proportions (parts by weight) described in Table 1-2, and the polyimine composition 1-2 to the polyimine composition 1-16 were obtained in the same manner as in Example 1-1. In addition, the "DDA composition" in Table 1-2 refers to a dimer diamine composition (the same in Table 1-3).

[Table 1-2] Example Polyimide composition type A component B component B component/A component [weight ratio] Phosphorus concentration [wt%] Phosphorus in component B/component A [weight ratio] Phosphorus in component B/DDA composition [weight ratio] Polyimide solution [solid content: parts by weight] Phosphorus compound [parts by weight] 1-1 1-1 1-1a (100) SR-3000 (10) 0.1 0.62 0.007 0.011 1-2 1-2 1-1a (100) SR-3000 (20) 0.2 1.13 0.014 0.021 1-3 1-3 1-1a (100) SR-3000 (25) 0.25 1.36 0.018 0.027 1-4 1-4 1-1a (100) SR-3000 (30) 0.3 1.57 0.021 0.032 1-5 1-5 1-1a (100) SR-3000 (50) 0.5 2.28 0.035 0.053 1-6 1-6 1-1a (100) PX-200 (25) 0.25 1.75 0.023 0.034 1-7 1-7 1-1a (100) PX-202 (25) 0.25 1.57 0.020 0.031 1-8 1-8 1-1a (100) PX-202 (28) 0.28 1.72 0.023 0.035 1-9 1-9 1-1a (100) PX-202 (31) 0.31 1.61 0.022 0.038 1-10 1-10 1-1a (100) DA-850 (25) 0.25 3.11 0.040 0.061 1-11 1-11 1-1b (100) SR-3000 (10) 0.1 0.62 0.007 0.011 1-12 1-12 1-1b (100) SR-3000 (20) 0.2 1.13 0.014 0.021 1-13 1-13 1-1b (100) SR-3000 (25) 0.25 1.36 0.018 0.027 1-14 1-14 1-1c (100) SR-3000 (10) 0.1 0.62 0.007 0.011 1-15 1-15 1-1c (100) SR-3000 (20) 0.2 1.13 0.014 0.023 1-16 1-16 1-1c (100) SR-3000 (25) 0.25 1.36 0.018 0.029

Using the obtained polyimide composition 1-2 to polyimide composition 1-16, the same as in Example 1-1 was used to prepare polyimide film 1-2 to polyimide film 1-16 . The various evaluation results of the polyimide film 1-2 to the polyimide film 1-16 are as follows. <Polyimide film 1-2> Relative permittivity (ε ₁ ): 2.7, dielectric loss tangent (Tanδ ₁ ): 0.0022, tensile elasticity: 0.7 GPa, peel strength: 1.4 kN/m ＜poly Diimide film 1-3> relative permittivity (ε ₁ ): 2.6, dielectric loss tangent (Tanδ ₁ ): 0.0020, relative permittivity (ε ₂ ): 2.6, dielectric loss tangent (Tanδ ₂ ): 0.0021, water absorption: 0.1%, Tg: 54°C, tensile elastic coefficient: 0.7 GPa, peel strength: 1.4 kN/m <Polyimide film 1-4> Relative permittivity (ε ₁ ): 2.6 , Dielectric loss tangent (Tanδ ₁ ): 0.0024, tensile elastic coefficient: 0.5 GPa, peel strength: 1.5 kN/m <Polyimide film 1-5> Relative permittivity (ε ₁ ): 2.6, dielectric Electrical loss tangent (Tanδ ₁ ): 0.0022, tensile elastic coefficient: 0.7 GPa <Polyimide film 1-6> Relative permittivity (ε ₁ ): 2.7, dielectric loss tangent (Tanδ ₁ ): 0.0023 , Tensile elastic coefficient: 0.1 GPa, peel strength: 1.6 kN/m <Polyimide film 1-7> Relative permittivity (ε ₁ ): 2.6, dielectric loss tangent (Tanδ ₁ ): 0.0022, water absorption Rate: 0.29%, tensile elastic coefficient: 0.5 GPa, peel strength: 1.6 kN/m <Polyimide film 1-8> Relative permittivity (ε ₁ ): 2.7, dielectric loss tangent (Tanδ ₁ ) ：0.0021, water absorption: 0.54%, tensile elasticity: 0.4 GPa, peel strength: 1.3 kN/m <Polyimide film 1-9> Relative permittivity (ε ₁ ): 2.6, dielectric loss tangent (Tanδ ₁ ): 0.0021, water absorption: 0.91%, tensile elasticity coefficient: 0.3 GPa, peel strength: 1.4 kN/m <Polyimide film 1-10> Relative permittivity (ε ₁ ): 2.7, medium Electrical loss tangent (Tanδ ₁ ): 0.0020, peel strength: 0.7 kN/m <Polyimide film 1-11> Relative permittivity (ε ₁ ): 2.6, dielectric loss tangent (Tanδ ₁ ): 0.0022 <Polyimide film 1-12> Relative permittivity (ε ₁ ): 2.7, Dielectric loss tangent ( _{Tanδ 1} ): 0.0021 <Polyimide film 1-13> Relative permittivity (ε ₁ ) ：2.6. Dielectric loss tangent ( _{Tanδ 1} ): 0.0020 <Polyimide film 1-14> Relative permittivity (ε ₁ ): 2.8, Dielectric loss tangent (Tanδ ₁ ): 0.0027 <Polyimide film 1-15> Relative permittivity (ε ₁ ): 2.7, Dielectric loss tangent ( _{Tanδ 1} ): 0.0026 <Polyimide film 1-16> Relative permittivity (ε ₁ ) ：2.7, Dielectric loss tangent (Tanδ ₁ ): 0.0025

[Reference example 1-1~Reference example 1-18] The respective components were blended in the proportions (parts by weight) described in Table 1-3, and the polyimine composition 1-17 to the polyimine composition 1-34 were obtained in the same manner as in Example 1-1.

[Table 1-3] Reference example Polyimide composition type A component B component B component/A component [weight ratio] Phosphorus concentration [wt%] Phosphorus in component B/component A [weight ratio] Phosphorus in component B/DDA composition [weight ratio] Polyimide solution [solid content: parts by weight] Phosphorus compound [parts by weight] 1-1 1-17 1-1a (100) - - - - - 1-2 1-18 1-1a (100) CM-6R(25) 0.25 - - - 1-3 1-19 1-1a (100) TPP (5) 0.05 0.355 0.004 0.007 1-4 1-20 1-1a (100) TPP (10) 0.10 0.685 0.008 0.015 1-5 1-21 1-1a (100) TCP (5) 0.05 0.314 0.003 0.006 1-6 1-22 1-1a (100) TCP (10) 0.10 0.606 0.007 0.013 1-7 1-23 1-1a (100) TXP (5) 0.05 0.284 0.003 0.006 1-8 1-24 1-1a (100) TXP (10) 0.10 0.548 0.006 0.012 1-9 1-25 1-1a (100) CR-733 (5) 0.05 0.408 0.004 0.008 1-10 1-26 1-1a (100) CR-733 (10) 0.10 0.786 0.009 0.017 1-11 1-27 1-1a (100) CR-741 (5) 0.05 0.333 0.004 0.007 1-12 1-28 1-1a (100) CR-741 (10) 0.10 0.642 0.007 0.014 1-13 1-29 1-1b (100) TPP (5) 0.05 0.355 0.004 0.007 1-14 1-30 1-1b (100) TCP (5) 0.05 0.314 0.004 0.006 1-15 1-31 1-1c (100) TPP (5) 0.05 0.355 0.004 0.008 1-16 1-32 1-1c (100) TCP (5) 0.05 0.314 0.004 0.007 1-17 1-33 1-1a (100) MC-6000 (25) 0.25 - - - 1-18 1-34 1-1a (100) SR-3000 (80) 0.8 3.05 0.056 0.085

Using the obtained polyimide composition 1-17 to polyimide composition 1-34, the same as in Example 1-1 was used to prepare polyimide film 1-17 to polyimide film 1-34 . The various evaluation results of the polyimide film 1-17 to the polyimide film 1-34 are as follows. <Polyimide film 1-17> Relative permittivity (ε ₁ ): 2.7, Dielectric loss tangent (Tanδ ₁ ): 0.0024, Relative permittivity (ε ₂ ): 2.7, Dielectric loss tangent ( Tanδ ₂ ): 0.0034, water absorption: 0.2%, tensile elasticity coefficient: 0.9 GPa, peeling strength: 1.2 kN/m <polyimide film 1-18> relative permittivity (ε ₁ ): 2.9, dielectric Loss tangent (Tanδ ₁ ): 0.0025, tensile elastic coefficient: 0.6 GPa, peel strength: 0.4 kN/m <Polyimide film 1-19> Relative permittivity (ε ₁ ): 2.6, dielectric loss angle Tangent (Tanδ ₁ ): 0.0031, tensile elasticity coefficient: 0.3 GPa <Polyimide film 1-20> Relative permittivity (ε ₁ ): 2.8, dielectric loss tangent (Tanδ ₁ ): 0.0041, stretch Elastic coefficient: 0.1 GPa <Polyimide film 1-21> Relative permittivity (ε ₁ ): 2.6, Dielectric loss tangent (Tanδ ₁ ): 0.0028, Tensile elastic coefficient: 0.2 GPa <Polyimide Film 1-22> Relative permittivity (ε ₁ ): 2.8, Dielectric loss tangent (Tanδ ₁ ): 0.0033, Tensile elastic coefficient: 0.0 GPa <Polyimide film 1-23> Relative permittivity ( ε ₁ ): 2.7, Dielectric loss tangent (Tanδ ₁ ): 0.0026, Tensile elastic coefficient: 0.3 GPa <Polyimide film 1-24> Relative permittivity (ε ₁ ): 2.8, Dielectric loss angle Tangent (Tanδ ₁ ): 0.0028, tensile elasticity coefficient: 0.0 GPa <Polyimide film 1-25> Relative permittivity (ε ₁ ): 2.7, dielectric loss tangent (Tanδ ₁ ): 0.0028, stretch Elastic coefficient: 0.3 GPa <Polyimide film 1-26> Relative permittivity (ε ₁ ): 2.7, Dielectric loss tangent (Tanδ ₁ ): 0.0034, Tensile elastic coefficient: 0.1 GPa <Polyimide Film 1-27> Relative permittivity (ε ₁ ): 2.7, Dielectric loss tangent (Tanδ ₁ ): 0.0027, Tensile elastic coefficient: 0.4 GPa <Polyimide film 1-28> Relative permittivity ( ε ₁ ): 2.7, Dielectric loss tangent (Tanδ ₁ ): 0.0031, Tensile elastic coefficient: 0.2 GPa <Polyimide film 1-29> Relative permittivity (ε ₁ ): 2.7, Dielectric loss angle Tangent ( _{Tanδ 1} ): 0.0031 <Polyimide film 1-30> Relative permittivity (ε ₁ ): 2.6, Dielectric loss tangent (Tanδ ₁ ): 0.0027 <Polyimide film 1-31> Relative permittivity (ε ₁ ): 2.8, Dielectric loss tangent ( _{Tanδ 1} ): 0.0035 <Polyimide film 1-32> Relative permittivity (ε ₁ ) ：2.9. Dielectric loss tangent ( _{Tanδ 1} ): 0.0031 <Polyimide film 1-33> Relative permittivity (ε ₁ ): 3.0, Dielectric loss tangent ( _{Tanδ 1} ): 0.0140 <Polyimide film 1-33> Amine film 1-34> relative permittivity (ε ₁ ): 2.6, dielectric loss tangent (Tanδ ₁ ): 0.0021

Summarizing the above results, the evaluation results of the dielectric properties of the polyimide film 1-1 to the polyimide film 1-34 are shown in Tables 1-4 and 1-5.

[Table 1-4] Example Polyimide film type Relative permittivity (ε ₁ ) Dielectric loss tangent (Tanδ ₁ ) 1-1 1-1 2.6 0.0022 1-2 1-2 2.7 0.0022 1-3 1-3 2.6 0.0020 1-4 1-4 2.6 0.0024 1-5 1-5 2.6 0.0022 1-6 1-6 2.7 0.0023 1-7 1-7 2.6 0.0022 1-8 1-8 2.7 0.0021 1-9 1-9 2.6 0.0021 1-10 1-10 2.7 0.0020 1-11 1-11 2.6 0.0022 1-12 1-12 2.7 0.0021 1-13 1-13 2.6 0.0020 1-14 1-14 2.8 0.0027 1-15 1-15 2.7 0.0026 1-16 1-16 2.7 0.0025

[Table 1-5] Reference example Polyimide film type Relative permittivity (ε ₁ ) Dielectric loss tangent (Tanδ ₁ ) 1-1 1-17 2.7 0.0024 1-2 1-18 2.9 0.0025 1-3 1-19 2.6 0.0031 1-4 1-20 2.8 0.0041 1-5 1-21 2.6 0.0028 1-6 1-22 2.8 0.0033 1-7 1-23 2.7 0.0026 1-8 1-24 2.8 0.0028 1-9 1-25 2.7 0.0028 1-10 1-26 2.7 0.0034 1-11 1-27 2.7 0.0027 1-12 1-28 2.7 0.0031 1-13 1-29 2.7 0.0031 1-14 1-30 2.6 0.0027 1-15 1-31 2.8 0.0035 1-16 1-32 2.9 0.0031 1-17 1-33 3.0 0.0140 1-18 1-34 2.6 0.0021

[Example 1-17] The ingredients were blended in the proportions (parts by weight) described in Table 1-2, and the prepared polyimide composition 1-2 was applied to the polyimide film material P1 (Toray) in the same manner as in Example 1-1. Manufactured by DuPont, trade name: Kapton 50EN, relative permittivity at a frequency of 10 GHz = 3.6, dielectric loss tangent at a frequency of 10 GHz = 0.0084, longitudinal × transverse × thickness = 200 mm × 300 mm×12 μm), dried at 80°C for 15 minutes to obtain a cover film 1-17 with an adhesive layer thickness of 25 μm. The state of warpage of the obtained cover film 1-17 was "good".

[Example 1-18] The release PET film was laminated so that the adhesive layer side of the cover film 1-17 was in contact with each other, and pressure-bonded using a vacuum laminator at a temperature of 160° C. and a pressure of 0.8 MPa for 2 minutes. After that, the polyimide composition 1-2 was applied to the polyimide film material P1 side of the cover film 1-17 in the state where the release PET film was crimped so that the thickness after drying was 25 μm , Drying at 80°C for 15 minutes. Then, the release PET film was laminated with the surface after the polyimide composition 1-2 was coated and dried in contact with each other, and pressure-bonded using a vacuum laminator at a temperature of 160°C and a pressure of 0.8 MPa for 2 minutes, thereby A laminate 1-18 including adhesive layers on both sides of the polyimide film material P1 was obtained.

[Example 1-19] The polyimide composition 1-2 was coated on one side of an electrolytic copper foil with a thickness of 12 μm, and dried at 80°C for 15 minutes to obtain a copper foil with resin 1 with an adhesive layer of 25 μm in thickness. -19. The state of warpage of the obtained copper foil with resin 1-19 was "good".

[Example 1-20] Polyimide composition 1-2 was coated on one side of an electrolytic copper foil with a thickness of 12 μm, and dried at 80°C for 30 minutes to obtain a copper foil with resin 1 with an adhesive layer of 50 μm in thickness. -20. The state of warpage of the obtained copper foil with resin 1-20 was "good".

[Example 1-21] The surface of the adhesive layer of the resin-coated copper foil 1-19 was further coated with polyimide composition 1-2 and dried at 80°C for 30 minutes to obtain a tape with a total thickness of 100 μm for the adhesive layer Resin copper foil 1-21. The state of warpage of the obtained copper foil with resin 1-21 was "good".

[Example 1-22] The polyimide composition 1-2 was coated on one side of a release PET film, dried at 80°C for 30 minutes, and peeled from the release PET film, thereby obtaining a polyimide with a thickness of 50 μm Amine film 1-35.

[Example 1-23] Layer polyimide film 1-2 and polyimide film material P2 (manufactured by DuPont, trade name: Kapton 100-EN, thickness 25 μm) on electrolytic copper foil with a thickness of 12 μm in sequence. Relative dielectric constant at a frequency of 10 GHz = 3.6, dielectric loss tangent at a frequency of 10 GHz = 0.0084), polyimide film 1-2 and electrolytic copper foil with a thickness of 12 μm, using a vacuum laminator at the temperature After crimping at 160°C and a pressure of 0.8 MPa for 2 minutes, the temperature was raised from room temperature to 160°C and heat-treated at 160°C for 4 hours to obtain copper-clad laminate 1-23.

[Example 1-24] Laminate the adhesive layer side of the cover film 1-17 on the copper foil with a thickness of 12 μm on an electrolytic copper foil with a thickness of 12 μm. Use a vacuum laminator to press at a temperature of 160°C and a pressure of 0.8 MPa for 2 minutes, then from room temperature The temperature was raised to 160°C, and the heat treatment was performed at 160°C for 2 hours to obtain copper clad laminate 1-24.

[Example 1-25] A polyimide film 1-2 is laminated on a rolled copper foil with a thickness of 12 μm, and the polyimide film material P1 side of the cover film 1-17 is laminated so that the polyimide film 1-2 is in contact with the polyimide film 1-2. Laminate rolled copper foils with a thickness of 12 μm on the adhesive layer side of the cover film 1-17 in sequence, and use a vacuum laminator to press at a temperature of 160°C and a pressure of 0.8 MPa for 2 minutes, and then heat up from room temperature to 160°C. Heat treatment at 160°C for 2 hours to obtain copper clad laminates 1-25.

[Example 1-26] Prepare two copper foils 1-19 with resin, using polyimide film material P3 (manufactured by DuPont, trade name: Kapton 200-EN, thickness 50 μm, relative dielectric at a frequency of 10 GHz) Constant = 3.6, the dielectric loss tangent at a frequency of 10 GHz = 0.0084) Laminate the adhesive layer side of two copper foils 1-19 with resin in contact with each other, and use a vacuum laminator at a temperature of 160°C and pressure After 5 minutes of crimping at 0.8 MPa, the temperature was raised from room temperature to 160°C, and the heat treatment was performed at 160°C for 4 hours to obtain copper-clad laminate 1-26.

[Example 1-27] Coating polyimide composition 1-2 on single-sided copper-clad laminate M1 (manufactured by Nittetsu Chemical & Materials Co., Ltd., trade name: Espanex (Espanex) MC12-25-00UEM, vertical × horizontal) ×thickness=200 mm×300 mm×25 μm) on the resin layer side surface, dried at 80°C for 30 minutes to obtain an adhesive copper-clad laminate with an adhesive layer thickness of 50 μm 1- 27. Laminate so that the resin layer side of the single-sided copper clad laminate M1 is in contact with the adhesive layer side of the adhesive copper clad laminate 1-27, using a small precision press at a temperature of 160°C and a pressure of 4.0 MPa Press down for 120 minutes to obtain copper clad laminates 1-27.

[Example 1-28] Laminate the polyimide film 1-2 on the resin layer side of the single-sided copper-clad laminate M1, and then place the resin layer side of the single-sided copper-clad laminate M1 in contact with the polyimide film 1-2 For lamination, a small precision pressing machine was used for pressure bonding at a temperature of 160°C and a pressure of 4.0 MPa for 120 minutes to obtain a copper-clad laminate 1-28.

[Example 1-29] The polyimide composition 1-2 was coated on one side of the mold-releasing PET film, dried at 80°C for 15 minutes, and the adhesive layer was peeled from the mold-releasing PET film, thereby obtaining a thickness of 15 μm The polyimide film 1-36.

[Example 1-30] Prepare double-sided copper-clad laminate M2 (manufactured by Nippon Steel Chemical & Materials Co., Ltd., trade name: Espanex (Espanex) MB12-25-00UEG), and perform circuit processing on one side of the copper foil to obtain the formation Wiring board 1-1A with conductor circuit layer.

The copper foil on one side of the double-sided copper-clad laminated board M2 is etched away to obtain the copper-clad laminated board 1-1B.

The polyimide film 1-2 is sandwiched between the surface on the conductor circuit layer side of the wiring board 1-1A and the surface on the resin layer side of the copper-clad laminate 1-1B, in a laminated state, at a temperature of 160°C, The thermal compression bonding was performed under a pressure of 4.0 MPa for 120 minutes to obtain a multilayer circuit board 1-30.

[Example 1-31] The liquid crystal polymer film (manufactured by Kuraray Co., Ltd., trade name: CT-Z, thickness: 50 μm, CTE: 18 ppm/K, heat distortion temperature: 300°C, relative permittivity at a frequency of 10 GHz) =3.40, the dielectric loss tangent at a frequency of 10 GHz = 0.0022) As an insulating substrate, a copper-clad laminate 1-1C with 18 μm thick electrolytic copper foil is set on both sides of the copper-clad laminate 1-1C, and the copper foil on one side is borrowed Circuit processing was performed by etching, and a wiring board 1-1C on which a conductor circuit layer was formed was obtained.

The copper foil on one side of the copper-clad laminated board 1-1C is removed by etching to obtain the copper-clad laminated board 1-1D.

The polyimide film 1-2 is sandwiched between the surface on the conductor circuit layer side of the wiring board 1-1C and the surface on the insulating base material layer side of the copper-clad laminate 1-1D. The thermocompression bonding was performed at 160°C and a pressure of 4.0 MPa for 120 minutes to obtain a multilayer circuit board 1-31.

In the following examples, unless otherwise specified, various measurements and evaluations were performed as follows.

[Evaluation of Dielectric Properties] ＜Silicon dioxide particles＞ Use a vector network analyzer (manufactured by Keysight Technologies, trade name: vector network analyzer E8363C) and a relative permittivity measurement device manufactured by Kanto Electronics Application Development Co., Ltd. using the cavity perturbation method, and set It is the relative permittivity measurement mode: TM020, which measures the relative permittivity and dielectric loss tangent of silicon dioxide particles at a frequency of 10 GHz. Furthermore, the silica particles are in powder form and filled into a sample tube (inner diameter of 1.68 mm, outer diameter of 2.28 mm, and height of 8 cm) for measurement. ＜Resin film＞ Use vector network analyzer (manufactured by Keysight Technologies, trade name: vector network analyzer E8363C) and separate dielectric resonator (SPDR). After pressing the adhesive sheet under the condition of minutes, the relative dielectric constant and the dielectric loss tangent at a frequency of 20 GHz were measured after being placed for 24 hours under the conditions of temperature: 23°C and humidity: 50%.

[Determination of particle size] A laser diffraction particle size distribution measuring device (manufactured by Malvern, trade name: Master Sizer 3000) was used, water was used as the dispersion medium, and the laser was used under the condition of the particle refractive index of 1.54. The diffraction-scattering method is used to measure the particle size.

[Determination of true specific gravity] Use a continuous automatic powder true density measuring device (manufactured by Seishin Corporation, trade name: AUTO TRUE DENSERMAT-7000), using a pycnometer method (liquid phase displacement method) Determination of true specific gravity.

[Measurement of white silica crystal phase] Using an X-ray diffraction measuring device (manufactured by Bruker, trade name: D2PHASER), based on the source of the diffraction angle (Cu, Kα) 2θ=10°～90° All diffraction pattern on SiO ₂ (peak position, peak width and peak intensity) is calculated from the total area of all the peaks of SiO _2. Next, the peak position derived from the white silica crystal phase is determined, the total area of all peaks of the white silica crystal phase is calculated, and the ratio (weight%) to the total area of all peaks _{derived from SiO 2 is determined.} Furthermore, the attribution of each peak refers to the database of the International Centre for Diffraction Data (ICDD).

[Determination of Tensile Elastic Coefficient and Maximum Elongation] Using a tensile tester (Tensilon manufactured by Orientec), the test piece (width: 12.7 mm, length: 127 mm) was subjected to a tensile test of 50 mm/min to obtain the Tensile coefficient of elasticity and maximum elongation.

[Measurement of glass transition temperature (Tg)] The adhesive sheet pressed under the conditions of a temperature of 160°C, a pressure of 3.5 MPa, and a time of 60 minutes was cut into a test piece with a size of 5 mm×20 mm, and a dynamic viscoelasticity measuring device (DMA: manufactured by DBM Corporation, trade name: E4000F), measuring from 30°C to 300°C at a heating rate of 4°C/min and a frequency of 11 Hz, and the temperature at which the change in elastic coefficient (tanδ) is the largest is the glass transition temperature.

[Evaluation of membrane retention] The film retention was evaluated by the following procedure. The adhesive sheet was cut into a test piece with a width of 20 mm and a length of 20 mm, and was bent along the diagonal to form a crease, and then opened and observed the state of the film. At this time, set the test piece without cracks after opening with creases as "good", and set it as "not" if some cracks appear.

[Solder heat resistance test (dry)] Prepare the following printed circuit boards: Etch and remove one of the copper foils of the double-sided copper-clad laminate (manufactured by Nippon Steel Chemical & Materials Co., Ltd., trade name: Espanex MB12-25-12UEG), and the other copper foil Perform circuit processing to form a circuit with wiring width/wiring interval (L/S) = 1 mm/1 mm. Place the adhesive sheet on the wiring of the printed circuit board, and laminate a polyimide film (manufactured by Toray DuPont Co., Ltd., trade name: Kapton 50EN-S) on the adhesive sheet in contact with the printed circuit board After the opposite side of the surface, press under the conditions of temperature: 160°C, pressure: 3.5 MPa, and time: 60 minutes. After the copper foil-attached test piece was dried at 105°C, it was immersed in a solder bath set to each evaluation temperature for 10 seconds, and the bonding state was observed to confirm whether there were defects such as foaming, swelling, and peeling. The heat resistance is expressed by the upper limit temperature that does not cause defects. For example, "320°C" means that the evaluation was performed in a 320°C solder bath, and no defects were confirmed.

[Solder heat resistance test (moisture absorption)] Prepare the following printed circuit board: Etch and remove the copper foil on one side of the copper-clad laminate (manufactured by Nippon Steel Chemical & Materials Co., Ltd., trade name: Espanex MB12-25-12UEG), to the other copper The foil undergoes circuit processing to form a circuit with wiring width/wiring interval (L/S) = 1 mm/1 mm. Place the adhesive sheet on the wiring of the printed circuit board, and laminate a polyimide film (manufactured by Toray DuPont Co., Ltd., trade name: Kapton 50EN-S) on the adhesive sheet in contact with the printed circuit board After the opposite side of the surface, press under the conditions of temperature: 160°C, pressure: 3.5 MPa, and time: 60 minutes. After leaving the test piece with copper foil at 40°C and relative humidity: 80% for 72 hours, it was immersed in a solder bath set to each evaluation temperature for 10 seconds, and the bonding state was observed to confirm whether there was foaming, swelling, or swelling. Defects such as peeling. The heat resistance is expressed by the upper limit temperature that does not cause defects. For example, "260°C" means that the evaluation was performed in a 260°C solder bath, and no defects were confirmed.

[Measurement of peel strength] Cut the double-sided copper clad laminate (manufactured by Nippon Steel Chemical & Materials Co., Ltd., trade name: Espanex MB12-25-12UEG) into width: 50 mm, length: 100 mm, and then the adhesive sheet Place it on the copper foil side of the sample after etching and removing the copper foil on one side, and then laminate a polyimide film (manufactured by Toray DuPont Co., Ltd., trade name: Kapton 50EN-S) on the adhesive sheet ), under the conditions of temperature: 160°C, pressure: 3.5 MPa, and time: 60 minutes. The laminate was cut into a test piece with a width of 5 mm, and a tensile tester (manufactured by Toyo Seiki Seisakusho, trade name: Strograph VE) was used to stretch the test piece at a speed of 50 mm/min in the 90° direction to measure the Adhesive layer and copper foil peel strength.

[Evaluation method of flame retardancy] Laminate a polyimide film (manufactured by Toray DuPont Co., Ltd., trade name: Kapton 50EN-S) on both sides of the adhesive sheet at temperature: 160°C, pressure: 3.5 MPa, and time: 60 Suppress under the condition of minutes. Cut the sample into 200 mm±5 mm×50 mm±1 mm, round it into a cylindrical shape with a diameter of about 12.7 mm and a length of 200 mm±5 mm, make a test piece according to the UL94VTM standard, and perform a combustion test. The case where the judgment criterion of VTM-0 is reached is set to "good". The case where the judgment criterion of VTM-1 is reached is set to "Yes", and the case where the judgment criterion of VTM-1 is not reached is set to "Not possible".

(Synthesis example 2-1) Put 55.51 g of BTDA (0.1721 mol), 94.49 g of DDA2 (0.1735 mol), 210 g of NMP and 140 g of xylene into a 1000 ml separable flask, and mix thoroughly for 1 hour at 40°C , Preparation of polyamide acid solution. The polyimide solution was heated to 190°C, heated and stirred for 10 hours, and 125 g of xylene was added to prepare an imidized polyimide solution 2-1 (solid content: 30% by weight, weight Average molecular weight: 80,900).

[Example 2-1] 1.09 g of N-12 and 7.50 g of filler 1 were blended into 100 g of the polyimide solution 2-1 prepared in Synthesis Example 2-1, and xylene was added so that the solid content became 30% by weight for dilution and Stirring, thereby preparing polyimide varnish 2-1a.

[Example 2-2 to Example 2-8] Except changing the blending amounts of filler 1 and filler 2 as shown in Table 2-1, polyimide varnish 2-2a to polyimide varnish 2-8a were prepared in the same manner as in Example 2-1.

[Comparative Example 2-1] Except that the filler 1 was not prepared, polyimide varnish 2-9a was prepared in the same manner as in Example 2-1.

[table 2-1] Polyimide varnish Example Comparative example 2-1 2-2 2-3 2-4 2-5 2-6 2-7 2-8 2-1 type 2-1a 2-2a 2-3a 2-4a 2-5a 2-6a 2-7a 2-8a 2-9a Polyimide solution [g] 100 100 100 100 100 100 100 100 100 A Solid content of polyimide solution [g] 30 30 30 30 30 30 30 30 30 N-12[g] 1.09 1.09 1.09 1.09 1.09 1.09 1.09 1.09 1.09 B Filling 1[g] 7.5 15.0 22.5 30.0 0 3.3 9.7 3.1 0 Packing 2[g] 0 0 0 0 28.5 3.7 19.3 0 0 B/(A+B) [wt%] 19 33 42 49 48 18 48 9 0 B/(A+B) [vol%] 11 twenty one 28 34 34 11 34 5 0 Proportion of white silica crystal phase [wt%] 93 93 93 93 0 42 31 93 0 Xylene [g] twenty four 41 59 76 73 twenty three 70 13 6 Solid content concentration [wt%] 30 30 30 30 30 30 30 30 30

[Example 2-9] The polyimide varnish 2-1a prepared in Example 2-1 was coated on one side of the release-treated PET film, dried at 80°C for 15 minutes, and then peeled off, thereby preparing an adhesive sheet 2 -1b (thickness: 25 μm). The results of various evaluations of the adhesive sheet 2-1b are as follows. Relative permittivity: 2.7, dielectric loss tangent: 0.0015, coefficient of tensile elasticity: 0.6 GPa, maximum elongation: 165%, Tg: 56°C, film retention: good, solder heat resistance test (dry): 320°C , Solder heat resistance test (moisture absorption): 260°C, peel strength: 1.8 kN/m, flame retardancy: good

[Example 2-10] Using polyimide varnish 2-2a, an adhesive sheet 2-2b was prepared in the same manner as in Example 2-9. The results of various evaluations of the adhesive sheet 2-2b are as follows. Relative permittivity: 2.9, dielectric loss tangent: 0.0013, coefficient of tensile elasticity: 0.5 GPa, maximum elongation: 77%, Tg: 56°C, film retention: good, solder heat resistance test (dry): 320°C , Solder heat resistance test (moisture absorption): 260°C, peel strength: 1.8 kN/m, flame retardancy: good

[Example 2-11] Using polyimide varnish 2-3a, an adhesive sheet 2-3b was prepared in the same manner as in Example 2-9. The results of various evaluations of the adhesive sheet 2-3b are as follows. Relative dielectric constant: 2.8, dielectric loss tangent: 0.0012, tensile elastic coefficient: 0.6 GPa, maximum elongation: 59%, Tg: 56°C, film retention: good, solder heat resistance test (dry): 320°C , Solder heat resistance test (moisture absorption): 270℃, peel strength: 1.8 kN/m, flame retardancy: good

[Example 2-12] Using polyimide varnish 2-4a, an adhesive sheet 2-4b was prepared in the same manner as in Example 2-9. The results of various evaluations of the adhesive sheet 2-4b are as follows. Relative dielectric constant: 2.8, dielectric loss tangent: 0.0011, tensile elastic coefficient: 0.8 GPa, maximum elongation: 31%, Tg: 56°C, film retention: good, solder heat resistance test (dry): 320°C , Solder heat resistance test (moisture absorption): 280℃, peel strength: 1.9 kN/m, flame retardancy: good

[Example 2-13] Using polyimide varnish 2-5a, the adhesive sheet 2-5b was prepared in the same manner as in Example 2-9. Various evaluation results of Adhesive Sheet 2-5b are as follows. Relative permittivity: 2.8, dielectric loss tangent: 0.0016, coefficient of tensile elasticity: 0.8 GPa, maximum elongation: 29%, Tg: 56°C, film retention: good, solder heat resistance test (dry): 320°C , Solder heat resistance test (moisture absorption): 270℃, peel strength: 1.9 kN/m, flame retardancy: good

[Example 2-14] Using polyimide varnish 2-6a, the adhesive sheet 2-6b was prepared in the same manner as in Example 2-9. Various evaluation results of Adhesive Sheet 2-6b are as follows. Relative permittivity: 2.7, dielectric loss tangent: 0.0015, coefficient of tensile elasticity: 0.6 GPa, maximum elongation: 169%, Tg: 56°C, film retention: good, solder heat resistance test (dry): 320°C , Solder heat resistance test (moisture absorption): 260°C, peel strength: 1.7 kN/m, flame retardancy: good

[Example 2-15] Using polyimide varnish 2-7a, the adhesive sheet 2-7b was prepared in the same manner as in Example 2-9. Various evaluation results of Adhesive Sheet 2-7b are as follows. Relative dielectric constant: 2.8, dielectric loss tangent: 0.0012, tensile elastic coefficient: 0.7 GPa, maximum elongation: 28%, Tg: 56°C, film retention: good, solder heat resistance test (dry): 320°C , Solder heat resistance test (moisture absorption): 280℃, peel strength: 1.8 kN/m, flame retardancy: good

[Example 2-16] Using polyimide varnish 2-8a, the adhesive sheet 2-8b was prepared in the same manner as in Example 2-9. The results of various evaluations of Adhesive Tablets 2-8b are as follows. Relative permittivity: 2.6, dielectric loss tangent: 0.0016, coefficient of tensile elasticity: 0.5 GPa, maximum elongation: 177%, Tg: 56°C, film retention: good, solder heat resistance test (dry): 320°C , Solder heat resistance test (moisture absorption): 260°C, peel strength: 1.7 kN/m, flame retardancy: OK

[Comparative Example 2-2] Using polyimide varnish 2-9a, an adhesive sheet 2-9b was prepared in the same manner as in Example 2-9. The results of various evaluations of Adhesive Tablets 2-9b are as follows. Relative permittivity: 2.6, dielectric loss tangent: 0.0017, coefficient of tensile elasticity: 0.4 GPa, maximum elongation: 197%, Tg: 56°C, film retention: good, solder heat resistance test (dry): 320°C , Solder heat resistance test (moisture absorption): 220°C, peel strength: 1.6 kN/m, flame retardancy: no

The above results are summarized and shown in Table 2-2.

[Table 2-2] Adhesive tablets Example Comparative example 2-9 2-10 2-11 2-12 2-13 2-14 2-15 2-16 2-2 type 2-1b 2-2b 2-3b 2-4b 2-5b 2-6b 2-7b 2-8b 2-9b Relative permittivity 2.7 2.9 2.8 2.8 2.8 2.7 2.8 2.6 2.6 Dielectric loss tangent 0.0015 0.0013 0.0012 0.0011 0.0016 0.0015 0.0012 0.0016 0.0017 Tensile coefficient of elasticity [GPa] 0.6 0.5 0.6 0.8 0.8 0.6 0.7 0.5 0.4 Maximum elongation [%] 165 77 59 31 29 169 28 177 197 Tg[℃] 56 56 56 56 56 56 56 56 56 Membrane retention good good good good good good good good good Solder heat resistance test (dry) [℃] 320 320 320 320 320 320 320 320 320 Solder heat resistance test (moisture absorption) [℃] 260 260 270 280 270 260 280 260 220 Peel strength [kN/m] 1.8 1.8 1.8 1.9 1.9 1.7 1.8 1.7 1.6 Flame retardant good good good good good good good Can Can't

It was confirmed from Table 2-2 that, compared with the adhesive sheet 2-9b of Comparative Example 2-2, the adhesive sheet 2-1b of Example 2-9 to Example 2-16 to which filler 1 and filler 2 were added ~ The dielectric properties of the adhesive sheet 2-8b and the solder heat resistance temperature (moisture absorption) are improved. Based on these results, the adhesive sheet as the resin film of the present embodiment can be expected to reduce the transmission loss in the high frequency band of, for example, 20 GHz. In addition, it was confirmed that compared with the adhesive sheet 2-9b of Comparative Example 2-2, the adhesive sheet 2-1b to the adhesive sheet of Example 2-9 to Example 2-16 to which the filler 1 and the filler 2 were added 2-8b Improves heat resistance, peel strength and flame retardancy of moisture-absorbing solder while maintaining flexibility or film retention.

In the above, as shown in the respective examples, by adding white silica silica particles to the DDA/BTDA-based polyimide, a clear reduction effect of the dielectric loss tangent can be seen. In addition, the layer structure of polyimide film/adhesive layer/polyimide film was used to evaluate the flame retardancy. As a result, it was confirmed that the adhesive layer containing schistlite silica particles exhibited a resistance above the VTM-1 level. Flammability. Furthermore, the adhesive sheet obtained in each example maintained the shape as a film in the compounding amount of the silica particles in the practical range, and the adhesive force with respect to polyimide or copper was also improved. Although the mechanism of the increase in adhesive force cannot be clarified, it is speculated that it may contribute to the increase in the elastic modulus of the adhesive sheet. In addition, the solder heat resistance (drying and/or moisture absorption) of the adhesive sheet obtained in the example is equal to or higher than that of the comparative example without the preparation of white silica particles, and it is shown as an adhesive for high-frequency multilayer FPC Better characteristics.

Based on the above results, it was confirmed that the resin film of the present embodiment can be suitably used as a material for a flexible printed circuit board compatible with high frequency.

In the following examples, unless otherwise specified, various measurements and evaluations were performed as follows.

[Evaluation of Dielectric Properties] ＜Liquid crystal polymer filler＞ The dimethylacetamide dispersion liquid of the liquid crystal polymer filler adjusted to a solid content of 30% by weight was applied on the smooth surface of the copper foil, and dried at 120°C for 10 minutes. Thereafter, the temperature was gradually increased from 200°C to 360°C over 10 minutes, and the copper foil of the obtained laminate was etched and removed, thereby obtaining a liquid crystalline polymer film. Using a vector network analyzer (manufactured by Keysight Technologies, trade name: vector network analyzer E8363C) and a separated dielectric resonator (SPDR resonator), the obtained liquid crystal polymer film After leaving it for 24 hours under the conditions of temperature: 23°C and humidity: 50%, the relative dielectric constant and dielectric loss tangent at a frequency of 10 GHz were measured. ＜Resin film＞ Using a vector network analyzer (manufactured by Keysight Technologies, trade name: vector network analyzer E8363C) and SPDR resonator, after pressing at a temperature of 160°C, a pressure of 3.5 MPa, and a time of 60 minutes After leaving the resin film at a temperature of 23°C and a humidity of 50% for 24 hours, the relative dielectric constant and dielectric loss tangent at a frequency of 20 GHz were measured.

[Determination of Tensile Elastic Coefficient and Maximum Elongation] The coefficient of tensile elasticity and maximum elongation are determined by the following procedure. First, using a tensile testing machine (Tensilon manufactured by Orientec), a test piece (width 12.7 mm x length 127 mm) was made from a resin film. Using this test piece, a tensile test was performed at 50 mm/min, and the tensile elastic modulus and maximum elongation at 25°C were determined.

[Measurement of glass transition temperature (Tg)] The glass transition temperature (Tg) is a test piece of 5 mm×20 mm in size from the resin film pressed under the conditions of a temperature of 160°C, a pressure of 3.5 MPa and a time of 60 minutes, and a dynamic viscoelasticity measuring device (DMA: DBM) It is manufactured by the company, trade name: E4000F), measured from 30°C to 300°C at a heating rate of 4°C/min and a frequency of 11 Hz, and the temperature at which the coefficient of elasticity change (tanδ) is the largest is the glass transition temperature.

[Evaluation of membrane retention] The film retention was evaluated by the following procedure. The resin film was cut into a test piece with a width of 20 mm and a length of 20 mm, and the test piece was bent along the diagonal to form a crease, and then opened and observed the state of the film. At this time, set the test piece without cracks after opening with creases as "good", and set it as "not" if some cracks appear.

[Solder heat resistance test (dry)] Prepare the following printed circuit board: Conduct circuit processing on polyimide copper clad laminate (manufactured by Nippon Steel Chemical & Materials Co., Ltd., trade name: Espanex MB12-25-12UEG) to form wiring width/wiring Interval (L/S) = 1 mm/1 mm circuit. The resin film is placed on the wiring of the printed circuit board, and a polyimide film (trade name: Kapton 50EN-S manufactured by Toray DuPont Co., Ltd.) is laminated on the surface of the resin film in contact with the printed circuit board After the opposite side, press under the conditions of temperature: 160°C, pressure: 3.5 MPa, and time: 60 minutes. After the copper foil-attached test piece was dried at 105°C, it was immersed in a solder bath set to each evaluation temperature for 10 seconds, and the bonding state was observed to confirm whether there were defects such as foaming, swelling, and peeling. The heat resistance is expressed by the upper limit temperature that does not cause defects. For example, "320°C" means that the evaluation was performed in a 320°C solder bath, and no defects were confirmed.

[Solder heat resistance test (moisture absorption)] Prepare the following printed circuit board: Conduct circuit processing on polyimide copper clad laminate (manufactured by Nippon Steel Chemical & Materials Co., Ltd., trade name: Espanex MB12-25-12UEG) to form wiring width/wiring Interval (L/S) = 1 mm/1 mm circuit. The resin film is placed on the wiring of the printed circuit board, and a polyimide film (trade name: Kapton 50EN-S manufactured by Toray DuPont Co., Ltd.) is laminated on the surface of the resin film in contact with the printed circuit board After the opposite side, press under the conditions of temperature: 160°C, pressure: 3.5 MPa, and time: 60 minutes. After leaving the test piece with copper foil at 40°C and a relative humidity of 80% for 72 hours, it was immersed in a solder bath set to each evaluation temperature for 10 seconds, and the bonding state was observed to confirm whether there was foaming, swelling, or peeling. And other bad conditions. The heat resistance is expressed by the upper limit temperature that does not cause defects. For example, "260°C" means that the evaluation was performed in a 260°C solder bath, and no defects were confirmed.

[Measurement of peel strength] The measurement of peel strength was performed by the following method. One side of a polyimide copper-clad laminate (manufactured by Nippon Steel Chemical & Materials Co., Ltd., trade name: Espanex MB12-25-12UEG) with a width of 50 mm and a length of 100 mm on both sides Etch the copper foil, place the resin film on the other copper foil side, and layer the polyimide film (manufactured by Toray DuPont Co., Ltd., trade name: Kapton 50EN-S) on the resin The surface of the film opposite to the copper-clad laminate was pressed under the conditions of temperature: 160°C, pressure: 3.5 MPa, and time: 60 minutes. The laminate was cut into a test piece with a width of 5 mm. Using a tensile testing machine (manufactured by Toyo Seiki Seisakusho, Strograph VE), the test piece was stretched at a speed of 50 mm/min in the direction of 90°, and the adhesive was measured at this time. Peel strength of the resin film and copper foil of the layer.

[Evaluation method of flame retardancy] The evaluation of flame retardancy was performed by the following method. Laminate a polyimide film (manufactured by Toray DuPont Co., Ltd., trade name: Kapton 50EN-S) on both sides of a resin film formed by laminating four sheets to become 100 μm. At temperature: Pressing is performed under the conditions of 160°C, pressure: 3.5 MPa, and time: 60 minutes. Cut the sample into 200 mm±5 mm×50 mm±1 mm, round it into a cylindrical shape with a diameter of about 12.7 mm and a length of 200 mm±5 mm, make a test piece according to the UL94VTM standard, and perform a combustion test. If the time to fire is 0 seconds to 5 seconds, it is set to "◎" (excellent), if it is 6 seconds to 10 seconds, it is set to "○" (good), if it is 11 seconds to 20 seconds, it is set It is "△" (available), and the case of more than 21 seconds is set to "×" (unavailable).

[Synthesis Example 3-1] Put 55.51 g of BTDA (0.1721 mol), 94.49 g of DDA2 (0.1735 mol), 210 g of NMP and 140 g of xylene into a 1000 ml separable flask, and mix thoroughly for 1 hour at 40°C , Preparation of polyamide acid solution. The polyimide solution was heated to 190°C, heated and stirred for 10 hours, and 125 g of xylene was added to prepare an imidized polyimide solution 3-1 (solid content: 30% by weight, weight Average molecular weight: 80,900).

[Example 3-1] 1.09 g of N-12 and 7.50 g of LCP filler were blended into 100 g of the polyimide solution 3-1 prepared in Synthesis Example 3-1, and xylene was added to dilute it so that the solid content became 30% by weight. Stirring, thereby preparing polyimide varnish 3-1a.

[Example 3-2 to Example 3-4] Except for changing the blending amount of the LCP filler as shown in Table 3-1, polyimide varnish 3-2a to polyimide varnish 3-4a were prepared in the same manner as in Example 3-1.

[Example 3-5] In 100 g of the polyimide solution 3-1 prepared in Synthesis Example 3-1, 1.09 g of N-12, 7.50 g of LCP filler, and 7.50 g of flame retardant 1 were blended, and the solid content was 30% by weight Add xylene to dilute and stir to prepare polyimide varnish 3-5a.

[Example 3-6 to Example 3-7] Except that the amount of LCP filler was changed as shown in Table 3-1, polyimide varnish 3-6a to polyimide varnish 3-7a were prepared in the same manner as in Example 3-5.

[Example 3-8 to Example 3-10] Instead of flame retardant 1, flame retardant 2 was used in the blending amount of Table 3-1, and LCP filler was blended as shown in Table 3-1, except that polyimide varnish 3-8a was prepared in the same manner as in Example 3-5. ~ Polyimide varnish 3-10a.

[Comparative Example 3-1] A polyimide varnish 3-11a was prepared in the same manner as in Example 3-1 except that the LCP filler was not prepared.

[Comparative Example 3-2] The polyimide varnish 3-12a was prepared in the same manner as in Example 3-5 except that the LCP filler was not prepared.

[Table 3-1] Polyimide varnish Example Comparative example 3-1 3-2 3-3 3-4 3-5 3-6 3-7 3-8 3-9 3-10 3-1 3-2 type 3-1a 3-2a 3-3a 3-4a 3-5a 3-6a 3-7a 3-8a 3-9a 3-10a 3-11a 3-12a Polyimide solution [g] 100 100 100 100 100 100 100 100 100 100 100 100 A Solid content of polyimide solution [g] 30 30 30 30 30 30 30 30 30 30 30 30 B LCP filler [g] 7.5 15.0 22.5 30.0 7.5 15.0 22.5 7.5 15.0 22.5 0 0 B/(A+B) [vol%] 17.6 30.0 39.1 46.2 17.6 30.0 39.1 17.6 30.0 39.1 0 0 N-12[g] 1.09 1.09 1.09 1.09 1.09 1.09 1.09 1.09 1.09 1.09 1.09 1.09 Flame retardant 1 0 0 0 0 7.5 7.5 7.5 0 0 0 0 7.5 Flame retardant 2 0 0 0 0 0 0 0 7.5 7.5 7.5 0 0 Xylene [g] 20 38 55 73 38 55 73 38 55 73 3 20 Solid content concentration [wt%] 30 30 30 30 30 30 30 30 30 30 30 30

[Example 3-11] The polyimide varnish 3-1a prepared in Example 3-1 was coated on one side of the release-treated PET film, dried at 80°C for 15 minutes, and then peeled off, thereby preparing a resin film 3- 1b (thickness: 25 μm). The various evaluation results of the resin film 3-1b are as follows. Relative permittivity: 2.7, dielectric loss tangent: 0.0015, coefficient of tensile elasticity: 0.6 GPa, maximum elongation: 131%, Tg: 54°C, film retention: good, solder heat resistance test (dry): 320°C , Solder heat resistance test (moisture absorption): 260°C, peel strength: 1.6 kN/m, flame retardancy: ○

[Example 3-12] Using polyimide varnish 3-2a, a resin film 3-2b was prepared in the same manner as in Example 3-11. The various evaluation results of the resin film 3-2b are as follows. Relative permittivity: 2.7, dielectric loss tangent: 0.0014, coefficient of tensile elasticity: 0.7 GPa, maximum elongation: 80%, Tg: 54°C, film retention: good, solder heat resistance test (dry): 320°C , Solder heat resistance test (moisture absorption): 260°C, peel strength: 1.5 kN/m, flame retardancy: ○

[Example 3-13] Using polyimide varnish 3-3a, a resin film 3-3b was prepared in the same manner as in Example 3-11. The various evaluation results of the resin film 3-3b are as follows. Relative permittivity: 2.8, dielectric loss tangent: 0.0014, coefficient of tensile elasticity: 0.7 GPa, maximum elongation: 38%, Tg: 58°C, film retention: good, solder heat resistance test (dry): 320°C , Solder heat resistance test (moisture absorption): 270℃, peel strength: 1.2 kN/m, flame retardancy: ○

[Example 3-14] Using polyimide varnish 3-4a, a resin film 3-4b was prepared in the same manner as in Example 3-11. The various evaluation results of the resin film 3-4b are as follows. Relative permittivity: 2.9, dielectric loss tangent: 0.0013, coefficient of tensile elasticity: 0.8 GPa, maximum elongation: 18%, Tg: 58°C, film retention: good, solder heat resistance test (dry): 320°C , Solder heat resistance test (moisture absorption): 270℃, peel strength: 1.2 kN/m, flame retardancy: ○

[Example 3-15] Using polyimide varnish 3-5a, a resin film 3-5b was prepared in the same manner as in Example 3-11. The various evaluation results of the resin film 3-5b are as follows. Relative permittivity: 2.7, dielectric loss tangent: 0.0016, coefficient of tensile elasticity: 0.5 GPa, maximum elongation: 100%, Tg: 54°C, film retention: good, solder heat resistance test (dry): 320°C , Solder heat resistance test (moisture absorption): 270℃, peeling strength: 2.0 kN/m, flame retardancy: ◎

[Example 3-16] Using polyimide varnish 3-6a, a resin film 3-6b was prepared in the same manner as in Example 3-11. The various evaluation results of the resin film 3-6b are as follows. Relative permittivity: 2.8, dielectric loss tangent: 0.0015, coefficient of tensile elasticity: 0.7 GPa, maximum elongation: 33%, Tg: 58°C, film retention: good, solder heat resistance test (dry): 320°C , Solder heat resistance test (moisture absorption): 270℃, peel strength: 1.3 kN/m, flame retardancy: ◎

[Example 3-17] Using polyimide varnish 3-7a, a resin film 3-7b was prepared in the same manner as in Example 3-11. The various evaluation results of the resin film 3-7b are as follows. Relative permittivity: 2.8, dielectric loss tangent: 0.0014, coefficient of tensile elasticity: 0.7 GPa, maximum elongation: 11%, Tg: 58°C, film retention: good, solder heat resistance test (dry): 320°C , Solder heat resistance test (moisture absorption): 280℃, peel strength: 0.9 kN/m, flame retardancy: ◎

[Example 3-18] Using polyimide varnish 3-8a, a resin film 3-8b was prepared in the same manner as in Example 3-11. The various evaluation results of the resin film 3-8b are as follows. Relative permittivity: 2.7, dielectric loss tangent: 0.0015, coefficient of tensile elasticity: 0.5 GPa, maximum elongation: 114%, Tg: 54°C, film retention: good, solder heat resistance test (dry): 320°C , Solder heat resistance test (moisture absorption): 280℃, peel strength: 1.4 kN/m, flame retardancy: ◎

[Example 3-19] Using polyimide varnish 3-9a, a resin film 3-9b was prepared in the same manner as in Example 3-11. The various evaluation results of the resin film 3-9b are as follows. Relative permittivity: 2.8, dielectric loss tangent: 0.0014, coefficient of tensile elasticity: 0.6 GPa, maximum elongation: 52%, Tg: 56°C, film retention: good, solder heat resistance test (dry): 320°C , Solder heat resistance test (moisture absorption): 280℃, peel strength: 1.0 kN/m, flame retardancy: ◎

[Example 3-20] Using polyimide varnish 3-10a, a resin film 3-10b was prepared in the same manner as in Example 3-11. The various evaluation results of the resin film 3-10b are as follows. Relative permittivity: 2.9, dielectric loss tangent: 0.0013, coefficient of tensile elasticity: 0.6 GPa, maximum elongation: 22%, Tg: 56°C, film retention: good, solder heat resistance test (dry): 320°C , Solder heat resistance test (moisture absorption): 290℃, peel strength: 0.7 kN/m, flame retardancy: ◎

[Comparative Example 3-3] Using polyimide varnish 3-11a, a resin film 3-11b was prepared in the same manner as in Example 3-11. The various evaluation results of the resin film 3-11b are as follows. Relative permittivity: 2.6, dielectric loss tangent: 0.0017, coefficient of tensile elasticity: 0.4 GPa, maximum elongation: 197%, Tg: 56°C, film retention: good, solder heat resistance test (dry): 320°C , Solder heat resistance test (moisture absorption): 220°C, peel strength: 1.6 kN/m, flame retardancy: ×

[Comparative Example 3-4] Using polyimide varnish 3-12a, a resin film 3-12b was prepared in the same manner as in Example 3-11. The various evaluation results of the resin film 3-12b are as follows. Relative permittivity: 2.6, dielectric loss tangent: 0.0018, coefficient of tensile elasticity: 0.8 GPa, maximum elongation: 226%, Tg: 56°C, film retention: good, solder heat resistance test (dry): 320°C , Solder heat resistance test (moisture absorption): 280℃, peel strength: 1.7 kN/m, flame retardancy: △

The above results are summarized and shown in Table 3-2.

[Table 3-2] Resin film Example Comparative example 3-11 3-12 3-13 3-14 3-15 3-16 3-17 3-18 3-19 3-20 3-3 3-4 type 3-1b 3-2b 3-3b 3-4b 3-5b 3-6b 3-7b 3-8b 3-9b 3-10b 3-11b 3-12b Relative permittivity 2.7 2.7 2.8 2.9 2.7 2.8 2.8 2.7 2.8 2.9 2.6 2.6 Dielectric loss tangent 0.0015 0.0014 0.0014 0.0013 0.0016 0.0015 0.0014 0.0015 0.0014 0.0013 0.0017 0.0018 Tensile coefficient of elasticity [GPa] 0.6 0.7 0.7 0.8 0.5 0.7 0.7 0.5 0.6 0.6 0.4 0.8 Maximum elongation [%] 131 80 38 18 100 33 11 114 52 twenty two 197 226 Tg[℃] 54 54 58 58 54 58 58 54 56 56 56 56 Membrane retention good good good good good good good good good good good good Solder heat resistance test (dry) [℃] 320 320 320 320 320 320 320 320 320 320 320 320 Solder heat resistance test (moisture absorption) [℃] 260 260 270 280 270 270 280 280 280 290 220 280 Peel strength [kN/m] 1.6 1.5 1.2 1.2 2.0 1.3 0.9 1.4 1.0 0.7 1.6 1.7 Flame retardant ○ ○ ○ ○ ◎ ◎ ◎ ◎ ◎ ◎ X △

According to Table 3-2, it was confirmed that compared with the resin film 3-11b of Comparative Example 3-3, the resin film 3-1b to the resin film 3- of Example 3-11 to Example 3-14 to which the LCP filler was added were added. 4b's dielectric loss tangent, flame retardancy and solder heat resistance temperature (moisture absorption) have been improved. As the addition amount of LCP filler whose dielectric loss tangent is lower than that of DDA-based thermoplastic polyimide increases, the dielectric loss tangent of the resin film becomes smaller. In addition, by blending LCP filler with high aromatic ring concentration in easily combustible DDA-based thermoplastic polyimide, it exhibits excellent flame retardant effect. Furthermore, it can be considered that by adding the LCP filler, the moisture absorption component is reduced, and the coefficient of elasticity is increased, so that the solder heat resistance is improved.

In addition, the resin film 3-1b to the resin film 3-4b maintain film properties, and the adhesive strength also exceeds 0.6 kN/m, which is usually required for the production of flexible printed wiring boards. Therefore, the resin film of this embodiment is preferably A flexible printed wiring board that uses a high frequency band above 10 GHz is made. The DDA-based thermoplastic polyimide has a large elongation, so even if the LCP filler is added, the film properties can be maintained. Furthermore, since the Tg is sufficiently low for the pressing temperature, it is considered that the resin follows the fine irregularities on the surface of the copper foil and uses the carbonyl group of BTDA used as an acid anhydride to ensure adhesion.

In addition, according to Table 3-2, compared with the resin film 3-12b of the comparative example 3-4, the resin film 3-5b to the resin film 3- of the example 3-15 to the example 3-20 added with the LCP filler In 10b, the dielectric loss tangent is reduced, and the flame retardancy is greatly improved, for example, it is preferable as a material for a flexible printed wiring board for high-frequency corresponding to the increasing thickness of the dielectric layer. It is thought that in the combination of only DDA-based thermoplastic polyimide and phosphorus-based flame retardant, since the concentration of aromatic rings in DDA-based thermoplastic polyimide is low, in most cases the carbon formation of phosphorus-based flame retardant cannot be fully exhibited. In contrast to this, as shown in Examples 3-15 to 3-20, by using a combination of DDA-based thermoplastic polyimide, LCP filler, and phosphorus-based flame retardant, the aromatic ring in the composition As the concentration becomes higher, the flame retardant effect of the phosphorus-based flame retardant becomes greater.

As mentioned above, the embodiment of the present invention has been described in detail for the purpose of illustration, but the present invention is not restricted by the above-mentioned embodiment and can be variously modified.

This application is based on Japanese Patent Application No. 2019-196671 filed in Japan on October 29, 2019, and Japanese Patent Application No. 2019-238107 and Japanese Patent Application No. 2019- filed in Japan on December 27, 2019. The priority of No. 238108, all the contents of this application are cited in this article.

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Claims (22)

A resin composition containing the following components (A) and (B); (A) component: a thermoplastic resin containing a structural unit derived from a diamine component, the diamine component containing 40 mol% or more with respect to all diamine components with two terminal carboxylic acid groups of dimer acid A dimer diamine composition with a dimer diamine substituted with a primary amino methyl group or an amine group as the main component, and (B) Component: one or more selected from aromatic condensed phosphoric acid ester, silica particles, or liquid crystal polymer filler. The resin composition according to claim 1, wherein the component (A) is a tetracarboxylic anhydride component and the dimer diamine composition containing 40 mol% or more with respect to all diamine components The polyimide formed by the reaction of the diamine component of, and the component (B) is the aromatic condensed phosphate, The weight ratio of the (B) component to the (A) component is in the range of 0.05 to 0.7. The resin composition according to claim 2, wherein the weight ratio of the (B) component to the (A) component is in the range of 0.2 to 0.5. The resin composition according to claim 2, wherein the weight ratio of the phosphorus derived from the component (B) to the component (A) is in the range of 0.01 to 0.1. The resin composition according to claim 2, wherein the weight ratio of phosphorus derived from the component (B) to the dimer diamine composition in the component (A) is in the range of 0.01 to 0.15. The resin composition according to claim 2 further contains an amine compound having at least two primary amine groups as functional groups. The resin composition according to claim 1, wherein the component (A) is a tetracarboxylic anhydride component and the dimer diamine composition containing 40 mol% or more with respect to all diamine components The polyamide acid or polyimide formed by the reaction of the diamine component of, and the component (B) is silica particles having a white silica crystal phase or a quartz crystal phase, The (B) component is in the range of 5 wt% to 60 wt% with respect to the total of the (A) component and the (B) component, wherein the polyamide acid in the (A) component Converted to polyimidated polyimide. The resin composition according to claim 7, wherein the component (B) in the X-ray diffraction analysis spectrum using CuKα rays is relative to all peaks _{derived from SiO 2 in the range of 2θ=10° to 90°} The ratio of the total area derived from the total area of the peaks of the white silica crystal phase and the quartz crystal phase is 20% by weight or more. The resin composition according to claim 7, wherein, in the component (B), the cumulative value in the frequency distribution curve obtained by volume-based particle size distribution measurement using the laser diffraction scattering method is an average of 50% The particle size D ₅₀ is in the range of 6 μm to 20 μm. The resin composition according to claim 1, wherein the component (A) is a tetracarboxylic anhydride component and the dimer diamine composition containing 40 mol% or more with respect to all diamine components The polyimide formed by the reaction of the diamine component of, and the component (B) is the liquid crystal polymer filler, The (B) component is in the range of 15% by volume to 50% by volume with respect to the total of the (A) component and the (B) component. The resin composition according to claim 10, wherein the dielectric loss tangent of the component (A) at 10 GHz is Dfa, and the dielectric loss angle of the component (B) at 10 GHz is When the tangent is set to Dfb, Dfb is less than 0.0019, and Dfa>Dfb. The resin composition according to claim 10, wherein with respect to 100% by weight of the non-volatile organic compound component of the resin composition, 15% by weight to 30% by weight of a phosphorus-based flame retardant is further added. The resin composition according to claim 7 or claim 10, wherein the component (A) contains a total of 90 mol parts or more of the following general formula (1) relative to 100 mol parts of the tetracarboxylic anhydride component And/or tetracarboxylic anhydride represented by general formula (2),

In the general formula (1), X represents a single bond or a divalent group selected from the following formulas, and in the general formula (2), the cyclic moiety represented by Y represents the formation of a four-membered ring, a five-membered ring, and a six-membered ring. A cyclic saturated hydrocarbon group in a ring, a seven-membered ring or an eight-membered ring,

In the formula, Z represents -C ₆ H ₄ -, -(CH ₂ )n- or -CH ₂ -CH(-OC(=O)-CH ₃ )-CH ₂ -, n represents an integer of 1-20 . A resin film characterized by comprising a thermoplastic resin layer, wherein the resin film contains the following components (A) and (B); (A) component: a thermoplastic resin containing a structural unit derived from a diamine component, the diamine component containing 40 mol% or more with respect to all diamine components with two terminal carboxylic acid groups of dimer acid A dimer diamine composition with a dimer diamine substituted with a primary amino methyl group or an amine group as the main component, and (B) Component: one or more selected from aromatic condensed phosphoric acid ester, silica particles, or liquid crystal polymer filler. The resin film according to claim 14, wherein the thickness is in the range of 15 μm to 100 μm. The resin film according to claim 14, wherein the (B) component contains silica particles having a white silica crystal phase or a quartz crystal phase, and its content is relative to the (A) component and the (B) component. ) The total of the components is within the range of 3% by volume to 41% by volume. The resin film according to claim 14, wherein the (B) component contains the liquid crystalline polymer filler, and the content thereof is 15 volumes based on the total of the (A) component and the (B) component %～40% by volume. A laminated body characterized by having a base material and an adhesive layer laminated on at least one surface of the base material, wherein: The adhesive layer includes the resin film according to claim 14. A covering film characterized by having a covering film material layer and an adhesive layer laminated on the covering film material layer, wherein: The adhesive layer includes the resin film according to claim 14. A copper foil with resin, characterized in that it is formed by laminating an adhesive layer and copper foil, wherein: The adhesive layer includes the resin film according to claim 14. A metal-clad laminated board is characterized by having an insulating resin layer and a metal layer laminated on at least one surface of the insulating resin layer, wherein: At least one layer of the insulating resin layer includes the resin film according to claim 14. A circuit board obtained by performing wiring processing on the metal layer of the metal-clad laminate according to claim 21.